JPH10195001A - Production of methylcyclopentane-containing hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the production of the subject hydrocarbon useful as a high octane-number gasoline base material excellent in the acceleration response of an engine and having a low content of decomposition products and benzene at high yield by isomerizing a raw material such as a cyclohexane-containing hydrocarbon, etc., in the presence of a specific catalyst. SOLUTION: (A) Cyclohexane or a cyclohexane-containing hydrocarbon (e.g. catalytically reformed naphtha, light naphtha, a material obtained by hydrogen modification of cracked light oil, etc.) is isomerized in the presence of (B) a solid superacid catalyst. Used as the component B is a catalyst consisting, for example, of (B1 ) a (hydrated) oxide of an element of the group 4, 6, 13 or 14 of the periodic table in an amount of 100 pts.wt. expressed in terms of the oxide, (B2 ) an element of the group 7, 8, 9 or 10 of the periodic table in an amount of 0.001-15 pts.wt. expressed in terms of the metal and (B3 ) a sulfuric acid component (e.g. a compound of sulfuric acid and zirconia or sulfuric acid) in an amount of 0.05-10 pts.wt. expressed in terms of sulfur.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrocarbon, and more particularly, to a production process for converting a hydrocarbon containing cyclohexane into a hydrocarbon containing methylcyclopentane.

[0002]

2. Description of the Related Art In recent years, the influence of an aromatic hydrocarbon component, particularly benzene, on the human body has become a problem, and it has been required to reduce the blending amount of an aromatic hydrocarbon fraction, particularly benzene, in gasoline. However, it has become clear that reducing aromatic components such as benzene in gasoline and increasing the blending amount of aliphatic hydrocarbons and oxygenated compounds results in lower engine output and lower acceleration responsiveness. I have. This is largely due to a decrease in the amount of heat generated per volume.

[0003] 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-5-302090 describes a gasoline composition containing 1% or more of an alicyclic compound having a cyclo ring having a cyclohexane ring or more. In addition, Japanese Patent Laid-Open No. 6-1
No. 36372 discloses 1,3 cyclohexanediene,
A gasoline composition containing 10 to 90 g / l of 1,4 cyclohexanediene is described. However, when cyclohexane is added, the research octane number of cyclohexane is about 83, and when it is added in a large amount, it becomes difficult to maintain the octane number of gasoline.

[0004] Another problem in removing benzene from gasoline is that if benzene is recovered from petroleum refinery distillates, the supply of benzene to the market may become excessive. In order to avoid this, it is necessary to use benzene or chain hydrocarbons obtained by decomposing benzene-containing hydrocarbons, and cyclohexane-containing hydrocarbons obtained by hydrogenating benzene or benzene-containing hydrocarbons as gasoline base materials. Become. However, as described above, chain hydrocarbons cause a decrease in engine output, and cyclohexane has a problem of octane number. Therefore, there is a need for a method of converting a cyclohexane-containing hydrocarbon into a gasoline base material having a high octane number.

[0005] Among the alicyclic compounds same as cyclohexane, methylcyclopentane is promising as a gasoline base material because it has a high research octane number of 91 and a high calorific value per volume as compared with chain hydrocarbons. . Moreover,
Methylcyclopentane can be produced by isomerizing cyclohexane.

As for a method for producing methylcyclopentane by isomerization from cyclohexane, a method using a catalyst in which platinum is supported on an MFI-type aluminosilicate has been reported (Fujimoto et al .; Journal of Petroleum Institute, Vol. 38, No. 4, 2
86 (1995)). However, there is a problem that there are many decomposition products. 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. Also, in US Pat. No. 3,644,196, benzene was separated from a fraction mainly composed of a hydrocarbon having 6 carbon atoms obtained by a catalytic reforming treatment, and a Ni catalyst was supported on diatomaceous earth from the benzene. A process is described in which cyclohexane is formed using a catalyst or the like, and methylcyclopentane is formed using an alumina catalyst or the like supporting platinum. The reaction temperature and pressure of the first stage are about 200 ° C,
35 kgf / cm ² , and that of the second stage is about 260
° C and 35 kgf / cm ² . This method also has a problem that the rate of the decomposition reaction is large and the components having 4 or less carbon atoms increase.

[0007] As described above, the conventional method of producing methylcyclopentane-containing hydrocarbons from cyclohexane, cyclohexane-containing hydrocarbons obtained by hydrogenating a gasoline base material, and the like, have the problems that the decomposition reaction has priority. Have. This decomposition reaction occurs mainly in the isomerization reaction. For this reason, there has been a demand for an isomerization method of cyclohexane or the like which can produce a methylcyclopentane-containing hydrocarbon efficiently with little decomposition reaction.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve such a problem, and can not only process cyclohexane, a hydrocarbon containing cyclohexane, a raw material obtained by hydrogenating a hydrocarbon containing benzene, and the like, but also can reduce carbon dioxide. An object of the present invention is to provide a method for producing a methylcyclopentane-containing hydrocarbon having few decomposition products of several or less. As a result, there are obtained two effects of 1) that cyclohexane obtained by hydrogenating benzene contained in a gasoline base material can be used as a high octane number gasoline base material, and 2) an increase in methylcyclopentane concentration that improves the acceleration response of an engine. Can be

[0009]

As a result of intensive studies by the present inventors, as a cyclohexane-containing hydrocarbon raw material, a hydrogenated light fraction obtained from a catalytic reformer is used, and a cyclohexane-containing hydrocarbon feedstock is used as an isomerization catalyst. It has been found that when a solid superacid catalyst containing a Group 10 element is used, there are few decomposition products having 4 or less carbon atoms, and methylcyclopentane can be produced efficiently. In this case, it has also been found that the benzene content can be reduced to 0.01% or less as a secondary effect. Further, they have found that even if only cyclohexane is isomerized, it can be efficiently converted to methylcyclopentane, and thus completed the present invention. Here, the super-strong acid catalyst is a catalyst showing an acid strength stronger than 100% sulfuric acid (H ₀ (Hammet's acidity function) is -11.93).

The solid superacid catalyst is a catalyst comprising the following (a) and (b) or a catalyst comprising the following (a), (b) and (c). (A) Groups 4, 6, 13, and 14 of the periodic table
At least one element selected from the group consisting of a hydrated oxide and / or an oxide, 100 parts by weight as an oxide; (b) groups 7 and 8 of the periodic table , Ninth, and tenth
One or more elements selected from the group consisting of
0.01 to 15 parts by weight (c) 0.05 to 10 parts by weight of sulfuric acid as sulfur

The term "sulfuric acid" refers to a sulfur compound involved in the expression of a super strong acid in the catalyst, and its existing form may be a compound of sulfuric acid and zirconia, sulfuric acid, or the like. Also,
The oxide of “100 parts by weight of the elements of Groups 4, 6, 13 and 14 of the periodic table as oxides” means that the oxide is stable after firing at 600 to 800 ° C. in an air atmosphere. The oxides present in the above are shown. When a plurality of forms exist stably, it is the average oxide composition. 7th, 8th,
The Group 9 and Group 10 elements are extremely complicated in their presence because they are calcined and activated after being loaded on the catalyst in the form of a compound. For this reason, the final existence form is not particularly limited.

By using the above solid superacid catalyst as a catalyst for all or a part of the isomerization, the reaction rate is higher than that of the conventional catalyst at the same temperature. In addition, when the reaction rates were made equal, the number of carbon atoms was 4 compared with the conventional catalyst.
It has the characteristic that the amount of the following decomposition products is small.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the process for producing a methylcyclopentane-containing hydrocarbon of the present invention, the hydrocarbon containing cyclohexane as a starting material is defined as catalytically modified light naphtha,
Light naphtha, hydrocracked light oil, and the like can be mentioned. Among them, the catalytically modified light naphtha, particularly the fraction containing a large amount of the component having 5 to 7 carbon atoms, has a benzene concentration of about 20 to 40% and a high cyclohexane concentration after the hydrotreatment. Therefore, the concentration of methylcyclopentane after the isomerization treatment is also high, which is suitable as a gasoline base material. Naturally, it is also possible to treat a high-concentration cyclohexane-containing hydrocarbon obtained by hydrogenating benzene separated from the catalytically modified naphtha, or a raw material obtained by concentrating cyclohexane by distillation or the like. Further, even with a hydrocarbon raw material having a low cyclohexane content, when the treatment is performed using the present catalyst, the effect that the octane value is improved by isomerization of linear paraffin into branched paraffin, Obtained secondarily.

It is also possible to use a raw material obtained by hydrogenating light naphtha of petroleum. Benzene contained in light naphtha is about several percent, and the concentration of cyclohexane after hydrogenation does not increase. However, since a large amount of linear paraffin is contained, in addition to the action of converting cyclohexane to methylcyclopentane, linear paraffin can be isomerized into branched paraffin as described above, and the octane value can be increased. it can.

[0015] The basic component of the solid superacid catalyst is one or more elements selected from the elements of Groups 4, 6, 13 and 14, the form of which is hydrated oxide and / or oxidized. One or more selected from a product and, if necessary, a sulfuric acid content. If it does not contain sulfuric acid,
One or more components selected from Group 6 elements are essential.
Specific examples of the catalyst include zirconium, titanium, zirconium-titanium, zirconium-aluminum, titanium-aluminum, etc. in terms of availability and catalytic activity, and at least one selected from Group 6 elements and sulfuric acid. Compounded ones can be mentioned. Among these, a compound in which at least one selected from a tungsten compound and a sulfuric acid component is mixed with zirconium, zirconium-aluminum, or the like is particularly preferable.

The Group 4 element is at least one selected from titanium, zirconium and hafnium, but is preferably titanium and zirconium. The Group 6 element is at least one selected from chromium, molybdenum, and tungsten. The Group 13 element is at least one selected from aluminum, gallium, indium, and thallium.
Although it is a species, it is preferably aluminum or gallium. The Group 14 element is at least one selected from silicon, germanium, and tin, and is preferably silicon or tin.

The Group 7 to Group 10 elements are at least one selected from manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, but are preferably platinum, iridium,
Palladium, rhodium, ruthenium and iron.

Various methods can be used to contain sulfuric acid. For example, an impregnation method using sulfuric acid (Japanese Patent Publication No. 59-618)
Nos. 1 and 59-40056) and a solid-phase mixing method using ammonium sulfate (J. Chem. So.
c. Commun. 789 pages. 1995), and a method of kneading with a sulfuric acid-containing compound. The amount of sulfuric acid to be contained depends on Group 4, Group 6, Group 13 and Group 1.
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 per 100 parts by weight of oxide of one or more elements selected from Group 4 elements is there. 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.

Group 6 elements, especially tungsten and / or molybdenum, are preferred. When these are contained, the method of Arata et al. (Japanese Patent No. 2566814, Pro
c. Int. Cong. Catal. 9th. , 4 volumes,
1727, 1995), a method of kneading with an ammonium salt of tungstic acid and / or molybdic acid, and the like.

One or more hydrated oxides and / or oxides selected from the elements of Groups 4, 13 and 14 include
When the solid superacid is obtained by adding the group III element, the compounding amount is as follows. 1 to 40 parts by weight, preferably 2 to 35 parts by weight of a Group 6 element as a metal per 100 parts by weight of the oxide of at least one element selected from the elements belonging to Group 4, 13 and 14 , More preferably 5 to 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 catalyst may be used after adding sulfuric acid. When sulfuric acid is added, the addition amount of the Group 6 metal is 0.1 to 40 parts by weight, preferably 0.5 to 3 parts by weight.
It is 5 parts by weight, more preferably 2 to 30 parts by weight. Thus, when sulfuric acid is added, the amount of the Group 6 metal to be added can be reduced.

The above basic components are subjected to an activation treatment by firing, if necessary. The activation treatment is performed at a temperature higher than 600 ° C. and lower than 800 ° C. for 0.5 to 10 hours in a gas atmosphere such as air or nitrogen.

It is at least one element selected from the group 7, 8, 8, 9 and 10, and any known method can be used for containing these elements (for example, , Advance in Catalyst
sis, 37, 165, 1990, etc.). For example, in the case where iron or manganese is contained in the method of containing a Group 7 to Group 10 metal, Hino and Arata et al reported (Book of Abst .: 1995 In).
t. Chem. Congr. of Pacific B
asin Soc. Inorg. Chem. # 16
0) method and the like can be used. Also, for example, ruthenium, rhodium, palladium, osmium,
As a method for containing either iridium or platinum, a report by Hino and Arata (Catalysis Let) is available.
ters, No. 30, p. 25, 1995). These known methods may be used alone or in combination.

In addition, Group 7, Group 8, Group 9, and Group 10
At least one element selected from the group can be contained before, simultaneously with, or after containing at least one element selected from the group consisting of sulfuric acid and a group 6 element. However, since the platinum group element is expensive, it is common to use a supporting method capable of increasing the concentration near the catalyst surface in the sense of reducing the amount of platinum group element used. Specifically, an impregnation method is generally used.

At least one element selected from Group 7, 8, 8 and 9 is contained before or simultaneously with the addition of at least one element selected from sulfuric acid and Group 6 elements. In case, after drying, 800 ℃ higher than 600 ℃
By firing at a lower temperature for 0.5 to 10 hours,
The desired solid acid catalyst can be prepared.

The form in which one or more elements selected from the above groups 7 to 10 are carried is not particularly limited, but those containing a small amount of a catalyst poison such as an alkali metal are preferred. Can be 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 7-10 element is
1 selected from Group 6, Group 13, Group 13 and Group 14 elements
The weights of 100 or more parts of the oxide of at least one element are shown below. Regarding Group 7 elements, 0.1 to 1
The amount is 5 parts by weight, preferably 0.2 to 12 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 Group 8 to Group 10 elements is, for example, 0.1 to 15 parts by weight, preferably 0.2 parts by weight for iron, cobalt and nickel as metal.
To 12 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 content of ruthenium, rhodium, palladium, osmium, iridium and platinum is 0.001 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.1 to 5 parts by weight as a metal. 0.0
When the amount is less than 01 parts by weight, the activity is insufficient. Conversely, if it exceeds 10 parts by weight, the decomposition reaction becomes noticeable, which is not preferable.

The solid acid catalysts described so far can be suitably used mainly in the form of a powder catalyst. Of course, there is no problem in molding and using a tableting machine or the like. However, when it is used as a molding catalyst, a method by kneading molding, which is generally used industrially, is simple.

When kneading and molding, it is preferable to use alumina as a binder. Specifically, at least one element selected from the elements of Group 4, Group 6, Group 13 and Group 14, preferably at least one element selected from the elements of Group 4 and more preferably a hydroxide of zirconium, Hydrated oxide and / or
Alternatively, an oxide, a compound of one or more elements selected from Groups 7 to 10, a sulfuric acid component, and aluminum hydroxide, hydrated oxide, and / or alumina as binders are constituent components. Further, a tungsten and / or molybdenum compound may be used instead of the sulfuric acid content, or a tungsten and / or molybdenum compound may be added to the sulfuric acid content and used.

In order to obtain a molded catalyst, generally known methods can be applied. First, one or more hydrated oxides and / or oxides selected from Group 4, Group 6, Group 13, and Group 14 elements, which are basic components of the solid superacid catalyst, and a sulfuric acid-containing compound and / or Alternatively, a compound of tungsten and / or a compound of molybdenum, which are Group 6 elements, are kneaded. Subsequently, it is formed into an arbitrary shape such as a pellet shape or a honeycomb shape by a known device such as an ordinary screw type extruder.
After the drying, if necessary, an activation treatment by baking is performed.
The activation treatment is performed in a gas atmosphere such as air or nitrogen.
0.5 to 10 at a temperature higher than 600 ° C and lower than 800 ° C
Bake for hours. When the calcination temperature is lower than 600 ° C. or higher than 800 ° C., the catalytic activity decreases. After that, the 7th, 8th,
Impregnation with a compound containing at least one element selected from Group 9 and Group 10
Bake at a temperature lower than 00C for 0.5 to 10 hours.

In the case of producing a shaped catalyst, the distribution of the weight of alumina as a binder and the weight in terms of oxide of one or more elements selected from Group 4, Group 6, Group 13 and Group 14 elements. Affects the ease of catalyst production, the mechanical strength of the catalyst, and the catalytic activity. The ratio of the weight of alumina to the total weight of the alumina and the weight of one or more elements selected from the elements of Groups 4, 6, 13 and 14 is 20 to 80% by mass, Preferably, it is adjusted to 20 to 50% by mass. By doing so, not only kneading and molding are facilitated, but also a catalyst having high mechanical strength and high activity can be obtained.

The compound containing at least one element selected from Group 7, Group 8, Group 9 and Group 10 is
It is also possible to add at the time of kneading. In this case, the target solid acid catalyst can be prepared by firing at a temperature higher than 600 ° C. and lower than 800 ° C. for 0.5 to 10 hours after forming and drying.

As alumina, various forms can be used, and zirconium hydrated oxide and / or oxide,
When one or more elements selected from Group 8, Group 9, and Group 10 are combined with sulfuric acid, a pseudo boehmite form is preferred. The catalyst molded product obtained by this combination has a specific surface area of 150 to 300 m ² / g, and 2θ = 2
The X-ray diffraction peak area ratio of 8.2 ° and 2θ = 30.2 ° is 0.05 or less. Of course, a tungsten and / or molybdenum compound may be used in place of the sulfuric acid, or a tungsten and / or molybdenum compound may be added to the sulfuric acid and used.

Among the solid acid catalysts described above, a solid super-strong acid catalyst containing sulfuric acid-containing zirconia containing a platinum group metal, a solid super strong acid catalyst containing sulfuric acid-containing iron oxide zirconia containing a platinum group metal, and zirconia A solid superacid catalyst comprising alumina, a platinum group metal and a sulfuric acid component, and a solid superacid catalyst comprising zirconia containing tungsten and a platinum group metal can be suitably used. In particular, a molded solid superacid catalyst comprising zirconia, alumina, a platinum group metal and sulfuric acid,
The activity is higher than that of the powdered solid acid catalyst, and the reaction rate is higher than that of the powdered solid acid catalyst at the same reaction temperature.

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 isomerization reaction conditions used in the present invention are as follows:
Since a plurality of parameters are involved, the parameters cannot be fixed to specific conditions, and should be appropriately changed according to the raw material supply amount and the like. In the isomerization reaction equilibrium between cyclohexane and methylcyclopentane, the higher the temperature, the higher the amount of methylcyclopentane produced. For this reason, in order to efficiently produce methylcyclopentane, an optimum temperature range exists. The reaction temperature is 50 to 400 ° C, preferably 100 to 350 ° C, more preferably 150 to 330.
° C. 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 unnecessary, the temperature is preferably set to 400 ° C. or lower.

The reaction pressure is preferably as high as possible, but in consideration of 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 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.

The benzene-containing hydrocarbon hydrogenation catalyst for producing the cyclohexane-containing hydrocarbon material used in the present invention is (d) one selected from nickel, cobalt, copper, ruthenium, rhodium, palladium and platinum.
A combination of at least one active metal and at least one carrier selected from the group consisting of (e) alumina, silica, silica-alumina, magnesia, diatomaceous earth, zinc oxide, chromium oxide, and activated carbon is used. Known catalysts can be used. For example, nickel (Chem. Abstr.,
42 , 5286 (1948). ), Nickel-diatomaceous earth (Chemical Engineering, 27 (8), 558 (1963).), Nickel-silica (Chemical Engineering, 34 (4), 402 (19)
70). ), Nickel-alumina (Chem. Abst)
r. , 49 , 10717c (1955). ), Palladium-carbon (Chem. Abstr., 45 , 100).
20d (1951). ), Platinum-carbon (Chem.
Abstr. , 43 , 1249h (1949). ), Raney nickel, nickel-chromium oxide-diatomaceous earth and cobalt-chromium oxide-diatomaceous earth (Catalyst, 4 , 5 (196)
2). ), Nickel-chromium oxide, cobalt-chromium oxide and cobalt-alumina (Chem. Abstr.,
43 , 6172c (1949). ), Ruthenium-alumina, rhodium-alumina, palladium-alumina and platinum-alumina (Advances in Catal)
ysis, 9 , 716 (1957). ) And the like.

As a carrier for the hydrogenation catalyst, the above-mentioned alumina, silica, silica-alumina, magnesia, diatomaceous earth,
In addition to zinc oxide, chromium oxide, and activated carbon, zeolite, clay, zirconia containing sulfuric acid, titania containing sulfuric acid, and the like can also be used. From the viewpoint of catalytic activity, these supports have a specific surface area of 20 m ² / g or more and a pore volume of 0.2 m ² / g.
It is preferably at least cm ³ / g.

The hydrogenation reaction conditions vary depending on the type of catalyst used and the like, and cannot be fixed to specific conditions. 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.

[0041]

【Example】

(Example 1) Preparation of isomerization catalyst 100 g of zirconium oxychloride was added to 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.

The catalytic reforming naphtha in the isomerization reaction was separated by distillation to obtain a hydrocarbon mainly composed of 6 carbon atoms. This was hydrogenated to obtain a cyclohexane-containing hydrocarbon raw material. Subsequently, using the above solid superacid catalyst, the hydrogenated product was 3.0 × 10 ⁶ Pa, the liquid hourly space velocity was 1.0 h ⁻¹ , the temperature was 220 ° C., and the hydrogen / feedstock ratio was 500 ^l .
The isomerization was carried out under the condition of / l. Table 1 shows the feedstock and isomerization product compositions. The analysis of each component was performed using a gas chromatograph equipped with an FID detector.

[0043]

[Table 1]

Abbreviations used in Table 1 and subsequent tables are shown below. C3: C3 fraction C4: C4 fraction Branch C5: C5 isoparaffin fraction n-C5: C5 n-paraffin fraction MCP: Methylcyclopentane CH: Cyclohexane Branch C6: C6: isoparaffin fraction with 6 carbons nC6: n-paraffin fraction with 6 carbons MCH: methylcyclohexane Branched C7: isoparaffin fraction with 7 carbons nC7: n-paraffin fraction with 7 carbons

(Example 2) Isomerization Reaction After the catalytic reforming reaction, a fraction mainly composed of a hydrocarbon having 6 carbon atoms (C6) and a light naphtha mainly composed of 5 carbon atoms and 6 carbon atoms, etc. The volume mixture was hydrogenated to provide a cyclohexane-containing hydrocarbon feedstock. Using the same isomerization catalyst as in Example 1, 3.0 × 10 ⁶ Pa and a liquid hourly space velocity of 1.0 h
^The isomerization was carried out under the conditions of ⁻¹ , a temperature of 220 ° C., and a hydrogen / feed oil ratio of 500 l / l. Table 2 shows the feedstock and isomerization product compositions.

[0046]

[Table 2]

(Example 3) As the isomerization catalyst, a catalyst in which platinum was carried on a zirconia-sulfuric acid-containing alumina-containing carrier was used. The same raw materials as in Example 2 were used for the isomerization.

Method for Preparing Isomerization Catalyst 1 kg of commercially available zirconium oxychloride was dissolved in 20 l of distilled water, and 28 wt% aqueous ammonia was added to the solution while stirring at room temperature until the pH reached 8, to thereby form a precipitate. The formed hydrated zirconia was separated by filtration, washed with distilled water, and dried to obtain dried hydrated zirconia. 300 g of hydrated alumina (pseudo boehmite) powder was added to 300 g of the dried hydrated zirconia powder, and ammonium sulfate 115 was further added.
g while adding water with a kneader equipped with stirring blades.
Kneading was performed for a time. The obtained kneaded material was extruded from an extruder having a circular hole having a diameter of 1.6 mm, dried, and dried at 650 ° C.
For 3 hours to obtain a zirconia sulfate alumina catalyst.
An aqueous solution of chloroplatinic acid was spray-supported on 100 g of the catalyst so that the amount of platinum in the catalyst was 0.5%. After drying, the mixture was calcined at 500 ° C. for 3 hours to obtain a platinum-containing zirconia sulfate alumina catalyst. The specific surface area of this catalyst is 228
m ² / g, and the proportion of zirconia in the catalyst is 4
8.0%, the proportion of alumina is 36.7%, the proportion of alumina in the total of zirconia and alumina is 43.3%,
The crystal seed of zirconia in the catalyst was tetragonal, and no monoclinic crystal was observed. The catalyst has an average diameter of 1.27 m.
m and has an average lateral fracture strength of 4.6 kg
Met.

The isomerization reaction was carried out using the same raw materials as in Example 2 as the cyclohexane-containing hydrocarbon and using the above solid superacid catalyst. The reaction conditions were a pressure of 3.0 × 10 ⁶ Pa, a liquid hourly space velocity of 1.3 h ⁻¹ , a temperature of 215 ° C., and a hydrogen / feedstock ratio of 50.
0 l / l. Table 3 shows the feedstock and isomerization product compositions.

[0050]

[Table 3]

Comparative Example 1 A reaction was carried out in the same manner as in Example 3 except that platinum-zeolite was used as the isomerization catalyst and the reaction temperature was changed to 260 ° C. Table 4 shows the feedstock and isomerization product compositions. When a platinum-zeolite catalyst was used, the reaction temperature had to be 260 ° C. in order to make the concentration of methylcyclopentane equivalent to that in Example 3. Also, under these conditions, it can be seen that there are many decomposition products having 4 or less carbon atoms.

Method for Preparing Isomerization Catalyst A pentasil-type zeolite was synthesized according to a conventional method,
A zeolite was prepared. Liquid A was prepared by mixing 180 ml of distilled water, 14 g of aluminum sulfate, 17 g of tetra-n-propylammonium bromide and 15 g of concentrated sulfuric acid. Liquid B was prepared by mixing 207 g of water glass (No. 3) with 135 ml of distilled water. Further, 8.0 g of sodium chloride and tetra-n
5.7 g of propylammonium bromide in distilled water 31
This was mixed with 0 ml to obtain a liquid C. Solution A and solution B were added dropwise to solution C, and stirring was continued while adjusting the addition speed so that the pH became 10. This mixture was placed in a 1-liter autoclave and subjected to hydrothermal treatment at 160 ° C. for 24 hours while stirring. The solid content after the reaction was filtered off and washed several times with distilled water.
It was dried at 0 ° C. for 15 hours and calcined at 540 ° C. for 3 hours. After cooling, 90 ° C in 350 ml of 1M ammonium nitrate aqueous solution
The operation of soaking for 2 hours was repeated three times. This was dried at 120 ° C. for 15 hours and calcined at 540 ° C. for 3 hours to obtain 31 g of protonated pentasil-type zeolite. This 25
g was placed in 300 ml of distilled water, and while stirring, 12 m of an aqueous solution in which 0.23 g of tetraamminedichloroplatinum was dissolved.
1 was added dropwise, and stirring was continued for 20 hours. The zeolite was separated by filtration, dried at 120 ° C. for 6 hours, and calcined at 540 ° C. for 3 hours to obtain 25 g of an off-white platinum-zeolite catalyst.
The supported amount of platinum was 0.5% by mass, and the silica / alumina ratio of the pentasil-type zeolite was 24. The catalyst was formed into pellets, pulverized, sieved to 10 to 20 mesh, and 4 ml was taken and charged into a reaction vessel. Before performing the hydrogenation reaction, a reduction treatment was performed at 290 ° C. for 1 hour in a hydrogen stream.

[0053]

[Table 4]

[0054]

According to the present invention, it is possible to efficiently convert cyclohexane-containing hydrocarbons and the like obtained by subjecting catalytically modified naphtha to hydrogenation to methylcyclopentane. As a result, a gasoline raw material having a high octane number and excellent acceleration performance can be produced. In addition, since a raw material obtained by hydrotreating a benzene-containing hydrocarbon can be processed, gasoline with reduced harmful benzene can be produced.

Continuation of the front page (72) Inventor Yasuhiro Araki 3-17-3 Nishinaminami, Toda City, Saitama Prefecture Japan Energy Co., Ltd.

Claims (6)

[Claims] 1. A method for producing a methylcyclopentane-containing hydrocarbon, which comprises bringing cyclohexane or a cyclohexane-containing hydrocarbon into contact with a solid superacid catalyst to carry out an isomerization reaction. 2. The method for producing a hydrocarbon containing methylcyclopentane according to claim 1, wherein the solid superacid catalyst comprises the following (a) and (b). (A) Groups 4, 6, 13, and 14 of the periodic table
At least one element selected from the group consisting of a hydrated oxide and / or an oxide, 100 parts by weight as an oxide; (b) groups 7 and 8 of the periodic table , Ninth, and tenth
One or more elements selected from the group consisting of
01 to 15 parts by weight 3. The solid superacid catalyst according to the following (a ₁ ):
(A ₂ ), (b ₁ ) and (a ₃ ) as essential components, having a specific surface area of 150 to 300 m ² / g, an acid strength H ₀ (Hammet acidity function) higher than -11.93, 2θ = 2
3. The method for producing a methylcyclopentane-containing hydrocarbon according to claim 2, wherein an X-ray diffraction peak area ratio between 8.2% and 2θ = 30.2 ° is 0.05 or less. (A ₁ ) hydrated oxide and / or oxide of zirconium (a ₂ ) hydrated oxide and / or oxide of aluminum (b ₁ ) Group 7, 8, 9 and 10 of the periodic table
One or more elements selected from the group consisting of: (a ₃ ) one or more elements selected from tungsten and molybdenum, the form of which is hydrated oxide and / or oxide 4. The solid superacid catalyst according to the following (a):
The method for producing a methylcyclopentane-containing hydrocarbon according to claim 1, comprising (b) and (c). (A) Groups 4, 6, 13, and 14 of the periodic table
At least one element selected from the group consisting of a hydrated oxide and / or an oxide, 100 parts by weight as an oxide; (b) groups 7 and 8 of the periodic table , Ninth, and tenth
One or more elements selected from the group consisting of
0.01 to 15 parts by weight (c) 0.05 to 10 parts by weight of sulfuric acid as sulfur Wherein said solid superacid catalyst, the following (a _1),
(A ₂ ), (b ₁ ) and (c ₁ ) as essential components, having a specific surface area of 150 to 300 m ² / g, an acid strength H ₀ (Hammet acidity function) stronger than -11.93, 2θ = 2
The method for producing a methylcyclopentane-containing hydrocarbon according to claim 4, wherein an X-ray diffraction peak area ratio of 8.2 ° and 2θ = 30.2 ° is 0.05 or less. (A ₁ ) hydrated oxide and / or oxide of zirconium (a ₂ ) hydrated oxide and / or oxide of aluminum (b ₁ ) Group 7, 8, 9 and 10 of the periodic table
At least one element selected from the group consisting of (c ₁ ) sulfuric acid 6. The method for producing a hydrocarbon containing methylcyclopentane according to claim 1, wherein the solid acid catalyst is a molded product.