JPH05310604A - Catalytic conversion of hydrocarbon - Google Patents

Abstract

PURPOSE:To produce the objective product in high yield and efficiency while preventing the deposition of coke and remarkably prolonging the life of catalyst by carrying out the catalytic conversion of an olefin-containing hydrocarbon using a catalyst produced by mixing a porous carrier supporting a hydrogen- activated metal component and a solid acid. CONSTITUTION:An olefin-containing hydrocarbon raw material is converted into various useful hydrocarbons by contacting the raw material in the presence of hydrogen with a catalyst produced by mixing (A) a porous material obtained by supporting at least one kind of a metal having hydrogen activation function (preferably metal of the group VIII, especially Pt) or a compound of the metal in the pores of a porous carrier having pores capable of holding at least hydrogen molecule and rejecting the intrusion of raw material olefin (having a pore diameter of about 0.3-0.5nm in the case of olefins having carbon number of about 2-5) with (B) a solid acid such as amorphous compound oxide, a solid super-strong acid or heteropolyacid. Since the contact of the hydrogen-activation metal component with the olefin raw material is avoided in the above process, the hydrogenation of the olefin can be prevented and, at the same time, the deposition of coke on the metallic component is suppressed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for catalytic conversion of hydrocarbons, and more specifically, it is capable of reacting a hydrocarbon containing an olefin with a metal function such as hydrogenation ability and cyclization ability in the presence of hydrogen. By effectively utilizing the acid function such as chemical ability, alkylation ability and polymerization ability and the catalytic function such as reactant shape selectivity due to the carrier pores, the catalytic reaction is suppressed and the catalytic reaction is stable and with good selectivity. A method for efficiently catalytically converting various useful hydrocarbons, etc., for example, to advantageously produce a hydrocarbon distillate having a high added value such as alkylate gasoline, polymerized gasoline, and polymerized kerosene. And an improved method for catalytic conversion of hydrocarbons.

[0002]

2. Description of the Related Art When an olefin-containing hydrocarbon is brought into contact with a catalyst having a solid acid such as zeolite under appropriate conditions, various reactions [e.g. Reaction such as solzation), alkylation with olefins such as paraffin and aromatic hydrocarbons, cyclization reaction and cyclization dehydrogenation reaction of olefins and paraffins, aromatization reaction, isomerization reaction, heterogenization Reactions, hydrogen transfer reactions, decomposition reactions, etc.) are known to be induced.
It is also possible to carry out a wider variety of reactions by reacting olefin-containing hydrocarbons with other active reactants (eg hydrogen, mixtures of hydrogen and CO, etc.). Therefore, by using a catalyst having a solid acid function to change the type and composition of the olefin-containing hydrocarbon, or by adding various other components to the reaction to cause a reaction, a wide variety of hydrocarbon conversion reactions can be carried out. Becomes possible,
By properly selecting the reaction conditions, it becomes possible to obtain useful products such as various useful hydrocarbons.

For example, when a relatively light hydrocarbon fraction containing light olefins and light paraffins as main components is brought into contact with a catalyst containing a solid acid such as zeolite having an acid property under appropriate conditions, a polymerization reaction, alkyl It is possible to convert into useful hydrocarbons such as gasoline and kerosene by undergoing a chemical reaction and an isomerization reaction. As described above, since the conversion reaction of olefin-containing hydrocarbons using a solid acid catalyst is extremely important industrially, various techniques have been proposed so far.

However, in such a conversion reaction of an olefin-containing hydrocarbon, even if the solid acid catalyst has a sufficient acid function, it is often insufficient by itself, especially carbon (coke) on the catalyst. 2) is remarkably deposited, the catalytic activity is rapidly reduced, and there is a serious problem that the regeneration of the catalyst (removal of deposited carbon) is difficult.

[0005] For example, Japanese Patent Publication No. 47-31681 discloses an alkylation reaction of an isoparaffin with an olefin using a rare earth-supporting HY zeolite catalyst. This alkylation activity is remarkable in carbon deposition on the catalyst. Therefore, it has been shown to be easily deactivated. As described above, the problem of the activity decrease of the solid acid catalyst due to the carbon deposition is not limited to this example and is a very general problem. Therefore, it is important to suppress the carbon deposition and prolong the life of the catalyst. Is becoming

Therefore, in the conversion reaction of olefin-containing hydrocarbons utilizing such solid acid catalyst function, it has been conventionally performed to carry a metal having a hydrogenating ability such as Pt on a catalyst and to carry out the reaction in the presence of hydrogen. ing. By thus adding a metal having an appropriate hydrogenation ability to the solid acid catalyst, it is possible to suppress the deposition of carbon (coke) on the catalyst surface and prolong the life of the catalyst.
When a suitable metal such as Pt is supported, the catalyst can be easily regenerated, and the carbon (coke) deposited on the catalyst can be efficiently removed by treating with a gas containing hydrogen or oxygen, which is mild. The catalytic activity can be effectively recovered by treating for a short time under the conditions. Further, in this case, when the reaction is carried out in the coexistence of hydrogen, there are advantages such that a product rich in saturated hydrocarbon can be obtained.

However, in this case, a new problem arises in that simple hydrogenation (hydrogenation) of the starting olefin is likely to occur on the metal having hydrogenation ability. As a result, not only the raw material olefins are wasted, but also the efficiency of the desired conversion reaction such as the reduction of the reaction rate of paraffins is reduced, and, for example, useful middle distillates such as gasoline fraction and kerosene fraction. There are serious problems such as a decrease in the yield of Such a reduction in reaction efficiency due to hydrogenation of the raw material olefin itself is a major drawback of this type of conventional method.

In fact, for example, Japanese Patent Application Laid-Open No. 50-59303 discloses that the activity can be recovered by hydrotreating a Pt-supported Y-type zeolite catalyst that has been deactivated by use in an alkylation reaction. However, in this case, it is argued that the hydrogen concentration in the feedstock should be low because the raw material olefin is hydrogenated when the reaction is carried out in the presence of hydrogen. However, with the method by adjusting the concentration of the supplied hydrogen as in this case, it is extremely difficult to simultaneously satisfy the suppression of hydrogenation of the raw material olefin and the suppression of carbon (coke) precipitation during the reaction, and it is said that this is an effective method. It's hard.

That is, when a conventional catalyst in which a metal having a hydrogenating function such as Pt is supported on a solid acid is used, the precipitated carbon is removed by hydrogen treatment or the like to make catalyst regeneration advantageous, or in the presence of hydrogen. As a result of suppressing the carbon (coke) precipitation and suppressing the decrease in catalytic activity,
In that case, there has been a serious problem that hydrogenation of the raw material olefin occurs on the metal and the efficiency of the desired useful reaction is significantly reduced.

Therefore, in such a conversion reaction of an olefin-containing hydrocarbon, an effective catalyst which does not hydrogenate the raw material olefin, can sufficiently suppress carbon deposition, and is easy to regenerate the catalyst is obtained. Development was desired.

[0011]

An object of the present invention is to react a hydrocarbon containing an olefin in the presence of hydrogen by using a catalyst having at least a solid acid function to obtain various useful hydrocarbons (for example, gasoline). Distillation, kerosene gas fraction, etc.), etc., to improve the characteristics of the catalyst system by successfully adding a hydrogen-activated metal component to the catalyst system, and to use such improved catalyst system It suppresses the deposition of carbon (coke) during the reaction to suppress the reduction of the catalytic activity (prolongs the life of the catalyst), and also facilitates the removal of the deposited carbon by hydrogen treatment etc. during the regeneration of the catalyst. The catalyst regeneration is facilitated, while the hydrogenation of the starting olefin during the reaction is suppressed, and the desired reaction is allowed to proceed effectively, and the desired product can be efficiently obtained in high yield. It is to provide a catalytic conversion process of interest and improved hydrocarbon.

[0012]

[Means for Solving the Problems] The present inventors have conducted extensive studies to achieve the above-mentioned object. As a result, at least one hydrogen activating function is provided in the pores of the porous carrier having relatively small pores in which hydrogen molecules enter but the raw material olefin particularly effective for the target reaction does not enter. A metal or a metal compound (hereinafter referred to as a hydrogen-activated metal component) supported by the catalyst is used as one of the catalyst components, and a solid acid which is effective for the reaction by contact with the raw material olefin is used as the other catalyst component. When a catalyst mixed in the form of hydrogen is used, hydrogen is contacted with the hydrogen-activated metal component to be activated, but the raw material olefin is not directly contacted. It is possible to suppress carbon (coke) precipitation, while utilizing the fact that hydrogen atoms dissociated and activated by the hydrogen-activated metal component spillover from the porous catalyst component, and Carbon (coke) deposition on the portion other than hydrogen activated metal component carrying porous catalyst component ingredients such as can be prevented, therefore,
It is possible to prevent carbon (coke) from depositing on the entire catalyst and improve the catalyst life. Furthermore, when regenerating with hydrogen or oxygen-containing gas when regenerating the catalyst, it is effectively activated by the hydrogen-activated metal component etc. by the same principle. It was thought that catalyst regeneration (removal of deposited carbon by hydrogenation, oxidation, etc.) would be much easier due to the action of spillover hydrogen and oxygen produced by oxidization. At that time, the reaction product containing the raw material olefin is caused by a catalyst function having no strong hydrogenation function such as a solid acid or a portion (outer surface, etc.) of the hydrogen activation metal component-supporting porous catalyst particle having no hydrogen activation metal component. It will react effectively and the desired product can be obtained efficiently.

Therefore, based on this idea, hydrogen activation of Pt or the like is carried out in the pores of a porous carrier which does not incorporate the raw material olefin as described above but has pores capable of incorporating hydrogen. Various catalysts prepared by mixing a component carrying a metal component and a solid acid are prepared, and using this as a catalyst, olefin-containing hydrocarbons of various compositions are subjected to catalytic reaction in the presence of hydrogen to produce various hydrocarbons. As a result of studying the conversion reaction, as expected, the hydrogenation of the raw material olefin can be suppressed, the product of the desired reaction can be efficiently produced in high yield, and carbon (coke) deposition on the catalyst can be expected. Based on this finding, the present invention was completed based on the finding that the catalyst life is significantly improved and the catalyst life is significantly improved, and that the catalyst regeneration is significantly facilitated as expected.

That is, according to the present invention, at least one hydrogen-activated metal component is supported in the pores of a porous carrier having pores capable of containing at least hydrogen molecules and containing no raw material olefin. Provided is a method for catalytic conversion of hydrocarbon, which comprises bringing a hydrocarbon raw material containing an olefin into contact with a catalyst prepared by mixing a porous body supporting a hydrogen-activated metal component and a solid acid in the presence of hydrogen.

The catalyst used in the method of the present invention is a composite catalyst composed of at least a solid acid and a hydrogen-activated metal component-supporting porous body, and the hydrogen-activated metal component-supported porous body is porous. The porous carrier has at least one hydrogen-activated metal component supported in the pores of the porous carrier having a diameter in which hydrogen molecules are inserted and raw olefins are not inserted. The hydrogen-activated metal component supported on the porous carrier is used in an activated state so that hydrogen molecules can be activated. Therefore, the hydrogen-activated metal component-supporting porous body has the above-mentioned pores. Hydrogen molecules can be activated by the hydrogen activation function of the hydrogen-activated metal component inside the raw material olefin, but the raw material olefin cannot reach the hydrogen-activated metal component inside the narrow pores, It has a special function of not hydrogenating.

The hydrogen-activated metal component-supporting porous body is
When this is used as a catalyst in combination with a solid acid, the hydrogen-activated metal component contains hydrogen molecules in the pores where the raw material olefin does not enter so that the above-mentioned special function can be sufficiently exhibited. There is no particular limitation as long as it comprises a supported porous carrier, various types can be used, and it may be prepared by any raw material and method.

The porous carrier used as a constituent of the hydrogen-activated metal component-supporting porous body or as a raw material for its preparation has various pore diameters and structures in consideration of the size of the raw olefin. However, those having a uniform pore structure are usually preferably used.

The size of the porous carrier having a preferable pore size depends on the kind (effective molecular size) of the starting olefin in the hydrocarbon starting material to be used and cannot be determined uniformly. When a hydrocarbon raw material containing a relatively small olefin having a carbon number of about 2 to 5 as a main raw material olefin is subjected to the reaction, it is usually 0.
It is preferable to use one having a pore diameter (opening diameter) of about 2 to 1.0 nm, preferably about 0.3 to 0.5 nm.

Specific examples of the porous carrier having such a relatively small pore size include, for example, various A-type zeolites, mordenites, and barless type S (Barre).
Examples thereof include crystalline aluminosilicates such as sSpecies S), chabazite, and gmelinite.

Since the larger the molecular effective diameter of the raw material olefin in the hydrocarbon raw material to be used, the larger the pore diameter (opening diameter) of the porous carrier that can be used,
In such a case, a porous carrier having a larger pore size than the above may be used. Further, if the pores have an opening diameter small enough not to contain the raw material olefin, the pore diameter in the pores supporting the hydrogen-activated metal component may be larger than the opening diameter.

It is known that a porous carrier such as zeolite has a small change in pore size when a metal is loaded on it or activated. Therefore, what kind of pore size should be used? In addition to the type (size) of the olefin in the reaction raw material, it is desirable to select with respect to this point.

At least one kind of hydrogen-activated metal component is carried in the pores of the porous carrier, but the hydrogen-activated metal component is not particularly limited, and specifically, Pt, Ir, Os, Rh, Ru, Pd, Fe, C
Any of o, Ni, Zn, Ga, Mo and W can be used. Further, those metal oxides or metal sulfides can also be used. Among these, Group VIII metals are preferable, and Pt is particularly preferable.
These hydrogen-activated metal components may be used alone or in combination of two or more.

The method for supporting these hydrogen-activated metal components is not particularly limited, and they can be supported by various methods such as known methods. For example, an ion exchange method or an impregnation method can be applied to the appropriate porous carrier. It may be supported by, for example, or prepared so that the hydrogen-activated metal component is introduced and supported during the synthesis of the porous carrier such as the zeolite, and directly prepared as a hydrogen-activated metal component-supporting porous body. It may be either. The method for activating the hydrogen-activated metal component is not particularly limited, and any method may be used as long as hydrogenation activity (in this case, hydrogen molecule activation function) is sufficiently exerted. It may be activated. Usually, a treatment such as activation at a certain point in the reaction by a conventional method such as air calcination, hydrogen reduction, or the like is preferably adopted. It should be noted that, depending on the state of the compound form of the supported hydrogen-activated metal component, it may be sufficiently activated by heat treatment or contact with the reaction raw material. In this case, the activation treatment may be omitted in some cases. You can also

The amount of the hydrogen-activated metal component supported is preferably the type and combination of the hydrogen-activated metal components used, the type of porous carrier, the type of solid acid, the mixing ratio thereof, the type of reaction, etc. Since it depends on various conditions described above, it cannot be uniformly determined, but it is usually appropriate to set it in the range of 0.01 to 30% by weight calculated as a metal state with respect to the porous carrier. If the supported amount is less than 0.01, the amount of hydrogen-activating metal component is too small, and a sufficient hydrogen-activating function may not be exhibited. On the other hand, this carrying amount is 3
Even if the amount is more than 0% by weight, the corresponding effect of increasing the hydrogen activating function cannot be expected so much, and the production cost of the catalyst may be disadvantageous. The more preferable amount of the hydrogen-activated metal component supported on the hydrogen-activated metal component-supporting porous body is usually about 0.02 to 20% by weight.

The above-mentioned porous carrier or the hydrogen-activated metal component-supporting porous body may contain other components than the above components within the range not impairing the object of the present invention.

The component of the catalyst used in the method of the present invention or the solid acid used as a raw material for preparing the catalyst is not particularly limited, and various kinds can be used. Specifically, for example, various types of zeolites (including more general crystalline aluminosilicates, metallosilicates such as gallosilicates and silicalite), silica alumina, silica titania, various types of non-alumina boria, etc. Examples include crystalline composite oxides, solid superacids such as sulfuric acid-supported zirconia, clay minerals such as activated clay, heteropolyacids, isopolyacids, and ion exchange resins.

Incidentally, these solid acids may contain other components such as metal components as long as the object of the present invention is not impaired. For example, in the case of zeolite, not only partially or wholly H ⁺ type, but also La, Ce, F
It may be ion-exchanged with an appropriate metal ion such as e or Ca, or other component such as metal oxide may be introduced by loading or substitution. In this way, the solid acid may contain any metal component or the like, or may be modified to control the acidity, or may have a catalyst function other than the acid function, but in the case of the present invention, These solid acids include:
Hydrogenation of raw olefin does not occur, or
It is preferable to use a substance that is sufficiently small even if it occurs and does not hinder the intended reaction.

It should be noted that what kind of solid acid is preferably used as a constituent component of the catalyst in the method of the present invention depends on the kind and conditions of the intended reaction, and may be selected accordingly. Good. These solid acids are
They may be used alone or in combination of two or more as required.

The catalyst used in the method of the present invention can be obtained by mixing at least one kind of the hydrogen-activated metal component-supporting porous body and at least one kind of the solid acid. The mixing ratio of the hydrogen-activated metal component-supporting porous body and the solid acid is usually the ratio of the hydrogen-activated metal component-supporting porous body and the hydrogen-activated metal component-supporting porous body based on the total weight of the solid acid. , 1 to 95% by weight is preferable. Here, when the proportion of the hydrogen-activated metal component-supporting porous body is less than 1% by weight,
The function of activating hydrogen molecules of the hydrogen-activated metal component-supporting porous body based on the hydrogen-activated metal component becomes insufficient, and the effect of suppressing carbon (coke) precipitation cannot be sufficiently exerted, and the effect of suppressing the decrease in catalytic activity is insufficient. In some cases, the catalyst may be sufficient, or the regeneration-promoting effect such as removal of carbon by the hydrogen-activated metal component during catalyst regeneration may not be sufficiently obtained. On the other hand, when the proportion of the hydrogen-activated metal component-supporting porous body exceeds 95% by weight, the proportion of the solid acid decreases accordingly, so that the effect of promoting the reaction based on the solid acid is not sufficiently exerted, and the desired reaction May slow down.

There is no particular limitation on the mixing method and mixing form of the hydrogen-activated metal component-supporting porous body and the solid acid for forming the catalyst, and the hydrogen-activated metal component-supporting porous body and the solid acid are not particularly limited. Various methods are possible as long as the combined effect of 1) is sufficiently exerted. Generally, this mixing is preferably carried out uniformly so that the hydrogen-activated metal component-supporting porous body and the solid acid are in good contact with each other. For example, it is also possible to preliminarily mold the hydrogen-activated metal component-supporting porous body and the solid acid into a molded product having an appropriate particle size, and appropriately mix them to use as a physical mixture or a molded product thereof. Usually, a method in which each is uniformly mixed in the form of powder such as fine particles or in a slurry state (or gel or sol state) and then is molded is more suitably adopted.
Of course, one of them is used as a molded product or powder, and the other one is used as powder or slurry, and a method of mixing these or a method of mixing one by impregnating or depositing the other to form a composite is also appropriately used. It is possible. At the time of molding, an appropriate binder may be appropriately used. Usually, the use of a binder facilitates molding, and can also improve the strength and heat resistance of the molded body.

The catalyst may be appropriately subjected to pretreatment (activation treatment) such as calcination or hydrogen treatment before it is used in the reaction.

In the method of the present invention, a hydrocarbon raw material containing an olefin is used as a reaction raw material, and this is contacted with the catalyst in the presence of hydrogen to cause a reaction and converted into a desired product. The kind and composition of the olefin-containing hydrocarbon used as a raw material is appropriately selected according to the purpose. Among them, monoolefins having about 2 to 5 carbon atoms (specifically, ethylene, propylene, 1-
Butene, 2-butene, isobutene, 1-pentene, 2-
A hydrocarbon raw material containing one or more of (pentene, isopentene, etc.) is preferably used. This hydrocarbon raw material may be composed only of olefins, or may contain olefins and paraffins, alicyclic alkanes, aromatic hydrocarbons, and the like. The composition of the hydrocarbon raw material may be selected according to the type of the intended conversion reaction and the like.

In the method of the present invention, the type of reaction is not particularly limited, and a wide variety of conversion reactions can be selected as targets. Particularly preferable examples of the reaction include alkylation reaction of isoparaffin with olefin and polymerization of olefin (oligomerization, aromatization reaction, etc.). In any case, these reactions are carried out in the coexistence of hydrogen. Depending on the type of reaction, the type of catalyst, the composition and supply amount of hydrocarbons to be fed, and further the reaction conditions such as hydrogen partial pressure, reaction pressure, reaction temperature, contact time or space velocity are appropriately selected. Therefore, the reaction conditions are not particularly limited, and suitable reaction conditions vary depending on the intended reaction.

For example, when a mixed hydrocarbon containing a relatively light olefin and paraffin (particularly isoparaffin) as a main component is used as a raw material to carry out a reaction mainly for the alkylation of paraffin or isoparaffin with an olefin, Usually, the following reaction conditions are suitably adopted.

This alkylation reaction is usually -2.
It is suitably carried out in a temperature range of 0 to 200 ° C, preferably 0 to 150 ° C. The reaction pressure is usually atmospheric pressure to 200 k
g / cm ² G, preferably 5 to 100 kg / cm ² G
It is preferable to select the range. The paraffin / olefin ratio in the feed hydrocarbon feedstock is a molar ratio, usually
It is suitable to select in the range of 1 to 100, preferably 5 to 50. The hydrogen / olefin ratio in the feedstock is a molar ratio of usually 0.01 to 200, preferably 0.1 to 200.
It is preferable to select in the range of 100. The space velocity (WHSV) based on the olefin in the feed is usually 0.01 to 10 hr ^-1 , preferably 0.1 to 5 h.
It is preferable to select in the range of r ⁻¹ .

By carrying out the reaction under such conditions, the alkylation reaction between paraffin, particularly isoparaffin and olefin, can be efficiently carried out, and for example, olefin and paraffin (especially isoparaffin) having about 2 to 5 carbon atoms can be obtained. A mixed hydrocarbon product rich in alkylate gasoline fraction can be obtained in good yield from a light hydrocarbon mixture contained as a main component.

When a reaction mainly comprising a polymerization reaction (oligomerization) of an olefin is carried out using a relatively light olefin or a hydrocarbon containing the olefin as a main component as a raw material, it is usually as follows. The reaction conditions shown are preferably adopted.

This polymerization reaction is usually carried out at 50 to 500 ° C.
It is preferably carried out in a temperature range of 50 to 200 ° C. The reaction pressure is usually atmospheric pressure to 200 kg / cm ²
It is preferable to select G, preferably 5 to 100 kg / cm ² G. The hydrogen / olefin ratio in the feed is a molar ratio, usually 0.01 to 200, preferably,
It is preferable to select in the range of 0.1 to 100. Space velocity (WHSV) based on olefins in feedstock
Is usually 0.01 to 10 hr ^-1 , preferably 0.1
It is preferable to select in the range of 5 hr ^-1 .

By carrying out the reaction under such conditions, an olefin polymerization (oligomerization such as dimerization or trimerization) reaction can be efficiently carried out.
A mixed hydrocarbon product rich in a polymerized gasoline fraction can be obtained in good yield from an olefin having about 2 to 5 carbon atoms or a light olefin-containing hydrocarbon containing these as a main component.

Of course, the method of the present invention is not limited to these reaction examples, but can be suitably applied to various conversion reactions carried out using an olefin-containing hydrocarbon as a raw material or a raw material component.

In the present invention, the reaction and regeneration can be carried out by various operations using various types of devices. For example, fixed bed type, fluidized bed type, moving bed type,
It can be performed by a continuous operation or an intermittent operation by a swing type reactor type, a suspension bed type, or the like, or
If necessary, batch operation or semi-batch operation may be performed. Among these, a fixed bed type, a fluidized bed type capable of continuously and effectively performing reaction and regeneration, a moving bed type, or a swing type reactor type is preferably used. In the case of the fluidized bed type, a riser system may be adopted. These may be appropriately selected depending on the type and purpose of the reaction.

Therefore, the method of the present invention is remarkably superior to the case of using a conventional solid acid or a metal-supported solid acid catalyst, and can be advantageously applied as a method for converting a wide variety of olefin-containing hydrocarbons. You can

[0043]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples thereof, but the present invention is not limited to these.

Catalyst Preparation Example 1 Mobil Pt-supported A-type zeolite (Ca-type) (hereinafter
Pt / CaA) (J.Catal., L , 307 (196
Applying 2)), K type P with pores of 0.3 nm
A t-supported zeolite A (hereinafter referred to as Pt / KA) was synthesized. Sodium aluminate 80g (ASSAY Na
₂ O, 29.5-32.5%: Al ₂ O ₃ , 35.5-3
Solution A was prepared by dissolving 8.5%: H ₂ O, 18-19%) in 275 ml of water. Sodium metasilicate 1
Solution B was prepared by dissolving 13 g in 275 ml of water.
70 ml of 1.8 g of [Pt (NH ₃ ) ₄ ] Cl ₂ · H ₂ O
Was dissolved in water to prepare solution C. Solution A and solution C were mixed to prepare solution D. The solution D was stirred at room temperature, and the solution B was added thereto little by little with a liquid feed pump. This was refluxed for 7 hours in the solution with stirring. Generated Pt / N
aA is filtered and washed with 0.5M KCl in a wet state.
It was ion-exchanged into K type using an aqueous solution. Ion exchange is 8
It was carried out four times at 0 to 90 ° C. for 3 hours. This was filtered and washed, dried overnight at 120 ° C., and Pt (1.4 wt%) KA
Got

Catalyst Preparation Example 2 In the same manner as in Catalyst Example 1 above, a Ca-type Pt-supported zeolite A (hereinafter referred to as Pt / CaA) having pores having a pore diameter of 0.5 nm was prepared.

Reference Example 1 Pt / KA prepared in Preparation Example 1 was dried and then dried at 400 ° C.
After air calcination and hydrogen reduction at 400 ° C., the degree of dispersion of the supported metal was measured by the hydrogen adsorption method and the CO adsorption method. The results are shown in Table 1. H ₂ molecular diameter is 0.289 nm, zeolite A
Has a pore size of 0.3 nm and CO has a molecular size of 0.376 nm
Therefore, it was found that Pt was supported in the pores into which H ₂ was added and CO was not added.

Reference Example 2 The Pt / KA prepared in Catalyst Preparation Example 1 was molded into particles of 16 to 32 mesh and filled in a reaction tube in an amount of 0.3 g. In the reaction tube, the catalyst was air-baked at 400 ° C for 1 hour, 400 ° C,
After hydrogen reduction treatment for 1 hour, hydrogen, isobutane and isobutene were added at a reaction temperature of 120 ° C., a total pressure of 50 kg / cm ² G and a hydrogen: isobutane: isobutene ratio (molar ratio 12: 28: 1) of 8 g / h. Was introduced and reacted.
As a result, the hydrogenation rate of isobutene became 0%, and Pt /
It was confirmed that KA does not have the hydrogenation ability of isobutene.

Comparative Example 1 Acid-treated USY zeolite (SiO ₂ / Al ₂ O ₃ ratio of 8.9) was molded into 16 to 32 mesh, and 1.
2 g was filled. After pretreatment in the reaction tube in the same manner as in Reference Example 1, the reaction temperature was 100 ° C., the total pressure was 28 kg / cm ² G,
Hydrogen: isobutane: isobutene ratio (molar ratio 4:50:
8) hydrogen, isobutane and isobutene under the condition 1)
It was introduced at a rate of g / h and reacted. Table 2 shows the change in product yield with respect to the amount of olefin oil passed. Table 3 shows the carbon deposition amount of the catalyst after passing 0.7 g of olefin.

Comparative Example 2 USY used in Comparative Example 1 was converted to [Pt (NH ₃ ) ₄ ] (N
In an O ₃ ) ₂ aqueous solution, the mixture was stirred at 90 ° C. for 3 hours, filtered and washed,
US at Pt (1.1%) after drying at 120 ° C for 24 hours
Y (Pt / USY) was prepared. 1.2 g of this Pt / USY was filled in a reaction tube, and after pretreatment was carried out in the reaction tube in the same manner as in Reference Example 1, comparison was made except that the hydrogen: isobutane: isobutene ratio (molar ratio 3: 25: 1) was used. Under the same conditions as in Example 1, hydrogen, isobutane and isobutene were introduced and reacted. Table 2 shows the change in product yield with respect to the amount of olefin oil passed.

Example 1 USY used in Comparative Example 1 and Pt prepared in Catalyst Preparation Example 2
/ CaA is physically mixed in a mortar at a weight ratio of 4: 1,
It was molded into 32 mesh and 1.5 g was filled in a reaction tube. After performing pretreatment in the reaction tube in the same manner as in Reference Example 1, hydrogen and isobutane were added under the conditions of a reaction temperature of 120 ° C., a total pressure of 50 kg / cm ² G, and a hydrogen: isobutane: isobutene ratio (molar ratio 12: 28: 1). And isobutene were introduced at 8 g / h and reacted. In order to enhance the effect of hydrogen and prolong the life of the catalyst, a high temperature, high pressure and high hydrogen ratio was used. Table 2 shows the change in product yield with respect to the amount of olefin oil passed.

Example 2 USY used in Comparative Example 1 and Pt prepared in Catalyst Preparation Example 1
/ KA is physically mixed in a mortar at a weight ratio of 4: 1 to obtain 16 to 3
It was molded into 2 mesh and 1.5 g was filled in a reaction tube. After pretreatment was carried out in the reaction tube in the same manner as in Reference Example 1, hydrogen, isobutane and isobutene were introduced at 8 g / h and reacted under the same conditions as in Example 1. Table 2 shows the change in product yield with respect to the amount of olefin oil passed. In Table 3, olefin 0.
The amount of carbon deposited on the catalyst after passing 7 g of oil was shown.

From Table 2, it can be seen that USY alone deteriorates immediately, the isooctane yield decreases, and the production of C9-16 polymer increases. Pt / USY is PT / CaA + U
It can be seen that the isooctane yield and C5 + yield are lower than those of SY and Pt / KA + USY. The catalyst in which USY is physically mixed with Pt / KA in which the hydrogenation ability of isobutene is not recognized can obtain isooctane in a high yield and has a long life. Further, from Table 3, it can be seen that carbon precipitation is suppressed in Pt / KA + USY as compared with USY.

[0053]

[Table 1]

[0054]

[Table 2] Change in product yield with respect to olefin oil flow rate in alkylation reaction ──────────────────────────────── ─ ─ ─ Yield of olefin product ^{* 1} Amount of catalyst oil (g) C5-7 TMP ^{* 2} DMH ^{* 3} C8 ^{* 4} C9-16 C5 + ──────────────── ─────────────────── Comparative Example 1 USY 0.5 33 33 51 2 0 25 111 111 1.0 2 8 0 7 66 83 83 Comparative Example 2 Pt / USY 0.5 5 30 0 0 15 50 50 1.0 5 30 0 0 12 48 Example 1 Pt / CaA + USY 0.5 16 28 28 0 6 52 1.0 1.0 13 37 2 0 8 60 Example 2 Pt / KA + USY 0 .5 2 50 0 30 30 82 1.0 2 54 0 0 29 85 85 ────────────────────────────────── ── * 1 Yield based on raw material olefin (% * 2 trimethylpentane (isooctane) * 3 dimethylhexane * 4 C8 olefins

[0055]

[Table 3]

[0056]

INDUSTRIAL APPLICABILITY In the process of the present invention, the above-mentioned specific catalyst (that is, the function of activating hydrogen, that is, the hydrogen-activated metal component designed so as not to directly hydrogenate the raw material olefin) is used as the catalyst. Since the conversion reaction of the olefin-containing hydrocarbon is carried out in the coexistence of hydrogen using a supported porous body and a catalyst having a solid acid), the conversion of the olefin-containing hydrocarbon on the active component of the raw olefin is carried out even in the coexistence of hydrogen. Since the hydrogenation of hydrogen peroxide is controlled, it can be effectively used for the desired reaction, the product of the desired reaction can be efficiently obtained in high yield, and the fine particles of the hydrogen-activated metal component-supporting porous material can be obtained. Carbon (coke) to the catalyst during the reaction by the action of active hydrogen activated by the action of the hydrogen-activated metal component in the pores
Precipitation can be sufficiently suppressed, so that the activity decrease is significantly suppressed, and the reaction time until regeneration (catalyst use life) can be greatly increased. Also, during catalyst regeneration, carbon (coke) deposited on the catalyst due to the hydrogen activation function and the oxidation function of the hydrogen-activated metal component.
Since it can be efficiently removed under mild conditions, the regeneration of the catalyst is significantly facilitated.

Therefore, the method of the present invention is remarkably superior to the case of using the conventional solid acid or metal-supported solid acid catalyst alone, and is advantageously applied as a method for converting a wide variety of olefin-containing hydrocarbons. can do.

That is, according to the present invention, it is possible to provide an excellent hydrocarbon conversion method which is extremely advantageous as compared with the conventional method as described above.

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Claims (5)

[Claims] 1. At least hydrogen molecules can be introduced,
Further, a hydrogen-activated metal component-supporting porous body and a solid in which at least one metal or metal compound having a hydrogen activation function is supported in the pores of the porous carrier having the pores in which the raw material olefin is not put. A method for catalytic conversion of hydrocarbon, which comprises bringing a hydrocarbon raw material containing an olefin into contact with a catalyst mixed with an acid in the presence of hydrogen. 2. The method for catalytic conversion of hydrocarbon according to claim 1, wherein the porous carrier is A-type zeolite. 3. The method for catalytic conversion of hydrocarbons according to claim 1, wherein the metal or metal compound having a hydrogen activation function is a metal or metal compound of Group VIII of the periodic table. 4. The method for catalytic conversion of hydrocarbons according to claim 3, wherein the Group VIII metal of the periodic table is Pt. 5. The method for catalytic conversion of hydrocarbons according to claim 1, 2, 3 or 4, wherein the olefin is an olefin having 2 to 5 carbon atoms.