JP2742191B2 - Method for catalytic conversion of organic compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for catalytically converting an organic compound, and more particularly, to a method of exposing a catalyst to a steam atmosphere in any step such as a catalyst reaction and a catalyst regeneration. The organic compound conversion process is a method for producing various useful organic compounds efficiently by efficiently using a galloaluminosilicate-based catalyst having a small activity decrease even when exposed to water vapor. About.

[0002]

2. Description of the Related Art Zeolite catalysts are extremely important industrially because they exhibit activity in the catalytic conversion of various organic compounds. There are various types of zeolites depending on their structures and compositions, and these are widely used as catalysts or catalyst components in various organic compound conversion processes. Among these zeolites having various structures and compositions, galloaluminosilicate has recently been particularly noticed because of its excellent catalytic activity for catalytic conversion of various hydrocarbons such as aromatization of paraffins and olefins. ing.

However, even in the case of a galloaluminosilicate catalyst, coke precipitates on the catalyst during a hydrocarbon conversion reaction at a high temperature such as the aromatization reaction, similarly to a general zeolite catalyst. Therefore, the catalytic activity is reduced. This decrease in catalytic activity is generally remarkable when a hydrocarbon having a large number of carbon atoms is used as a raw material, and coke tends to be formed more easily in the case of olefins than in the case of paraffins. In fact, in the case of the aromatization reaction of hydrocarbons on a galloaluminosilicate catalyst, when using very low-grade paraffin such as propane or butane as a raw material, the catalytic activity is not significantly reduced, but higher paraffin or olefin is used. When a hydrocarbon containing a compound is used as a raw material, the activity decreases significantly, and it is usually extremely difficult to maintain a high activity for 100 hours or more.

[0004] Therefore, in the case of a reaction such as the aromatization reaction, in which the activity is likely to be reduced due to the deposition of coke, it is necessary to frequently regenerate the catalyst by burning the coke at a high temperature. At that time, the catalyst is exposed to steam generated by coke combustion at a high temperature every regeneration, so if the hydrothermal resistance of the catalyst is insufficient, the activity of the catalyst is greatly reduced at every regeneration. ,as a result,
This causes a serious problem in the process that the cycle life of the catalyst is significantly shortened. Therefore, in the catalytic conversion method of the organic compound in which the catalyst is brought into contact with water vapor at a high temperature during the regeneration of the catalyst as in the above-mentioned aromatization reaction, not only the catalytic function is excellent, but also the hydrothermal resistance is sufficiently excellent. There is a strong need to use galloaluminosilicate.

[0005] Various techniques have been proposed for the aromatization reaction using a galloaluminosilicate catalyst. For example, Japanese Patent Publication No. 60-501357 discloses that a certain galloaluminosilicate is steamed (steamed) to increase the aromatization activity. However, the publication states that the change in activity during long-term steam treatment (that is, the catalyst activity is sufficiently maintained even under high temperature and long-time steam treatment required during catalyst regeneration or repeated regeneration). Is not found, and the difference in hydrothermal resistance due to the method of preparing galloaluminosilicate (synthesis method) (that is, what is required to obtain galoaluminosilicate having excellent hydrothermal resistance) The question of whether the synthesis method should be used).

[0006] Japanese Patent Application Laid-Open (JP-A) No. 1-103916 discloses that aromatic hydrocarbons can be obtained in high yield from various hydrocarbon raw materials by using galloaluminosilicate modified by firing at 700 to 1000 ° C. Is described. However, in this case, there is no description about a change in activity when the galloaluminosilicate is brought into contact with water vapor.

That is, although these prior arts can be evaluated for the fact that galloaluminosilicate is a highly active catalyst for the aromatization reaction of hydrocarbons, the galloaluminosilicate can be evaluated for any production method and composition. Since it is unknown whether aluminosilicate has high hydrothermal resistance and sufficiently withstands catalyst regeneration and its repetition,
Regeneration of the catalyst, especially in the process of frequently repeating the reaction and regeneration, is not practical.

Therefore, it is important to clarify which galloaluminosilicate of the production method and composition has sufficient catalytic activity and high hydrothermal resistance enough to withstand regeneration and repetition of the catalyst. Is an important issue.

[0009] Such improvement in hydrothermal resistance is an important issue not only for galloaluminosilicate but also for other zeolites.

For example, in the catalytic cracking of gas oil, a zeolite (FCC catalyst) having a pore size larger than 7 angstroms is added to ZS which is a kind of MFI type zeolite.
It has been shown that the use of a catalyst to which M-5 is added results in an improvement in both the octane number and the yield of the resulting gasoline as compared to the case where no catalyst is added (Japanese Patent Application Laid-Open No. 47-8074). No.). However, ZSM-5 synthesized by the method described in this publication is inferior in hydrothermal resistance, and its activity is remarkably reduced every time it comes into contact with a steam atmosphere during catalyst regeneration, and the effect of its addition is rapidly lost. For this reason, in the above catalytic cracking process, it is necessary to continuously add ZSM-5, and a large amount of ZSM-5 is required.

[0011] It has also been reported that when large crystal ZSM-5 is added to the FCC catalyst, the activity decrease due to steam treatment is less than when small crystal ZSM-5 is added (see, for example, Japanese Patent Application Laid-Open No. H11-157556). JP-A-60-208395). However, also in this case, the problem of the decrease in activity due to the steam treatment has not been sufficiently solved.

Therefore, various studies have been made to improve the hydrothermal resistance of ZSM-5. For example, ZSM-5
It has been argued that the ion-exchange and introduction of a Group IB metal (Cu, Ag), a Group IIB metal (Zn), or a Group VIII metal into the material improves its hydrothermal resistance (Japanese Patent Laid-Open No. 55-51440). Gazette, JP 59-117584 A). However, the improvement effect is not enough,
For example, when an exchanged cation such as Ag ⁺ is reduced, its effect is lost.

[0013] As described above, it is generally not easy to sufficiently improve the hydrothermal resistance of zeolite, and the galloaluminosilicate can be sufficiently excellent in hydrothermal resistance only after sufficiently examining the production method and composition. Seems to be found.

Here, if a galloaluminosilicate excellent in hydrothermal resistance is found, the galloaluminosilicate not only reacts to the above-mentioned aromatization reaction of hydrocarbon but also to the above-mentioned ZSM- It can also be expected that it can be effectively used for various reactions using other zeolites such as 5. In addition, not only during the regeneration of the catalyst, but also at the time of the reaction and the like at a high temperature, the contact conversion with a variety of organic compounds is required (for example, water is generated by a reaction such as an alcohol dehydration reaction or a CO hydrogenation reaction). Such a reaction, or a reaction using water as a raw material such as a hydration reaction of an olefin, and a reaction performed by adding water to a raw material system) can be expected to be effectively used. .

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances.

An object of the present invention is to provide a method for catalytic conversion of various organic compounds in which a catalyst may come into contact with water vapor, such as a galo-alumino compound having a small activity reduction even when exposed to water vapor at a high temperature during a reaction or regeneration of a catalyst. It is an object of the present invention to provide a method for converting an organic compound, wherein silicate is used as a catalyst or a catalyst component, and at least the activity and the function of the catalyst due to contact with water vapor are sufficiently suppressed and the process efficiency is remarkably improved.

[0017]

Means for Solving the Problems The present inventors have described a method for catalytically converting various organic compounds in which a catalyst may come into contact with steam during a reaction or during regeneration of a catalyst, even when exposed to steam at a high temperature. If galloaluminosilicate having a small activity decrease can be used as a catalyst or a catalyst component, it is considered that the efficiency of the process can be remarkably improved, and the hydrothermal resistance of the conventional MFI-type zeolite such as ZSM-5 is considered. We conducted intensive research to improve. as a result,
Specific composition {SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio and SiO ₂ / Ga ₂ O ₃ ratio} and properties (SiO ₂ by NMR
G / aluminosilicate having an H / acid OH ratio) satisfies the conditions, and is extremely effective as a catalyst or a catalyst component of the catalytic conversion reaction in a catalytic conversion method of an organic compound of a type in which various water vapors come into contact with a catalyst. Was found.

The present inventors have completed the present invention based on these findings.

That is, according to the present invention, there is provided a method for catalytically converting an organic compound comprising a step of bringing a catalyst into contact with steam, wherein the catalyst has a SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio (molar ratio) of 20. ２００200, the SiO ₂ / Ga ₂ O ₃ ratio (molar ratio) is 50 or more, and H
In the case of a mold, the strength I of SiOH by ¹ H-NMR I
The ratio (I _SiOH / I _H +) of the intensity I _H + between _{SiO H} and acidic OH is 0 to
An object of the present invention is to provide a method for catalytically converting an organic compound, which comprises using a catalyst containing an MFI type galloaluminosilicate of 0.5.

In the method of the present invention, the MFI-type galloaluminosilicate used as a catalyst or a catalyst component for the conversion reaction of an organic compound is not only of the MFI type but also of SiO ₂ / (Al ₂ O ₃ + Ga ₂ O). ₃ ) The ratio is 2 in molar ratio
0 to 200, when the molar ratio of SiO ₂ / Ga ₂ O ₃ is 50 or more and the galloaluminosilicate is substantially completely H-type by ion exchange, the strength of SiOH by ¹ H-NMR It is important that the ratio (I _SiOH / I _H +) of the intensity I _H + of I _{S iOH} to the acid OH be in the range of 0 to 0.5.

The above-mentioned M satisfying the above conditions is satisfied.
FI-type galloaluminosilicates can provide sufficient catalytic activity for catalytic conversion reactions of various organic compounds such as, for example, aromatization reactions of hydrocarbons, and have excellent hydrothermal resistance, and can be used during reaction and catalyst regeneration. Catalyst or catalyst for catalytic conversion reaction of organic compounds in various organic compound catalytic conversion methods including a step in which the catalyst is brought into contact with water vapor even when exposed to a steam atmosphere at a high temperature at a high temperature. Very effective as a component. That is, in a reaction under a steam atmosphere such as a reaction in which water is produced or water is added, the activity of the catalyst is less reduced, and the catalyst activity can be suitably maintained for a long time. Further, even when the catalyst is regenerated in a steam atmosphere such as a regeneration process in which steam is generated during a regeneration process such as a regeneration process using a steam-containing gas or a combustion removal of coke with air or the like, the catalyst activity is hardly reduced, and therefore, such a catalyst is not used. It can also be suitably used for a catalytic conversion process of an organic compound, which requires frequent repetition of a regeneration treatment.

Here, the I _SiOH / I _H + ratio is ¹ H-N
It shall be obtained again when the measurement by MR is performed as follows.

That is, H-type galloaluminosilicate obtained by substantially completely ion-exchanging galloaluminosilicate prepared by various methods with, for example, a mineral acid such as hydrochloric acid or an ammonium salt, and calcining the same, After evacuation at 400 ° C. for 1 hour, the ¹ H-NMR spectrum is measured at room temperature according to a conventional method. In the NMR spectrum obtained at this time, the peak intensity (peak area) of the OH of the silanol group (SiOH) appearing at around 1.8 ppm is defined as I _SiOH , while the peak intensity (peak) of the acidic OH appearing at around 4.5 ppm the area) and I _H +, and defines the + and the ratio I _SiOH / I _H and the I _SiOH / I _H +.

The MFI-type galloaluminosilicate in which I _SiOH / I _H + is in the range of 0 to 0.5 means that I _{SiO H} / I _H + by ¹ H-NMR measurement when the H-type is used as described above. This means that the I _H + ratio should be in the range of 0 to 0.5, and does not mean that I _SiOH / I _H + when the galloaluminosilicate is used must be in this range. That is, in the present invention,
As described later, the MFI-type galloaluminosilicate is not limited to the H-type, but is exchanged with ions such as various metal ions, carries various components, performs various treatments, and performs other processes. And can be used in various forms. In such a case,
_SiOH / I _H + values are necessarily to be noted that not to be in the above range.

When the SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio is 2
0 to 200, and even when the SiO ₂ / Ga ₂ O ₃ ratio is in the range of 50 or more, the MFI in which the I _SiOH / I _H + is larger than 0.5.
The type galloaluminosilicate has insufficient hydrothermal resistance, a large decrease in activity due to steam, and in some cases, the activity itself (or the activity improving effect) itself is small. On the other hand, even if I _SiOH / I _H + is in the range of 0 to 0.5, the SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio is 2
Less than 0 or greater than 200, or SiO ₂ / Ga ₂ O
_{In the case where the} ratio is less than 50, the activity is greatly reduced by steam. Above all, SiO ₂ / (Al ₂
In the case of low silica having an O ₃ + Ga ₂ O ₃ ) ratio of less than 20, the deposition of carbonaceous material may be remarkable, and in any case, the object of the present invention cannot be achieved.

The preferred range of the SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio cannot be determined uniformly since it varies depending on the purpose of use such as the type of reaction to be performed and the operating conditions such as reaction conditions. , In terms of catalytic activity,
It is 20-100, more preferably 40-100.

The preferable range of the SiO ₂ / Ga ₂ O ₃ ratio is usually 100 or more. When the SiO ₂ / Ga ₂ O ₃ ratio is in this range, the MFI-type galloaluminosilicate is more excellent in hydrothermal resistance and catalytic activity, and is particularly high in aromatization reaction of, for example, paraffin or olefin. Show activity. A more preferable range of the SiO ₂ / Ga ₂ O ₃ ratio is 300 to 10,000.

The MFI-type galloaluminosilicate used in the method of the present invention is not particularly limited as long as it has an MFI-type crystal structure. For example, ZSM-5, ZSM-5
SM-8, zeta 1, zeta 3, Nu-4, Nu-5,
ISI-3, ISI-5, TZ-1, TPZ-1, TS
1, various zeolites such as TSZ and the like.

In the method of the present invention, the MFI-type galloaluminosilicate used as a catalyst or a catalyst component uses (a) a raw material mixture consisting of only an inorganic compound (that is, a raw material mixture to which no organic compound is added). Or by using a raw material mixture obtained by adding at least one of alcohols, amines and amino alcohols to a raw material comprising an inorganic compound (b). In both the synthesis method (a) and the synthesis method (b), SiO ₂ / (Al ₂ O ₃ +
It can be carried out according to a conventional method, taking into account that the (Ga ₂ O ₃ ) ratio (molar ratio) and the SiO ₂ / Ga ₂ O ₃ ratio (molar ratio) fall within the above specific ranges.

That is, in the case of the method (a),
As a silica source component, for example, water glass, at least one of silica sol and the like is used, and as an alumina source component, for example,
Use at least one of aluminum sulfate, aluminum nitrate, sodium aluminate, alumina sol, aluminum hydroxide and the like, and use at least one of gallium nitrate, gallium sulfate, gallium oxide, gallium metal and the like as a gallium source component. Accordingly, a suitable inorganic additive is further added, and the liquid properties such as the composition and pH are appropriately adjusted to prepare a raw material mixture consisting of only the inorganic compound. From the raw material mixture, hydrothermal synthesis is performed at an appropriate temperature and pressure. Thus, a predetermined MFI-type galloaluminosilicate may be synthesized.

At that time, a method of suitably adding a zeolite such as mordenite or the previously prepared MFI-type galloaluminosilicate as a seed crystal to the synthesis system as a seed crystal is also suitably adopted.

In the case of the above method (b), at least one of alcohol, amine and amino alcohol is added to a synthetic raw material system comprising at least a silica source component, an alumina source component and a gallium source component, and Si
O ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio and SiO ₂ / Ga ₂ O ₃
A ratio of MFI type galloaluminosilicate is synthesized. Various alcohols can be used as the alcohol to be added here. Among them, usually, for example, propyl alcohol such as n-propyl alcohol, methanol, ethanol,
Monovalent relatively lower alcohols such as butyl alcohol and amyl alcohol such as n-butanol, and divalent or polyvalent relatively lower alcohols such as ethylene glycol, propylene glycol and glycerin are preferably used. As the amine, various ones can be used, and among them, usually, for example, morpholine, relatively lower primary such as propylamine such as n-propylamine, butylamine, tripropylamine, ethylenediamine, and pyrrolidine are used. Primary to tertiary amines are preferably used. As the amino alcohol, various ones can be used, and among them, for example, relatively lower amino alcohols such as ethanolamine, diethanolamine, propanolamine, and triethanolamine are preferably used. One of these alcohols, amines and amino alcohols may be added alone, or two or more thereof may be added. Also,
In the case of the method (b), the organic compound may be synthesized by adding other organic compounds as necessary, as long as the object of the present invention is not impaired.

In the synthesis according to the above method (b), a method in which another zeolite such as mordenite or the previously prepared MFI-type galloaluminosilicate or the like prepared as a seed crystal is appropriately added to the synthesis system as a seed crystal is also used. You can also.

In the above synthesis methods (a) and (b), water glass or the like is usually particularly preferably used as a silica source, and aluminum sulfate or the like is usually particularly preferably used as an alumina source. In addition, as the gallium source, gallium sulfate, gallium nitrate, or the like is usually particularly preferably used, but is not necessarily limited thereto.

In the synthesis according to the methods (a) and (b), it is preferable to appropriately add other salts such as sodium chloride as an additive to the synthesis system.

The conventional MFI-type galloaluminosilicate is often synthesized by converting a quaternary ammonium salt such as tetrapropylammonium bromide as a crystallization agent. In this case, SiO ₂ / (Al ₂ O ₃ +
The Ga ₂ O ₃ ) ratio can be easily adjusted, but it is difficult to adjust I _SiOH / I _H + to the above-mentioned specific range. In fact, according to such a conventional method, a gallon containing a large amount of internal SiOH groups is used. Aluminosilicate was obtained, and its ¹ H-NM
The I _SiOH intensity in the R spectrum is large, and I _SiOH / I _H + is larger than 0.5 even in the H type. Such a conventional galloaluminosilicate has low hydrothermal resistance, and its activity is easily reduced when exposed to water vapor at a high temperature. On the other hand, without using a quaternary ammonium compound such as tetrapropyl ammonium, methanol, ethanol, n-propyl alcohol, n-butyl alcohol,
When alcohols such as i-butyl alcohol, n-amyl alcohol and morpholine, amines and amino alcohols are used, or when synthesized without using any organic compound, the above-mentioned I _SiOH / I _H + is used. The MFI galloaluminosilicate, in which I _SiOH / I _H + is in the range of 0 to 0.5 when the H type is used, can be easily controlled to a low value in a wide range. It has been found that even when used in an atmosphere where steam is present at a high temperature, the decrease in activity is small.

In view of the above, the synthesis of the MFI-type galloaluminosilicate used in the present invention requires the above (a)
And the synthesis method of (b) is preferably used.

The MFI-type galloaluminosilicate synthesized by the above-mentioned method (a) or (b) may be used, if necessary, for example, with various metals or metal compounds such as Pt, Ni, Ga, Zn, Cu, Co, Fe and the like. Or various components such as an H ⁺ source such as ammonium ion or a component serving as an H ⁺ source, are supported by various supporting methods such as an ion exchange method, an impregnation method, an immersion method, or contain these various elements. It can also be used as a composition by appropriately mixing with the compound or composition to be prepared by a physical mixing method or the like. Further, if necessary, two or more kinds of MFI-type galloaluminosilicates synthesized or prepared by the above method can be mixed or used by mixing with another zeolite. Then, it may be formed by using a suitable binder such as alumina, silica, silica alumina, zirconia, magnesia, boria, alumina boria, titania, silica titania, magnesia, clay mineral and the like. By using an appropriate binder in this way, the hydrothermal resistance can be further improved.

It is preferable that the MFI-type galloaluminosilicate synthesized by the above-described method is usually used after calcining at an appropriate temperature. In this case, calcining at a high temperature of 700 to 1000 ° C. further improves the catalytic activity. Can be done. This baking may be performed on the composition or the molded product after adding the various additives or supporting various metal components, or may be performed before that. In addition, the galloaluminosilicate synthesized or prepared as described above is optionally treated with an appropriate treating agent such as an acid, an alkali, ammonia, or a variety of nonmetallic compounds such as halogen, or a heat treatment, a steaming treatment, or the like. Can be used after being appropriately processed.

In the method of the present invention, if necessary, the MFI-type galloaluminosilicate obtained by the method (a) and the MFI-type galloaluminosilicate obtained by the method (b) can be used in combination.

That is, the MFI-type galloaluminosilicate may be subjected to various treatments as necessary, or may carry a desired component, similarly to a conventional zeolite catalyst.
Alternatively, it can be used in various forms by mixing with other components.

The MFI used in the method of the present invention
When used as a catalyst or a catalyst component in the catalytic conversion reaction of various organic compounds, the galloaluminosilicate exhibits excellent catalytic activity or catalytic function unique to the MFI-type galloaluminosilicate, and also has excellent hydrothermal resistance. ,
Even when exposed to a steam atmosphere at a high temperature during a reaction or regeneration of a catalyst, the decrease in activity is extremely small, and the original catalytic function is maintained for a long time. Therefore, by using the MFI-type galloaluminosilicate as a catalyst or a catalyst component, the catalytic conversion process of various organic compounds including the step of bringing the catalyst into contact with steam can be performed at least by the conventional M
Compared to the case where FI-type zeolite is used, it can be carried out extremely efficiently and advantageously.

That is, in the process of the present invention, the catalytic conversion process of an organic compound to be carried out is a process of a type in which a catalyst comes into contact with steam in any step such as a catalyst reaction or a catalyst regeneration. There is no particular limitation, and various reactions can be targeted as well as various reactions performed using at least a conventional MFI zeolite as a catalyst or a catalyst component. Here, not only when the contact between the catalyst used and the steam occurs during the reaction, but also when the catalyst does not contact the steam during the reaction, the catalyst and the steam are generated during the reaction other than during the regeneration of the catalyst or during the pretreatment. It should be noted that contact is also an object of the present invention.

That is, in the present invention, for example,
(1) A process in which water vapor is brought into contact with a catalyst during a reaction such as a reaction in which water is produced or water is added to a reaction system as a raw material or an additive. (2) A catalyst always comes into contact with water vapor during a catalytic reaction. Alternatively, various types of processes, such as a type in which the catalyst comes into contact with steam during catalyst regeneration, can be employed. Of course, it is also possible to use a process in which the catalyst comes into contact with steam both during the reaction and during catalyst regeneration, or in which the catalyst comes into contact with steam during pretreatment.

In the case of the process of the type (1), examples of the target contact reaction include various dehydration reactions such as alcohol dehydration reaction, and water reactions such as a conversion reaction of an oxygen-containing compound such as alcohol into gasoline. Reactions using water as a reaction material, such as various reactions involving by-products of olefins, hydration reactions of olefins, and the like. Among them, in particular, conversion reaction of methanol to gasoline (MTG reaction), conversion reaction of alcohol to gasoline or olefin with by-product of water such as dehydration reaction of alcohol, and synthesis reaction of alcohol by hydration of olefin, etc. Is preferred.

The process of the type (2) covers a wide variety of catalytic reactions such as catalytic decomposition, aromatization, alkylation, disproportionation, polymerization and isomerization of various organic compounds. More specifically, for example, cracking reaction of various hydrocarbons, aromatization reaction of paraffin and olefin, aromatic compound, paraffin, alkylation reaction of hydrocarbon such as olefin with olefin, aromatic compound and Examples include a disproportionation reaction, an isomerization reaction, and a polymerization reaction of paraffin and olefin.
This reaction is not limited to a simple reaction, but may be a complex reaction such as the above-described reaction such as a petroleum fraction reforming reaction.

In the case of the aromatization reaction of a hydrocarbon, a process using a hydrocarbon having 12 or less carbon atoms, preferably 2 to 12 carbon atoms as a raw material is suitably employed. As the hydrocarbon, an olefin, a paraffin, a diene compound, a naphthenic compound, or a hydrocarbon mixture containing one or more of these can be used as appropriate.

In such a hydrocarbon conversion reaction, etc.,
Generally, carbonaceous material (coke) composed of carbon and hydrogen gradually precipitates on the catalyst, and the catalytic activity decreases. Therefore, the catalyst is regenerated at appropriate intervals. This catalyst regeneration is usually suitably carried out using a gas containing steam and / or oxygen. Here, it should be noted that even when steam is not contained in the regeneration gas, the catalyst comes into contact with water vapor generated by combustion of coke by oxygen during regeneration of the catalyst.

In the case of the process of the type (2), the catalyst is regenerated at least so that the catalyst comes into contact with steam. The regeneration conditions at that time cannot be uniformly defined because they depend on the catalyst to be used, the target reaction, or other various conditions such as reaction conditions, reaction times, and process selection conditions. Can usually be suitably performed under the following conditions.

That is, the regeneration of the catalyst is usually performed at 400
To 850 ° C, preferably 500 to 650 ° C. If the regeneration temperature is less than 400 ° C., coke may not be sufficiently removed. On the other hand, if the regeneration temperature exceeds 850 ° C., sintering of the catalyst and decomposition of the zeolite skeleton may occur.

The oxygen concentration of the regeneration gas used in the regeneration of the catalyst is usually 0 to 21% by volume. On the other hand, the concentration of water vapor in the regeneration gas may be appropriately selected from the range of usually 0 to 30% by volume, preferably 1 to 10% by volume. As gas components other than oxygen and water vapor,
Usually, an inert gas such as nitrogen or carbon dioxide is suitably used, but various components may be contained as necessary.

Of course, air or a mixed gas of air and water vapor is preferably used as the regeneration gas.

The above-mentioned regenerating conditions are particularly suitably employed particularly when the above-described various types of hydrocarbon conversion reactions are carried out.

The regeneration of the catalyst can be carried out generally at an arbitrary interval. However, usually, a method in which the regeneration is carried out at every reaction time within 150 hours is preferably employed. When the conversion reaction is carried out, the catalyst is preferably regenerated every reaction time within 150 hours.

In the present invention, the above-mentioned reaction and regeneration can be carried out by various operations using various types of apparatuses. For example, fixed bed type, fluidized bed type, moving bed type,
Swing type reactor type, can be performed by continuous operation or intermittent operation by suspension bed type, or
If necessary, it may be performed by a batch operation or a semi-batch operation. Among these, when the process of the type (2) is used, particularly when the conversion reaction of the various hydrocarbons exemplified above is performed, the reaction and the regeneration can be performed continuously and more effectively. From the viewpoint that it is possible, it is usually preferable to employ a process using any of a fluidized bed type, a moving bed type and a swing type reactor type as a reactor type. In the case of a fluidized bed type, a riser type may be adopted. On the other hand, when the process of the type (1) is used, the reaction type is not particularly limited, and various desired reaction types can be used. For example, a fixed floor type or the like is also suitably adopted.

[0056]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1 Catalyst Production Example 1 (Catalyst I comprising galloaluminosilicate)
370 g of aluminum sulfate (18-hydrate), 116 g of gallium nitrate (9-hydrate), 228 g of sulfuric acid (concentration: 97% by weight)
And 8000 ml of water were mixed, and the resulting solution was used as solution A. On the other hand, water glass (SiO ₂ : 29% by weight, Na ₂ O:
(9.4% by weight, water: 61.6% by weight) 5275 g and water 4
500 ml were mixed, and the obtained solution was used as solution B.

The above solution A and solution B were gradually dropped into 3050 ml of water and mixed. After adding 12 g of mordenite powder to this raw material mixture, 269 g of 50% sulfuric acid was added to adjust the pH to 9.5.
Put into a 5-liter autoclave and rotate at 300r
The reaction was carried out at 170 ° C. under self-pressure for 46 hours while stirring at pm. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid was heated to 120 ° C.
At 550 ° C. for 6 hours in air.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 35.1 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
76 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 29.3 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI type galloaluminosilicate) is referred to as galloaluminosilicate I. The ¹ H-NMR spectrum of this galloaluminosilicate I was measured as follows. Galloaluminosilicate I 0.18
g was evacuated at 400 ° C. for 1 hour, allowed to cool to room temperature, and the spectrum was measured. Silanol group (1.8pp
m) and the peak area ratio I _SiOH / I _H + of the acid OH group (4.5 ppm) was 0.39.

In order to use the galloaluminosilicate I obtained above as a catalyst, the galloaluminosilicate I is compression-molded and then pulverized and sieved to a particle size of 16 to 32.
A mesh catalyst was obtained. This catalyst is called catalyst I.

Reaction Example 1 (Evaluation of catalytic performance) The catalytic performance of the catalytic conversion method for organic compounds was evaluated as follows.
The reaction was carried out as follows, taking as an example the catalytic decomposition reaction of n-hexane.

As the catalyst, the catalyst I obtained in Catalyst Production Example 1 was used. The reaction temperature was 480 ° C., the reaction pressure was normal pressure, the gas hourly space velocity (WHSV) was 48 hr ⁻¹ , helium (carrier gas) / n-hexane (raw material). ) Catalytic decomposition of n-hexane was performed under the reaction conditions of ratio = 4 (molar ratio). At that time,
The catalyst was heated at 600 ° C. and normal pressure in air containing 2% by volume of steam (feed gas flow rate GHSV = 1600 hr ⁻¹ ).
The difference in the decomposition activity of n-hexane was evaluated between the case where steam treatment was performed (after steaming) and the case where steam treatment was not performed (before steaming). Table 1 shows the results.

Example 2 Catalyst Production Example 2 (Catalyst I comprising galloaluminosilicate
Production of I) 18.8 g of aluminum sulfate (18-hydrate), 1.4 g of gallium nitrate (9-hydrate), sulfuric acid (concentration: 97% by weight)
9 g and 250 ml of water were mixed, and the resulting solution was used as solution A. On the other hand, water glass (SiO ₂ : 29.0% by weight, N
a ₂ O: 9.4 wt%, water: 61.6 wt%) 211 g
And 250 ml of water were mixed to obtain a solution B.
In addition, 39.5 g of sodium chloride and 122 ml of water were mixed, and the resulting solution was used as solution C.

While stirring the above solution C, the above solution A and solution B were gradually added dropwise thereto at room temperature and mixed. After adding 0.5 g of mordenite powder to this raw material mixture, 5
4.5 g of 0% sulfuric acid was added to adjust the pH to 9.5, and the obtained mixture was placed in an autoclave having an internal volume of 1 liter, and stirred at 300 rpm for 20 hours at 170 ° C. under self-pressure. Reacted. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid was dried at 120 ° C. for 6 hours, and then calcined in air at 550 ° C. for 6 hours.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 28.1 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 6
25 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 26.9 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI type galloaluminosilicate) is referred to as galloaluminosilicate II. I _SiOH / I _H + of this galloaluminosilicate II was measured by the same method as in Example 1 and found to be 0.30.

Galloaluminosilicate II obtained above
The galloaluminosilicate I is used as a catalyst.
I is compression molded and then crushed and sieved to a particle size of 16 to
A 32 mesh catalyst was obtained. This catalyst is called catalyst II.

Reaction Example 2 (Evaluation of Catalytic Performance) The catalytic performance of the catalytic conversion method for organic compounds was evaluated as follows.
The catalytic cracking reaction of n-hexane was performed as an example.

The catalytic cracking reaction of n-hexane and the evaluation of the catalytic performance were carried out by using the catalyst II obtained in the above catalyst production example 2 in place of the catalyst I obtained in the catalyst production example 1 of the example 1.
The reaction was carried out in the same manner as described in Reaction Example 1 of Example 1 except that was used. Table 1 shows the results.

Example 3 Catalyst Production Example 3 (Catalyst I comprising galloaluminosilicate
Production of II) 9.67 g of aluminum sulfate (18-hydrate), 6.07 g of gallium nitrate (9-hydrate), sulfuric acid (concentration 97% by weight) 1
1.7 g and 250 ml of water were mixed, and the resulting solution was mixed with A
Liquid. On the other hand, water glass (SiO ₂ : 29.0% by weight, Na ₂ O: 9.4% by weight, water: 61.6% by weight) 2
11 g and 250 ml of water were mixed, and the resulting solution was used as solution B. Also, 39.5 g of sodium chloride and 122 m of water
and the resulting solution was used as solution C.

While stirring the liquid C, the liquid A and the liquid B were gradually added dropwise thereto at room temperature and mixed. After adding 0.5 g of mordenite powder to this raw material mixture, 5
5.8 g of 0% sulfuric acid was added to adjust the pH to 9.5, and the obtained mixture was placed in an autoclave having an internal volume of 1 liter, and stirred at a rotation speed of 300 rpm for 20 hours at 170 ° C. under self-pressure. Reacted. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid was dried at 120 ° C. for 6 hours, and then calcined in air at 550 ° C. for 6 hours.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 50.3 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
18 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 35.3 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI galloaluminosilicate) is referred to as galloaluminosilicate III. I _SiOH / I _H + of this galloaluminosilicate III was measured by the same method as in Example 1 and found to be 0.17.

Galloaluminosilicate II obtained above
In order to use I as a catalyst, the galloaluminosilicate III is compression-molded and then crushed and sieved to a particle size of 1%.
A 6-32 mesh catalyst was obtained. This catalyst is referred to as catalyst III.
Call.

Reaction Example 3 (Evaluation of Catalytic Performance) The catalytic performance of the catalytic conversion method for organic compounds was evaluated as follows.
The catalytic cracking reaction of n-hexane was performed as an example.

The catalytic cracking reaction of n-hexane and the evaluation of the catalytic performance were carried out by using the catalyst II obtained in the above catalyst production example 3 in place of the catalyst I obtained in the catalyst production example 1 of the example 1.
The reaction was performed in the same manner as described in Reaction Example 1 of Example 1 except that I was used. Table 1 shows the results.

Example 4 Catalyst Production Example 4 (Catalyst I comprising galloaluminosilicate
Production of V) 14.1 g of aluminum sulfate (18-hydrate), 4.64 g of gallium nitrate (9-hydrate), and sulfuric acid (concentration: 97% by weight)
1 g and 320 ml of water were mixed, and the resulting solution was used as solution A. On the other hand, water glass (SiO ₂ : 29.0% by weight, N
a ₂ O: 9.4 wt%, water: 61.6 wt%) 211 g
And 180 ml of water were mixed to obtain a solution B.
In addition, 79.0 g of sodium chloride and 122 ml of water were mixed, and the resulting solution was used as solution C.

While stirring the above solution C, the above solution A and solution B were gradually and simultaneously dropwise added thereto at room temperature.
3.7 g of 50% sulfuric acid was added to adjust the pH to 9.5, and 6.0 g of n-propyl alcohol was further added and mixed.
The mixture thus obtained was placed in an autoclave having an internal volume of 1 liter and stirred at a rotation speed of 300 rpm.
The reaction was carried out at 170 ° C. under self-pressure for 20 hours. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. 50 g of this solid product per gram
Washed 5 times with 1 liter of water. After repeating washing and filtration in this manner, the collected solid was dried at 120 ° C. for 6 hours, and then calcined in air at 550 ° C. for 6 hours.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 32.6 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
48 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 26.7 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI type galloaluminosilicate) is referred to as galloaluminosilicate IV. When I _SiOH / I _H + of this galloaluminosilicate IV was measured by the same method as in Example 1, it was 0.43.

Galloaluminosilicate IV obtained above
The galloaluminosilicate I is used as a catalyst.
V is compression molded, then crushed and sieved to a particle size of 16 to
A 32 mesh catalyst was obtained. This catalyst is called catalyst IV.

Reaction Example 4 (Evaluation of Catalyst Performance) The evaluation of the catalyst performance for the catalytic conversion method of an organic compound was as follows.
The catalytic cracking reaction of n-hexane was performed as an example.

The catalytic cracking reaction of n-hexane and the evaluation of the catalytic performance were carried out by using the catalyst IV obtained in the above catalyst production example 4 in place of the catalyst I obtained in the catalyst production example 1 of the embodiment 1.
The reaction was carried out in the same manner as described in Reaction Example 1 of Example 1 except that was used. Table 1 shows the results.

Example 5 Catalyst Production Example 5 (Catalyst V comprising galloaluminosilicate)
14.8 g of aluminum sulfate (18-hydrate), 4.64 g of gallium nitrate (9-hydrate), sulfuric acid (concentration: 97% by weight) 1
7.6 g and 320 ml of water were mixed, and the obtained solution was mixed with A
Liquid. On the other hand, water glass (SiO ₂ : 29.0% by weight, Na ₂ O: 9.4% by weight, water: 61.6% by weight) 2
11 g and 180 ml of water were mixed, and the resulting solution was used as solution B. In addition, 79 g of sodium chloride and 122 ml of water were mixed, and the resulting solution was used as solution C.

While stirring the liquid C, the liquid A and the liquid B were gradually dropped and mixed simultaneously at room temperature.
4.4 g of 50% sulfuric acid was added to adjust the pH to 9.5, and 8.7 g of morpholine was further added and mixed. The mixture thus obtained was placed in an autoclave having an internal volume of 1 liter and stirred at a rotation speed of 300 rpm at 170 ° C.
The reaction was carried out for 20 hours under self pressure. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid was dried at 120 ° C. for 6 hours, and then calcined in air at 550 ° C. for 6 hours.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 32.6 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
48 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 26.7 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI type galloaluminosilicate) is referred to as galloaluminosilicate V. I _SiOH / I _H + of this galloaluminosilicate V was measured by the same method as in Example 1, and it was 0.38.

In order to use the galloaluminosilicate V obtained above as a catalyst, the galloaluminosilicate V is compression-molded and then pulverized and sieved to a particle size of 16 to 32.
A mesh catalyst was obtained. This catalyst is called catalyst V.

Reaction Example 5 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of organic compounds was carried out as follows.
The catalytic cracking reaction of n-hexane was performed as an example.

The catalytic cracking reaction of n-hexane and the evaluation of the catalytic performance were carried out by using the catalyst V obtained in the above catalyst production example 5 in place of the catalyst I obtained in the catalyst production example 1 of the embodiment 1. The procedure was performed in the same manner as described in Reaction Example 1 of Example 1 except for the above. Table 1 shows the results.

Comparative Example 1 Catalyst Preparation Example CR1 ( Production of Catalyst CR1 as Comparative Example) 82.6 g of aluminum sulfate (18-hydrate), 75 g of gallium nitrate (octahydrate), sulfuric acid (concentration 97% by weight) 163
g, tetrapropylammonium bromide 287 g and water 2700 ml, and the resulting solution was used as solution A. On the other hand, water glass (SiO ₂ : 29.0% by weight, Na ₂
(O: 9.4% by weight, water: 61.6% by weight) 2326 g and water (2300 ml) were mixed, and the resulting solution was used as solution B.
Further, 870 g of sodium chloride and 1330 ml of water were mixed, and the obtained solution was used as solution C. While stirring the above solution C, the above solution A and solution B were gradually and simultaneously dropped dropwise at room temperature, and then 8.3 g of 50% sulfuric acid was added.
Adjusted to H9.5. The mixture thus obtained was placed in an autoclave having an internal volume of 25 liters,
20 minutes at 170 ° C. under self-pressure while stirring at rpm.
Allowed to react for hours. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid is
C. for 6 hours and then calcined in air at 550.degree. C. for 6 hours.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 66.7 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
13 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 41.9 (molar ratio) was confirmed to be H-form ZSM-5 (galloaluminosilicate). Hereinafter, this calcined product (HZSM type galloaluminosilicate) is referred to as galloaluminosilicate CR1. I _SiOH / I _H + of this galloaluminosilicate CR1 was measured by the same method as in Example 1 to be 2.8.

Galloaluminosilicate CR obtained above
The galloaluminosilicate CR1 was compression-molded to use 1 as a catalyst, and then pulverized and sieved to a particle size of 1
A 6-32 mesh catalyst was obtained. This catalyst was used as catalyst CR1.
Call.

Reaction Example CR1 (Evaluation of Catalytic Performance) The catalytic performance of the catalytic conversion method for organic compounds was evaluated as follows .
The catalytic cracking reaction of n-hexane was performed as an example.

The catalytic cracking reaction of n-hexane and the evaluation of the catalytic performance were performed using the catalyst CR1 obtained in the above-mentioned catalyst production example CR1 in place of the catalyst I obtained in the catalyst production example 1 of the example 1. The procedure was performed in the same manner as described in Reaction Example 1 of Example 1 except for the above. Table 1 shows the results.

Example 6 Reaction Example 6 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of organic compounds was carried out as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

As the catalyst, the catalyst I obtained in Catalyst Production Example 1 was used, n-hexane was used as a reaction raw material, the reaction temperature was 500 ° C., the reaction pressure was normal pressure, and the gas space velocity (WHS
V) An aromatization reaction of n-hexane was performed under a reaction condition of 2 hr ^-1 . In this case, the catalyst was heated at 600 ° C. and normal pressure.
GHSV1600 in air containing 2% by volume of steam
The difference between the conversion rate of n-hexane and the yield of BTX was evaluated between the case where steam treatment was performed under the condition of hr ^-1 for 120 hours (after steaming) and the case where steam treatment was not performed (before steaming). Table 2 shows the results.

Example 7 Reaction Example 7 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of organic compounds was carried out as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

The aromatization reaction of n-hexane and the evaluation of the catalytic performance were carried out in the same manner as in Example 3 except that the catalyst I obtained in Example 1 was used instead of the catalyst I obtained in Example 1. The reaction was carried out in the same manner as described in Reaction Example 6 of Example 6, except that Catalyst III was used. Table 2 shows the results.

Example 8 Reaction Example 8 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of an organic compound was as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

The aromatization reaction of n-hexane and the evaluation of the catalyst performance were carried out in the same manner as in Example 1 except that the catalyst I obtained in Example 1 was used instead of the catalyst I obtained in Example 1. The reaction was carried out in the same manner as in Reaction Example 6 of Example 6, except that the catalyst IV was used. Table 2 shows the results.

Example 9 Reaction Example 9 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of organic compounds was carried out as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

The aromatization reaction of n-hexane and the evaluation of the catalytic performance were carried out in the same manner as in Example 5 except that the catalyst I obtained in Example 1 was used as the catalyst. The reaction was carried out in the same manner as in Reaction Example 6 of Example 6, except that the catalyst V was used. Table 2 shows the results.

Example 10 Catalyst Production Example 6 (Catalyst V composed of galloaluminosilicate
Preparation of I) 14.8 g of aluminum sulfate (18-hydrate), 4.6 g of gallium nitrate (9-hydrate), 9.1 of sulfuric acid (concentration 97% by weight)
g and 250 ml of water were mixed, and the resulting solution was used as solution A. On the other hand, water glass (SiO ₂ : 29.0% by weight, Na ₂
(O: 9.4% by weight, water: 61.6% by weight) 211 g and water (250 ml) were mixed to obtain a solution B. Also, 79 g of sodium chloride and 122 ml of water are mixed,
The obtained solution was used as solution C.

While stirring the solution C, the solution A and the solution B were gradually dropped at room temperature and mixed. Then
To the obtained mixture, 5.9 g of 50% sulfuric acid was added, and the pH was adjusted.
The mixture was adjusted to 9.5, and 55 g of diethanolamine was added and mixed. The raw material mixture obtained in this way was
Liter in an autoclave, 300 rpm
The reaction was carried out at 170 ° C. under self-pressure for 20 hours while stirring at m. After the reaction, the reaction mixture was cooled to room temperature, and then a solid product was recovered by filtration. The solid product was washed five times with 50 ml of water per gram. After repeating washing and filtration in this manner, the collected solid was heated to 120 ° C.
At 550 ° C. for 6 hours in air.

Next, the fired product 1
After performing ion exchange twice at 80 ° C. for 4 hours using 10 ml of 1N ammonium nitrate aqueous solution per gram, washing with pure water, then drying the ion exchange product at 120 ° C., and then in air, It baked at 720 degreeC for 4 hours.

The fired product obtained in this way is SiO ₂ / A
l ₂ O ₃ = 33.8 (molar ratio), SiO ₂ / Ga ₂ O ₃ = 1
56 (molar ratio) and SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ )
= 27.8 (molar ratio) was confirmed to be an H-type MFI-type galloaluminosilicate. Hereinafter, this calcined product (H-type MFI galloaluminosilicate) is referred to as galloaluminosilicate VI. I _SiOH / I _H + of this galloaluminosilicate VI was measured by the same method as in Example 1 and found to be 0.41.

Galloaluminosilicate VI obtained above
The galloaluminosilicate V
I is compression molded and then crushed and sieved to a particle size of 16 to
A 32 mesh catalyst was obtained. This catalyst is called catalyst VI.

Reaction Example 10 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of organic compounds was carried out as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

The aromatization reaction of n-hexane and the evaluation of the catalyst performance were carried out by using the catalyst V obtained in the above-mentioned Catalyst Production Example 6 in place of the catalyst I obtained in the Catalyst Production Example 1 of Example 1.
The reaction was carried out in the same manner as described in Reaction Example 6 of Example 6 except that I was used. Table 2 shows the results.

Comparative Example 2 Reaction Example CR2 (Evaluation of catalytic performance) Evaluation of catalytic performance for the catalytic conversion method of an organic compound was as follows.
The aromatization reaction of n-hexane was performed as an example as follows.

The aromatization reaction of n-hexane and the evaluation of the catalytic performance were carried out in the same manner as in Comparative Example 1 except that the catalyst I obtained in Example 1 was used instead of the catalyst I obtained in Example 1. The reaction was carried out in the same manner as in Reaction Example 6 of Example 6, except that the catalyst CR1 was used. Table 2 shows the results.

[0115]

[Table 1] * K / K ₀ = ln (unreacted rate of catalyst after steaming) /
ln (unreacted rate of catalyst before steaming)

[0116]

[Table 2] ┌───────────────┬────┬────┬────┐ │ │Example 6│Example 7│Example 8│触媒 │ catalyst used │ catalyst I │ catalyst III │ catalyst I V │ ├─── ───┬────────┼────┼────┼────┤ │ steaming │ n-hexane │ 100.0 │ 100.0 │ 100.0 │ │ untreated │ conversion (% ) │ │ │ │ │ │ │ BTX yield (%) │ 54.7 │ 53.3 │ 54.9 │ ├──────┼────────┼────┼────┼─── │ │Steaming│n-hexane│ 100.0 │ 100.0 │ 100.0 │ │ After treatment │Conversion (%) │ │ │ │ │ │ │ BTX yield (%) │ 54.7 │ 53.2 │ 51.7 │ └───── ─┴────────┴────┴────┴────┘ ┌─ ─────────────┬────┬─────┬────┐ │ │ Example 9│ Example 10│ Comparative Example 2 │ ├─────触媒 │ Catalyst used │ Catalyst V │ Catalyst VI │ Catalyst CR 2 │ ├──────┬─ │ │Steaming│n-hexane│ 100.0 │ 100.0 │ 100.0 │ │ Untreated │Conversion (%) │ │ │ │ │ │ BTX yield (%) │ 52.7 │ 53.0 │ 55.1 │ ├──────┼────────┼────┼─────┼────┤ │ Steaming | n-hexane | 100.0 | 100.0 | 87.9 | | | After treatment | Conversion (%) | | | | | | | | BTX yield (%) | 52.5 | 52.0 | 35.0 | ───────┴────┴─────┴────┘

As is clear from Table 1, the MFI-type galloaluminosilicate catalysts (catalysts I to V) used in Examples 1 to 5 according to the method of the present invention were all used in Comparative Example 1. Conventional ZSM-5 type catalyst (Catalyst CR1)
The K / K ₀ value, which is an index of hydrothermal resistance, is larger than
It was also found to be extremely excellent in hydrothermal resistance and to have high n-hexane decomposition activity even after steam treatment.

Further, from the above Table 2, it can be seen from Examples 6 to 10 that
The MFI-type galloaluminosilicate catalysts (catalysts I, III to VI) according to the present invention used in Example 1 were all more hydrothermally resistant than the conventional ZSM-5 type catalyst (catalyst CR1) used in Comparative Example 2. And a high BTX yield even after steam treatment.

Catalyst Production Examples 7 to 23 Catalyst Production Examples 7, 8 and 18 Synthesis of MFI-type galloaluminosilicates in the same manner as in Catalyst Production Example 2 and using the raw materials shown in Tables 3 and 5 in the amounts shown in the same table. Was done. Mordenite used in Catalyst Production Example 8 ^*
Was synthesized according to the method described in JP-A-62-52121 and Example 1 as follows.

Aluminum sulfate (18-hydrate) 21.1 g
And a mixture of water and 200 ml of water to obtain a liquid a, which is colloidal silica (SiO ₂ 30% by weight and water 70% by weight)
53 g was used as solution b, a mixture of 15.2 g of sodium hydroxide, 21.3 g of potassium hydroxide and 500 ml of water was used as solution C, and 91 ml of piperazine ethanol was used as solution d.

Solution a and solution b were gradually and simultaneously dropped into solution C. Next, the liquid d was added to the obtained liquid mixture and mixed well until the mixture became homogeneous to prepare an aqueous mixture. Ratio of each component of the aqueous _{mixture, SiO 2 / Al 2 O 3} =
40 (molar _{^{ratio), OH - / SiO 2 =}} 0.45 ( molar ratio)
(However, OH ^- is the amount of the inorganic base added minus the amount of the inorganic acid.), Piperazine ethanol / SiO ₂
= 0.6 (molar ratio), sodium / SiO ₂ = 0.3
(Molar ratio), potassium / SiO ₂ = 0.3 (molar ratio).

Next, the aqueous mixture was transferred to a 1-liter autoclave and reacted at 190 ° C. under self-pressure for 4 days with stirring. Thereafter, the reaction mixture was cooled and the resulting product was washed five times with 1.5 l of water.

Subsequently, the solid content was separated by filtration,
Drying at 15 ° C. for 15 hours gave large crystalline mordenite.

Catalyst Production Examples 9 to 17 and 19 to 23 In the same manner as in Catalyst Production Example 4, MFI-type galloaluminosilicates were synthesized using the starting materials shown in Tables 3 to 6 in the amounts shown in the same Table. However, in Catalyst Production Example 21, sodium chloride was not used.

In these catalyst production examples, Tables 3 to
The amount of water described in 6 is the total amount of water used for preparing the solution A, the solution B, and the solution C. Tables 3 and 4 show the composition and ¹ H-NMR measurement results of the obtained MFI-type galloaluminosilicate.

The obtained MFI-type galloaluminosilicate was compression-molded and then pulverized and sieved to a particle size of 16 to 3
A 2-mesh catalyst was obtained.

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

[Table 5]

[0130]

[Table 6]

Examples 11 to 30 Using the catalysts obtained in Catalyst Production Examples 1, 3, 5, and 7 to 23, a reaction temperature of 480 ° C., a reaction pressure of normal pressure, a gas hourly space velocity (WHSV) of 48 hr ⁻¹ , helium ( Carrier gas)
The catalytic decomposition reaction of n-hexane was performed under the reaction conditions of / n-hexane = 4 (molar ratio). At this time, the catalyst was changed to 6
At a temperature of 00 ° C. and normal pressure, in air with a water vapor concentration of 10% by volume (supply gas flow rate GHSV = 1600 hr ⁻¹ , steam treatment for a treatment time of 36 hours (after steaming) or not (before steaming) ) Were evaluated for differences in the decomposition activity of n-hexane, and the results are shown in Tables 7-9.

[0132]

[Table 7]

[0133]

[Table 8]

[0134]

[Table 9] K / K ₀ = ln (unreacted ratio of catalyst after steaming) / l
n (Unreacted rate of catalyst before steaming)

Examples 31 to 40 The above catalyst production examples 1, 3, 4, 5, 7, and 1 were used as catalysts.
Using the catalysts obtained in 1, 12, 16, 18 and 22, using n-hexane as a reaction raw material, at a reaction temperature of 500 ° C,
The aromatization reaction of n-hexane was performed under the reaction conditions of normal pressure and gas hourly space velocity (WHSV) of 2 hr ^-1 . In addition,
At this time, the catalyst was subjected to 36 hours at 600 ° C. and normal pressure in air having a water vapor concentration of 10% by volume under the condition of GHSV = 1600 hr ^−1.
BTX from n-hexane
Was evaluated. The results are shown in Tables 10 and 11.

[0136]

[Table 10]

[0137]

[Table 11]

As is clear from Tables 10 and 11, galloaluminosilicates having a SiO ₂ / Ga ₂ O ₃ ratio of 300 or more after Catalyst Production Example 7 maintain a particularly high BTX yield even after the steaming treatment. It turns out that it is extremely excellent in hydrothermal resistance.

As can be seen from the results of the above reaction examples, the specific MFI-type galloaluminosilicate having excellent catalytic activity and sufficiently excellent hydrothermal resistance is used as a catalyst (or a catalyst component). It is apparent that the method of the present invention can be advantageously used as a method for catalytically converting a wide variety of organic compounds including a step of bringing a catalyst into contact with steam, without being limited to the above reaction.

[0140]

According to the method of the present invention, a specific MFI-type galloaluminosilicate obtained by a specific synthesis method and having a specific structure and composition is used as a catalyst or a catalyst component. Even when exposed to water vapor at a high temperature at the time of catalyst regeneration or the like, the decrease in activity is significantly suppressed, and the excellent catalytic function (activity and the like) inherent in the catalyst can be maintained for a long time.

Accordingly, the process of the present invention is suitable for a zeolite having a low hydrothermal resistance such as a conventional ZSM-5 zeolite-based galloaluminosilicate for a variety of catalytic conversion processes of organic compounds in which the catalyst may come into contact with steam. It can be applied significantly more advantageously than the method using a catalyst, and its industrial value is extremely large.

Continued on the front page (51) Int.Cl. ⁶ identification code FI C07C 5/41 C07C 5/41

Claims (11)

(57) [Claims] 1. A method for catalytically converting an organic compound comprising the step of contacting a catalyst with water vapor, wherein the catalyst comprises SiO 2
_{The 2} / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio (molar ratio) is 20 to 20.
0, the SiO ₂ / Ga ₂ O ₃ ratio (molar ratio) is 50 or more, and ¹ H
Using a catalyst containing an MFI-type galloaluminosilicate having a ratio (I _SiOH / I _H +) of the intensity I _{SiOH of the SiOH} to the intensity I _H + of the acidic OH (I _SiOH / I _H +) by NMR of 0 to 0.5. Method for catalytic conversion of organic compounds. 2. The method for catalytically converting an organic compound according to claim 1, wherein the MFI-type galloaluminosilicate is synthesized using a raw material mixture consisting of only an inorganic compound. 3. The method according to claim 2, wherein the MFI-type galloaluminosilicate is obtained by adding zeolite as a seed crystal. 4. The MFI-type galloaluminosilicate is synthesized using a raw material mixture obtained by adding at least one of organic compounds selected from alcohols, amines and amino alcohols to an inorganic compound. 2. The method for catalytic conversion of an organic compound according to item 1. 5. An organic compound comprising: methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, propylamine, tripropylamine, butylamine, ethylenediamine, pyrrolidine, morpholine, monoethanolamine, The method for catalytically converting an organic compound according to claim 4, wherein the method comprises at least one selected from the group consisting of diethanolamine, triethanolamine and propanolamine. 6. An SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio (molar ratio) of 20 to 100, wherein SiO ₂ / Ga ₂ O ₃
The method according to claim 1, wherein the ratio (molar ratio) is 100 or more. 7. An SiO ₂ / (Al ₂ O ₃ + Ga ₂ O ₃ ) ratio (molar ratio) of 40 to 100, and SiO ₂ / Ga ₂ O ₃
The method according to claim 1, wherein the ratio (molar ratio) is from 300 to 10,000. 8. The method for catalytically converting an organic compound comprises the step of contacting the catalyst with steam during regeneration of the catalyst, wherein at least one of catalytic cracking, aromatization, disproportionation, alkylation, polymerization and isomerization of the organic compound is carried out. The catalytic conversion method for an organic compound according to claim 1, wherein the process is a process for performing a reaction comprising a seed, and the process for regenerating the catalyst is performed for each reaction time within 150 hours. 9. The reactor used for the reaction may be any of a fluidized bed type, a moving bed type and a swing type reactor type, wherein the catalyst is regenerated at a temperature of 400 to 850 ° C., and the oxygen concentration of the regenerated gas is zero. The method for catalytically converting an organic compound according to claim 8, wherein the method is carried out in the presence of an inert gas under the conditions of ２１21% by volume and water vapor concentration of 0-30% by volume. 10. The process according to claim 9, wherein the catalytic conversion of the organic compound is a process for producing an aromatic compound from a hydrocarbon containing at least one of paraffins, olefins, diene compounds and naphthenic compounds having 12 or less carbon atoms. Method for catalytic conversion of organic compounds. 11. The method for catalytically converting an organic compound according to claim 1, wherein the method for catalytically converting an organic compound is a process for performing a hydration reaction of an olefin or a conversion reaction of an alcohol that generates water.