CA2093511C - Process for producing dialkylnaphthalene - Google Patents
Process for producing dialkylnaphthaleneInfo
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- CA2093511C CA2093511C CA002093511A CA2093511A CA2093511C CA 2093511 C CA2093511 C CA 2093511C CA 002093511 A CA002093511 A CA 002093511A CA 2093511 A CA2093511 A CA 2093511A CA 2093511 C CA2093511 C CA 2093511C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for for preparing a dialkylnaphthalene in one step by contacting an dialkylbenzene compound with a solid catalyst in a gas or liquid phase in the presence of hydrogen, using a catalyst having composition (I) or (II) below:
(1) (M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (2) Mixture of II-(i) and II-(ii):
(M3)d~(Al2O3) II-(i) (M4)e~(SiO2~XAl2O3) II-(ii) wherein M1 is a metal selected from the group consisting of metals belonging to group VIII of a periodic table and ruthenium;
M2 is a member selected from the group consisting of zinc, gallium, and oxides thereof;
M3 is a metal belonging to group VIII of a periodic table;
M4 is at least one alkali metal; and a, b, e, d, e, and X represent proportions, respectively.
(1) (M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (2) Mixture of II-(i) and II-(ii):
(M3)d~(Al2O3) II-(i) (M4)e~(SiO2~XAl2O3) II-(ii) wherein M1 is a metal selected from the group consisting of metals belonging to group VIII of a periodic table and ruthenium;
M2 is a member selected from the group consisting of zinc, gallium, and oxides thereof;
M3 is a metal belonging to group VIII of a periodic table;
M4 is at least one alkali metal; and a, b, e, d, e, and X represent proportions, respectively.
Description
_ 1 Description METHOD FOR PREPARING DIALKYLNAPHTHALENE
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a method for preparing dialkylnaphthalenes from alkenylbenzene com-pounds as a starting material. More particularly, the present invention relates to a method for preparing dialkylnaphthalenes by cyclizing and dehydrogenating alkenylbenzene compounds in one step.
DESCRIPTION OF THE PRIOR ART
Naphthalenedicarboxylie acids obtained by the oxidation of dialkylnaphthalenes are useful as a dibasic acid component for preparing polyesters. In particular, polyesters containing naphthalene-2,6-diearboxylie acid as a dibasic acid component are well known to have excel-lent properties.
Roughly grouping, two methods have hitherto been known for the preparing of dialkylnaphthalenes.
More specifically, there have been proposed a method which derives dialkylnaphthalene from naphthalene com-pounds, and a method which derives them from benzene compounds.
Examples of the method which uses naphthalene compounds as a starting material include methods in which naphthalenes are methylated (Japanese Patent Applications Laid-Open Nos. 45536/1985 and 172937/1985), a method in which naphthalenes are ethylated (Japanese Patent Appli-cations Laid-Open Nos. 6953/1976 and 50017911991 corres-ponding to U. S. Patent 4,873,386), methods in which naphthalenes are propylated (W090/03961, and Japanese 30 Patent Applications Laid.-Open Nos. 9942/1989 and 9943/1989), methods in which naphthalenes are acylated (Japanese Patent Applications Laid-Open Nos. 53937/1987, 188343/1985 and 135756/1979), and so on. These methods not only suffer from problems of impurities contained in the naphthalene compounds used as a raw material, and supply of purified naphthalenes, but also are less com-petitive from the viewpoint of cost.
On the other hand, the following methods have been proposed that derive dialkylnaphthalenes from alkyl-benzenes. One is a method in which a starting material obtained by acylating alkylbenzene in the presence of a HF/BF3 catalyst is subjected to a hydrogenating step, a dehydrating step and a cyelizing and dehydrogenating step to prepare a dialkylnaphthalene (Japanese Patent Applica-tions Laid-Open Nos. 9650/1990 and 167237/1990). This method cannot be said to be advantageous industrially because of long procedure and use of a HF/BF3 catalyst.
Further, as the cyclizing and dehydrogenating catalyst, there have been proposed metal oxide catalysts such as alumina-chromia and iron oxide catalysts, or those cata-lysts containing precious metals such as platinum and palladium carried on alumina or activated carbon. There is cited Cr203-K20-A1203 as an example, which gives a very low selectivity for the objective compound.
Whereas a method has been known in which di-methylnaphthalene is obtained from a tolylpentene com-pound as a starting material by cyclization-dehydrogena-tion in one step. For example, U. S. Patent 3,931,3$
discloses use of a catalyst containing a combination of an alkali metal and chromia-alumina, a catalyst contain-ing rhenium oxide, an alkali metal, and an alkaline earth metal carried on alumina, etc., as a cyclization-dehydro-genation catalyst. Their yields are too low to be Indus-trially acceptable.
U. S) Patent 3,24,758 suggests a method in which cyclization and dehydrogenation are performed simultaneously using platinum-alumina or platinum-silica alumina as a catalyst, without showing concrete data of actual reactions. Further, Japanese Patent Publication ~U~~~~
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a method for preparing dialkylnaphthalenes from alkenylbenzene com-pounds as a starting material. More particularly, the present invention relates to a method for preparing dialkylnaphthalenes by cyclizing and dehydrogenating alkenylbenzene compounds in one step.
DESCRIPTION OF THE PRIOR ART
Naphthalenedicarboxylie acids obtained by the oxidation of dialkylnaphthalenes are useful as a dibasic acid component for preparing polyesters. In particular, polyesters containing naphthalene-2,6-diearboxylie acid as a dibasic acid component are well known to have excel-lent properties.
Roughly grouping, two methods have hitherto been known for the preparing of dialkylnaphthalenes.
More specifically, there have been proposed a method which derives dialkylnaphthalene from naphthalene com-pounds, and a method which derives them from benzene compounds.
Examples of the method which uses naphthalene compounds as a starting material include methods in which naphthalenes are methylated (Japanese Patent Applications Laid-Open Nos. 45536/1985 and 172937/1985), a method in which naphthalenes are ethylated (Japanese Patent Appli-cations Laid-Open Nos. 6953/1976 and 50017911991 corres-ponding to U. S. Patent 4,873,386), methods in which naphthalenes are propylated (W090/03961, and Japanese 30 Patent Applications Laid.-Open Nos. 9942/1989 and 9943/1989), methods in which naphthalenes are acylated (Japanese Patent Applications Laid-Open Nos. 53937/1987, 188343/1985 and 135756/1979), and so on. These methods not only suffer from problems of impurities contained in the naphthalene compounds used as a raw material, and supply of purified naphthalenes, but also are less com-petitive from the viewpoint of cost.
On the other hand, the following methods have been proposed that derive dialkylnaphthalenes from alkyl-benzenes. One is a method in which a starting material obtained by acylating alkylbenzene in the presence of a HF/BF3 catalyst is subjected to a hydrogenating step, a dehydrating step and a cyelizing and dehydrogenating step to prepare a dialkylnaphthalene (Japanese Patent Applica-tions Laid-Open Nos. 9650/1990 and 167237/1990). This method cannot be said to be advantageous industrially because of long procedure and use of a HF/BF3 catalyst.
Further, as the cyclizing and dehydrogenating catalyst, there have been proposed metal oxide catalysts such as alumina-chromia and iron oxide catalysts, or those cata-lysts containing precious metals such as platinum and palladium carried on alumina or activated carbon. There is cited Cr203-K20-A1203 as an example, which gives a very low selectivity for the objective compound.
Whereas a method has been known in which di-methylnaphthalene is obtained from a tolylpentene com-pound as a starting material by cyclization-dehydrogena-tion in one step. For example, U. S. Patent 3,931,3$
discloses use of a catalyst containing a combination of an alkali metal and chromia-alumina, a catalyst contain-ing rhenium oxide, an alkali metal, and an alkaline earth metal carried on alumina, etc., as a cyclization-dehydro-genation catalyst. Their yields are too low to be Indus-trially acceptable.
U. S) Patent 3,24,758 suggests a method in which cyclization and dehydrogenation are performed simultaneously using platinum-alumina or platinum-silica alumina as a catalyst, without showing concrete data of actual reactions. Further, Japanese Patent Publication ~U~~~~
No. 1036/1975 describes a method in which the aforemen-tioned one-step reaction is performed in a gas phase using a palladium catalyst. This method suffers from vigorous decomposition of the starting material and yield of dimethylnaphthalene, the objective compound, is low.
Further, Japanese Patent Publication No. 1037/1975 des-cribed a method in which the aforementioned one-step reaction in a liquid phase using a silica alumina cata-lyst carrying thereon a metal such as platinum, palla-dium, rhodium or' rhenium. This method, too, gives a low conversion of the starting material, and suffers from decomposition of the starting material, resulting in that it is unsuitable as an industrial process.
Also, a method has been proposed in which dimethylnaphthalene is prepared from xylenes and buta-diene (Japanese Patent Publication Nos. 1230/1975 and ~~~9~/1981). This method uses tolylpentenes obtained by alkenylating xylene with butadiene as a starting material and prepares dimethylnaphthalene compounds, the objective compounds, via a cyclizing step, a dehydrogenating step and a isomerizing step.
While this method is featured in that each reaction thereof has a very good selectivity and proceeds in a high yield, it is disadvantageous in that not only it involves a long series of steps but also it requires a complicated apparatus since the cyclizing step, which is an exothermic reaction, and the dehydrogenating step, which is an endothermic reaction, are independent of each other. Conventional proposals for carrying out these reactions in one step reaction have been unacceptable industrially as described above. In particular, alkenyl-benzene compounds which are a starting material are susceptible to hydrogenation reaction, a side reaction, with hydrogen generated or carrier hydrogen and converted to alkylbenzene compounds. As a result, cyclization reaction is difficult to proceed, thus giving poor selec--tivity and yield.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide an industrial process for obtaining dialkylben-zene directly from alkenylbenzene compounds which carries out cyelizing and dehydrogenating reaction in one step.
A second object of the present invention is to provide a method for preparing dialkylbenzene which carries out the aforementioned one step reaction at high selectivity.
Other object of the present invention is to provide a solid catalyst suitable for carrying out the aforementioned one step reaction on an industrial scale.
DETAILED DESCRIPTION OF THE INVENTION
MEANS FOR SOLVING THE PROBLEMS
As a result of investigation by the present inventors, it has now been found that in a method far preparing a dialkylnaphthalene compound by contacting an alkenylbenzene compound represented by formula LA]
~~z wherein R1 is a butenyl group substituted with a C1-C
alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R-' is a hydrogen atom or a C1-C~ alkyl group), and R2 is a C1-C~ alkyl group, with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, use of the following composition (I) or (II) gives rise to a dialkylnaphthalene at a high conversion and a high selectivity.
Thus, it has been found that according to the present invention, the aforementioned object is achieved by use of the catalyst having the following composition (I) or (II).
Catalyst Composition (I) This composition is represented by formula (I) below:
(M1)a~(M2)b°(Si02~XA1203)~(A1203)c (I) wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VTII of a periodic table and ruthenium;
M2 represents at least one member selected from the group consisting of zinc, gallium and oxides thereof;
X is a molar ratio of A1203 to Si02 in (Si02.XA1203) and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (Si02~XA1203) and (A1203)c, and is within the range of 0.01 to 5;
b is ~ by weight of M2 as metal based on the weight of (Si02~XA1203), and is within the range of 0.1 to 50; and a is a weight ratio of (A1203) to (Si02~XA1203), and is within the range of 0 to 5.
Catalyst Composition (II) This composition is represented by formula (IT) below:
(M3)d~(A1203) II-(i) and (M~~)e.(Si02~XA1203) II-(ii) wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is ~ by weight of M3 based on (A1203), and is within the range of 0.05 to 5;
M~ represents at least one alkali metal;
a is % by weight of M~ based on (Si02~XA1203), and is within the range of 0.05 to 10; and X is a molar ratio of A1203 to Si02 in (Si02~XA1203), and is within the range of 0.05 to 5.
Thus, according to the present invention, it is ~~9~a~
possible to carry out a cyclization reaction and a dehy-drogenation reaction in one step reaction by contacting an alkenylbenzene compound represented by the aforemen-tioned formula CA7 with the aforementioned catalyst composition (I) or (II) in a gas or liquid phase, thus achieving a high conversion of the starting material and a high selectivity of the objective compound to obtain a dialkylnaphthalene in a high yield.
Hereinafter, the method of the present inven-Lion will be described in more detail.
In the method of the present invention, an alkenylbenzene compound represented by the aforementioned formula CA] is used as a starting material. In the aforementioned formula CA7, the alkenylbenzene compound includes a benzene ring which has two substituents R1 and R2 thereon. R1 is a butenyl group substituted with a C~-C4 alkyl group or a group -CHI-CH2-CH2-CH=C-R3 (where R is a hydrogen atom or' a G1-C~ alkyl group). Here, the aforementioned butenyl group is a group -C~H2-C~H2-C~H~CH2 of which any one C~ among the three Cg's is substituted with a C1-C4 alkyl group, preferably a methyl group. On the other hand, the substituent R2 is a C1-C~
alkyl group, whose specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc., with an methyl group being preferred.
The positions of the two substituents R1 and R2 may be any of ortho-, mete- and pare-positions. The positions of R1 and R2 and the kind of the substituent on R1 give a great influence on the position of the dialkyl group on the objective dialkylnaphthalene.
Specific examples of the alkenylbenzene com-pound represented by the aforementioned formula CA7 include, for example, o-tolyl-2-methylbutene-3, o-tolyl-3-methylbutene-3, m-tolyl-2-methylbutene-3, m-tolyl-3-methylbutene-3, p-tolyl-2-methylbutene-3, p-tolyl-3-_ 7 _ methylbutene-3, o-tolylpentene-3, o-tolylpentene-4, m-tolylpentene-3, m-tolylpentene-4, p-tolylpentene-3, p-tolylpentene-4, o-ethylphenyl-2-methylbutene-3, o-ethylphenyl-3-methylbutene-3, m-ethylphenyl-2-methyl-butene-3, p-ethylphenyl-2-methylbutene-3, o-ethylphenyl-pentene-3, o-ethylphenylpentene-4, m-ethylphenylpentene-3, m-ethylphenylpentene-4, p-ethylphenylpentene-3, p-ethylphenylpentene-~, o-propylphenyl-2-methylbutene-3, o-propylphenyl-3-methylbutene-3, m-propylphenyl-2-methyl-butene-3, m-propylphenyl-3-methylbutene-3, p-propyl-phenyl-2-methylbutene-3, p-propylphenyl-3-methylbutene-3, o-propylphenylpentene-3, o-propylphenylpentene-~, m-propylphenylpentene-3, m-propylphenylpentene-b, p-propyl-phenylpentene-3, p-propylphenylpentene-~, o-tolyl-2-ethylbutene-3, m-tolylethylbutene-3, p-tolyl-2-ethyl-butene-3, o-tolyl-3-ethYlbutene-3, m-tolyl-3-ethyl-butene-3, p-tolyl-3-ethylbutene-3, o-tolylhexene-3, o-tolylhexene-~E, m-tolylhexene-3, m-tolylhexene-~, m-tolylhexene-5, p-tolylhexene-3, p-tolylhexene-4, p-tolyl-hexene-5, etc.
As described above, the kinds of the substi-tuents R1 and R2 and bonding positions of R1 and R2 of the alkenylbenzene compound give an influence on the kind of the dialkylnaphthalene obtained as a result of the reaction. To take some preferred examples thereof, there are prepared mainly 2,7-dimethylnaphthalene when m-tolyl-2-methylbutene-2 or -3 is used as a starting material;
2,6-dimethylnaphthalene in the case of m-tolyl-3-methyl-butene-2 or -3, and p-tolyl-2-methylbutene-2 or -3;
1,5-dimethylnaphthalene in the ease of o-tolylpentene-2, -3 or -~; 1,6-dimethylnaphthalene in the case of o-tolyl-3-methylbutene-2 or -3; 1,7-dimethylnaphthalene in the case of o-tolyl-2-methylbutene-2 or -3.
Among the aforementioned alkenylbenzene com-~5 pounds, o-tolylpentene-2, -3, or -4 is preferred in view of availability and type of the objective dimethylnaph-- g _ thalene.
In the method of the present invention, a dialkylnaphthalene is prepared by a one step reaction in which an alkenylbenzene compound represented by the aforementioned formula (A7 is contacted with the afore-mentioned catalyst composition (I) or (II). Therefore, these catalysts used in the method of the present inven-tion are multifunctional catalysts which have a cycliza-tion function which forms a dialkyltetraline compound from an alkenylbenzene compound, and a dehydrogenation function which convarts the tetraline compound into a dialkylnaphthalene compound under the same reaction conditions. In addition, the aforementioned catalysts used in the method of the present invention retain the aforementioned desired functions for a long time without causing any side reactions such as hydrogenation of alkenyl groups in the starting material under hydrogen atmosphere conditions.
Next, the catalyst compositions (I) and (II), and their preparation will be described concretely.
(1) Catalyst Composition (I) and Its Preparation:
Catalyst composition (I) is represented by formula (I) below as described above.
(M1)a~(M2)b~(Si02~XA1203)~(A1203)c (I) In short, the aforementioned composition (I) can be said to be a solid catalyst composed of siliea-alumina represented by (SiOZ~XA1~03) having carried thereon M1 and M2 components, and optionally.alumina represented by (A1203)c mixed therewith.
M1 is at least one metal selected from the group consisting of group VIII metals of a periodical table and rhenium. More specifically, there can be cited Pt (platinum), Pd (palladium), Rh (rhodium), Ru (ruthe-nium), Os (osmium), Ir (iridium) or Re (rhenium). Those may be used singly or in admixture.
Among them) preferred are/is Pt (platinum) and/or Re (rhenium).
M2 is at least one metal selected from the group consisting of zinc (Zn) and gallium (Ga), or its oxide.
In the aforementioned composition (I), (Si02~XA1203) is a silica-alumina component, and X is a molar ratio of A1203 to Si02, which is within the range of 0.05 to 5, and preferably 0.1 to 3.
The proportion (a) of the M1 component is within the range of 0.01 to 5~ by weight, and preferably 0.1 to 3~ by weight based on the sum of (Si02~XA1203) and (Al?03>.
The proportion (b) of the M2 component is within the range of 0.1 to 50~ by weight, and preferably 1 to 40~ by weight, as metal, based on the weight of (Si02~XA1203).
The proportion (c) of alumina (A1203) is within the range of 0 to 5 parts by weight, and preferably 0.2 to 4 parts by weight per part by weight of silica-alumina component (Si02~XA1203). The alumina (A1203) is in the form of a mixture with (M1)a~(M2)b~(Si02~XA1~03)~
(A1203)c, and also serves as a diluent or binder (modling aid). On the other hand, as another embodiment, the catalyst composition (I) may also be a solid catalyst in the form of a mixture of alumina (A1203) having carried thereon a portion or all of the M1 component, and (MZ)b~(Si02~XA1203). This solid catalyst is inoluded in the catalyst composition (I) of the present invention so far as it has the aforementioned composition.
The aforementioned catalyst composition (I) can be prepared by the following method. That is, an aqueous solution of salts) of zinc (Zn) and/or gallium (Ga) and silica-alumina (Si02~XA1203) powder are mixed, and the salts) is/are carried on the silica-alumina by evapora-Lion to dryness or dipping and filtration, and then the caleined to obtain silica-alumina having carried thereon 20~3a~.~.
zinc and/or gallium oxide(s). Next, the silica-alumina thus obtained and an aqueous solution of a compound of the metal in the M1 component are mixed, and calcined at a temperature of, for example, 450 to 500°C so that an oxide of the metal in the M1 component is carried on the aforementioned silica-alumina (which carries thereon the M2 component). The powder thus obtained may be molded as it is, or mixed with alumina (A1203) and molded into granules or pellets. The molded catalyst may be further caleined, or reduced in a hydrogen atmosphere before use to exhibit its activity.
As the salt of zinc (Zn) to be introduced into the M2 component used in the preparation of the aforemen-tioned catalyst composition (I), are preferred those which are water-soluble and can be converted into zinc oxide under calcination conditions. For example, there can be cited zinc nitrate, zinc chloride, zinc acetate, ete. As the salt of gallium, are preferred similarly those which are water-soluble and can be converted into gallium oxide under caleination conditions. For example, there can be cited gallium nitrate, gallium chloride, gallium acetate, ete. The salts of zinc and those of gallium may be used singly or as mixture.
On the other hand, as the at least one metal selected from the group consisting of metals belonging to group VIII of a periodical table and rhenium, are pre-ferred those which are water-soluble and can be converted into an oxide under caleination conditions. For example, chlorides, nitrates, or acetates of the aforementioned metals can be used.
(2) Catalyst Composition (II) and Its Preparation:
Catalyst composition (II) is a mixture of the following formula II-(i) and TI-(ii):
(M3)d~(A1203) II-(i) (M4)e~(Si02~XA1203) II-(ii) The above-described formula IT-(i) represents alumina (A1203) on which thelM3 component is carried. M3 represents at least one metal belonging to group VIII of a periodical table. Specifically Pt (platinum), Pd (palladium) and Rh (rhodium) are preferred, with Pt (platinum) being particularly preferred. The proportion (d) of M3 is within the range of 0.05 to 5~ by weight, and preferably 0.1 to 3% by weight based on alumina (A1203).
The above-described formula II-(ii) represents silica-alumina (Si02~XA1203) which includes an alkali metal (M4) being ion exchanged or carried thereon. As the alkali metal (M4), are preferred Na (sodium) and K
(potassium), with Na (sodium) being particularly pre-ferred. The proportion (e) of M4 is within the range of 0.05 to 10~ by weight, and preferably 0.1 to 5~ by weight. On the other hand, X in the silica-alumina represents a molar ratio of A1203 to Si02, and is within the range of 0.05 to 3, and preferably 0.1 to 3.
The aforementioned catalyst composition (II) is a mixture of the above formulae II-(i) and II-(ii) as described above, and is preferably a uniform mixture of the powder of TI-(i) and the powder of IT-(ii). The mixing proportion, by weight, of the two is within the range of 1:10 to 10:1, and preferably 1:5 to 5:1.
The aforementioned II-(i) can be prepared by impregnating alumina posader (A1203) with an aqueous solution of a compound of a metal in the M3 component, having the compound of M3 carried an the alumina (A1203) by evaporation to dryness or dipping and filtration, and caleining it. This caleinat,ion may be carried out at a temperature of 400 to 500°C, or may be performed after the mixing with the component II-(ii). As the compound of M3 to be used, those compounds are suitable which are water-soluble compounds of group VIII metals and can form oxides by caleination. For example, chlorides and nitrates are preferred.
~fl~ i~l~
On the other hand, the aforementioned II-(ii) can be prepared by impregnating silica-alumina powder (Si02~XA1203) with an aqueous solution of a compound of a metal in the M4 component, having the compound M4 carried on the silica-alumina (Si02.XA1203) by evaporation to dryness or dipping and filtration, and caleining it.
This calcination may be carried out at a temperature of 400 to 500°C, or may be performed after the mixing with the component II-(i). As the compound of M4 to be used for the preparation of II-(ii), those compounds are preferred which are water-soluble and can form oxides upon calcination. For example, chlorides, hydroxides or nitrates are preferred.
The catalyst composition (IT) can be prepared by mixing the powders II-(i) and II-(ii) obtained as described above in the aforementioned proportions. The catalyst composition (II) may be supplied to the reaction after the powder mixture is molded into granules or pellets by a process known per se. To do so is Preferred.
The catalyst compositions (I) and (IT) of the present invention described above: each are novel as catalysts for cyclizaiton~dehydrogenation, and the use of them as catalysts in reaction methods and under reaction conditions described below can give rise to dialkylnaph-thalenes in high yields. Also, a specified dialkylnaph-thalene can be obtained at a high selectivity.
III. Reaction method and Conditions Thereof:
In the method of the present invention, the reaction is carried out by contacting the alkenylbenzene compound of the aforementioned formula CA7 as a starting material with the aforementioned catalyst composition (I) or (II) in a hydrogen atmosphere. In this case, the reaction may be carried out either in a gas phase reac-tion in which the starting material is contacted with the catalyst in the form of vapor, or in a liquid phase reae-tion in which the starting material is contacted with the catalyst in the form of a liquid. In the both gas phase reaction and liquid phase reaction, the catalyst may be of an type such as a fixed bed type, a mobile bed type, a fluidized bed type, or a suspension type. Further, the reaction may be a continuous type, batch type, or the like.
The reaction temperature is 150°C to 500°C, and preferably 200°C to 450°C, and the reaction pressure may be either atmospheric or superatmospheric. In a liquid phase reaction, the reaction may be carried out under pressure so that the alkenylbenzene compound as a start-ing material can be retained in the form of a liquid.
Upon the reaction, the starting material may be diluted with another stable diluent. For example, there can be used organic diluents, e.g., benzene compounds such as benzene, toluene, and xylene; naphthalene deriva-tive compounds such as naphthalene, alkylnaphthalene, tetraline, alkyltetraline, decaline, alkyldecalines; and further' inorganic diluents, e.g., gases such as nitrogen.
In order to increase yiehd, and prevent deactivation of the catalyst, hydrogen gas is made present. When the starting material of the reaction is diluted, molar proportion of the diluent/starting material of the reac-tion 0.5 to 30, and preferably 1 to 15. WHSV, which is a contact time during which the starting material contacts the catalyst, is 0.1 to 20, and preferably 0.2 to 10.
EFFECT OF THE INVENTION
According to the present invention, reaction of a specified alkenylbenzene compound using a specified catalyst prepares a dialkylnaphthalene, and therefore a specified dialkylnaphthalene can be obtained at a high selectivity and in a high yield. Further, the reaction which has been carried out in two steps conventionally can be performed in one step, and hence the method of the present invention is economically excellent.
1 ~4 -In particular, the method of the present inven-tion is excellent in that a specified dialkylnaphthalene aimed at can be obtained at a very high selectivity.
Hereinafter, this advantage will be described in more detail.
Dialkyltetraline, which are products of the cyclization reaction derived from alkenylbenzene com-pounds and intermediate products in the method of the present invention, can isomerize freely on acid catalysts and give rise to various isomers. Once they are dehydro-genated and converted into dialkylnaphthalenes, they are classified into four groups as shown in the following table. While isomerization reactions can readily occur between iosmers within each groups, generally isomeriza-tion reactions between groups are difficult to occur.
No. Group Isomer 1 2,3-Group 1,4-, 1,3-, ~,3-Dialkylnaphthalenes 2 1,6-Group 1,5-, 1,6-, 2,b-Dialkylnaphthalenes 3 2,7-Group 1,8-, 1,7-, ?.,7-Dialkylnaphthalenes 4 Others 1,2-Dialkylnaphthalene, and others Therefore, in the method for preparing an objective dimethylnaphthalene compound from an alkenyl-benzene compound which is obtained by alkenylation of xylenes with butadiene as a starting material by a cyclizing step, a dehydrogenating step, and an isomeriz-ing step, it is important that the reaction product in the dehydrogenating step is a specified dimethylnaphtha-lene or that belonging to a specified group since it is only necessary to proceed isomerization reactions between those isomers that are included in each selected group to proceed, that is those reactions which can take place readily in the subsequent isomerization step. In the case where the cyclizing step, which is an exothermic reaction, and the hydrogenating step, which is an endo-thermie reaction, are practiced in a one-step reaction, it is similarly important to proceed the dehydrogenation reaction efficiently while suppressing the isomerization reaction of dialkyltetraline produced by the cyclization reaction in order to obtain the objective dialkylnaphtha-lene compound.
The use of the catalyst compositions (I) and (II), in particular composition (II), in the method of the present invention substantially suppresses the iso-merization reaction of dialkyltetraline, intermediate product of the reaction, resulting in that dialkylnaph-thalene of a specified group can be obtained at a high conversion and a high selectivity. For example, dialkyl-naphthalenes of 2,6-group are preferred as a starting material for 2,6- .naphthalenedicax~boxylic acid. For this, purpose, for example; mainly 2,6.-dimethylnaphthalene is obtained from m-tolyl-3-methylbutene-2 or -3, and p-tolyl-2-methylbutene-2 or -3, mainly 1,5-dimethylnaph-thalene from o-tolylpentene-2, -3 or -4; and mainly 1,6-dimethylnaphthalene is obtained from o-tolyl-3-methylbutene-2 or -3.
Preparation of Dialkyltetralines According to another investigation by the present inventors, there has been found the following method for preparing a dialkyltetraline from the alkenyl-benzene compound represented by the aforementioned for-mula CA7 at a high conversion and a high selectivity.
The dialkyltetraline thus obtained can readily be con-verted into a dialkylnaphthalene by contacting it with a dehydrogenating catalyst.
That is, according to the present invention, there is provided a method for preparing a dialkyltetra-~~9~511 - 1s -line compound by contacting an alkenylbenzene compound represented by formula CA7 below:
RI
LAJ
wherein R1 is a butenyl group substituted with a C1-C
alkyl group or a group -CH2-CH2-CH2-CH~CH-R3 (where R~ is a hydrogen atom or a C1-C~ alkyl group), and R2 is a C1-C4 alkyl group, with a solid catalyst in a gas or liquid phase at a temperature of 200 to 500°C substan-tially in the absence of hydrogen, wherein as said solid catalyst is used a cata-lyst having a composition represented by formula (III) below:
M5f~(Si02~XA1203) (III) where M5 represents at least one metal selected from the group consisting of alkali metals, zinc, gallium and oxides thereof;
f is ~ by weight of M5 as metal based on (Si02~XA120~), and is within the range of 0.01 to 50; and X is a molar ratio of A1203 to Si02 in (Si02~XA1203), and is within the range of 0.05 to 5.
Tn the aforementioned method, the alkenylben-zene compound represented by formula CA7 and used as a starting material may be the same as that described in the preparation of the aforementioned dialkylnaphthalene.
Preferred starting material may be the same as that described above as t~referred ones.
Referring to the solid catalyst having the composition represented by formula (III) used in the aforementioned method, this is a catalyst which contains silica-alumina (Si02~XA1203) having carried thereon the M5 component. In the composition (III), M5 is at least one metal selected from the group consisting of alkali metals, zinc and gallium, and oxides thereof. As the alkali metal, sodium or potassium is preferred. f is by weight of M5 as metal based on the silica-alumina (SiO~~XA1203), and is within the range of 0.01 to 50~ by weight, and preferably 0.1 to 40% by weight. Most pre-ferred range of f i.s 0.1 to 30~ by weight when M5 is an alkali metal, and 1 to 40~ by weight when M5 is zinc, gallium or their oxides. X is the silica-alumina (Si02.XA1203) is a molar ratio of A1203 to Si02, and is within the range of 0.05 to 5, and preferably 0.1 to 3~
The composition (III) can be prepared by mixing an aqueous solution of a compound of the metal in the M5 component with a silica-alumina powder (Si02.XA1203), subjecting the mixture to evaporation to dryness or dipp-ing filtration to have the salt of the metal in the M5 component carried on the silica-alumina, and then calcin-ing. The caleination is performed suitably at a tempera-ture of 450 to 500°C. As the salt of the alkali metal used in the aforementioned preparation, there can be cited, far example, sodium hydroxide, potassium hydrox-ide, etc. As 'the salt of zinc or gallium, there can be cited, for' example, zinc nitrate, zinc chloride, zinc acetate, gallium nitrate, gallium chloride, gallium acetate, ete.
The powder obtained by the aforementioned preparation method can be molded into granules or pellets by a suitable method. In this ease, any method may be used as the molding method, or a molding aid may be used.
That is, molded article obtained by mixing the above-des-cribed powder with a molding aid, molding and calcining may be used in the reaction. As the molding aid, there can be used clay, silica--alumina, boehmite, alumina, etc,, with alumina being preferred. It is preferred that the molding aid be used in a weight proportion of 0.5 to 1.9 to the above--described catalyst.
2~~a~~.
The catalyst composition (III) obtained by the aforementioned preparation method is a novel catalyst composition as a catalyst for the preparation of a dialkylbenzene by cyclization of an alkenylbenzene com-pound.
The catalytic reaction of an alkenylbenzene compound using the catalyst composition (III) thus obtained may be carried out either in a gas phase reac-tion in which the starting material is contacted with the catalyst in the form of vapor, or in a liquid phase reaction in which the starting material is contacted with the catalyst in the form of a liquid. In the both gas phase reaction and liquid phase reaction, the catalyst may be of any type such as a fixed bed type, a mobile bed type, a fluidized bed type, or a suspension type. Fur-ther, the reaction may be a continuous type, batch type, or the like.
The reaction temperature is 200°C to 500°C, and preferably 200°C to 450°C, and the reaction pressure may be either atmospheric or superatmospherie. In a liquid phase reaction, the reaction may be carried out under pressure so that the alkenylbenzene compound as a start-ing material can be retained in 'the form of a liquid, Upon the reaction, the starting material may be diluted with another stable diluent. For example, there can be used organic diluents, e.g., benzene compounds such as benzene, toluene, and xylene; and further inorga-nic diluents, e.g., gases such as nitrogen. When the starting material of the reaction is diluted, molar proportion of the diluent/starting material of the reac-tion is 0.5 to ~0, and preferably 1 to 15. WHSU, which is a contact time during which the starting material of the reaction contacts the catalyst, is 0.1 to 20, and preferably 0.2 to 10.
The reaction of the present invention must be carried out substantially in the absence of hydrogen ~~~~~1~
since in the presence of hydrogen no objective compound can be obtained, According to the present invention, the cyeli zation reaction of an alkenylbenzene compound, which has been carried out using silica-alumina or the like cata lyst at a low temperature (for example, at a temperature of 150 to 180°C) in order to prevent side reactions, can be performed at a relatively high temperature and at a high selectively and in a high yield.
The dialkyltetraline thus obtained can be converted into a dialkylnaphthalene by a method known per se, for example, by a method in which it is contacted with a dehydrogenating catalyst, e.g., plantinum-alumina at a temperature of 300 to 500°C to carry out dehydroge-nation.
For example, in the case where 1,5-dimethyl-tetraline and/or 1,6-dimethyltetraline are/is reacted in a gas phase using a platinum-alumina catalyst to obtain 1,5-dimethylnaphthalene and/or 1,6-dimethylnaphthalene can be prepared efficiently by setting up the catalyst caleination temperature to 300 to 400°C, the catalyst reduction temperature to 400 to 500°C, and the reaction temperature to 350 to 450°C; or 'the catalyst cal.cination temperature to 400 to 500°C, the catalyst reduction temperature to 300 to 400°C, and the reaction temperature to 350 to 450°C.
The present invention enables the cyclization reaction of alkenylbenzene compounds at substantially the same temperature range as that of the dehydrogenation reaction of dialkyltetralines, thus making it possible to carry out the cyclization reaction and dehydrogenation reaction at high energy efficiency without change in the reaction temperature.
Since a series of the cyelization and dehydro-genation reactions proceed in substantially the same temperature range, they can be carried out in the same - 20 .~ ~~~~
reaction vessel or in respective reaction vessels, in a continuous process, a sequential process or in combina-tion thereof.
EXAMPLES
Hereinafter, the present invention will be described in detail by examples.
Example 1 Preparation of Catalyst of Composition (I) Powder (10 g) of silica-alumina catalyst (N631HN produced by Japan Gasoline Corporation, eontain-ing 28% by weight of A1203) was charged in 50 ml o.f deionized water containing 6.8 g of zinc nitrate hexahyd-rate while stirring, and stirred at 50°C for 4 hours.
Then, after it was evaporated to dryness using a rotary evaporator, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was caleined in an air atmosphere in a muffle furnace at 500°C for 8 hours to prepare silica-alumina powder carrying thereon 15% zinc.
The above-described silica-alumina powder (5.75 g) carrying thereon 15% zinc was suspended in 50 m1 of deionized water, to which was added 1 ml of an aqueous solution of chloroplatinic acid containing 5.75 mg of Pt, and the mixture was stirred at 50°C for 4 hours. Then, after it was evaporated to dryness using a rotary evapo-rator, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was calcined in an air atmosphere in a muffle furnace at 500°C for 8 hours, and thereafter, the same weight of '~ alumina was well mixed therewith. The resulting mixture was molded into pellets with adjusting the grain size to 10 to 20 mesh to obtain catalyst A-1.
Catalyst A-1 contains 0.05% of platinum based on the total weight of the silica-alumina and alumina, and 15% of zinc based on the weight of the silica-alumina) Similarly to the above-described catalyst A-1, 2~9~~a~.1 catalysts A-2 to A-4 which contain platinum and zinc, catalysts B-1 to B-6 which contain group VTII metals other than platinum, or rhenium, and zinc, catalysts C-1 to C-6 which contain platinum and gallium, catalyst D-1 which contains rhenium and gallium, as shown in Table 1 were prepared.
Also, catalyst E which contains no metal, and catalyst F' which contains only platinum were prepared similarly as described above as comparative catalysts.
Example 2 Evaluation of performances of Catalyst of Composition (I) The catalyst (5 g) obtained as described above was precalcined in an air atmosphere in an electric furnace at 450°C for 4 hours, and then filled in a reac-tion tube made of glass. After practicing reduction with hydrogen in a stream of hydrogen at 500°C for 2 hours, the temperature was adjusted to a reaction temperature, and 10~ toluene solution of a mixture of o-tolylpentene-3 and o-tolylpentene-4 was fed under the condition of WHSV
° 1~ After 12 hours and 24 hours, respectively, from the supply of the oil, samples were collected, and analyzed by gas chromatography. Results obtained are shown in Table 1.
(In Table 1, molar ratio means a molar ratio of carrier gas to starting material.) Terms used in Table 1 are defined as follows:
Conversion Amount of o-tolylpentene-3 or -4 converted (mole) x 100 Amount of o-tolylpentene-3 or -4 supplied (mole) Loss Ratio =
Amount of o-tolylpentene-3 or -4 formed (mole) x 100 ' Amount of o-tolylpentene-3 or -4 converted (mole) Seleetivity-1 -Amount of dimethyltetraline formed (mole) x 100 Amount of o-tolylpentene-3 or -4 converted (mole) Selectivity-2 =
Amount of dimethylnaphthalene formed (mole) x 100 Amount of o-tolylpeptene-3 or -4 converted (mole) _ 23 _ w ~.
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_ 27 Example 3 (Example in which o-tolyl-2-methylbutene-3 was used as alkenylbenzene compound) Catalyst A-2 (5 g) in Example 1 above was filled in a reaction tube and subjected to reduction with hydrogen in the same manner as in Example 2 above.
Thereafter, 10% toluene solution of o-tolyl-2-methyl-butene-3 was fed WHSV = 1 under the conditions of a reaction temperature of 450°C, and a hydrogen car.rier/-starting material molar ratio of 4. After 12 hours a sample was collected and analyzed by gas chromatography.
As a result, the following performances were confirmed.
Conversion: 100.0 %, Loss ratio: 0.6 %, Selectivity-1: 7.0 %, , Selectivity-2: 89.5 %, Dialkylnaphthalene distribution:
2,3-group 1.0 %
2,6-group 18.3 %
2,7-group 80.6 %
Othars 0.1 %
Example 4 Preparation of Catalyst of Composition (II) Preparation of Composition II-(i) ~'-Alumina powder (ACP-1) produced by Shokubai Kasei Co., Ltd.) (50 g) was suspended in 200 ml. of water, to which Was charged 26.56 ml of an aqueous solution of chloroplatinic acid containing 7.53 mg of platinum/ml, and the resulting mixture was stirred at 50 to 60°C for 5 hours. Then, after it was evaporated to dryness using a rotary evaporator, the mixture was dried in an air atmos-phere in an electric drier at 120°C for one night, and then at 200°C for 3 hours.
Preparation of Composition TI-(ii) Powder (10 g) of silica-alumina catalyst (N631HN produced by Japan Gasoline Corporation, contain-ing 28% by weight of A1203) was charged in 30 ml of deionized water containing 1.04 g of sodium hydroxide and stirred at 50°C for 24 hours. Then, after it was fil-tered and washed with water, the content was dried in an air atmosphere in an electric drier at 120°C for one night, and then calcined at 500°C for 5 hours.
Preparation of Catalyst of Composition (II) The powder of alumina carrying thereon platinum thus obtained and the powder of silica-alumina carrying sodium were mixed in a weight proportion of 2/1. After it was adjusted to 10 to 20 mesh, the resulting mixture was calcined at 450°C for 8 hours to prepare catalyst G-1 which contained 0.4~ of platinum and 2.34 of sodium.
In the same manner as the above-described catalyst, catalysts G-2 to G-8 were prepared which con-tained different group VIII metals and different alkali metals in different amounts as shown in Table 2.
Example 5 Evaluation of Performances of Catalyst of Composition (II) Reactions were performed in the same manner as in Example 2, and results 'obtained are shown in Table 2.
In Table 2, terms are the same as in Table 1.
As will be understood from Tables 1 and 2, according to the present invention, objective dialkyl-naphthalene can be obtained in one step reaction in a high yield from o-tolylpentene-3 and -4 as starting material.
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_ 31 Example 6 Preparation of Catalyst for Synthesis of Dialkyltetraline Powder (10 g) of silica-alumina catalyst (Nb31HN produced by Japan Gasoline Corporation, contain-s ing 28~ by weight of alumina) was charged in 100 ml of an aqueous solution containing 70 mmol of NaOH, and stirred at room temperature for 4 hours. Then, after it was filtered and well washed with 500 ml of deionized water, the powder was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was calcined in an air' atmosphere in a muffle furnace at 500°C for 8 hours. As a result to analysis, this con-tained 1.91 by weight of Na based on silica-alumina powder.
The above-described silica-alumina powder containing Na was well mixed with the same weight of ~'-alumina (Wako Pure Chemical Industry Co., Ltd. for chromatography), and molded into pellets, whose grain size was adjusted to 10 to 20 mesh to obtain catalyst H-1.
Catalysts H-2, H-3, and I-1 were prepared in the same manner as described above except that the amount of NaOH used was varied, or~ K2C03 was used instead of NaOH.
The same silica-alumina powder (10 g) as used above was added to 50 ml of an aqueous solution contain-ing 6.8 g of zinc nitrate hexahydrate, and the mixture was stirred at 50°C for 4 hours.
Then, after it was evaporated to dryness, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night, the powder was ealeined in an air atmosphere in a muffle furnace at 500°C for 8 hours to prepare silica-alumina powder carrying 15~ by weight of zinc. This was molded in the same manner as described above to obtain catalyst J-1.
Catalysts J-2 and J-3 were prepared by varying ~~~~a~:~.
_ 32 -the amount of zinc nitrate used, and catalyst K-1 was prepared using silica-alumina powder containing 0.63% of Na, and further catalysts L-1 to L-3 were prepared using gallium chloride instead of zinc nitrate.
Example 7 Evaluation of Performances of Catalyst for Synthesis of Dialkyltetralines The catalyst (5 g) obtained as described above was precalcined in an air atmosphere in an electric muffle furnace at 450°C for 4 hours, and then filled in a reaction tube made of glass. The catalyst layer was adjusted to a reaction temperature, and 10% toluene solution of a mixture of o-tolylpentene-3 and o-tolyl-pentene-4 was fed at WHSV = 1. After 12 hours from the supply of the oil, sample was collected, and analyzed by gas chromatography. Results obtained are shown in Table 3.
Catalyst E prepared in Example 1 was used as comparative catalyst.
Terms used in Table 3 are defined as follows:
Conversion (%) =
Amount of o-tolylpentene-3 or -4 converted (mole) x 100 Amount of o-tolylpentene-3 or -4 supplied (mole) Selectivity (%) _ Amount of dimethyltetraline formed (mole) x 100 Amount of o-tolylpentene converted (mole) Table 3 Catalyst Reaction Con- Selec-Catalyst CompositionTemperature version tivity M5 wt~ (C) (~) Compara- - 200 100.0 86.3 five E
Compara- -- 250 100.0 80.1 tive E
H-2 Na, 0.63 200 100.0 95.7 H-1 Na, 1.91 200 98.5 96.3 H-1 Na, 1.91 250 100.0 94.1 H-3 Na, 3.81 250 93.9 97.5 H-3 Na, 3.81 350 100.0 91.4 H-3 Na, 3.81 450 100.0 89.8 I-1 K , 3.23 200 100.0 91.5 J-2 Zn, 5 200 100.0 93.5 J-1 Zn, 15 200 100.0 92.3 J-1 Zn, 15 250 100.0 89.6 J-3 Zn, 30 300 100.0 86.9 K-1 Zn, 15 Na, 0.63 300 100.0 95.6 L-1 Ga, 5 200 100.0 91.5 L-2 Ga, 15 200 100.0 89.3 L-2 Ga, 15 250 100.0 87.1 L-3 Ga, 30 300 100.0 85.6 2~~~~~.
Example 8 Dehydrogenation Reaction of Dialkyltetraline Composition II-(i) prepared in Example 3 (alumina carrying 0.4~ of platinum) was pulverized after molding to adjust the grain size to 10 to 20 mesh. This composition (5.0 g) was precalcined in an air atmosphere in an electric muffle furnace at 450°C for ~-I hours, and then filled in a reaction tube made of glass. After practicing reduction with hydrogen in a hydrogen stream at 400°C for 2 hours, 10% toluene solution of 1,5-di-methyltetraline was fed at WHSV = 1 hr-1. The molar ratio of hydrogen gas/starting material supplied was 4.
After 20 hours from the supply of the oil, product was collected, and analyzed. As a result, conversion was 98.5, selectivity 91.5, and yield 90.1%.
Terms used in Table are defined a.s follows:
DMT (mol) Conversion (~) _ {1 - r ~ x 100 DMTf (mol) DMN formed (mol) Selectivity (~) = x 100 DMTf - DMTr (mol) DMN formed (mol) Yield (~) = x 100 DMTf (mol) where DMTr is 1,5-dimethyltetraline remaining in the dehydrogenation product;
DMTf is 1,5-dimethyltetraline fed to the reac-tion tube; and DMN is 1,5-dimethylnaphthalene.
Further, Japanese Patent Publication No. 1037/1975 des-cribed a method in which the aforementioned one-step reaction in a liquid phase using a silica alumina cata-lyst carrying thereon a metal such as platinum, palla-dium, rhodium or' rhenium. This method, too, gives a low conversion of the starting material, and suffers from decomposition of the starting material, resulting in that it is unsuitable as an industrial process.
Also, a method has been proposed in which dimethylnaphthalene is prepared from xylenes and buta-diene (Japanese Patent Publication Nos. 1230/1975 and ~~~9~/1981). This method uses tolylpentenes obtained by alkenylating xylene with butadiene as a starting material and prepares dimethylnaphthalene compounds, the objective compounds, via a cyclizing step, a dehydrogenating step and a isomerizing step.
While this method is featured in that each reaction thereof has a very good selectivity and proceeds in a high yield, it is disadvantageous in that not only it involves a long series of steps but also it requires a complicated apparatus since the cyclizing step, which is an exothermic reaction, and the dehydrogenating step, which is an endothermic reaction, are independent of each other. Conventional proposals for carrying out these reactions in one step reaction have been unacceptable industrially as described above. In particular, alkenyl-benzene compounds which are a starting material are susceptible to hydrogenation reaction, a side reaction, with hydrogen generated or carrier hydrogen and converted to alkylbenzene compounds. As a result, cyclization reaction is difficult to proceed, thus giving poor selec--tivity and yield.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide an industrial process for obtaining dialkylben-zene directly from alkenylbenzene compounds which carries out cyelizing and dehydrogenating reaction in one step.
A second object of the present invention is to provide a method for preparing dialkylbenzene which carries out the aforementioned one step reaction at high selectivity.
Other object of the present invention is to provide a solid catalyst suitable for carrying out the aforementioned one step reaction on an industrial scale.
DETAILED DESCRIPTION OF THE INVENTION
MEANS FOR SOLVING THE PROBLEMS
As a result of investigation by the present inventors, it has now been found that in a method far preparing a dialkylnaphthalene compound by contacting an alkenylbenzene compound represented by formula LA]
~~z wherein R1 is a butenyl group substituted with a C1-C
alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R-' is a hydrogen atom or a C1-C~ alkyl group), and R2 is a C1-C~ alkyl group, with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, use of the following composition (I) or (II) gives rise to a dialkylnaphthalene at a high conversion and a high selectivity.
Thus, it has been found that according to the present invention, the aforementioned object is achieved by use of the catalyst having the following composition (I) or (II).
Catalyst Composition (I) This composition is represented by formula (I) below:
(M1)a~(M2)b°(Si02~XA1203)~(A1203)c (I) wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VTII of a periodic table and ruthenium;
M2 represents at least one member selected from the group consisting of zinc, gallium and oxides thereof;
X is a molar ratio of A1203 to Si02 in (Si02.XA1203) and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (Si02~XA1203) and (A1203)c, and is within the range of 0.01 to 5;
b is ~ by weight of M2 as metal based on the weight of (Si02~XA1203), and is within the range of 0.1 to 50; and a is a weight ratio of (A1203) to (Si02~XA1203), and is within the range of 0 to 5.
Catalyst Composition (II) This composition is represented by formula (IT) below:
(M3)d~(A1203) II-(i) and (M~~)e.(Si02~XA1203) II-(ii) wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is ~ by weight of M3 based on (A1203), and is within the range of 0.05 to 5;
M~ represents at least one alkali metal;
a is % by weight of M~ based on (Si02~XA1203), and is within the range of 0.05 to 10; and X is a molar ratio of A1203 to Si02 in (Si02~XA1203), and is within the range of 0.05 to 5.
Thus, according to the present invention, it is ~~9~a~
possible to carry out a cyclization reaction and a dehy-drogenation reaction in one step reaction by contacting an alkenylbenzene compound represented by the aforemen-tioned formula CA7 with the aforementioned catalyst composition (I) or (II) in a gas or liquid phase, thus achieving a high conversion of the starting material and a high selectivity of the objective compound to obtain a dialkylnaphthalene in a high yield.
Hereinafter, the method of the present inven-Lion will be described in more detail.
In the method of the present invention, an alkenylbenzene compound represented by the aforementioned formula CA] is used as a starting material. In the aforementioned formula CA7, the alkenylbenzene compound includes a benzene ring which has two substituents R1 and R2 thereon. R1 is a butenyl group substituted with a C~-C4 alkyl group or a group -CHI-CH2-CH2-CH=C-R3 (where R is a hydrogen atom or' a G1-C~ alkyl group). Here, the aforementioned butenyl group is a group -C~H2-C~H2-C~H~CH2 of which any one C~ among the three Cg's is substituted with a C1-C4 alkyl group, preferably a methyl group. On the other hand, the substituent R2 is a C1-C~
alkyl group, whose specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc., with an methyl group being preferred.
The positions of the two substituents R1 and R2 may be any of ortho-, mete- and pare-positions. The positions of R1 and R2 and the kind of the substituent on R1 give a great influence on the position of the dialkyl group on the objective dialkylnaphthalene.
Specific examples of the alkenylbenzene com-pound represented by the aforementioned formula CA7 include, for example, o-tolyl-2-methylbutene-3, o-tolyl-3-methylbutene-3, m-tolyl-2-methylbutene-3, m-tolyl-3-methylbutene-3, p-tolyl-2-methylbutene-3, p-tolyl-3-_ 7 _ methylbutene-3, o-tolylpentene-3, o-tolylpentene-4, m-tolylpentene-3, m-tolylpentene-4, p-tolylpentene-3, p-tolylpentene-4, o-ethylphenyl-2-methylbutene-3, o-ethylphenyl-3-methylbutene-3, m-ethylphenyl-2-methyl-butene-3, p-ethylphenyl-2-methylbutene-3, o-ethylphenyl-pentene-3, o-ethylphenylpentene-4, m-ethylphenylpentene-3, m-ethylphenylpentene-4, p-ethylphenylpentene-3, p-ethylphenylpentene-~, o-propylphenyl-2-methylbutene-3, o-propylphenyl-3-methylbutene-3, m-propylphenyl-2-methyl-butene-3, m-propylphenyl-3-methylbutene-3, p-propyl-phenyl-2-methylbutene-3, p-propylphenyl-3-methylbutene-3, o-propylphenylpentene-3, o-propylphenylpentene-~, m-propylphenylpentene-3, m-propylphenylpentene-b, p-propyl-phenylpentene-3, p-propylphenylpentene-~, o-tolyl-2-ethylbutene-3, m-tolylethylbutene-3, p-tolyl-2-ethyl-butene-3, o-tolyl-3-ethYlbutene-3, m-tolyl-3-ethyl-butene-3, p-tolyl-3-ethylbutene-3, o-tolylhexene-3, o-tolylhexene-~E, m-tolylhexene-3, m-tolylhexene-~, m-tolylhexene-5, p-tolylhexene-3, p-tolylhexene-4, p-tolyl-hexene-5, etc.
As described above, the kinds of the substi-tuents R1 and R2 and bonding positions of R1 and R2 of the alkenylbenzene compound give an influence on the kind of the dialkylnaphthalene obtained as a result of the reaction. To take some preferred examples thereof, there are prepared mainly 2,7-dimethylnaphthalene when m-tolyl-2-methylbutene-2 or -3 is used as a starting material;
2,6-dimethylnaphthalene in the case of m-tolyl-3-methyl-butene-2 or -3, and p-tolyl-2-methylbutene-2 or -3;
1,5-dimethylnaphthalene in the ease of o-tolylpentene-2, -3 or -~; 1,6-dimethylnaphthalene in the case of o-tolyl-3-methylbutene-2 or -3; 1,7-dimethylnaphthalene in the case of o-tolyl-2-methylbutene-2 or -3.
Among the aforementioned alkenylbenzene com-~5 pounds, o-tolylpentene-2, -3, or -4 is preferred in view of availability and type of the objective dimethylnaph-- g _ thalene.
In the method of the present invention, a dialkylnaphthalene is prepared by a one step reaction in which an alkenylbenzene compound represented by the aforementioned formula (A7 is contacted with the afore-mentioned catalyst composition (I) or (II). Therefore, these catalysts used in the method of the present inven-tion are multifunctional catalysts which have a cycliza-tion function which forms a dialkyltetraline compound from an alkenylbenzene compound, and a dehydrogenation function which convarts the tetraline compound into a dialkylnaphthalene compound under the same reaction conditions. In addition, the aforementioned catalysts used in the method of the present invention retain the aforementioned desired functions for a long time without causing any side reactions such as hydrogenation of alkenyl groups in the starting material under hydrogen atmosphere conditions.
Next, the catalyst compositions (I) and (II), and their preparation will be described concretely.
(1) Catalyst Composition (I) and Its Preparation:
Catalyst composition (I) is represented by formula (I) below as described above.
(M1)a~(M2)b~(Si02~XA1203)~(A1203)c (I) In short, the aforementioned composition (I) can be said to be a solid catalyst composed of siliea-alumina represented by (SiOZ~XA1~03) having carried thereon M1 and M2 components, and optionally.alumina represented by (A1203)c mixed therewith.
M1 is at least one metal selected from the group consisting of group VIII metals of a periodical table and rhenium. More specifically, there can be cited Pt (platinum), Pd (palladium), Rh (rhodium), Ru (ruthe-nium), Os (osmium), Ir (iridium) or Re (rhenium). Those may be used singly or in admixture.
Among them) preferred are/is Pt (platinum) and/or Re (rhenium).
M2 is at least one metal selected from the group consisting of zinc (Zn) and gallium (Ga), or its oxide.
In the aforementioned composition (I), (Si02~XA1203) is a silica-alumina component, and X is a molar ratio of A1203 to Si02, which is within the range of 0.05 to 5, and preferably 0.1 to 3.
The proportion (a) of the M1 component is within the range of 0.01 to 5~ by weight, and preferably 0.1 to 3~ by weight based on the sum of (Si02~XA1203) and (Al?03>.
The proportion (b) of the M2 component is within the range of 0.1 to 50~ by weight, and preferably 1 to 40~ by weight, as metal, based on the weight of (Si02~XA1203).
The proportion (c) of alumina (A1203) is within the range of 0 to 5 parts by weight, and preferably 0.2 to 4 parts by weight per part by weight of silica-alumina component (Si02~XA1203). The alumina (A1203) is in the form of a mixture with (M1)a~(M2)b~(Si02~XA1~03)~
(A1203)c, and also serves as a diluent or binder (modling aid). On the other hand, as another embodiment, the catalyst composition (I) may also be a solid catalyst in the form of a mixture of alumina (A1203) having carried thereon a portion or all of the M1 component, and (MZ)b~(Si02~XA1203). This solid catalyst is inoluded in the catalyst composition (I) of the present invention so far as it has the aforementioned composition.
The aforementioned catalyst composition (I) can be prepared by the following method. That is, an aqueous solution of salts) of zinc (Zn) and/or gallium (Ga) and silica-alumina (Si02~XA1203) powder are mixed, and the salts) is/are carried on the silica-alumina by evapora-Lion to dryness or dipping and filtration, and then the caleined to obtain silica-alumina having carried thereon 20~3a~.~.
zinc and/or gallium oxide(s). Next, the silica-alumina thus obtained and an aqueous solution of a compound of the metal in the M1 component are mixed, and calcined at a temperature of, for example, 450 to 500°C so that an oxide of the metal in the M1 component is carried on the aforementioned silica-alumina (which carries thereon the M2 component). The powder thus obtained may be molded as it is, or mixed with alumina (A1203) and molded into granules or pellets. The molded catalyst may be further caleined, or reduced in a hydrogen atmosphere before use to exhibit its activity.
As the salt of zinc (Zn) to be introduced into the M2 component used in the preparation of the aforemen-tioned catalyst composition (I), are preferred those which are water-soluble and can be converted into zinc oxide under calcination conditions. For example, there can be cited zinc nitrate, zinc chloride, zinc acetate, ete. As the salt of gallium, are preferred similarly those which are water-soluble and can be converted into gallium oxide under caleination conditions. For example, there can be cited gallium nitrate, gallium chloride, gallium acetate, ete. The salts of zinc and those of gallium may be used singly or as mixture.
On the other hand, as the at least one metal selected from the group consisting of metals belonging to group VIII of a periodical table and rhenium, are pre-ferred those which are water-soluble and can be converted into an oxide under caleination conditions. For example, chlorides, nitrates, or acetates of the aforementioned metals can be used.
(2) Catalyst Composition (II) and Its Preparation:
Catalyst composition (II) is a mixture of the following formula II-(i) and TI-(ii):
(M3)d~(A1203) II-(i) (M4)e~(Si02~XA1203) II-(ii) The above-described formula IT-(i) represents alumina (A1203) on which thelM3 component is carried. M3 represents at least one metal belonging to group VIII of a periodical table. Specifically Pt (platinum), Pd (palladium) and Rh (rhodium) are preferred, with Pt (platinum) being particularly preferred. The proportion (d) of M3 is within the range of 0.05 to 5~ by weight, and preferably 0.1 to 3% by weight based on alumina (A1203).
The above-described formula II-(ii) represents silica-alumina (Si02~XA1203) which includes an alkali metal (M4) being ion exchanged or carried thereon. As the alkali metal (M4), are preferred Na (sodium) and K
(potassium), with Na (sodium) being particularly pre-ferred. The proportion (e) of M4 is within the range of 0.05 to 10~ by weight, and preferably 0.1 to 5~ by weight. On the other hand, X in the silica-alumina represents a molar ratio of A1203 to Si02, and is within the range of 0.05 to 3, and preferably 0.1 to 3.
The aforementioned catalyst composition (II) is a mixture of the above formulae II-(i) and II-(ii) as described above, and is preferably a uniform mixture of the powder of TI-(i) and the powder of IT-(ii). The mixing proportion, by weight, of the two is within the range of 1:10 to 10:1, and preferably 1:5 to 5:1.
The aforementioned II-(i) can be prepared by impregnating alumina posader (A1203) with an aqueous solution of a compound of a metal in the M3 component, having the compound of M3 carried an the alumina (A1203) by evaporation to dryness or dipping and filtration, and caleining it. This caleinat,ion may be carried out at a temperature of 400 to 500°C, or may be performed after the mixing with the component II-(ii). As the compound of M3 to be used, those compounds are suitable which are water-soluble compounds of group VIII metals and can form oxides by caleination. For example, chlorides and nitrates are preferred.
~fl~ i~l~
On the other hand, the aforementioned II-(ii) can be prepared by impregnating silica-alumina powder (Si02~XA1203) with an aqueous solution of a compound of a metal in the M4 component, having the compound M4 carried on the silica-alumina (Si02.XA1203) by evaporation to dryness or dipping and filtration, and caleining it.
This calcination may be carried out at a temperature of 400 to 500°C, or may be performed after the mixing with the component II-(i). As the compound of M4 to be used for the preparation of II-(ii), those compounds are preferred which are water-soluble and can form oxides upon calcination. For example, chlorides, hydroxides or nitrates are preferred.
The catalyst composition (IT) can be prepared by mixing the powders II-(i) and II-(ii) obtained as described above in the aforementioned proportions. The catalyst composition (II) may be supplied to the reaction after the powder mixture is molded into granules or pellets by a process known per se. To do so is Preferred.
The catalyst compositions (I) and (IT) of the present invention described above: each are novel as catalysts for cyclizaiton~dehydrogenation, and the use of them as catalysts in reaction methods and under reaction conditions described below can give rise to dialkylnaph-thalenes in high yields. Also, a specified dialkylnaph-thalene can be obtained at a high selectivity.
III. Reaction method and Conditions Thereof:
In the method of the present invention, the reaction is carried out by contacting the alkenylbenzene compound of the aforementioned formula CA7 as a starting material with the aforementioned catalyst composition (I) or (II) in a hydrogen atmosphere. In this case, the reaction may be carried out either in a gas phase reac-tion in which the starting material is contacted with the catalyst in the form of vapor, or in a liquid phase reae-tion in which the starting material is contacted with the catalyst in the form of a liquid. In the both gas phase reaction and liquid phase reaction, the catalyst may be of an type such as a fixed bed type, a mobile bed type, a fluidized bed type, or a suspension type. Further, the reaction may be a continuous type, batch type, or the like.
The reaction temperature is 150°C to 500°C, and preferably 200°C to 450°C, and the reaction pressure may be either atmospheric or superatmospheric. In a liquid phase reaction, the reaction may be carried out under pressure so that the alkenylbenzene compound as a start-ing material can be retained in the form of a liquid.
Upon the reaction, the starting material may be diluted with another stable diluent. For example, there can be used organic diluents, e.g., benzene compounds such as benzene, toluene, and xylene; naphthalene deriva-tive compounds such as naphthalene, alkylnaphthalene, tetraline, alkyltetraline, decaline, alkyldecalines; and further' inorganic diluents, e.g., gases such as nitrogen.
In order to increase yiehd, and prevent deactivation of the catalyst, hydrogen gas is made present. When the starting material of the reaction is diluted, molar proportion of the diluent/starting material of the reac-tion 0.5 to 30, and preferably 1 to 15. WHSV, which is a contact time during which the starting material contacts the catalyst, is 0.1 to 20, and preferably 0.2 to 10.
EFFECT OF THE INVENTION
According to the present invention, reaction of a specified alkenylbenzene compound using a specified catalyst prepares a dialkylnaphthalene, and therefore a specified dialkylnaphthalene can be obtained at a high selectivity and in a high yield. Further, the reaction which has been carried out in two steps conventionally can be performed in one step, and hence the method of the present invention is economically excellent.
1 ~4 -In particular, the method of the present inven-tion is excellent in that a specified dialkylnaphthalene aimed at can be obtained at a very high selectivity.
Hereinafter, this advantage will be described in more detail.
Dialkyltetraline, which are products of the cyclization reaction derived from alkenylbenzene com-pounds and intermediate products in the method of the present invention, can isomerize freely on acid catalysts and give rise to various isomers. Once they are dehydro-genated and converted into dialkylnaphthalenes, they are classified into four groups as shown in the following table. While isomerization reactions can readily occur between iosmers within each groups, generally isomeriza-tion reactions between groups are difficult to occur.
No. Group Isomer 1 2,3-Group 1,4-, 1,3-, ~,3-Dialkylnaphthalenes 2 1,6-Group 1,5-, 1,6-, 2,b-Dialkylnaphthalenes 3 2,7-Group 1,8-, 1,7-, ?.,7-Dialkylnaphthalenes 4 Others 1,2-Dialkylnaphthalene, and others Therefore, in the method for preparing an objective dimethylnaphthalene compound from an alkenyl-benzene compound which is obtained by alkenylation of xylenes with butadiene as a starting material by a cyclizing step, a dehydrogenating step, and an isomeriz-ing step, it is important that the reaction product in the dehydrogenating step is a specified dimethylnaphtha-lene or that belonging to a specified group since it is only necessary to proceed isomerization reactions between those isomers that are included in each selected group to proceed, that is those reactions which can take place readily in the subsequent isomerization step. In the case where the cyclizing step, which is an exothermic reaction, and the hydrogenating step, which is an endo-thermie reaction, are practiced in a one-step reaction, it is similarly important to proceed the dehydrogenation reaction efficiently while suppressing the isomerization reaction of dialkyltetraline produced by the cyclization reaction in order to obtain the objective dialkylnaphtha-lene compound.
The use of the catalyst compositions (I) and (II), in particular composition (II), in the method of the present invention substantially suppresses the iso-merization reaction of dialkyltetraline, intermediate product of the reaction, resulting in that dialkylnaph-thalene of a specified group can be obtained at a high conversion and a high selectivity. For example, dialkyl-naphthalenes of 2,6-group are preferred as a starting material for 2,6- .naphthalenedicax~boxylic acid. For this, purpose, for example; mainly 2,6.-dimethylnaphthalene is obtained from m-tolyl-3-methylbutene-2 or -3, and p-tolyl-2-methylbutene-2 or -3, mainly 1,5-dimethylnaph-thalene from o-tolylpentene-2, -3 or -4; and mainly 1,6-dimethylnaphthalene is obtained from o-tolyl-3-methylbutene-2 or -3.
Preparation of Dialkyltetralines According to another investigation by the present inventors, there has been found the following method for preparing a dialkyltetraline from the alkenyl-benzene compound represented by the aforementioned for-mula CA7 at a high conversion and a high selectivity.
The dialkyltetraline thus obtained can readily be con-verted into a dialkylnaphthalene by contacting it with a dehydrogenating catalyst.
That is, according to the present invention, there is provided a method for preparing a dialkyltetra-~~9~511 - 1s -line compound by contacting an alkenylbenzene compound represented by formula CA7 below:
RI
LAJ
wherein R1 is a butenyl group substituted with a C1-C
alkyl group or a group -CH2-CH2-CH2-CH~CH-R3 (where R~ is a hydrogen atom or a C1-C~ alkyl group), and R2 is a C1-C4 alkyl group, with a solid catalyst in a gas or liquid phase at a temperature of 200 to 500°C substan-tially in the absence of hydrogen, wherein as said solid catalyst is used a cata-lyst having a composition represented by formula (III) below:
M5f~(Si02~XA1203) (III) where M5 represents at least one metal selected from the group consisting of alkali metals, zinc, gallium and oxides thereof;
f is ~ by weight of M5 as metal based on (Si02~XA120~), and is within the range of 0.01 to 50; and X is a molar ratio of A1203 to Si02 in (Si02~XA1203), and is within the range of 0.05 to 5.
Tn the aforementioned method, the alkenylben-zene compound represented by formula CA7 and used as a starting material may be the same as that described in the preparation of the aforementioned dialkylnaphthalene.
Preferred starting material may be the same as that described above as t~referred ones.
Referring to the solid catalyst having the composition represented by formula (III) used in the aforementioned method, this is a catalyst which contains silica-alumina (Si02~XA1203) having carried thereon the M5 component. In the composition (III), M5 is at least one metal selected from the group consisting of alkali metals, zinc and gallium, and oxides thereof. As the alkali metal, sodium or potassium is preferred. f is by weight of M5 as metal based on the silica-alumina (SiO~~XA1203), and is within the range of 0.01 to 50~ by weight, and preferably 0.1 to 40% by weight. Most pre-ferred range of f i.s 0.1 to 30~ by weight when M5 is an alkali metal, and 1 to 40~ by weight when M5 is zinc, gallium or their oxides. X is the silica-alumina (Si02.XA1203) is a molar ratio of A1203 to Si02, and is within the range of 0.05 to 5, and preferably 0.1 to 3~
The composition (III) can be prepared by mixing an aqueous solution of a compound of the metal in the M5 component with a silica-alumina powder (Si02.XA1203), subjecting the mixture to evaporation to dryness or dipp-ing filtration to have the salt of the metal in the M5 component carried on the silica-alumina, and then calcin-ing. The caleination is performed suitably at a tempera-ture of 450 to 500°C. As the salt of the alkali metal used in the aforementioned preparation, there can be cited, far example, sodium hydroxide, potassium hydrox-ide, etc. As 'the salt of zinc or gallium, there can be cited, for' example, zinc nitrate, zinc chloride, zinc acetate, gallium nitrate, gallium chloride, gallium acetate, ete.
The powder obtained by the aforementioned preparation method can be molded into granules or pellets by a suitable method. In this ease, any method may be used as the molding method, or a molding aid may be used.
That is, molded article obtained by mixing the above-des-cribed powder with a molding aid, molding and calcining may be used in the reaction. As the molding aid, there can be used clay, silica--alumina, boehmite, alumina, etc,, with alumina being preferred. It is preferred that the molding aid be used in a weight proportion of 0.5 to 1.9 to the above--described catalyst.
2~~a~~.
The catalyst composition (III) obtained by the aforementioned preparation method is a novel catalyst composition as a catalyst for the preparation of a dialkylbenzene by cyclization of an alkenylbenzene com-pound.
The catalytic reaction of an alkenylbenzene compound using the catalyst composition (III) thus obtained may be carried out either in a gas phase reac-tion in which the starting material is contacted with the catalyst in the form of vapor, or in a liquid phase reaction in which the starting material is contacted with the catalyst in the form of a liquid. In the both gas phase reaction and liquid phase reaction, the catalyst may be of any type such as a fixed bed type, a mobile bed type, a fluidized bed type, or a suspension type. Fur-ther, the reaction may be a continuous type, batch type, or the like.
The reaction temperature is 200°C to 500°C, and preferably 200°C to 450°C, and the reaction pressure may be either atmospheric or superatmospherie. In a liquid phase reaction, the reaction may be carried out under pressure so that the alkenylbenzene compound as a start-ing material can be retained in 'the form of a liquid, Upon the reaction, the starting material may be diluted with another stable diluent. For example, there can be used organic diluents, e.g., benzene compounds such as benzene, toluene, and xylene; and further inorga-nic diluents, e.g., gases such as nitrogen. When the starting material of the reaction is diluted, molar proportion of the diluent/starting material of the reac-tion is 0.5 to ~0, and preferably 1 to 15. WHSU, which is a contact time during which the starting material of the reaction contacts the catalyst, is 0.1 to 20, and preferably 0.2 to 10.
The reaction of the present invention must be carried out substantially in the absence of hydrogen ~~~~~1~
since in the presence of hydrogen no objective compound can be obtained, According to the present invention, the cyeli zation reaction of an alkenylbenzene compound, which has been carried out using silica-alumina or the like cata lyst at a low temperature (for example, at a temperature of 150 to 180°C) in order to prevent side reactions, can be performed at a relatively high temperature and at a high selectively and in a high yield.
The dialkyltetraline thus obtained can be converted into a dialkylnaphthalene by a method known per se, for example, by a method in which it is contacted with a dehydrogenating catalyst, e.g., plantinum-alumina at a temperature of 300 to 500°C to carry out dehydroge-nation.
For example, in the case where 1,5-dimethyl-tetraline and/or 1,6-dimethyltetraline are/is reacted in a gas phase using a platinum-alumina catalyst to obtain 1,5-dimethylnaphthalene and/or 1,6-dimethylnaphthalene can be prepared efficiently by setting up the catalyst caleination temperature to 300 to 400°C, the catalyst reduction temperature to 400 to 500°C, and the reaction temperature to 350 to 450°C; or 'the catalyst cal.cination temperature to 400 to 500°C, the catalyst reduction temperature to 300 to 400°C, and the reaction temperature to 350 to 450°C.
The present invention enables the cyclization reaction of alkenylbenzene compounds at substantially the same temperature range as that of the dehydrogenation reaction of dialkyltetralines, thus making it possible to carry out the cyclization reaction and dehydrogenation reaction at high energy efficiency without change in the reaction temperature.
Since a series of the cyelization and dehydro-genation reactions proceed in substantially the same temperature range, they can be carried out in the same - 20 .~ ~~~~
reaction vessel or in respective reaction vessels, in a continuous process, a sequential process or in combina-tion thereof.
EXAMPLES
Hereinafter, the present invention will be described in detail by examples.
Example 1 Preparation of Catalyst of Composition (I) Powder (10 g) of silica-alumina catalyst (N631HN produced by Japan Gasoline Corporation, eontain-ing 28% by weight of A1203) was charged in 50 ml o.f deionized water containing 6.8 g of zinc nitrate hexahyd-rate while stirring, and stirred at 50°C for 4 hours.
Then, after it was evaporated to dryness using a rotary evaporator, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was caleined in an air atmosphere in a muffle furnace at 500°C for 8 hours to prepare silica-alumina powder carrying thereon 15% zinc.
The above-described silica-alumina powder (5.75 g) carrying thereon 15% zinc was suspended in 50 m1 of deionized water, to which was added 1 ml of an aqueous solution of chloroplatinic acid containing 5.75 mg of Pt, and the mixture was stirred at 50°C for 4 hours. Then, after it was evaporated to dryness using a rotary evapo-rator, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was calcined in an air atmosphere in a muffle furnace at 500°C for 8 hours, and thereafter, the same weight of '~ alumina was well mixed therewith. The resulting mixture was molded into pellets with adjusting the grain size to 10 to 20 mesh to obtain catalyst A-1.
Catalyst A-1 contains 0.05% of platinum based on the total weight of the silica-alumina and alumina, and 15% of zinc based on the weight of the silica-alumina) Similarly to the above-described catalyst A-1, 2~9~~a~.1 catalysts A-2 to A-4 which contain platinum and zinc, catalysts B-1 to B-6 which contain group VTII metals other than platinum, or rhenium, and zinc, catalysts C-1 to C-6 which contain platinum and gallium, catalyst D-1 which contains rhenium and gallium, as shown in Table 1 were prepared.
Also, catalyst E which contains no metal, and catalyst F' which contains only platinum were prepared similarly as described above as comparative catalysts.
Example 2 Evaluation of performances of Catalyst of Composition (I) The catalyst (5 g) obtained as described above was precalcined in an air atmosphere in an electric furnace at 450°C for 4 hours, and then filled in a reac-tion tube made of glass. After practicing reduction with hydrogen in a stream of hydrogen at 500°C for 2 hours, the temperature was adjusted to a reaction temperature, and 10~ toluene solution of a mixture of o-tolylpentene-3 and o-tolylpentene-4 was fed under the condition of WHSV
° 1~ After 12 hours and 24 hours, respectively, from the supply of the oil, samples were collected, and analyzed by gas chromatography. Results obtained are shown in Table 1.
(In Table 1, molar ratio means a molar ratio of carrier gas to starting material.) Terms used in Table 1 are defined as follows:
Conversion Amount of o-tolylpentene-3 or -4 converted (mole) x 100 Amount of o-tolylpentene-3 or -4 supplied (mole) Loss Ratio =
Amount of o-tolylpentene-3 or -4 formed (mole) x 100 ' Amount of o-tolylpentene-3 or -4 converted (mole) Seleetivity-1 -Amount of dimethyltetraline formed (mole) x 100 Amount of o-tolylpentene-3 or -4 converted (mole) Selectivity-2 =
Amount of dimethylnaphthalene formed (mole) x 100 Amount of o-tolylpeptene-3 or -4 converted (mole) _ 23 _ w ~.
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_ 27 Example 3 (Example in which o-tolyl-2-methylbutene-3 was used as alkenylbenzene compound) Catalyst A-2 (5 g) in Example 1 above was filled in a reaction tube and subjected to reduction with hydrogen in the same manner as in Example 2 above.
Thereafter, 10% toluene solution of o-tolyl-2-methyl-butene-3 was fed WHSV = 1 under the conditions of a reaction temperature of 450°C, and a hydrogen car.rier/-starting material molar ratio of 4. After 12 hours a sample was collected and analyzed by gas chromatography.
As a result, the following performances were confirmed.
Conversion: 100.0 %, Loss ratio: 0.6 %, Selectivity-1: 7.0 %, , Selectivity-2: 89.5 %, Dialkylnaphthalene distribution:
2,3-group 1.0 %
2,6-group 18.3 %
2,7-group 80.6 %
Othars 0.1 %
Example 4 Preparation of Catalyst of Composition (II) Preparation of Composition II-(i) ~'-Alumina powder (ACP-1) produced by Shokubai Kasei Co., Ltd.) (50 g) was suspended in 200 ml. of water, to which Was charged 26.56 ml of an aqueous solution of chloroplatinic acid containing 7.53 mg of platinum/ml, and the resulting mixture was stirred at 50 to 60°C for 5 hours. Then, after it was evaporated to dryness using a rotary evaporator, the mixture was dried in an air atmos-phere in an electric drier at 120°C for one night, and then at 200°C for 3 hours.
Preparation of Composition TI-(ii) Powder (10 g) of silica-alumina catalyst (N631HN produced by Japan Gasoline Corporation, contain-ing 28% by weight of A1203) was charged in 30 ml of deionized water containing 1.04 g of sodium hydroxide and stirred at 50°C for 24 hours. Then, after it was fil-tered and washed with water, the content was dried in an air atmosphere in an electric drier at 120°C for one night, and then calcined at 500°C for 5 hours.
Preparation of Catalyst of Composition (II) The powder of alumina carrying thereon platinum thus obtained and the powder of silica-alumina carrying sodium were mixed in a weight proportion of 2/1. After it was adjusted to 10 to 20 mesh, the resulting mixture was calcined at 450°C for 8 hours to prepare catalyst G-1 which contained 0.4~ of platinum and 2.34 of sodium.
In the same manner as the above-described catalyst, catalysts G-2 to G-8 were prepared which con-tained different group VIII metals and different alkali metals in different amounts as shown in Table 2.
Example 5 Evaluation of Performances of Catalyst of Composition (II) Reactions were performed in the same manner as in Example 2, and results 'obtained are shown in Table 2.
In Table 2, terms are the same as in Table 1.
As will be understood from Tables 1 and 2, according to the present invention, objective dialkyl-naphthalene can be obtained in one step reaction in a high yield from o-tolylpentene-3 and -4 as starting material.
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_ 31 Example 6 Preparation of Catalyst for Synthesis of Dialkyltetraline Powder (10 g) of silica-alumina catalyst (Nb31HN produced by Japan Gasoline Corporation, contain-s ing 28~ by weight of alumina) was charged in 100 ml of an aqueous solution containing 70 mmol of NaOH, and stirred at room temperature for 4 hours. Then, after it was filtered and well washed with 500 ml of deionized water, the powder was dried in an air atmosphere in an electric drier at 120°C for one night. The powder obtained was calcined in an air' atmosphere in a muffle furnace at 500°C for 8 hours. As a result to analysis, this con-tained 1.91 by weight of Na based on silica-alumina powder.
The above-described silica-alumina powder containing Na was well mixed with the same weight of ~'-alumina (Wako Pure Chemical Industry Co., Ltd. for chromatography), and molded into pellets, whose grain size was adjusted to 10 to 20 mesh to obtain catalyst H-1.
Catalysts H-2, H-3, and I-1 were prepared in the same manner as described above except that the amount of NaOH used was varied, or~ K2C03 was used instead of NaOH.
The same silica-alumina powder (10 g) as used above was added to 50 ml of an aqueous solution contain-ing 6.8 g of zinc nitrate hexahydrate, and the mixture was stirred at 50°C for 4 hours.
Then, after it was evaporated to dryness, the mixture was dried in an air atmosphere in an electric drier at 120°C for one night, the powder was ealeined in an air atmosphere in a muffle furnace at 500°C for 8 hours to prepare silica-alumina powder carrying 15~ by weight of zinc. This was molded in the same manner as described above to obtain catalyst J-1.
Catalysts J-2 and J-3 were prepared by varying ~~~~a~:~.
_ 32 -the amount of zinc nitrate used, and catalyst K-1 was prepared using silica-alumina powder containing 0.63% of Na, and further catalysts L-1 to L-3 were prepared using gallium chloride instead of zinc nitrate.
Example 7 Evaluation of Performances of Catalyst for Synthesis of Dialkyltetralines The catalyst (5 g) obtained as described above was precalcined in an air atmosphere in an electric muffle furnace at 450°C for 4 hours, and then filled in a reaction tube made of glass. The catalyst layer was adjusted to a reaction temperature, and 10% toluene solution of a mixture of o-tolylpentene-3 and o-tolyl-pentene-4 was fed at WHSV = 1. After 12 hours from the supply of the oil, sample was collected, and analyzed by gas chromatography. Results obtained are shown in Table 3.
Catalyst E prepared in Example 1 was used as comparative catalyst.
Terms used in Table 3 are defined as follows:
Conversion (%) =
Amount of o-tolylpentene-3 or -4 converted (mole) x 100 Amount of o-tolylpentene-3 or -4 supplied (mole) Selectivity (%) _ Amount of dimethyltetraline formed (mole) x 100 Amount of o-tolylpentene converted (mole) Table 3 Catalyst Reaction Con- Selec-Catalyst CompositionTemperature version tivity M5 wt~ (C) (~) Compara- - 200 100.0 86.3 five E
Compara- -- 250 100.0 80.1 tive E
H-2 Na, 0.63 200 100.0 95.7 H-1 Na, 1.91 200 98.5 96.3 H-1 Na, 1.91 250 100.0 94.1 H-3 Na, 3.81 250 93.9 97.5 H-3 Na, 3.81 350 100.0 91.4 H-3 Na, 3.81 450 100.0 89.8 I-1 K , 3.23 200 100.0 91.5 J-2 Zn, 5 200 100.0 93.5 J-1 Zn, 15 200 100.0 92.3 J-1 Zn, 15 250 100.0 89.6 J-3 Zn, 30 300 100.0 86.9 K-1 Zn, 15 Na, 0.63 300 100.0 95.6 L-1 Ga, 5 200 100.0 91.5 L-2 Ga, 15 200 100.0 89.3 L-2 Ga, 15 250 100.0 87.1 L-3 Ga, 30 300 100.0 85.6 2~~~~~.
Example 8 Dehydrogenation Reaction of Dialkyltetraline Composition II-(i) prepared in Example 3 (alumina carrying 0.4~ of platinum) was pulverized after molding to adjust the grain size to 10 to 20 mesh. This composition (5.0 g) was precalcined in an air atmosphere in an electric muffle furnace at 450°C for ~-I hours, and then filled in a reaction tube made of glass. After practicing reduction with hydrogen in a hydrogen stream at 400°C for 2 hours, 10% toluene solution of 1,5-di-methyltetraline was fed at WHSV = 1 hr-1. The molar ratio of hydrogen gas/starting material supplied was 4.
After 20 hours from the supply of the oil, product was collected, and analyzed. As a result, conversion was 98.5, selectivity 91.5, and yield 90.1%.
Terms used in Table are defined a.s follows:
DMT (mol) Conversion (~) _ {1 - r ~ x 100 DMTf (mol) DMN formed (mol) Selectivity (~) = x 100 DMTf - DMTr (mol) DMN formed (mol) Yield (~) = x 100 DMTf (mol) where DMTr is 1,5-dimethyltetraline remaining in the dehydrogenation product;
DMTf is 1,5-dimethyltetraline fed to the reac-tion tube; and DMN is 1,5-dimethylnaphthalene.
Claims (32)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for preparing a dialkylnaphthalene by contacting an alkenylbenzene compound represented by formula [A]:
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4, alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a composition (I):
(M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50;
c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5), or a mixture of II-(i) and II-(11):
(M3)d~(Al2O3) II-(i) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
e is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4, alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a composition (I):
(M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50;
c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5), or a mixture of II-(i) and II-(11):
(M3)d~(Al2O3) II-(i) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
e is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
2. The method as claimed in claim 1, wherein M1 is platinum.
3. The method as claimed in claim 1 or 2, wherein M3 is platinum.
4. The method as claimed in claim 1, 2 or 3, wherein M4 is sodium or potassium.
5. The method as claimed in any one of claims 1 to 4, wherein X is within the range of 0.1 to 3.
6. The method as claimed in any one of claims 1 to 5, wherein a is within the range of 0.1 to 3.
7. The method as claimed in any one of claims 1 to 6, wherein b is within the range of 1 to 40.
8. The method as claimed in any one of claims 1 to 7, wherein c is within the range of 0.2 to 4.
9. The method as claimed in claim 1, wherein d is within the range of 0.1 to 3.
10. The method as claimed in claim 1 or 9, wherein e is within the range of 0.1 to 5.
11. The method as claimed in claim 1, 9 or 10, wherein the mixture contains formula II-(i) and formula II-(ii) at a weight ratio within the range of 1:10 to 10:1.
12. The method as claimed in any one of claims 1 to 11, wherein the compound represented by the formula [A] is one in which R1 is a butenyl group substituted with a methyl group or a group -CH2-CH2-CH2-CH=CH2, and R2 is a methyl group.
13. The method as claimed in any one of claims 1 to 11, wherein the compound represented by the formula [A] is an o-tolylpentene.
14. A method for preparing a dialkylnaphthalene by contacting an alkenylbenzene compound represented by formula [A]:
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4 alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a composition (I) below:
(M1)a~(M2)b~(SiO2~XA12O3~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50; and c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5).
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4 alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a composition (I) below:
(M1)a~(M2)b~(SiO2~XA12O3~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50; and c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5).
15. The method as claimed in claim 14, wherein M1 is platinum.
16. The method as claimed in claim 14 or 15, wherein X
is within the range of 0.1 to 3.
is within the range of 0.1 to 3.
17. The method as claimed in claim 14, 15 or 16, wherein a is within the range of 0.1 to 3.
18. The method as claimed in any one of claims 14 to 17, wherein b is within the range of 1 to 40.
19. The method as claimed in any one of claims 14 to 18, wherein c is within the range of 0.2 to 4.
20. The method as claimed in any one of claims 14 to 19, wherein the compound represented by the formula [A] is one in which R1 is a butenyl group substituted with a methyl group or a group -CH2-CH2-CH2-CH=CH2, and R2 is a methyl group.
21. The method as claimed in any one of claims 14 to 19, wherein the compound represented by said formula [A] is an o-tolylpentene.
22. A method for preparing a dialkylnaphthalene by contacting an alkenylbenzene compound represented by formula [A]:
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4 alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a mixture of II-(i) and II-(ii) below:
(M3)d~(Al2O3) II-(i) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table:
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
a is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
(wherein R1 is a butenyl group substituted with a C1-C4 alkyl group or a group -CH2-CH2-CH2-CH=CH-R3 (where R3 is a hydrogen atom or a C1-C4 alkyl group), and R2 is a C1-C4 alkyl group), with a solid catalyst in a gas or liquid phase at a temperature of 150 to 500°C in the presence of hydrogen, wherein as the solid catalyst is used a catalyst comprising a mixture of II-(i) and II-(ii) below:
(M3)d~(Al2O3) II-(i) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table:
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
a is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
23. The method as claimed in claim 22, wherein M3 is platinum.
24. The method as claimed in claim 22 or 23, wherein M4 is sodium or potassium.
25. The method as claimed in claim 22, 23 or 24, wherein X is within the range of 0.1 to 3.
26. The method as claimed in any one of claims 22 to 25, wherein d is within the range of 0.1 to 3.
27. The method as claimed in any one of claims 22 to 26, wherein a is within the range of 0.1 to 5.
28. The method as claimed in any one of claims 22 to 27, wherein the mixture contains formula II-(i) and formula II-(ii) at a molar ratio within the range of 1:10 to 10:1.
29. The method as claimed in any one of claims 22 to 28, wherein the compound represented by the formula [A] is one in which R1 is a butenyl group substituted with a methyl group or a group -CH2-CH2-CH2-CH=CH2, and R2 is a methyl group.
30. The method as claimed in any one of claims 22 to 28, wherein the compound represented by the formula [A] is an o-tolylpentene.
31. A catalyst composition for preparing a dialkylnaphthalene by cyclization-dehydrogenation of an alkenyl-benzene compound, comprising a composition (I) below:
(M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50; and c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5).
(M1)a~(M2)b~(SiO2~XAl2O3)~(Al2O3)c (I) (wherein M1 represents at least one metal selected from the group consisting of metals belonging to group VIII of a periodic table and rhenium;
M2 represents at least one member selected from the group consisting of zinc, gallium, and oxides thereof;
X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5;
a is % by weight of M1 based on the sum of (SiO2~XAl2O3) and (Al2O3)c, and is within the range of 0.01 to 5;
b is % by weight of M2 as metal based on the weight of (SiO2~XAl2O3), and is within the range of 0.1 to 50; and c is weight ratio of (Al2O3) to (SiO2~XAl2O3), and is within the range of 0 to 5).
32. A catalyst composition for preparing a dialkyl-naphthalene by cyclization-dehydrogenation of an alkenyl-benzene compound, comprising a mixture (II) of compositions represented by formulae II-(i) and II-(Ii) below:
(M3)d~(AL2o3) II-(I) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
a is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
(M3)d~(AL2o3) II-(I) and (M4)e~(SiO2~XAl2O3) II-(ii) (wherein M3 represents at least one metal belonging to group VIII of a periodical table;
d is % by weight of M3 based on (Al2O3), and is within the range of 0.05 to 5;
M4 represents at least one alkali metal;
a is % by weight of M4 based on (SiO2~XAl2O3), and is within the range of 0.05 to 10; and X is a molar ratio of Al2O3 to SiO2 in (SiO2~XAl2O3), and is within the range of 0.05 to 5).
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22244091 | 1991-08-08 | ||
| JP3/222440 | 1991-08-08 | ||
| JP3/250341 | 1991-09-04 | ||
| JP25034191 | 1991-09-04 | ||
| JP25279391 | 1991-09-05 | ||
| JP3/252793 | 1991-09-05 | ||
| JP4/57950 | 1992-03-16 | ||
| JP05795092A JP3176688B2 (en) | 1992-03-16 | 1992-03-16 | Method for producing dialkylnaphthalene |
| PCT/JP1992/001006 WO1993002995A1 (en) | 1991-08-08 | 1992-08-06 | Process for producing dialkylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2093511A1 CA2093511A1 (en) | 1993-02-09 |
| CA2093511C true CA2093511C (en) | 1999-09-21 |
Family
ID=27463592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093511A Expired - Lifetime CA2093511C (en) | 1991-08-08 | 1992-08-06 | Process for producing dialkylnaphthalene |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5365001A (en) |
| EP (1) | EP0594856B1 (en) |
| CA (1) | CA2093511C (en) |
| DE (1) | DE69218775T2 (en) |
| WO (1) | WO1993002995A1 (en) |
Family Cites Families (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3244758A (en) * | 1963-03-20 | 1966-04-05 | Sun Oil Co | Reaction of aromatic hydrocarbons with diolefins |
| US3431219A (en) * | 1967-03-08 | 1969-03-04 | Mobil Oil Corp | Crystalline galliosilicates |
| JPS50665B1 (en) * | 1970-06-13 | 1975-01-10 | ||
| JPS504655B1 (en) * | 1970-09-04 | 1975-02-22 | ||
| JPS501269B1 (en) * | 1970-10-02 | 1975-01-16 | ||
| JPS5022551B1 (en) * | 1970-10-03 | 1975-07-31 | ||
| JPS5017985B1 (en) * | 1970-11-05 | 1975-06-25 | ||
| GB1448136A (en) * | 1972-12-25 | 1976-09-02 | Mitsui Petrochemical Ind | Process for preparing dimethyl naphthalenes |
| US3811491A (en) * | 1973-03-01 | 1974-05-21 | Jones & Laughlin Steel Corp | Method and apparatus for minimizing surface defects on itr cast strip |
| JPS501037A (en) * | 1973-05-07 | 1975-01-08 | ||
| JPS50665A (en) * | 1973-05-09 | 1975-01-07 | ||
| JPS501269A (en) * | 1973-05-11 | 1975-01-08 | ||
| JPS504655A (en) * | 1973-05-16 | 1975-01-18 | ||
| JPS5012430A (en) * | 1973-06-05 | 1975-02-08 | ||
| JPS531150B2 (en) * | 1973-06-18 | 1978-01-14 | ||
| JPS5022551A (en) * | 1973-06-27 | 1975-03-11 | ||
| JPS5648494B2 (en) * | 1974-07-02 | 1981-11-16 | ||
| JPS582223B2 (en) * | 1974-07-02 | 1983-01-14 | 三菱化学株式会社 | 2.6- Naphthalene dicarbonate |
| JPS5929178B2 (en) * | 1978-04-08 | 1984-07-18 | 丸善石油化学株式会社 | Process for producing 2-alkyl-6-acylnaphthalene |
| US4530645A (en) * | 1979-09-21 | 1985-07-23 | Hydraunit Venture | Oil well pumping apparatus |
| US4392989A (en) * | 1981-05-11 | 1983-07-12 | Mobil Oil Corporation | Zinc-gallium zeolite |
| US4458025A (en) * | 1982-09-20 | 1984-07-03 | Chevron Research Company | Method of zeolitic catalyst manufacture |
| JPS6045536A (en) * | 1983-08-22 | 1985-03-12 | Teijin Yuka Kk | Trans-methylation of methyl-substituted naphthalene |
| JPS60172937A (en) * | 1984-02-16 | 1985-09-06 | Teijin Yuka Kk | Method of methylation of naphthalenes |
| JPS60188343A (en) * | 1984-03-07 | 1985-09-25 | Mitsubishi Gas Chem Co Inc | Preparation of aromatic ketone |
| US4623632A (en) * | 1984-11-05 | 1986-11-18 | Uop Inc. | Catalytic composite for conversion of hydrocarbons and the method of preparation and use thereof |
| JPH0684328B2 (en) * | 1985-08-31 | 1994-10-26 | 三菱瓦斯化学株式会社 | Method for producing aromatic ketone |
| US4985384A (en) * | 1986-08-25 | 1991-01-15 | W. R. Grace & Co-Conn. | Cracking catalysts having aromatic selectivity |
| JPS649943A (en) * | 1987-07-02 | 1989-01-13 | Nippon Steel Chemical Co | Production of alkylnaphthalenes |
| JPS649942A (en) * | 1987-07-02 | 1989-01-13 | Nippon Steel Chemical Co | Production of dialkylnaphthalenes |
| US4824816A (en) * | 1987-09-21 | 1989-04-25 | Exxon Research & Engineering Company | Method for producing stabilized zeolite catalysts |
| US5030781A (en) * | 1990-06-15 | 1991-07-09 | Amoco Corporation | Preparation of a dimethyltetralin |
| US4873386A (en) * | 1988-06-28 | 1989-10-10 | Amoco Corporation | Selective production of 2,6-diethylnaphthalene |
| JPH02167237A (en) * | 1988-09-27 | 1990-06-27 | Mitsubishi Gas Chem Co Inc | Production of 1-(alkyl or alkenyl)-6'-methylnaphthalene |
| US5008479A (en) * | 1988-09-27 | 1991-04-16 | Mitsubishi Gas Chemical Company, Inc. | Process for production of 2,6-dimethylnaphthalene |
| JPH0296540A (en) * | 1988-10-03 | 1990-04-09 | Mitsubishi Gas Chem Co Inc | Production of 2,6-dimethylnaphthalene |
| US5003122A (en) * | 1988-10-05 | 1991-03-26 | Catalytica, Inc. | Process for selective diisopropylation of naphthyl compounds using shape selective acidic crystalline molecular sieve catalysts |
| JPH03251545A (en) * | 1990-02-27 | 1991-11-11 | Mitsubishi Gas Chem Co Inc | Production of 2,6-dimethylnaphthalene |
| DE69004542T2 (en) * | 1989-12-01 | 1994-03-10 | Mitsubishi Gas Chemical Co | Process for the preparation of 2,6-dimethylnaphthalene. |
-
1992
- 1992-08-06 US US08/039,067 patent/US5365001A/en not_active Expired - Lifetime
- 1992-08-06 CA CA002093511A patent/CA2093511C/en not_active Expired - Lifetime
- 1992-08-06 DE DE69218775T patent/DE69218775T2/en not_active Expired - Lifetime
- 1992-08-06 WO PCT/JP1992/001006 patent/WO1993002995A1/en active IP Right Grant
- 1992-08-06 EP EP92916964A patent/EP0594856B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2093511A1 (en) | 1993-02-09 |
| US5365001A (en) | 1994-11-15 |
| WO1993002995A1 (en) | 1993-02-18 |
| EP0594856A1 (en) | 1994-05-04 |
| DE69218775D1 (en) | 1997-05-07 |
| EP0594856A4 (en) | 1993-12-22 |
| DE69218775T2 (en) | 1997-07-10 |
| EP0594856B1 (en) | 1997-04-02 |
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