JPH1036295A - Production of methylcyclopentene-containing hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject hydrocarbon by hydrogenation and isomerization of benzene in the presence of a solid superacid catalyst to enable the benzene in a gasoline base material to be diminished and the benzene to be converted efficiently to methylcyclopentene. SOLUTION: (A) Benzene or a benzene-contg. hydrocarbon is brought into contact with (B) a solid superacid catalyst to subject the component A to hydrogenating isomerization, and the methylcyclopentane contained in the reaction product is either separated or not separated, and the system is then brought into contact with (C) a dehydrogenation catalyst to conduct a dehydrogenation reaction. It is preferable that the component B be a composition comprising (i) 100 pts.wt., on an oxide basis, of hydrous oxide and/or oxide of at least one kind of metal selected from group IV, group 13 and group 14 metals and (ii) 0.001-40 pts.wt., on a metal basis, of at least one kind of metal and/or compound of metal selected from group VI, group VII, group VIII, group IX, group X and group 16 metals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing hydrocarbons, and more particularly to a process for efficiently converting benzene to methylcyclopentene.

[0002]

2. Description of the Related Art Automobiles are required to have low harmful substances contained in exhaust gas and good fuel economy. One way to improve fuel efficiency is to increase the compression ratio of the engine to improve thermal efficiency. However, an engine having a high compression ratio is apt to knock, and therefore requires gasoline having a high octane number.

[0003] Such gasoline can be produced by adjusting the composition. Specifically, in order to improve the octane number of gasoline, this is a method of increasing the amount of a heavy aromatic hydrocarbon fraction that is a component having a high octane number. However, in recent years, the effect of the aromatic hydrocarbon component, particularly benzene, on the human body has become a problem, and it has been required to reduce the blending amount of the aromatic hydrocarbon fraction in gasoline. For this reason, gasoline containing a light aliphatic hydrocarbon component having a high octane value, and gasoline containing an oxygen-containing organic compound such as methyl-t-butyl ether, have become commercially available.

In general gasoline, aromatic hydrocarbon components have become a problem similarly to high octane number gasoline, and it has been required to reduce the blending amount of the aromatic hydrocarbon fraction. For this reason, gasoline containing an increased number of aliphatic hydrocarbon-based light components has been marketed.

Since a gasoline base used for producing such gasoline must naturally have a low benzene concentration, methods for removing benzene from the gasoline base have been studied. Separation of benzene from a petroleum refinery fraction, which is a gasoline raw material, is difficult by a conventional distillation method, and requires new equipment such as sulfolane extraction. Furthermore, if benzene regulations in gasoline are implemented on a global scale, benzene recovery from petroleum refining fractions will become active not only domestically but also abroad, which may result in excess benzene supply to the market. . For this reason, there is a need for a method capable of efficiently removing benzene and converting benzene to hydrocarbons other than aromatics. If possible, a method that can convert benzene in a gasoline base material into non-aromatic hydrocarbons without separation is desired.

Further, benzene in gasoline is reduced,
It has become clear that when an aliphatic hydrocarbon or an oxygen-containing compound having a high octane number is contained, the output of the engine is reduced and the acceleration responsiveness is reduced. This is largely due to a decrease in the amount of heat generated per volume. For this reason, attempts have been made to increase the content of naphthenic hydrocarbons having a relatively high calorific value per volume in order to prevent a decrease in the calorific value. For example, JP-A-5-3020
No. 90 describes a gasoline composition containing 1% or more of an alicyclic compound having a cyclo ring having a cyclohexane ring or more. JP-A-6-136372 describes a gasoline composition containing 10-90 g / l of 1,3 cyclohexanediene and 1,4 cyclohexanediene. However, when cyclohexane is added, the research octane number of cyclohexane is 83.
If it is added in a large amount, it becomes difficult to maintain the octane number of gasoline.

On the other hand, among the same alicyclic compounds,
Methylcyclopentene has a research octane number of 94.
And high. Further, since the calorific value per volume is higher than that of a chain hydrocarbon, it is promising as a gasoline base material. Moreover, since the number of carbon atoms is 6, which is the same as that of benzene, there is a possibility that methylcyclopentene can be produced by dehydrogenating benzene after hydroisomerization.

There are several reports on the method for hydroisomerizing benzene to produce methylcyclopentane. US Pat. No. 3,644,196 describes a C6 hydrocarbon obtained by catalytic reforming. A process is described in which benzene is separated from a fraction containing as a main component, the benzene is converted to cyclohexane using a catalyst such as diatomaceous earth-supported Ni catalyst, and methylcyclopentane is further used using an alumina catalyst or the like supporting platinum. Have been. The reaction temperature and pressure of the first stage are about 200 ° C. and 35 kgf / cm ² ,
That of the second stage is about 260 ° C. and 35 kgf / cm ² . Since the reaction is a two-stage reaction, it is disadvantageous in terms of equipment and operating costs. Further, Fujimoto et al. Obtained cyclohexane isomerization using a catalyst in which platinum was supported on an MFI-type aluminosilicate to obtain methylcyclopentane, but there was a problem that there were many decomposition products (Journal of the Petroleum Institute of Japan,
38, No. 4, p. 286 (1995)). Separately, a method has been proposed in which benzene contained in a gasoline base material is converted to methylcyclopentane or the like by hydrogenation or isomerization to reduce it. JP-A-7-278569 discloses a method using a catalyst in which platinum is supported on an MFI-type aluminosilicate. In this example, although the reaction is completed in one stage and the generation ratio of methylcyclopentane is high, the ratio of decomposition reaction is high due to high catalytic activity, and there is a problem that components having 4 or less carbon atoms increase.

As described above, any of the methods reported to date for producing hydrocarbons containing methylcyclopentane from benzene, cyclohexane and gasoline base materials are complicated in the process or cause decomposition reactions. It has problems such as priority.

There have been some reports on a method for producing methylcyclopentene from methylcyclopentane. For example, Amano et al. Reported a production method using a platinum-carbon based catalyst (Asahi Glass Industrial Technology Promotion Association Research Report, Vol. 25, p. 269 (1974)). Chromina-alumina series (edited by the Japan Petroleum Institute, petrochemical process 3-hydrogenation / dehydrogenation, p. 258 (1963)), decationized and treated with neodymium oxide clinoptilotite
(Mamedova, ZM, Kinet. Ka
tal. Vol. 31, No. 1, 237 (199
0), etc.), a copper oxide-alumina system containing potassium to suppress the aromatization of the product (Mamedalie)
va, Yu. G. FIG. , CA 108: 149938).

As described above, there are reports on the hydroisomerization reaction of benzene and on the method for producing methylcyclopentene from the product, methylcyclopentane, respectively. But,
There is no report of producing methylcyclopentene by hydrogenating / isomerizing benzene or a benzene-containing hydrocarbon and subjecting the resulting methylcyclopentane-containing hydrocarbon to a further dehydrogenation reaction. Moreover, as described above, in the existing hydroisomerization reaction, the process is complicated,
There is a problem that the decomposition reaction has priority. For this reason, it has been difficult to produce a methylcyclopentene-containing hydrocarbon from benzene only by combining existing processes.

[0012]

SUMMARY OF THE INVENTION The present invention is intended to solve such a problem, and is intended to convert benzene or benzene in a gasoline base into other hydrocarbon components.
Provided is a production process capable of obtaining a methylcyclopentene-containing gasoline base material having a low octane number with a small amount of decomposition products having 4 or less carbon atoms, capable of almost completely removing benzene, having a relatively large calorific value per unit volume, and having a high octane number. The purpose is to do. If this can be achieved, the following effects can be obtained: 1) reduction of benzene in gasoline base material and its effective use; 2) improvement of engine output and acceleration and improvement of octane number.

[0013]

As a result of intensive studies by the present inventors, when benzene is hydrogenated and isomerized in the presence of a solid superacid catalyst, decomposition products are reduced and methylcyclopentane is produced in high yield. Found that When the obtained methylcyclopentane is further dehydrogenated with a dehydrogenation catalyst, methylcyclopentene having a relatively large calorific value per volume can be obtained.

As a result of further study, when the light fraction obtained from the catalytic reformer is hydrogenated and isomerized in the presence of a solid superacid catalyst, there are almost no decomposition products having 4 or less carbon atoms, and benzene Was efficiently converted to methylcyclopentane, and the benzene content was reduced to 0.01% or less. Further, they have found that methylcyclopentene can be efficiently obtained by dehydrogenating methylcyclopentane contained in the product oil obtained here, and completed the present invention.

The hydrogenation and the isomerization may use the same catalyst or different catalysts. Two or more different catalysts may be used by filling two or more layers. In any case, the use of a solid superacid catalyst as all or a part of the hydrogenation and / or isomerization catalysts has the advantage that the reaction proceeds at a low temperature and the amount of catalyst is small. Also,
Even when the reaction temperature is high, the amount of decomposition products having 4 or less carbon atoms is very small. Further, for dehydrogenation of methylcyclopentene, chromia
A generally known catalyst such as alumina, zeolite, copper oxide-alumina, and platinum-carbon can be used.

The research octane number of methylcyclopentene is determined by the method of Technical Data Book, P.
etroleum Refining English
Edition Volume I (Americic
According to an Petroleum Institute, 94 (1-methylcyclopentene; in the past, AST
M No. 225 (1958) describes a value of 184), but the present inventors added methylcyclopentene to ordinary gasoline (synthesized by the present inventors;
(About 65% of 1-methylcyclopentene) was added, and it was found that the base material had a research octane number of about 110. Thus, it has been clarified that methylcyclopentene effectively acts as a component for improving the octane number of gasoline.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method for producing gasoline of the present invention, the benzene-containing fraction as a starting material includes catalytically modified light naphtha, light naphtha, cracked gas oil and the like. Of these, those useful as gasoline base materials are catalytically modified light naphtha. Among the catalytically modified naphtha, a fraction containing a large amount of a component having 5 to 7 carbon atoms is preferable, and such a fraction contains about 20 to 40% of benzene. Further, even when the catalytically modified naphtha having a low benzene content is treated with the solid superacid catalyst according to the present invention, the linear paraffin isomerized into the branched paraffin, thereby increasing the octane number. Is obtained as a secondary effect.

In addition, petroleum light naphtha can be used although the benzene content is small. Benzene contained in light naphtha is about several percent. However, since a large amount of linear paraffin is contained, in addition to the action of converting benzene to methylcyclopentane and methylcyclopentene, linear paraffin can be isomerized into branched paraffin in the same manner as described above, and the octane value can be reduced. Can be greatly increased.

Other benzene-containing raw materials include, for example, cracked gas oil which is a by-product of ethylene production, and carbonized oil produced when carbonizing coal. Crude benzene containing about 50 to 80% of benzene and surplus benzene obtained by dealkylation of aromatic hydrocarbons in the petrochemical industry can of course be used. Similar processing is possible even when these benzene-containing raw materials contain useful substances such as toluene. Of course, it is also possible to subject the reaction after separating and removing toluene by distillation or the like. For example, when crude benzene containing about 30% of toluene is used as a starting material, it may be subjected to hydroisomerization as it is and further subjected to dehydrogenation, or a benzene fraction obtained after separating toluene may be subjected to hydroisomerization, It may be dehydrogenated. When the benzene concentration contained in the starting material for the hydroisomerization reaction is high, particularly when benzene of 90% or more is used as the starting material, the concentration of methylcyclopentane in the hydroisomerization product also increases, and This is preferable because the production of methylcyclopentene by the reaction is facilitated.

The raw material after the hydroisomerization can be used as it is for the dehydrogenation reaction. However, when the benzene concentration is low or when useful substances coexist, the product of the hydroisomerization is obtained. , A concentrated fraction obtained by a method such as distillation under reduced pressure. Whether to use the hydroisomerate as it is or to use a concentrated fraction of methylcyclopentane obtained by separating from the hydroisomerate may be selected depending on the raw material, catalyst, reaction conditions, equipment conditions, and the like. For example, catalytic reforming naphtha has 5 to 7 carbon atoms.
When a distillate is used as a starting material, a paraffin having a high octane value coexists in the hydroisomerate, so that a methylcyclopentane fraction is separated by distillation, and this is dehydrogenated into methylcyclopentene. And a method of merging with isomerized paraffin. Further, when a raw material having a high methylcyclopentane concentration is used, the concentration of olefin by-produced at the time of dehydrogenation becomes low, so that it can be suitably used as a gasoline base material.

The solid superacid catalyst used in the present invention is a catalyst comprising the following (a), (b) and (c) and / or a catalyst comprising the following (a) and (b). A solid superacid catalyst is defined as 100% sulfuric acid (H ₀ (Hammet acidity function) is −
11.93). (A)
100 parts by weight of at least one hydrated oxide and / or oxide selected from Group 4 metals, Group 13 metals and Group 14 metals (b) 0.05 to 10 parts by weight of sulfuric acid as sulfur Part (c) at least one metal and / or metal compound selected from Group 6 metals, Group 7 metals, Group 8 metals, Group 9 metals, Group 10 metals and Group 16 metals as metals 0.001 to 40 parts by weight.

The Group 4 metal is at least one selected from titanium, zirconium and hafnium, but is preferably titanium and zirconium. The Group 13 metal is at least one selected from aluminum, gallium, indium, and thallium, and is preferably aluminum or gallium. The Group 14 metal is at least one selected from silicon, germanium, and tin, and is preferably silicon or tin.

The Group 6 metals and Group 16 metals are chromium,
It is at least one selected from molybdenum, tungsten, selenium, and tellurium, but is preferably chromium, molybdenum, or tungsten. The Group 7 metal is at least one metal selected from manganese and rhenium, but is preferably manganese. The Group 8 to Group 10 metals are at least one metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, but preferably,
Platinum, iridium, palladium, rhodium, ruthenium and iron.

One or more hydrated oxides and / or oxides (hereinafter abbreviated as carriers) selected from Group 4 metals, Group 13 metals and Group 14 metals, or a sulfuric acid component contained in the carrier. Let it be the basic component. Various methods can be used to make the carrier contain sulfuric acid. For example, impregnation with sulfuric acid (Japanese Patent Publication No. 59-6181, 59-400)
No. 56, etc.) and a solid-phase mixing method using ammonium sulfate (J. Chem. Soc. Commun. 789).
page. 1995).

The amount of sulfuric acid to be contained is 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight as sulfur with respect to 100 parts by weight of the carrier. If it is less than 0.05 parts by weight, the activity is insufficient.
On the other hand, if it exceeds 10 parts by weight, not only does the catalyst activity not improve any more, but also sulfuric acid released from the catalyst increases, which is not preferable.

The carrier or the carrier containing a sulfuric acid component includes a Group 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal,
At least one kind of metal and / or metal compound selected from Group 10 metals and Group 16 metals is contained, and a known method can be used for any metal component (for example, Advance in
Catalysis, 37, 165, 1990 etc.). As a method for containing a Group 6 metal, for example, when tungsten or molybdenum is contained, the method of Arata et al. (JP-A-1-288339, p.
rc. Int. Cong. Catal. 9th. , 4
Vol., P. 1727, 1995). As a method for containing a Group 6 to Group 10 metal and a Group 16 metal, for example, when iron or manganese is contained, Hino, Arata et al. Reported (Book of Ab).
st. : 1995 Int. Chem. Congr. o
fPacific Basin Soc. ; Inor
g. Chem. # 160) The method can be used. Further, for example, as a method for containing any of ruthenium, rhodium, palladium, osmium, iridium, and platinum, a report by Hino, Arata et al.
ysis Letters, No. 30, p. 25, 1995
Year). These known methods may be used alone or in combination.

The form in which the metal component is supported on the carrier is not particularly limited, but those having a low content of catalyst poisons such as alkali metals can be suitably used. For example, oxides, chlorides, sulfates, nitrates, sulfides, ammonium salts of oxyacids, complexes with chloride ions, complexes with ammonium ions, complexes with cyanide ions, complexes with thiocyanate ions, Examples of the complex include an ion complex complex and an ammonium salt of the complex. After being supported on a carrier, the state of the metal compound changes due to calcination, activation of a catalyst, and the like. Therefore, the final form of the metal compound may be any.

The amount of the Group 6 and Group 16 metals to be contained is 1 to 40 parts by weight, preferably 2 to 35 parts by weight, more preferably 5 to 35 parts by weight of the metal based on 100 parts by weight of the carrier.
30 parts by weight. If the amount is less than 1 part by weight, the activity is insufficient. Conversely, if it exceeds 40 parts by weight, the activity is lowered, which is not preferable. The amount of the Group 7 metal is 0.1 to 15 parts by weight, preferably 0.2 to 12 parts by weight, per 100 parts by weight of the carrier.
Parts by weight, more preferably 0.3 to 10 parts by weight.
If the amount is less than 0.1 part by weight, the activity is insufficient. Conversely, if the amount exceeds 15 parts by weight, the activity is lowered, which is not preferable.

The amount of the Group 8 to 10 metal to be contained is, for example, for iron, cobalt and nickel,
0.1 to 15 parts by weight of metal, preferably 0.2 to 12 parts by weight, more preferably 0.3 to 1 part by weight with respect to parts by weight.
0 parts by weight. If the amount is less than 0.1 part by weight, the activity is insufficient. Conversely, if the amount exceeds 15 parts by weight, the activity is lowered, which is not preferable. For ruthenium, rhodium, palladium, osmium, iridium and platinum,
0.001 to 10 as metal for 100 parts by weight of carrier
Parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.1 to 5 parts by weight. If the amount is less than 0.001 part by weight, the activity is insufficient. Conversely, if it exceeds 10 parts by weight, the decomposition reaction becomes noticeable, which is not preferable.

Among them, sulfuric acid-containing zirconia,
A solid superacid catalyst comprising sulfuric acid-containing iron oxide and tungsten compound-containing zirconia containing platinum and / or palladium can be most preferably used.

As the solid superacid catalyst, one kind may be used, or two or more kinds of catalysts having different compositions may be used in combination. Needless to say, each catalyst or a mixture thereof can be filled in two or more layers in a reactor and used.

The hydrogenation and isomerization reaction conditions used in the present invention cannot be fixed to specific conditions because a plurality of parameters are involved, and should be appropriately changed according to the raw material supply amount and the like. However, the hydrogenation reaction is a volume reduction reaction that generates cyclohexane from benzene and three molecules of hydrogen, and is an exothermic reaction. Therefore, in order to shift the amount of cyclohexane to be produced, the reaction pressure is preferably higher and the reaction temperature is preferably lower. On the other hand, in the isomerization reaction equilibrium between cyclohexane and methylcyclopentane, the higher the temperature, the higher the amount of methylcyclopentane produced. From the above, there is an optimum temperature range for efficiently producing methylcyclopentane. The reaction temperature is from 50 to 400C, preferably from 100 to 350C, more preferably from 150 to 330C. If the temperature is lower than 50 ° C., the reaction rate becomes slow, so that the production volume may not be secured. At 400 ° C. or higher, the decomposition reaction becomes conspicuous, and the amount of gaseous hydrocarbons having 3 to 4 carbon atoms increases. Therefore, when gaseous hydrocarbons are not required, 400 ° C.
It is preferable to set the following.

The reaction pressure is preferably as high as possible, but considering the operational efficiency, it is 4.0 × 10 ⁵ to
1.5 × 10 ⁷ Pa (about 3 to 150 kgf / c at gauge pressure)
m ² ), preferably 5.9 × 10 ^{5 to} 9.8 × 10 ⁶ Pa
(5 to 100 kgf / cm ² ). 4.0 × 10 ⁵ P
When a is cut off, the reaction rate decreases. Also, 1.5 × 10
^A pressure exceeding ⁷ Pa is not preferable for operation safety.

The liquid hourly space velocity can be appropriately selected in consideration of the temperature and pressure, but is usually 0.2 to 15 h _-1 , preferably 0.5 to 10 h _-1 . Similarly, for the volume ratio of hydrogen / raw material, an appropriate value may be selected.
It is 0-10000, preferably 300-5000.
As for the reactors, the isomerization and hydrogenation may be performed in one stage in one reactor, or the isomerization and hydrogenation may be performed in two stages in two reactors.

The catalyst used for the dehydrogenation reaction is a chromia-alumina-based catalyst (edited by the Japan Petroleum Institute, petrochemical process 3-hydrogenation).
Dehydrogenation, p. 258 (1963), decationized and treated with neodymium oxide, Clinoptilolite (Mame
dova, ZM, Kinet. Katal.Vol.31, No.1, 237 (1990)
), A copper oxide-alumina system containing potassium to suppress the aromatization of the product (Mamedalieva, Yu. G., C
A 108: 149938), and platinum-carbon based catalysts (Amano et al., Asahi Glass Industrial Technology Promotion Association Research Report, Vol. 25, p. 269 (1974)).

The dehydrogenation reaction conditions vary depending on the type of catalyst used and cannot be fixed to specific conditions. However, since the reaction is an endothermic reaction, a higher reaction temperature is preferable. Usually, the reaction is carried out at a reaction temperature of 400 to 600 ° C. under normal pressure or under pressure. The liquid space velocity can be selected an appropriate value in consideration of the temperature, etc.
Usually 0.1 to 15 h ^-1 , preferably 0.2 to 10 h ^-1
It is. An appropriate value may be selected for the volume ratio of hydrogen / raw material, but it is usually 100 to 5,000, preferably 300 to 3,000. It is desirable to carry out the reaction under a hydrogen stream.

The dehydrogenation reaction product obtained in the present invention may contain some methylcyclopentadiene. If it is necessary to remove this, the boiling point of the dimer of methylcyclopentadiene is 200 ° C., which is very high as compared with the boiling points of other products, so that it can be easily separated by ordinary separation methods such as distillation. it can.

The hydrogen consumed in the hydrogenation reaction is at least three times the mole of benzene, which is one of the causes of the increase in production cost. On the other hand, in the dehydrogenation step, about twice as much hydrogen as methylcyclopentane is generated. In the present invention, since the dehydrogenation step is provided after the hydroisomerization step, the hydrogen obtained in the dehydrogenation step can be sent to the hydrogenation step and used for hydrogenation of benzene or the like. Can be reduced to about one.

[0039]

【Example】

(Example 1) Preparation of solid superacid catalyst 100 g of zirconium oxychloride in 2000 ml of distilled water
And 28% aqueous ammonia was added until a final pH of 8 was formed to form a precipitate. This precipitate is filtered, washed with water,
It was dried to obtain a white powder of dried hydrated zirconium. After 20 g of the dried hydrated zirconia was brought into contact with 300 ml of a 0.5 mol / l sulfuric acid aqueous solution, excess sulfuric acid was removed by filtration and dried at 100 ° C. Subsequently, after impregnated with 3.0 ml of an aqueous solution containing 0.38 g of chloroplatinic acid hexahydrate, dried and calcined at 590 ° C., a zirconia containing sulfuric acid containing platinum was obtained. The composition of this catalyst is such that the zirconium component is 100 parts by weight as zirconium oxide, the sulfuric acid component is 2.1 parts by weight as sulfur, and the platinum compound is 0.1 part by weight as platinum.
It was 7 parts by weight. This catalyst was formed into pellets, pulverized, sieved to 10 to 20 mesh, filled into a 4 ml catalyst layer, and filled with 5.9 × 10 ⁵ Pa (approximately 5 g at a gauge pressure).
kgf / cm ² ), temperature 300 ° C, hydrogen flow rate 50ml /
The reduction treatment was performed for 1.5 minutes.

[0040]Hydrogenation / isomerization reaction  3.0 × 10⁶Pa (about 30kgf / c at gauge pressure)
m^Two), Liquid space velocity 2.0h^-1, Temperature 230 ° C, hydrogen /
Hydrogenation / isomerization treatment is performed under the condition of feedstock ratio of 500 l / l.
became. The sample used had a carbon number of 6 (C
This is a fraction containing a hydrocarbon as a main component. Test conditions
Table 1 shows the feedstock and product composition. Minutes of each component
For analysis, use a gas chromatograph equipped with an FID detector.
Done. In gas chromatography, 0.01
% Level of benzene and toluene cannot be analyzed
is there. In such cases, high performance liquid chromatography
Was performed.

[0041]

[Table 1]

[0042]

[Table 2]

Abbreviations used in Table 2 and subsequent tables are shown below. C3: a fraction having 3 carbon atoms C4: a fraction having 4 carbon atoms Branched C5: an isoparaffin fraction having 5 carbon atoms nC5: an n-paraffin fraction having 5 carbon atoms MCPA: methylcyclopentane MCPE: methylcyclopentene MCPD: Methyl cyclopentadiene CH: cyclohexane Branch C6: isoparaffin fraction having 6 carbons n-C6: n-paraffin fraction having 6 carbons MCH: methylcyclohexane Branch C7: isoparaffin fraction having 7 carbons n-C7: carbon number 7 N-paraffin fraction

[0044]Dehydrogenation reaction  33 kg of product obtained by hydrogenation / isomerization reaction is distilled under reduced pressure
7K concentrated fraction of methylcyclopentane having the composition shown in Table 3
g (methylcyclopentane purity 89%) was obtained. This stay
The dehydrogenation reaction was carried out as follows using the respective components. used
Catalyst extruded platinum-activated carbon catalyst (platinum 0.5wt%)
Molded product crushed and sieved to 10-20 mesh
2 ml was filled in the catalyst layer, and normal pressure, reaction temperature 500 ° C, L
HSV = 2.0h^-1Under hydrogen flow, hydrogen / raw material ratio 100
The reaction was performed at 0 (l / l). Table 4 shows the obtained results.
Show.

[0045]

[Table 3]

[0046]

[Table 4]

Example 2 Using benzene (special grade reagent having a purity of 99.5%) as a raw material for the hydrogenation / isomerization reaction , a liquid hourly space velocity of 1.1 h ^-1 and a hydrogen / feed oil ratio of 20 were used.
00 l / l, pressure 5.9 × 10 ⁵ (approx.
kgf / cm ² ) and the reaction temperature was 240 ° C.
The test was performed in the same manner as in Example 1. Table 1 shows the test conditions and Table 5 shows the results.

[0048]

[Table 5]

Dehydrogenation reaction The product obtained by the above hydrogenation / isomerization reaction was subjected to distillation to obtain a fraction having a purity of methylcyclopentane of 99%, and a dehydrogenation reaction was carried out in the same manner as in Example 1. . Table 6 shows the results.

[0050]

[Table 6]

(Example 3) Hydroisomerization was carried out in the same manner as in Example 1, using the same fraction as the raw material containing C6 hydrocarbon after the catalytic reforming reaction as in Example 1. Subsequently, the reaction product was directly subjected to a dehydrogenation reaction in the same manner as in Example 1. The composition of the final product is shown in Table 7.

[0052]

[Table 7]

[0053]

According to the present invention, benzene can be efficiently converted to methylcyclopentene from a benzene-containing fraction such as benzene or light naphtha. This allows
Not only can harmful benzene be reduced, but also gasoline raw materials with high octane number and excellent acceleration can be produced.

Claims (4)

[Claims] (1) benzene or a benzene-containing hydrocarbon,
Hydroisomerization is carried out by contacting with a solid superacid catalyst, and methylcyclopentane contained in the hydroisomer is separated or contacted with a dehydrogenation catalyst without separation to carry out a dehydrogenation reaction. For producing a methylcyclopentene-containing hydrocarbon. 2. The solid superacid catalyst is a composition comprising the following (a) and (b):
3. The method for producing a methylcyclopentene-containing hydrocarbon according to 1.). (A) 100 parts by weight, as an oxide, of at least one hydrated oxide and / or oxide selected from metals of Groups 4, 13 and 14 of the periodic table. (B) at least one metal and / or metal compound selected from a Group 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal and a Group 16 metal, 0.001 to 40 parts by weight. 3. The solid superacid catalyst according to the following (a),
The method for producing a methylcyclopentene-containing hydrocarbon according to claim 1, which is a composition comprising (b) and (c). (A) 100 parts by weight, as an oxide, of at least one hydrated oxide and / or oxide selected from metals of Groups 4, 13 and 14 of the periodic table. (B) at least one metal and / or metal compound selected from a Group 6 metal, a Group 7 metal, a Group 8 metal, a Group 9 metal, a Group 10 metal and a Group 16 metal, 0.001 to 40 parts by weight. (C) 0.05 to 10 parts by weight of sulfuric acid as sulfur. 4. The methylcyclopentene-containing hydrocarbon according to claim 1, wherein the dehydrogenation catalyst is at least one selected from chromia-alumina, zeolite, copper oxide-alumina, and platinum-carbon. Production method.