JP2021159884A - Alcohol conversion catalyst - Google Patents

Abstract

To provide an alcohol conversion catalyst having high productivity and a long catalyst life.SOLUTION: An alcohol conversion catalyst contains a 10 membered-ring pore zeolite with an average particle size of 100 nm or less and has an amount of Bronsted acid on the external surface of 0.1-10.0 μmol/g and a silver content of 0.05-3 wt.%.SELECTED DRAWING: None

Description

The present invention relates to an alcohol conversion catalyst capable of stably converting an alcohol typified by methanol, ethanol or the like into an aliphatic hydrocarbon such as paraffin or olefin, an aromatic hydrocarbon or the like with excellent productivity.

In recent years, C1 chemistry using natural gas and coal as raw materials has been attracting attention as a resource for obtaining raw materials for chemical products instead of petroleum resources. Among them, the method of producing aromatic hydrocarbons such as xylene from methanol as a raw material is an important field as a method for producing basic chemicals in the petroleum chemical industry. However, in this reaction system, it is a big problem that water generated from methanol by an acid catalyst promotes dealumination of zeolite and causes rapid catalyst deterioration. Further, in the aromatization system, catalyst deterioration due to cork precipitation is also an unavoidable problem. Therefore, high water heat resistance, caulking resistance, and aromatic hydrocarbon selectivity are indispensable for the catalyst of the reaction system.

As a method for producing an aromatic hydrocarbon from methanol, for example, a production method using a fluidized bed catalyst containing phosphorus and zinc in a silica molded product composed of MFI-type zeolite and a silica binder (see Patent Document 1), silica. A method for producing an aromatic hydrocarbon using a catalyst in which zinc is supported on a crystalline aluminosilicate modified with (see Patent Document 2) has been proposed, and any of Ag, Cu, and Ni is added to ZSM-5. It has been reported that the selectivity of aromatic hydrocarbons is improved by using a catalyst supporting the above (see Non-Patent Document 1).

Patent No. 6574059 JP-A-2010-208948

Catalysis Science & Technology Volume 2, p. 105 (2012)

However, in the method proposed in Patent Document 1, continuous catalyst regeneration is possible by circulating between the reactor and the regenerator, while since it is a fluidized bed reactor, the time lapse during circulation is achieved. There was a problem in that the catalyst cost became high as a result, that is, the productivity was not avoided. Further, the method proposed in Patent Document 2 has a problem that hydrothermal synthesis is required a plurality of times when the zeolite is coated with a silicate, and is specialized in improving the selectivity of p-xylene. Therefore, a satisfactory study has not been made from the viewpoint of the yield of aromatic hydrocarbons and the hydrothermal resistance of the catalyst. Further, in the method proposed in Non-Patent Document 1, although the effect of improving the selectivity of aromatic hydrocarbons by the supported metal was verified, the point of catalyst life was not discussed, and there was room for improvement. It was a thing.

Therefore, as a result of diligent studies to solve the above problems, the present inventors have specified 10-membered ring-pore zeolite having a specific average particle size, and the outer surface blended acid content and silver content are specified. By using an alcohol conversion catalyst, which is characterized by an amount, the water heat resistance, coking resistance, catalyst life, and productivity of paraffin, olefin, and aromatic hydrocarbon are improved, and the catalyst exhibits excellent performance. It was found that this was the case, and the present invention was completed.

That is, the present invention contains a 10-membered ring-pore zeolite having an average particle diameter of 100 nm or less, an outer surface Bronsted acid content of 0.1 to 10.0 μmol / g, and a silver content of 0.05 to 3 wt%. It relates to an alcohol conversion catalyst characterized by the above.

Hereinafter, the present invention will be described in detail.

In the alcohol conversion catalyst of the present invention, the alcohol is an aliphatic hydrocarbon represented by paraffins such as ethane, propane and butane, olefins such as ethylene, propylene and butene, and aromatics represented by benzene, xylene and toluene. It is a catalyst that enables stable conversion to hydrocarbon compounds such as hydrocarbons, contains 10-membered ring-pore zeolite with an average particle size of 100 nm or less, and has an outer surface blended acid amount of 0.1 to 10. It is an alcohol conversion catalyst characterized by having 0 μmol / g and a silver content of 0.05 to 3 wt%.

The alcohol conversion catalyst of the present invention contains zeolite having an average particle size (hereinafter, also referred to as PD) of 100 nm or less, and is particularly excellent in thermal stability. Therefore, 5 nm ≦ PD It is desirable that the value is ≦ 100 nm. Here, when PD exceeds 100 nm, the efficiency of the alcohol conversion reaction is inferior.

The measurement method of PD in the present invention is not limited. For example, 100 or more arbitrary particles are selected from photographs of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the average diameter thereof is obtained. Any method can be mentioned, such as a method, a method of calculating from the outer surface surface of zeolite using the following formula (1), and the like.
PD = 6 / S × (1 / (2.29 × 10 ⁶ ) + 0.18 × ^10-6 ) (1)
(Here, S indicates the outer surface area (m ² / g).)
The outer surface area (S (m ² / g)) in the formula (1) can be obtained from the t-prot method using a general nitrogen adsorption method at a liquid nitrogen temperature. For example, when t is the thickness of the adsorption amount, the measurement points in the range of 0.6 to 1 nm are linearly approximated with respect to t, and the outer surface surface of the zeolite is obtained from the slope of the obtained regression line.

And, above all, the method by SEM or TEM is preferable because simple measurement is possible.

The alcohol conversion catalyst of the present invention comprises a 10-membered ring-pore zeolite, and any zeolite having a skeleton structure having a 10-membered ring structure and pores may be used. Specific examples of the zeolite having a pore structure include zeolites of AEL, EUO, FER, HEU, MEU, MEL, MFI, NES type and the like, and are particularly expected as alcohol conversion catalysts. It is preferably MFI type or MEL type. And, for example, as the MFI type, an aluminosilicate compound belonging to the structure code MFI defined by the International Zeolite Society can be mentioned.

The alcohol conversion catalyst of the present invention has an outer surface Bronsted acid amount (hereinafter, may be referred to as B acid amount) of 0.1 to 10.0 μmol / g, and the outer surface B acid within a specific range. Having an amount will show particularly excellent catalytic performance. Here, when the amount of B acid on the outer surface is less than 0.1 μmol / g, the production efficiency at the time of alcohol conversion and the catalytic performance of selectivity are inferior. On the other hand, if it is larger than 10.0 μmol / g, side reactions and caulking on the catalyst surface are likely to occur, and the catalyst performance is deteriorated.

The alcohol conversion catalyst of the present invention contains 0.05 to 3 wt% of silver because the effect of protecting the acid spot by silver can be obtained. Here, when the silver content is less than 0.05 wt%, the effect of protecting the acid spot by silver cannot be sufficiently obtained. On the other hand, if it is more than 3 wt%, a side reaction is likely to occur on the surface of the agglutinated particles of silver, and the catalytic performance is deteriorated.

Since the alcohol conversion catalyst is a catalyst having excellent alcohol conversion efficiency and hydrocarbon compound selectivity, the amount of B acid is preferably 0.01 to 1.0 mmol / g, and particularly 0.01 to 1.0 mmol / g. It is preferably 0.09 mmol / g.

Here, the amount of B acid in the alcohol conversion catalyst indicates the amount of B acid point, and indicates the acidic OH group present in the zeolite. Zeolites usually have B acid points on their outer surface and in (micro) pores. And, having only a few B acid points on the outer surface means that most of the B acid points are present in the (micro) pores.

As a method for confirming the amount of B acid on the outer surface of the alcohol conversion catalyst, any method can be used as long as the confirmation can be performed. For example, 2,4 having an adsorptivity to the B acid point. -It can be confirmed by adsorption of dimethylquinoline. 2,4-Dimethylquinoline has an adsorptive property with the B acid point (acidic OH group) present in zeolite (including in the pores). However, when the (micro) pore diameter of the zeolite is smaller than the 2,4-dimethylquinoline molecule as in the MFI type, it cannot penetrate into the (micro) pores and the B acid point in the (micro) pores. Cannot be adsorbed. That is, it adsorbs only the B acid point on the outer surface of the zeolite. Therefore, the amount of B acid on the outer surface can be quantified by determining the amount of 2,4-dimethylquinoline adsorbed on the B acid point on the outer surface of the MFI-type zeolite.

As a more specific method, infrared absorption spectrum measurement at 150 ° C. is performed on a sample that has been degassed and dehydrated at 400 ° C. for 2 hours as a pretreatment. Then, 2,4-dimethylquinoline gas is introduced into the degassed / dehydrated sample and adsorbed for 30 minutes, and excess 2,4-dimethylquinoline is removed by exhaust at 150 ° C. to remove 2,4-dimethylquinoline. The adsorption sample is prepared and the infrared absorption spectrum is measured at 150 ° C. That is, the amount of B acid on the outer surface can be obtained by quantifying the difference (decrease) in infrared absorption in the range of ^{3600 to 3650 cm -1} in the infrared absorption difference spectrum before and after adsorption of 2,4-dimethylquinoline. can. Although 2,4-dimethylquinoline is also adsorbed on the silanol site on the zeolite surface, absorption derived from the oh expansion and contraction vibration of silanol is observed at ^{3700 to 3800 cm -1.} On the other hand, absorption derived from the OH expansion and contraction vibration of the B acid point on the outer surface of the zeolite ^{was observed at 3600 to 3650 cm -1} , adsorbing 2,4-dimethylquinoline and OH expansion and contraction vibration of the B acid point. The decrease in the infrared absorption spectrum in the range of absorption 3600 to 3650 cm ^-1 derived from the above indicates that 2,4-dimethylquinoline was adsorbed on the B acid point on the outer surface of the zeolite.

Further, as a method for measuring the amount of B acid (B acid point existing on the outer surface and in the (micro) pores) of the alcohol conversion catalyst, any method can be used as long as the measurement can be performed. It is possible, for example, it can be confirmed by adsorption of pyridine having adsorptivity to the B acid point. Pyridine has an adsorption property with the B acid point (acidic OH group) existing in the zeolite (including in the pores), and when the (micro) pore diameter of the zeolite is larger than the pyridine, the (micro) pores It can also penetrate inside and can adsorb both the outer surface and the B acid points in the (micro) pores. Therefore, the amount of B acid present in the zeolite can be quantified, including the B acid point existing in the pores of the MFI type zeolite.

As a more specific method, infrared absorption spectrum measurement at 150 ° C. is performed on a sample that has been degassed and dehydrated at 400 ° C. for 2 hours as a pretreatment. Then, pyridine gas is introduced into the degassed / dehydrated sample and adsorbed for 10 minutes, excess pyridine is removed by exhaust at 150 ° C., a pyridine adsorbed sample is prepared, and infrared absorption spectrum measurement at 150 ° C. is performed. conduct. That is, in the infrared absorption difference spectrum before and after pyridine adsorption, the amount of B acid including the inside of the pores can be obtained by quantifying the difference (decrease) in infrared absorption in the range of ^{1515 to 1565 cm -1.}

Since the alcohol conversion catalyst is particularly excellent in alcohol conversion efficiency and hydrocarbon compound selectivity, it has a slight B acid point on the outer surface, and most of the B acid points are (micro) pores. It is preferable that the compound is present inside, and the B acid point present on the outer surface thereof is preferably 1 to 10% of the total B acid point. The ratio of the B acid point on the outer surface is determined by using the amount of B acid on the outer surface of the above-mentioned zeolite as the ratio of the amount of B acid present in the zeolite (including the inside of the pores).

Then, the 10-membered ring-pore zeolite having PD ≦ 100 nm can be obtained by using a generally known method. Specifically, it can be produced by mixing a compound containing an alkali metal and / or an alkaline earth metal as a cation, an organic structure-directing agent and an aluminosilicate gel, and calcining the obtained crystal product. Examples of the compound containing an alkali metal and an alkaline earth metal at that time include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like, and sodium hydroxide is particularly preferable. Examples of the organic structure-directing agent include tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and tetraethylammonium hydroxide. Moreover, as an aluminosilicate gel, for example, an amorphous aluminosilicate gel and the like can be mentioned.

Further, when producing a zeolite having a specific amount of outer surface B acid, ion exchange is performed before firing the crystal obtained as described above, and a part or all of the firing is subjected to hydrothermal treatment. After that, it can be produced by a method of further ion exchange, a method of calcining the crystal obtained as described above, then ion exchange to obtain a proton-type zeolite, and then calcining in a hydrothermal atmosphere. ..

As the firing conditions at that time, the treatment temperature is preferably 300 to 900 ° C, particularly preferably 400 to 700 ° C. The treatment time is industrially preferably 5 minutes to 25 hours. The atmosphere may also include, for example, nitrogen, air, oxygen, argon, or any other combination of one or more of the inert gases. Then, by performing a hydrothermal (steam) treatment in part or all of the firing step, the aluminum at the B acid point is desorbed. The treatment temperature of the hydrothermal treatment is preferably 400 to 750 ° C, particularly preferably 500 to 650 ° C. The water vapor concentration is preferably 5 to 100%, particularly preferably 10 to 80%.

Further, the ion exchange is performed before and after the firing step, and may be divided into a plurality of times of ion exchange. Further, the ion exchange includes ion exchange using an acid such as ammonium chloride, hydrochloric acid and nitric acid, and those using hydrochloric acid and nitric acid are preferable. In addition, ion exchange can be replaced by washing with water.

Examples of the method for introducing silver of the alcohol conversion catalyst include a method of introducing silver into a zeolite or zeolite molded product having the above characteristics by a method such as ion exchange or impregnation support.

The alcohol conversion catalyst of the present invention has an action as a catalyst having excellent productivity and selectivity in producing a hydrocarbon compound from an alcohol.

When the alcohol conversion catalyst is used, it is preferable to give the shape as a molded product because the catalyst is excellent in handleability and catalytic performance. When the shape is imparted, it may be molded by any method. For example, a method in which zeolite powder is directly molded into a predetermined shape by compression molding or the like to form a molded product, a predetermined ratio of binder is mixed with zeolite, and in some cases, the zeolite is mixed. Examples thereof include a method in which further additives and the like are mixed at a predetermined ratio and the mixture is molded into a predetermined shape to form a molded product, and a method in which sintering is accompanied to form a molded product. When the alcohol conversion catalyst of the present invention is used, not only is it excellent in moldability as a molded body, but it also exhibits high crushing strength and is excellent in handleability and catalyst life. Therefore, the zeolite and the binder are excellent. A molded body made of the above is preferable, and a molded body made of the zeolite and silica is more preferable because it exhibits better catalytic performance. The silica at that time may be any silica as long as it belongs to the category called silica, and may have a specific crystal structure or may be amorphous. Furthermore, there are no restrictions on the particle size, agglutination diameter, etc. of silica. Further, the mixing ratio of the zeolite and silica is arbitrary, and the zeolite: silica = 50 to 95: 50 to 5 (weight) because the alcohol conversion catalyst exhibits particularly excellent catalyst performance, handleability, and catalyst life. The ratio) is preferably 60 to 90:40 to 10.

The alcohol conversion catalyst may have any shape, for example, a cylindrical shape, a cylindrical shape, a triangular prism shape, a quadrangular prism shape, a pentagonal prism shape, a hexagonal prism shape, or the like, a hollow polygonal prism shape, or a sphere. The shape and the like can be mentioned, and among them, a cylindrical shape and a cylindrical shape are preferable because the catalyst has excellent continuous productivity and high crushing strength. In addition, the size such as diameter, width, and length, and the density such as bulk density and true density can be arbitrarily selected in consideration of filling efficiency and the like, and in particular, a hydrocarbon compound can be effectively produced. Since it serves as a catalyst, it preferably has a cylindrical shape having a diameter of 1 to 10 mm or a cylindrical shape having a thickness of 0.5 to 5.0 mm. Further, the alcohol conversion catalyst may be one in which any metal species is introduced by further treatments such as loading, ion exchange, physical mixing, and vapor deposition.

Examples of the method for producing a hydrocarbon compound using the alcohol conversion catalyst include a method in which an alcohol typified by methanol, ethanol, butanol or the like is brought into contact with the raw material. Generally, in a conversion reaction using alcohol as a raw material using zeolite, an acid-catalyzed dehydration reaction of alcohol occurs, and a large amount of water is generated. Then, the dealumination of the zeolite is promoted under the conditions of high temperature and high concentration water vapor caused by the generation of a large amount of water, and the deterioration of the catalyst is promoted. However, the zeolite constituting the alcohol conversion catalyst of the present invention has high water heat resistance and can suppress dealumination of the zeolite due to high temperature and steam, so that deterioration of the catalyst can be suppressed. Further, since the amount of acid on the outer surface is a specific amount, it has high caulking resistance against coke precipitation accompanying the formation of hydrocarbon compounds. From these points, it becomes possible to exhibit excellent productivity and catalyst life even in the reaction system.

In addition, since it has high water heat resistance, even if methanol, which generates a large amount of water because of its high ratio of hydroxyl groups to carbon number, is used as a raw material, from methanol having 1 carbon number to aliphatic hydrocarbons having 2 or more carbon atoms, aromatics. Since it is possible to efficiently produce a hydrocarbon compound such as a hydrocarbon, it is preferable to carry out a methanol conversion reaction, and it is preferable to use it as a methanol conversion catalyst.

The reaction temperature at the time of producing the hydrocarbon compound is not particularly limited, as long as the hydrocarbon compound can be produced. Above all, the range of 350 to 650 ° C. is desirable because it is an efficient method for producing a hydrocarbon compound that does not require an unnecessarily heat-resistant reactor. Further, the reaction pressure is not limited, and the operation can be performed in a pressure range of, for example, about 0.05 MPa to 5 MPa. The supply of the reaction raw material is not particularly limited as the ratio of the volume of the raw material gas to the volume of the catalyst, and for example, a space velocity of about ^{1h -1 to 50,000h -1 can be mentioned.} In that case, it can also be used as a diluted gas with an inert gas such as nitrogen, hydrogen, carbon monoxide, or carbon dioxide selected from a single gas or a mixed gas.

Further, examples of the hydrocarbon compound to be produced include aliphatic hydrocarbons and aromatic hydrocarbons, and examples of the aliphatic hydrocarbons may be those belonging to the category referred to as aliphatic hydrocarbons, for example, ethane. , Paraffins such as propane, butane and hexane; olefins such as ethylene, propylene, butene and hexene can be mentioned, and aromatic hydrocarbons are particularly limited as long as they belong to the category called aromatic hydrocarbons. However, for example, benzene, toluene, xylene, trimethylbenzene, ethylbenzene, ethyltoluene, propylbenzene, butylbenzene, naphthalene, methylnaphthalene and the like can be mentioned.

The alcohol conversion catalyst of the present invention has excellent hydrothermal resistance, coking resistance, selectivity and catalyst life, and can stably produce hydrocarbon compounds typified by aliphatic hydrocarbons and aromatic hydrocarbons over a long period of time. Since it is possible, it is expected to be industrially useful.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

The 10-membered ring-pore zeolite used in Examples and Comparative Examples was prepared based on Japanese Patent No. 60070336. The zeolite and alcohol conversion catalyst were measured by the following methods.

~ Measurement of average particle size ~
The average particle size was measured with a transmission electron microscope (hereinafter, may be referred to as TEM). For TEM, a transmission electron microscope (manufactured by JEOL Ltd., (trade name) JEM-2100, acceleration voltage 200 kV, observation magnification 30,000 times) was used, and a sample lightly crushed in a dairy pot was ultrasonically dispersed in acetone. A sample was taken as a sample for a microscope, which was dropped on a plastic support film and naturally dried. For each primary particle in the photograph, the average of the diameters in the direction perpendicular to the longest diameter and its midpoint was measured, and the average of a total of 300 particles was taken as the average particle diameter.

~ 2,4-Dimethylquinoline adsorption infrared absorption spectroscopy ~
The infrared absorption spectroscopy was measured by a transmission method using an FT-IR measuring device ((trade name) FT / IR-6700, manufactured by Nippon Spectroscopy Co., Ltd.). A spectrum was obtained after 256 integrations using an MCT detector. The sample was formed into a disc having a diameter of 13 mm and then placed in a disc holder in a quartz vacuum degassing cell, so that the sample was placed vertically on the infrared optical path. As a pretreatment of the sample, the temperature was raised to 400 ° C. at 10 ° C./min under vacuum exhaust and held for 2 hours. After cooling to 150 ° C., the infrared absorption spectrum before adsorption of 2,4-dimethylquinoline was measured. 2,4-Dimethylquinoline gas was introduced, adsorbed for 30 minutes, evacuated at 150 ° C. for 1 hour, and then the infrared absorption spectrum after adsorbing 2,4-dimethylquinoline was measured. The difference between the infrared absorption spectrum after adsorption of 2,4-dimethylquinoline and the spectrum before adsorption was taken, and the change in infrared absorption due to adsorption was measured. Of this difference spectrum, ^{the peak near 3600 cm -1 is} the peak of the absorption spectrum of 2,4-dimethylquinoline adsorbed on Bronsted acid, and after determining this area intensity, Lamber-berr's law The amount of B acid was calculated from the following formula (2).
Amount of B acid (μmol / mg) = A · S / (W · ε) (2)
(Here, A; peak area intensity of the target peak (cm ^-1 ), S; sample cross-sectional area (cm ² ), W; sample weight (mg), ε; integral extinction coefficient, 3.7 cm · μmol. ^-1 and each are shown.)
~ Pyridine adsorption infrared absorption spectroscopy measurement ~
In the above 2,4-dimethylquinoline adsorption infrared absorption spectroscopic measurement, pyridine gas was introduced and only the point of adsorption for 10 minutes was changed, and the measurement was carried out by the same apparatus and the same method.

^{However, the peak near 1545 cm -1} in the difference spectrum is used as the peak in the absorption spectrum of pyridine adsorbed on Bronsted acid, the integrated absorption coefficient is 1.67 cm · μmol ^-1 , and the amount of B acid is calculated from the above formula (2). Asked.

-Measurement of the shortest distance from the outermost side of the molded body to the center of the molded body (center of the cross section of the molded body) or the side surface of the molded body cylinder-
30 randomly selected molded particles were measured using calipers, and the average was used as the measured value.

~ Measurement of powder X-ray diffraction ~
It was measured in the atmosphere using an X-ray diffraction measuring device (manufactured by Spectris, (trade name) X'pert PRO MPD), using CuKα1 as a tube voltage of 45 kV and a tube current of 40 mA. The range of 0.04 to 5 degrees was analyzed at 0.08 degrees / step and 200 seconds / step. In addition, the background corrected by the absorption rate of the direct beam is removed.

The crystal structure was identified by visually confirming the presence or absence of peaks. As another method, a peak search program may be used. As the peak search program, a general program can be used. For example, when the measurement results of 2θ (degrees) on the horizontal axis and intensity (a.u.) on the vertical axis are smoothed by the SAVITSKY & GOLAY equation and the Sliding Polynomial filter, and then the second derivative is performed, three or more points are continuous. If there is a negative value, it can be determined that a peak exists.

~ Alcohol conversion reactor and its reaction method ~
Using the catalysts obtained in Examples and Comparative Examples, a methanol conversion reaction was carried out by the following method to evaluate the performance as a catalyst for alcohol conversion.

A fixed-bed gas-phase flow reactor having a stainless steel reaction tube (inner diameter 16 mm, length 600 mm) was used. The middle stage of the stainless steel reaction tube was filled with a molded product, pretreated by heating under dry air flow, and then the raw material was fed by a liquid feed pump. Then, a ceramic tube furnace was used for heating, and the temperature of the catalyst (mold) layer was controlled. The reaction outlet gas and the reaction solution were collected, and the gas component and the liquid component were analyzed individually using a gas chromatograph. The gas component is a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC) equipped with a TCD detector and having a filler (manufactured by Waters Corp., (trade name) PorapakQ or GL Science Co., Ltd., (trade name) MS-5A). -1700) was used for analysis. The liquid components were analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-2015) equipped with a FID detector and having a capillary column (manufactured by GL Science, Inc. (trade name) TC-1) as a separation column. ..

The reaction conditions were set as follows.

(Reaction condition)
Catalyst weight: 1.5g.
Flowing gas: Methanol 0.07 ml / min + nitrogen 40 Nml / min.
Reaction temperature: 450 ° C.
Reaction time: 29 hours.

(Pretreatment conditions)
Catalyst temperature: 450 ° C.
Flowing gas: 40 Nml / min of air.
Processing time: 2 hours.

Preparation Example 1
Atypical aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight _{of Al 2} O ₃ and SiO _{2 in the raw material composition.} In addition, the by-produced ethanol was removed by evaporation.

The composition of the raw material composition is as follows.
SiO ₂ / Al ₂ O ₃ molar ratio = 48, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H ₂ O / Si molar ratio = 10
The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixed solution. The slurry-like mixed solution after crystallization was solid-liquid separated by a centrifugal settler, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.

The obtained dry powder was dispersed in hydrochloric acid at room temperature of 1 mol / L, filtered, and then the solid particles were washed with a sufficient amount of pure water, filtered again, and dried at 100 ° C. overnight. After firing at 550 ° C. for 1 hour under air, it was treated with 30% steam at 600 ° C. for 2 hours.

The obtained powder was dispersed in hydrochloric acid at room temperature of 1 mol / L, filtered, and then the solid particles were washed with a sufficient amount of pure water and filtered again to obtain a proton-type zeolite. This zeolite is a 10-membered ring-pore zeolite having a skeleton structure of an MFI-type zeolite, and the average particle size measured by TEM was 24 nm.

To 100 parts by weight of the obtained zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 5 parts by weight of cellulose, and 40 parts by weight of pure water were added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 1.5 mm and a length of 1.0 to 7.0 mm (average length of 3.5 mm). This was dried at 100 ° C. overnight. The dried molded product was calcined at 600 ° C. for 2 hours under air flow to obtain a proton-type zeolite molded product.

Example 1
5 g of the proton-type zeolite molded product obtained in Preparation Example 1 was filled in a borosilicate glass tube having an inner diameter of 9.5 mm. Separately, 0.3 g of silver nitrate was dissolved in 25 ml of pure water to prepare a 0.05 mol / L silver nitrate aqueous solution. A circulation pump and the lower part of the glass tube were connected using a chemical-resistant polyolefin hose, and the silver nitrate aqueous solution was circulated for 2 hours in a dark place. After extracting all the silver nitrate aqueous solution and circulating 30 ml of pure water for 30 minutes, all the washing liquid was extracted and the pH was measured. Then, washing was repeated until the pH was within the range of 5 to 6. After washing, the zeolite was collected in a magnetic dish, heated to 110 ° C. at a heating rate of 10 ° C./min, and dried overnight. Subsequently, the temperature was raised to 550 ° C. at a heating rate of 2 ° C./min and calcined for 6 hours. The silver content of the obtained silver-containing zeolite molded product was 1.3 wt%.

2,4-Dimethylquinoline was adsorbed on the obtained silver-containing zeolite molded product, and the amount of B acid on the outer surface obtained from the decrease in the peak derived from OH of the zeolite B acid point of ^{3600 cm -1 was 1.8 μmol / g.} Met. Further, the amount of B acid obtained by adsorbing pyridine and increasing the peak derived from pyridine adsorbed on the zeolite B acid point of ^{1545 cm-1 was 0.05 mmol / g.} Therefore, the outer surface B acid ratio was 3.6%.

The results of the methanol conversion reaction under the above conditions using the obtained silver-containing zeolite molded product as an alcohol conversion catalyst are shown in Table 1, FIG. 1 and FIG. It was confirmed that the 29-hour average conversion rate, paraffin, olefin, and aromatic hydrocarbon yields all remained stable, and that the alcohol conversion catalyst was excellent in high hydrothermal resistance, cork resistance, and durability.

Example 2
The proton-type zeolite molded product obtained in Preparation Example 1 was subjected to ion exchange in the same manner as in Example 1 except that the amount of silver nitrate was changed to 0.2 g. The silver content of the obtained silver-containing zeolite molded product was 1.1 wt%.

2,4-Dimethylquinoline was adsorbed on the obtained silver-containing zeolite molded product, and the amount of B acid on the outer surface obtained from the decrease in the peak derived from OH of the zeolite B acid point of ^{3600 cm -1 was 3.3 μmol / g.} Met. Further, the amount of B acid obtained by adsorbing pyridine and increasing the peak derived from pyridine adsorbed on the zeolite B acid point of ^{1545 cm-1 was 0.06 mmol / g.} Therefore, the outer surface B acid ratio was 5.5%.

The results of the methanol conversion reaction under the above conditions using the obtained silver-containing zeolite molded product as an alcohol conversion catalyst are shown in Table 1, FIG. 1 and FIG. It was confirmed that the 29-hour average conversion rate, paraffin, olefin, and aromatic hydrocarbon yields all remained stable, and the catalyst was excellent in high hydrothermal resistance, cork resistance, and durability.

Comparative Example 1
Crystallization, washing, and drying of zeolite by autoclave were carried out in the same manner as in Preparation Example 1.

The obtained dry powder is calcined under air at 550 ° C., the obtained powder is dispersed in 1 mol / L hydrochloric acid at room temperature, filtered, and then the solid particles are washed with a sufficient amount of pure water and again. After filtration, it was dried at 100 ° C. overnight to obtain a proton-type zeolite. This zeolite was a 10-membered ring-pore zeolite having a skeleton structure of an MFI-type zeolite, and had an average particle size of 26 nm measured using a TEM.

To 100 parts by weight of the obtained zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 5 parts by weight of cellulose, and 40 parts by weight of pure water were added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 1.5 mm and a length of 1.0 to 7.0 mm (average length of 3.5 mm). This was dried at 100 ° C. overnight. The dried molded product was fired at 600 ° C. for 2 hours under air flow to obtain a molded product.

The obtained proton-type zeolite molded product was supported on silver by an ion exchange method. 0.3 g of silver nitrate was dissolved in 100 ml of pure water, 3 g of the above proton-type zeolite molded product was added to the aqueous solution, and the mixture was stirred at room temperature for 2 hours. After filtering with a Buchner funnel, 35 g of pure water was added, and the mixture was stirred in the same manner. After stirring with pure water a total of 3 times, the filtered zeolite molded product was dried at 110 ° C. overnight and calcined at 550 ° C. for 6 hours. The silver content of the obtained silver-containing zeolite molded product was 1.2 wt%.

2,4-Dimethylquinoline was adsorbed on the obtained silver-containing zeolite molded product, and the amount of B acid on the outer surface obtained from the decrease in the peak derived from OH of the zeolite B acid point of ^{3600 cm -1 was 10.1 μmol / g.} Met. Further, the amount of B acid obtained by adsorbing pyridine and increasing the peak derived from pyridine adsorbed on the zeolite B acid point of ^{1545 cm-1 was 0.10 mmol / g.} Therefore, the outer surface B acid ratio was 10.1%.

The results of the methanol conversion reaction under the above conditions using the obtained silver-containing zeolite molded product as a catalyst are shown in Table 2, FIG. 1 and FIG. Although the 29-hour average conversion rate and the yields of paraffin and olefin were high, the yield of aromatic hydrocarbons tended to decrease significantly due to the dealumination of zeolite. Therefore, it was confirmed that the catalyst was inferior in durability.

Comparative Example 2
The proton-type zeolite molded product obtained in Preparation Example 1 was used as a catalyst.

The amount of B acid on the outer surface obtained by adsorbing 2,4-dimethylquinoline was 3.0 μmol / g as determined from the decrease in the peak derived from OH of the zeolite B acid point of ^{3600 cm -1.} Further, the amount of B acid obtained by adsorbing pyridine and increasing the peak derived from pyridine adsorbed on the zeolite B acid point of ^{1545 cm-1 was 0.12 mmol / g.} Therefore, the outer surface B acid ratio was 2.5%.

The results of the methanol conversion reaction under the above conditions using the zeolite molded product as a catalyst are shown in Table 2, FIGS. 1 and 2. Although the 29-hour average conversion rate and the yields of paraffin and olefin were high, the yield of aromatic hydrocarbons tended to decrease significantly due to the dealumination of zeolite. Therefore, it was confirmed that the catalyst was inferior in durability.

Comparative Example 3
The proton-type zeolite molded product obtained in Preparation Example 1 was supported on silver by an impregnation method. 1.0 g of silver nitrate was dissolved in 7 ml of pure water, 15 g of the above MFI-type zeolite was added to the aqueous solution, and the mixture was immersed at room temperature for 5 minutes. The zeolite was then dried at 110 ° C. overnight and calcined at 550 ° C. for 6 hours. The silver content of the obtained silver-containing zeolite molded product was 3.8 wt%.

2,4-Dimethylquinoline was adsorbed on the obtained silver-containing zeolite molded product, and the amount of B acid on the outer surface obtained from the decrease in the peak derived from OH of the zeolite B acid point of ^{3600 cm -1 was 8.9 μmol / g.} Met. Further, the amount of B acid obtained by adsorbing pyridine and increasing the peak derived from pyridine adsorbed on the zeolite B acid point of ^{1545 cm-1 was 0.06 mmol / g.} Therefore, the outer surface B acid ratio was 14.8%.

The results of the methanol conversion reaction under the above conditions using the obtained silver-containing zeolite molded product as a catalyst are shown in Table 2, FIG. 1 and FIG. Although the 29-hour average conversion rate and the yields of paraffin and olefin were high, the yield of aromatic hydrocarbons tended to decrease significantly due to the dealumination of zeolite. Therefore, it was confirmed that the catalyst was inferior in durability.

It is a figure which showed the time change of the conversion rate in the methanol conversion reaction by the alcohol conversion catalyst obtained in Examples 1 and 2 and Comparative Examples 1, 2 and 3. It is a figure which showed the time change of the yield of an aromatic hydrocarbon in the methanol conversion reaction by the alcohol conversion catalyst obtained in Examples 1 and 2 and Comparative Examples 1, 2 and 3.

The alcohol conversion catalyst containing a 10-membered ring-pore zeolite having an average particle size of 100 nm or less and having a specific amount of outer surface Bronsted acid content and silver content of the present invention has specific stability. -It exhibits efficiency and durability, and its industrial value as a catalyst is extremely high.

Claims (8)

An alcohol containing 10-membered ring-pore zeolite having an average particle size of 100 nm or less, having an outer surface Bronsted acid content of 0.1 to 10.0 μmol / g and a silver content of 0.05 to 3 wt%. Conversion catalyst. The alcohol conversion catalyst according to claim 1, wherein the 10-membered ring-pore zeolite is of the MFI type or the MEL type. The alcohol conversion catalyst according to claim 1 or 2, further satisfying that the amount of Bronsted acid is 0.01 to 1.0 mmol / g. The alcohol conversion catalyst according to any one of claims 1 to 3, further comprising silica. The alcohol conversion catalyst according to any one of claims 1 to 4, wherein the molded product has a cylindrical shape or a cylindrical shape. The alcohol conversion catalyst according to claim 5, wherein the molded body has a cylindrical shape having a diameter of 1 to 10 mm or a molded body having a cylindrical shape having a thickness of 0.5 to 5.0 mm. The alcohol conversion catalyst according to any one of claims 1 to 6, wherein the alcohol is used for converting an alcohol into a hydrocarbon compound. A method for producing a hydrocarbon compound, which comprises contacting an alcohol raw material with an alcohol raw material to obtain a paraffin, an olefin and / or an aromatic hydrocarbon in the presence of the alcohol conversion catalyst according to any one of claims 1 to 7.

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