JPS62240631A - Production of naphthalene or such - Google Patents

Abstract

PURPOSE:To obtain naphthalenes in high selectivity and in high yield, by reacting an alkyl-substituted benzene in the presence of a compound metallic oxide catalyst consisting of a metallic oxide selected from Zr, In, V and Mo and an alkaline earth metallic oxide. CONSTITUTION:A compound shown by the formula (R is 1-2C alkyl; n is 0-2, m is 4-6; p is 0-2) in a gaseous phase is brought into contact with (A) a compounded metallic oxide catalyst consisting of a metallic oxide selected from Zr, In, V and Mo and an alkaline earth metallic oxide or (B) a compounded metallic oxide catalyst consisting of a metallic oxide selected from V and Mo and titanium oxide or tin oxide at normal pressure at 450-600 deg.C to give naphthalenes. The catalyst is obtained by impregnating the oxide of one metallic component with an aqueous solution of metallic salt of the other metallic component, drying and calcining.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing naphthalenes, and more particularly to a method for producing naphthalenes using alkyl-substituted benzenes as raw materials.

2. Naphthalenes such as 6-dimethylnaphthalene are expected to be used in polyester fibers, polyester films, etc. Such naphthalenes are made from alkyl-substituted benzenes having an alkyl group main chain having 4 or more carbon atoms. Attempts have been made to 4JW. For example, a method of cyclodehydrogenating the alkyl-substituted benzenes to naphthalenes in the presence of a chromium-alumina catalyst is described in Ru5s, Chem, Rev, 40.9.
97 (1971), Chem, Ray, 40.7
15 (1971), Chem.

ReV, 53.353 (1953) M Ruiha J,
0r(J.

Chem, 30.3530 (1965), etc. Further, JP-A-48-32857 discloses a method for producing alkylnaphthalenes in the presence of a solid phosphoric acid catalyst. However, the method for producing naphthalenes by the above method has problems such as low selectivity of the target compound and long steps.

Further, Japanese Patent Application Laid-Open No. 49-62453 discloses a method for producing dimethylnaphthalenes using a chromium-alumina catalyst. However, the selectivity of dimethylnaphthalenes obtained by this method is low, or (
There was a problem in that the conversion rate of dimethylbutenylbenzene, a raw material, was low.

Purpose of the Invention The present invention is intended to solve the problems associated with the prior art as described above. Another object of the present invention is to provide a method for producing naphthalenes that can produce naphthalenes in high yield.

Summary of the Invention Process for Producing Naphthalenes According to the Invention At least one (Φ) metal oxide and an alkaline earth metal oxide selected from the group consisting of I, J, zirconium, indium, vanadium and molybdenum are The presence of a composite metal oxide catalyst (a) consisting of a composite metal oxide catalyst W (a), or a composite metal oxide catalyst (b) consisting of at least one metal oxide selected from the group consisting of vanadium and molybdenum and titanium oxide or tin oxide. Below is a reaction mixture represented by the following general formula [■] (which is characterized by reacting moxibustion benzenes).

[Wherein, R is an alkyl group having 1 to 2 carbon atoms, n indicates the number of R groups and is an integer of 0 to 2, m is an integer of 4 to 6, and P is an integer of 0 to 2. ] According to the present invention, since naphthalenes are produced by reacting substituted benzenes using a specific catalyst, naphthalenes can be obtained with high selectivity and high yield.

DETAILED DESCRIPTION OF THE INVENTION The method for producing naphthalenes according to the present invention will be specifically described below.

Reaction raw material In the present invention, substituted benzenes represented by the following general formula [■] are used as reaction raw materials.

[Wherein, R is an alkyl group having 1 to 2 carbon atoms, n indicates the number of R groups and is an integer of 0 to 2, m is an integer of 4 to 6, and P is an integer of 0 to 2. ] The substituent in the above substituted benzenes is Cm "2m
+2p-3, but when P=2, the substituent is a saturated aliphatic hX alkyl group, and when P=1, there is one double bond, and P= In the case of O, it is a substituent having two double bonds.

(i) When P=2, examples of the substituent include the groups shown below.

)-butyl group (m=4> n-pentyl group (m=5> 1-methylbutyl group (m=5) 2-methylbutyl group (m=5> 3-methylbutyl group (m=5> 1-methylpentyl group (m=6> 2-methylpentyl group (m=6> 3-methylpentyl group (m=6>, etc.) (ii) When p=1, the substituent is as shown in the following group. Examples include groups.

1-butenyl group (m=4>2-butenyl group (m=4>3-butenyl group)m=4>1-pentenyl group (m=5>2-pentenyl group (m=5>3-pentenyl group) m=5>1-methyl-1-butenyl group (m=5>2-methyl-1
-butenyl group (m=5>1-methyl-2-butenyl group (
m=5>2-methyl-2-butenyl group (m=5) 1-methyl-3-butenyl group (m=5>2-methyl-3-butenyl group (m=5>1-methyl-1-pentenyl I(m=
6> etc. (iii) In the case of o=o, examples of the substituent include the groups shown below.

1.3-butadienyl group (m=4>2-methyl-1,3-butadienyl group (m=5>1.3
-Pentadienyl (m=5>1-methyl-1,3-pentadienyl (m=6)3-
Methyl-1,3-butadienyl group (m=5) 2-methyl-1,3-butadienyl group (m=5>3-methyl-1,
3-pentadienyl group (m=6>4-methyl-1,3-
Pentadienyl group (m=6> etc.

In the present invention, the raw material substituted benzenes having a substituent represented by the above C-order H+2P-3 is reacted in the presence of the catalyst according to the present invention, and the substituent is converted into a benzene nucleus or the above-mentioned general formula [ A bonding reaction occurs with the alkyl group represented by R in 11 to produce naphthalenes. For example, when r)-butylbenzene is used as a raw material, naphthalene is produced, and when 2,5-dimethyl-(2-butenyl)benzene is used as a raw material, the 2-butenyl trap is converted into a benzene nucleus. 1,4-dimethylpphthalene is produced when a carbon-carbon bond is formed, and 2,6-dimethylnaphthalene is produced when a methyl group in a side chain is bonded to a carbon-carbon bond. During the reaction, the methyl group is isomerized and even 1,3 monomers may be produced as by-products.

In the present invention, a catalyst is used in producing naphthalenes from substituted benzenes as described above.

The catalyst used in the present invention is a composite metal oxide catalyst (a) consisting of at least one metal oxide selected from the group consisting of zirconium, indium, vanadium, and molybdenum and an alkaline earth metal oxide, or a vanadium and a composite metal oxide catalyst tR(b) consisting of at least one metal oxide selected from the group consisting of molybdenum and titanium oxide or tin oxide.

In this composite metal oxide catalyst (a), specific examples of the alkaline earth metal oxide include magnesium oxide, calcium oxide, strontium oxide, barium oxide, etc., which occupy the alkaline earth metal oxide in the catalyst. The proportion is usually 30 to 98% by weight, preferably 50 to 95% by weight of the total weight of the catalyst.

In addition, in the composite metal oxide catalyst (b), in the case of a catalyst made of badge lamb oxide or molybdenum oxide and titanium oxide, the proportion of titanium oxide in the catalyst is usually 60 to 98%.
% by weight, preferably 80-95% by weight.

In addition, in the composite metal oxide catalyst (b), in the case of a catalyst consisting of vanadium oxide or molybdenum oxide and tin oxide, the proportion of tin oxide in the catalyst is usually 55 to 98% by weight, preferably 80 to 95% by weight. .

In the present invention, (a) of any of these composite metal oxide catalysts
Also in (b), any conventionally known method may be used to prepare the catalyst. Examples of such a preparation method include the following method.

The catalyst can be prepared by a so-called impregnation method in which a metal oxide of one metal component constituting the catalyst is impregnated with an aqueous solution of a metal salt of the other metal component, then dried and then calcined. Here, the above-mentioned one metal component and the other metal component may be a single component or a mixed component consisting of a plurality of metal components. As for the preparation method of the catalyst, this method also involves mixing a mixed solution of metal salts of metal components constituting the catalyst with an alkaline solution, adjusting the pH to precipitate the metal hydroxide as a coprecipitate, and forming the coprecipitate. The catalyst can also be prepared by drying and firing, the so-called coprecipitation method. In this case, metal salts include zirconium, indium, vanadium, molybdenum and tin oxynitrate rli salts, nitrate M salts, sulfates, oxychlorides, chlorides,
Examples include acetate, formate, oxalate, and ammonium salt. Examples of alkaline solutions include ammonia, ammonium carbonate, caustic alkali, sodium carbonate, and urea. In addition to the above methods for preparing the catalyst, metal oxides of the metal components constituting the catalyst or metal compounds (metal salts and organometallic compounds as described above) that are converted into oxides by calcination may be mixed with other metal oxides or the metals. The catalyst can also be prepared by kneading the compounds or the metal oxide and the metal compound with the addition of a known binder if necessary, followed by drying and baking.

The drying of the catalyst is usually carried out at a temperature of 80 to 250 °C, and the calcination of the catalyst is carried out at a temperature of 350 to 400 °C, preferably 400 °C.
Performed at a temperature of ~650'C.

Furthermore, in order to improve the selectivity of the target compound, an alkali such as sodium hydroxide or potassium hydroxide can be added to the catalyst by an impregnation method or the like. It is preferable that the amount of alkali added is up to 20% by weight of the total weight.

Further, for the same purpose, in the present invention, the above-mentioned composite metal oxide catalyst tR (a> or (b)) can be used by attaching IB to an inert finger body by a known method. Compatibility ratio of catalyst The amount is usually 2 to 30% by weight based on the carrier.As a supporting method, after kneading the sample hydroxide and the carrier or adding a metal salt solution to the carrier, the supporting method is as follows: Shun impregnated into the carrier, dried as above,
An example of a firing method can be given.

Reaction conditions The reaction of substituted Hensenbal using the above catalyst is as follows:
It is preferable to carry out the reaction in the form of a gas phase in which the raw material is made into a vapor and brought into contact with a catalyst. For gas phase reactions, fixed bed method,
Fluidized bed method and moving bed method can be adopted.

The above reaction is carried out at 400-650'C, preferably at 450-650'C.
It is carried out at a temperature of 600'C. The reaction may be carried out under normal pressure or increased pressure, but it is preferably carried out under pressure.

During the reaction, it is preferable to dilute the reaction raw material with another stable organic solvent, and examples of such organic diluents include benzene, toluene, O-xylene, n-xylene, and P-xylene. When the reaction raw material is diluted with a diluent, the weight ratio of the organic diluent to the reaction raw material is 1 to 20, preferably 3 to 10.

It is the contact time between the reaction raw material and the catalyst, H, S.

V, (h') is 0.1 to 20, preferably 0.3 to 2.0
It is.

Effects of the Invention According to the present invention, naphthalenes are produced by reacting substituted benzenes using a specific catalyst, so naphthalenes can be obtained with high selectivity and high yield.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Wako Tsumugi company zirconium oxynitrate dihydrate 1i,
9 g (0,045 mol) dissolved in distilled water,
This was impregnated with 18.1 (0,457 mol) of Kyowa Kagaku Co., Ltd.'s ¥A magnesium oxide (Kyowa Mag 150) at room temperature, and after drying, it was fired in air at 50°C for 3 hours.

20 d (23 g) of the ZrO2-MqO (7) catalyst with an MgO content of 80% by weight prepared in this manner was fixed in a 30 mφ x 600 m high quartz tube with glass wool. 'C1 catalyst layer 500°
After setting to C, n-butylbenzene/toluene=1
/10 (ffflfl ratio), If, S, V, (h
When the reaction was carried out by supplying it to the catalyst layer under normal pressure at 0.5% of n-butylbenzene, the conversion rate of n-butylbenzene was 92%.
The selectivity of naphthalene, the target product, is 98%.
Met.

In Example 1 for preventing shearing, aluminum nitrate 9 manufactured by Wako Jun Co., Ltd.
Cr 203 A, l! by coprecipitation method using hydrate 136.1cj (0,363 mol) and 28°5 g (0,071 mol) of chromium nitrate nonahydrate manufactured by Wako Tsumugi Co., Ltd.
203 catalyst was prepared and a 1″:I catalyst was used.
As a result of carrying out the reaction in the same manner as in Example 1, the conversion rate of n-butylbenzene was 61%, and the selectivity of naphthalene was 57%.
Met.

Comparative Example 2 In Comparative Example 1, the reaction raw material n-butylbenzene was
, 5-dimethyl-(2-butenyl)benzene was used, and the reaction temperature was changed from 500'C to 550°C. Table 1 shows the results of the reaction carried out in the same manner as in Comparative Example 1.

Example 2 In Example 1, the reaction raw material n-butylbenzene was
．． Table 1 shows the results of a reaction carried out in the same manner as in Example 1, except that 5-dimethyl-(2-butenyl)benzene was used and the reaction temperature was changed from 500°C to 550'C.

Example 3 In Example 2, the reaction temperature was set to 600'C, and V205-MgO was prepared by a coprecipitation method from Wako Tsumugi Yakusei magnesium nitrate and ammonium vanadate manufactured by Wako Tsumugi Yakuhin Co., Ltd.
The reaction was carried out in the same manner as in Example 2, except that the catalyst obtained by preparing the above was used. The proportion of MQO in the catalyst is 90
% by weight. The results are shown in Table 1.

Example 4 In Example 2, the reaction temperature was set to 600'C, and V2O5-TiO2 was prepared by a coprecipitation method from titanium trichloride manufactured by Wako Tsumugi Co., Ltd. and ammonium vanodate manufactured by Wako MA Pharmaceutical Bl.
The reaction was carried out in the same manner as in Example 2, except that this was prepared and used as a catalyst.

The proportion of TlO2 in the catalyst was 90,000%. The results are shown in Table 1.

In Comparative Example 2, the reaction temperature was 600'C, and the catalyst was Cr203-A 1203, Wako Pure Mulberry Reiso Aluminum Nitrate Nonahydrate and Wako if'' II!
The reaction was carried out in the same manner as in Comparative Example 2, except that the V2O5-Al2O3 catalyst prepared from ammonium vanadate manufactured by I1 by the coprecipitation method was used instead. A1□ in the catalyst
The ratio of 03 was 90%.

The results are shown in Table 1.

In Example 2, the reaction temperature was 550'C, and 1q of M O
The reaction was carried out in the same manner as in Example 2 except that 03M gO catalyst was used. The proportion of MgO in the catalyst was 90% by weight. The results are shown in Table 1.

Comparative Example 4 In Comparative Example 2, the catalyst was changed from Cr203-Al2O3 to Wako Ifl! Aluminum nitrate nonahydrate Onibi Wako e'h! The reaction was carried out in the same manner as in Comparative Example 2, except that the catalyst was replaced with 1:7 MQO3-A I 203 catalyst prepared from ammonium molybdate manufactured by Co., Ltd. by a coprecipitation method. The proportion of A12o3 in the catalyst was 90% by weight. The results are shown in Table 1.

Example 6 V205-CaO was prepared and reacted in the same manner as in Example 1, Series 3. The proportion of CaO in the catalyst is 901
ffi%. The results are shown in Table 1.

X-healing fPI 7 M 003-T 1 02 was prepared and reacted in the same manner as in Example 4. The proportion of TiO2 in the catalyst is 90
It was 1% by weight. The results are shown in Table 1.

Example 8 V2O5-5n02 was prepared and reacted in the same manner as in Example 5. The proportion of S')02 in the catalyst was 90@fan%. The results are shown in Table 1.

Example 9 In Example 2, the reaction raw material 2,5-dimethyl-(2
-butenyl)benzene to 2,5-dimethyl-(1,3-
The reaction was carried out in the same manner as in Example 2, except that (butadienyl)benzene was used instead. The results are shown in Table 2.

Comparative Example 5 In Comparative Example 2, Wako IiT! was used instead of the Cr2o3-A I203 catalyst. Using 7r02-3i02 catalyst prepared by coprecipitation method from zirconyl oxynitrate and Snowdex (10% sol) manufactured by Nikki Chemical Co., Ltd., the reaction raw material 2,5-dimethyl-(2-butenyl)benzene was , 5-dimethyl-(1,3-butadienyl)benzene was used, but the reaction was carried out in the same manner as in Comparative Example 2. The proportion of S i 02 in the catalyst is 90% by weight
Met. The results are shown in Table 2.

Example 10 In Example 2, 2,5-dimedyru(
2-butenyl)benzene to 5eC-(2-hegysenyl)
The reaction was carried out in the same manner as in Example 2 except that benzene was used instead. As a result, the reaction proceeded with a raw material conversion rate of 90%,
The composition of the product was 58% 1,4-dimethylnaphthalene, 3% 1,3-dimethylnaphthalene, and 12% biphenyl.

Examples 11 to 15 In Example 2, as a catalyst, a203-Mq
o (Example 11), MnO2-MQO (Example 12)
, Ce02-MgO (Example 13), Ti02-M
qO (Example 14) and SnO2-MqO (Example 1
The reaction was carried out in the same manner as in Example 2 except that 3) was used. The results are shown in Table 3.

Each of the catalysts was prepared by the impregnation method under the same conditions as in Example 1, except that the metal compounds shown below were used as raw materials.

Magnesium oxide (Kyowa Mag 150), lanthanum nitrate hexahydrate, manganese nitrate hexahydrate, ceric nitrate hexahydrate, titanium tetraisopropoxide (dissolved in isopropanol and impregnated), tin acetate (dissolved in acetic acid) impregnation).

In each of the catalysts obtained, the proportion of metal oxides other than magnesium oxide in the catalyst was 10% by weight based on the total weight.

Claims (1)

[Claims] (1) A composite metal oxide catalyst (a) consisting of at least one metal oxide selected from the group consisting of zirconium, indium, vanadium and molybdenum and an alkaline earth metal oxide, or a group consisting of vanadium and molybdenum Reacting substituted benzenes represented by the following general formula [I] in the presence of a composite metal oxide catalyst (b) consisting of at least one metal oxide selected from titanium oxide or tin oxide. Featured methods for producing naphthalenes: ▲Mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R is an alkyl group having 1 to 2 carbon atoms, and n indicates the number of R groups, 0 to 2 m is an integer of 4 to 6, and P is an integer of 0 to 2. ]