JPS5844412B2 - Functional material protection structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel functional substance protection structure in which a functional substance such as a catalyst or an adsorbent is protected by an outer shell.

Conventionally, functional substances such as catalysts or adsorbents that are used in the gas or liquid phase are used in powder form, used alone or mixed with a suitable binder and molded into granules, or used as a carrier. It is used by supporting it.

However, when using this type of functional substance as a powder, especially when using it in the gas phase, advanced technology is required to use the powder in a fluidized state, and losses due to fineness of the powder are high. There are many drawbacks.

Furthermore, when used in a liquid phase, there is a problem in the separation of the liquid and powder, making continuous operation difficult.

When functional substances such as catalysts and adsorbents are molded into granules and used,
This type of drawback can be solved, but when molded into granules, the catalytic ability and adsorption ability may be greatly reduced, the strength against breakage, impact, abrasion, etc. may be low, and there may be practical problems. There are many cases.

Further, even if the material has sufficient strength at the initial stage of use, the strength may gradually or suddenly decrease with use, and it may become difficult to continue operation due to powdering or the like.

Furthermore, even when a carrier is used, there are problems such as the release of the active ingredients of the functional substance, and it is often not possible to provide a fundamental solution in terms of strength.Moreover, in order to maintain the strength, a large amount of carrier is required. This is often difficult.

Solving the drawbacks caused by the pulverization of granulated catalysts and adsorbents is an extremely important issue in industrial and practical applications that use this type of functional materials, and is an extremely important issue for industrial and practical development. This is extremely important.

An object of the present invention is to provide a functional material protection structure that has high resistance to destruction, impact, abrasion, etc., and solves the industrial and practical drawbacks caused by powdering or disintegration of functional materials.

Another object of the present invention is to provide a functional material protection structure that does not break down even if the functional material changes in volume due to heat, reaction, etc. during use.

Another object of the present invention is to provide a functional material protection structure that is resistant to breakage, impact, abrasion, etc., and is a catalyst for synthesizing alkylphenols from phenols and methanol using manganese oxide as a functional material. There is something to do.

Another object of the present invention is to provide a functional substance protection structure in which adsorbents such as activated carbon, activated alumina, silica gel, molecular sieve, etc. are not scattered and a desired adsorption capacity can be obtained.

The functional material protection structure of the present invention has a granular structure in which a functional material is covered with a strong porous shell having communicating pores.

The functional substances herein include active substances such as catalysts and adsorbents, mixtures of these and inert W, and substances supported on inert substances.

The functional substance protection structure of the present invention is produced by granulating functional substances such as catalysts and adsorbents, coating the granules with aggregate for an outer shell, etc., and forming a tough outer shell with continuous pores by sintering or the like. It is manufactured by forming a porous shell.

At this time, the functional material is mixed with flammable organic powder, then covered with aggregate for the outer shell, etc., and the flammable organic material is burned during sintering, so that the functional material that covers the surface area becomes the inner core. It can be a functional material protection structure.

In addition, by coating the granulated functional material with combustible organic powder and then covering it with aggregate for the outer shell, and burning the combustible organic powder during sintering, the inner core and outer shell can be separated. A space can be formed in between.

As the functional substance, various powders or granulated catalysts and adsorbents can be used.

In particular, functional substances such as manganese oxide, which is used to synthesize alkylphenols from phenols and methanol, and activated carbon, which easily disintegrate physically and chemically during use or when the catalyst is regenerated with air. Functional substances that are easily scattered by themselves, such as molecular sieves, silica gel powder, etc., and which have difficulty in forming molding strength by themselves, can be used effectively in a stable state.

Moreover, two or more types of functional substances can be used in combination.

An example of a functional substance supported on a carrier is one in which an expensive catalyst such as platinum or palladium is used as the functional substance.

According to the present invention, there is an advantage that there is no need to use a strong dog as a carrier.

Combustible organic substances that are mixed with functional substances or used to coat the inner core made of functional substances in order to create voids between them and the outer shell include carbonized walnut powder, fibers, sawdust, cellulose-based substances, etc. Typical examples include hydrogen-based substances, polyolefins, combustible polymeric substances such as polystyrene, and the like.

This type of combustible organic material is preferably one that can be burned off at the sintering temperature during shell formation.

Note that instead of the flammable organic IN, an inorganic solid soluble in water, acid, alkali, etc. may be used, or a sublimable substance such as camphor may be used.

These pore-forming substances can be used as pore-forming substances in the outer shell.

Particularly suitable are microcrystalline cellulose and derivatives thereof, such as wheat flour and cornstarch.

As aggregate for the outer shell, fused alumina, silicon carbide, alumina, silica sand, inorganic abrasive grains such as zircon, soda glass,
Inorganic glass particles such as lead glass and silicate glass; metal particles such as iron, aluminum, copper, tin, lead, and zinc; and gun metal;
Various metal powder particles such as alloy particles of stainless steel, magnesium oxide, Portland cement, alumina cement, etc. are used.

Incidentally, the aggregate for the outer shell itself may have properties as a functional substance.

That is, when magnesium oxide is mainly used as the outer shell in the production of a catalyst for synthesizing alkylphenols, it itself acts as a catalyst at high temperatures.

Sintering only the shell aggregate at the contact points of the aggregate particles,
Some aggregates can be fused or hardened.

Examples include copper powder, glass powder, alumina cement, and Portland cement.

Many inorganic shell aggregates are difficult to sinter or harden on their own.

Therefore, it is desirable to include a binder such as clay, china clay, feldspar, glass powder, etc., which is melted or softened by heating and has the effect of sintering the aggregate particles.

That is, in many cases, the firing temperature for this sintering, fusing or hardening is in the range of about 400-1400°C.

It is desirable to include a binder that can sinter, fuse, or harden the outer shell at this temperature.

Furthermore, combustible organic substances such as walnut flour, fibers, and sawdust are mixed and coated with the aggregate, and the desired relatively large pores are formed in the outer shell by burning it out during sintering. I can do it.

Similarly, organic or inorganic granules or fibrous materials that are selectively soluble in specific acids, bases, and organic solvents are mixed into the outer shell and formed, and then the solvent is used to drain that part. Desired pores can also be obtained depending on the method.

It is desirable that this outer shell meet the following conditions.

(1) It can have sufficient strength to prevent destruction due to impact, abrasion, etc., which is necessary for practical use.

Compressive strength is expressed as the load at which a crack appears when a load is applied from the top of the object to be measured using a bookstore type hardness tester, and the compressive strength of the functional material protection structure of the present invention is determined by the It depends on the size and purpose, but preferably 3 kg or more.
Particularly preferred is one weighing 7 kg or more.

However, the required strength differs depending on the purpose of use, and it is sufficient that the strength can withstand the purpose of use.

(2) Having a large number of continuous pores that extend from the outer surface to the inner core.

A large number of continuous pores refers to pores obtained by firing a combustible material W contained in the aggregate for the outer shell, etc.
The pores are not closed or isolated as in other cases, but are intersected and continuous, and the pore size is such that gas or liquid molecules can sufficiently pass between the outer surface and the functional substance. That is, the pore diameter (measured using an Aminco porosimeter) is 0.05μ to 1000μ.
, preferably 0.5μ to 500μ, more preferably 1μ
The pores have a diameter of ~100μ and are interlaced to prevent the functional substance from coming out.

In addition to the above basic conditions, it is desirable to have an outer shell structure with large and numerous pores, and the apparent porosity (Japanese Industrial Standard JIS-R22051955 (confirmed in 1961))
(Measurement method for apparent porosity, water absorption and specific gravity of fireproofing/moth) is 20-70%, preferably 30-70%.
It is 65%.

Further, the pore volume (measured using a porosimeter manufactured by Aminco) is 0.01 to 0.7 cc/g, preferably 0.02 to 9.5 cc/g.

It also depends on the thickness of the outer shell & the required strength and pore size.

If the thickness of the outer shell is increased, the strength can be improved, but by increasing the thickness, the content of functional substances such as catalysts is relatively reduced, and the outer shell is less likely to contain fluids that should come into contact with internal functional substances. Since this will increase the flow resistance, it is desirable that the thickness be such that the desired strength can be obtained.

i.e. 5 to 1 for the internal diameter accommodating the functional material.
00%, preferably 6-50%, particularly preferably 8-2
A shell thickness of 0% is desired.

As the functional substance of the functional substance protection structure of the present invention, an active substance having a desired function, such as a catalyst or an adsorbent, is selected.

The type and amount of this functional material, the type and amount of aggregate for the outer shell, the type and amount of binder, the thickness of the outer shell, the particle size, the ratio of the functional material to the outer shell, the porosity of the outer shell, and the fineness of the outer shell. The pore diameter and pore volume can be selected as desired.

When the functional substance is relatively inexpensive, such as activated carbon or manganese oxide, and is formed into granules without using a carrier, the amount of active ingredient of the functional substance can be significantly increased.

On the other hand, if the active ingredient of the functional substance is an expensive substance and is used by being supported on a carrier or mixed, the amount of the active ingredient of the functional substance should be significantly reduced and the amount of the carrier to be supported or mixed should be increased. .

In the latter case, the carrier may be powder or disintegrating.

As mentioned above, the outer shell that protects this functional material must have a large number of communicating pores and must have sufficient strength to withstand damage caused by impact, abrasion, and the like.

The thickness of the shell is determined by the desired strength, which is influenced by the bonding forces at the points of contact between the shell aggregates used in the shell structure.

When this bonding is performed by sintering, particularly when sintering is performed using a binder that has a high bonding strength, a sufficiently high strength can be obtained even if the porosity is significantly increased.

If the strength of the outer shell is high enough, the thickness of the outer shell can be made relatively thin and the ratio of the functional substance to the outer shell can be increased.

The overall particle size is selected depending on the usage conditions of the packed column and other functional substances such as catalysts and adsorbents, but is generally about 1 to 25 mm.

The functional substance may be disintegrated into powder inside the outer shell.

Also, if the structure is such that there is a void between it and the outer shell,
This is particularly preferable since there is no fear that the outer shell will be destroyed due to a change in the volume of the functional substance.

For example, in the case of a manganese oxide catalyst, a volume change occurs during regeneration with air.

In such a case, a structure in which voids exist within the outer shell significantly increases the life of repeated reuse.

Generally, when the volume change due to heat or chemical changes in the functional material is significant, it is desirable to have voids inside the outer shell.

In addition to keeping the functional substance inside the functional substance protection structure & east outer shell of the present invention, the same or different type of functional substance may be present in the outer shell itself.

Generally, Function 'M' is added to the outer shell by impregnation and adhesion activation treatment after the outer shell is formed, and is present in a state attached to the outer shell. In this case, the outer shell itself or a part thereof may be made to be a functional material.

In particular, a catalyst protected inside the outer shell as a functional substance,
If the catalyst attached to the outer shell itself is of a different type, it can be a dual-functional catalyst, allowing for a wider operating temperature range and a fewer number of stages for multi-stage reactions compared to conventional catalysts. It becomes possible to improve selectivity.

Furthermore, a multilayer structure catalyst can be obtained by forming a plurality of outer shell layers and selecting the amount, characteristics, etc. of the catalyst present in each outer shell layer as desired.

Furthermore, even when using other functional substances such as an adsorbent, or when using different functional substances such as an adsorbent and a catalyst, this kind of functional substance protective structure having dual or multifunctional functions can be used. It can be done.

Hereinafter, a typical example of the method for manufacturing the functional substance protection structure of the present invention will be explained.

The functional material protection structure of the present invention can be manufactured by a normal granulation method.

Various methods are used to granulate the functional substance that forms the inner core.The functional substance is mixed with combustible organic substances as necessary, a sizing agent, and water, then extruded into rods using an extruder and broken. Granules of functional substances as an inner core can be made by granulating, granulating with a nine-mill machine, dish-type granulator, rotating disk-type transfer granulator, or compressing into tablets with a tablet machine. get.

The granulated product of the functional substance serving as the inner core is put into a dish-type granulator or a rotating disk-type transfer granulator and tumbled, and the mixture for the outer shell is sprinkled with atomized water as necessary. Sprinkle it in the snow to coat it while keeping it in the shade.

The raw material for the outer shell can also be coated by compression molding.

A special coating method includes a method in which the granulated material serving as the inner core is mixed into a slurry and spray-dried, but is not limited to the granulation method.

However, in order to construct an outer shell with a desired uniform thickness, it is desirable to use a granulation method using a dish-type granulator or a rotating disk-type transfer granulator.

In addition, prior to coating this raw material kneaded material for the outer shell, a combustible organic substance such as a cellulose material, sugar, polyvinyl alcohol, etc. is coated in the same manner as the coating of the raw material for the outer shell. This has the advantage of forming voids between the outer shell and the functional material, and this combustible organic material can be
When granulated by mixing with the functional material that forms the inner core, it is possible to form voids in the inner core that are effective in preventing damage to the outer shell due to changes in the volume of the functional material that forms the inner core. It also has the effect of increasing the surface area.

When the particles coated with the raw material for the outer shell are heated, the outer shell aggregate and binder are sintered, and the flammable thickener and combustible organic material are burned out, resulting in a tough structure with many communicating pores. It becomes a structure consisting of a porous outer shell, and the functional substance is activated.

Normally, it is sufficiently dried at a temperature of 200°C or less, then placed in a sagger and gradually heated in a firing furnace.From the temperature at which flammable organic substances begin to burn, the heating rate is further slowed down to remove flammable organic substances. It is heated to completely burn it out, heated further and held at a predetermined final temperature for several hours to sinter it.

Naturally, the firing conditions are selected depending on the functional material protection structure to be fired.

Note that in order to activate the functional substance, it may be desirable to carry out heat activation treatment in nitrogen, hydrogen, or other desired gas during or after the formation of the outer shell.

In addition, if the functional substance does not want to come into contact with a solvent such as water, it is possible to granulate the functional substance and coat it with sugar coating, coat this with the raw material for the outer shell, sinter it, and burn the sugar coating. This method can be used.

In addition, appropriate granulation and sintering conditions can be selected as desired.

Another example is a catalyst in which a mixture catalyst of manganese dioxide and ferric oxide is granulated, coated with alumina powder and a glass binder, and fired to form an outer shell.

This type of catalyst is useful as an oxidation catalyst for carbon monoxide, hydrocarbons, etc. in internal combustion engine exhaust gas.

Examples of the functional substance protection structure of the present invention, its manufacturing method, a method of manufacturing alkylphenols using the same, and oxidation of hydrocarbons (hexane) in exhaust gas will be shown below along with comparative examples.

Reference Example l Electrolytic manganese dioxide is mixed with io parts of manganese oxide heat-treated at 1000°C, 5 parts of wheat flour, and a small amount of water, and the mixture is put into a rotating disk-type transfer granulator to form a spray. Sprinkle water to make granules.

Atomized water is sprinkled on the granules, and at the same time a mixed substance is sprinkled on them to form spherical objects of a predetermined size in a snowball-like manner.

This completes the granulation of the inner core, and then molten alumina (120
80 parts of mesh), 15 parts of china clay as a binder, 5 parts of feldspar, 5 parts of wheat flour, and 20 parts of water were simultaneously kneaded to form a kneaded material for the outer shell. It was placed in a transfer granulator and sprinkled with atomized water and a kneaded material for the outer shell to coat it, and when it had been coated to a predetermined thickness, it was taken out and dried at 80 to 120°C. After that, put it in a sagger and gradually heat it in a kiln.
The temperature is heated particularly slowly from 50°C to 600°C, and then the temperature is raised to 1200°C, which is then held at 1200°C for 3 hours and fired to form a strong and porous outer shell as described above. Make it.

The functional material protection structure obtained in this way is spherical,
The particle size of the functional material in the inner core is manganese oxide, and the outer shell is porous alumina with a thickness of 0.5 mm, and the total particle size is 6.0 mm.

The physical properties of this functional material protection structure are as follows.

However, the pore diameter, pore volume, and apparent porosity of the outer shell are measured by destroying the outer shell of the extracted sample of the product.
I did what was there.

The same applies to the following experimental examples. A methylation reaction of phenol with methanol was carried out using the functional material protection structure thus prepared.

(The effectiveness of this catalyst on manganese oxides was disclosed in a patent application filed in 1973.
-62682, Japanese Patent Publication No. 51-11101, German Publication No. A2135602, publication date December 7, 1972.

) The reaction conditions were: phenol partial pressure 0.0803 atm, methanol partial pressure 0.803 atm, nitrogen 0, 1164a
At tm, the space velocity is 442 (hours) ~ 1 reaction rate 400°C
It is.

4 hours after the start of the reaction, the phenol conversion rate was 96.7%, 2.
Results were obtained in which the yield of 6-xylenol was 93.4% and the yield of O-cresol was 3.3%.

The compressive strength of this functional material protection structure after 50 hours of reaction was 10.0 kg.

No decrease in strength was observed even after further reaction.

As described above, this functional substance protective structure had sufficient strength and activity for practical use.

In addition, the manganese oxide in the inner core was powdered, but not scattered to the outside.

Comparative Example 1 The results of granulating only manganese oxide without forming an outer shell and using it in a reaction will be described below.

Manganese oxide, which had been subjected to the same heat treatment as in Reference Example 1, was molded into a cylinder with a diameter of 5 mm and a height of 51 rLTIt using a tablet molding machine, and fired at 1200° C. for 3 hours.

Using this catalyst, a reaction was carried out under the same conditions as in Reference Example 1.

5 hours after the start of the reaction, the phenol conversion rate was 98.5%, 2.
6-xylenol retention rate 86.0%, O-cresol yield 1
2.5% was obtained.

The compressive strength of the zero solvent before and after the reaction is shown below.

In other words, if manganese oxide alone is used, it undergoes ring breakage during the reaction and becomes powder, which is inconvenient for small to medium-sized practical applications, but when the outer shell is added, even if the inner core becomes powder, the strength is maintained by the outer shell.
In addition, there is no scattering of powder, which is very convenient from a practical standpoint.

Reference Example 2 60 parts of molten alumina (100m box), 40 parts of glass powder (all 400mesh) as a binder, 5 parts of wheat flour and 15 parts of water were kneaded at the same time, and this kneaded product was used as a kneaded product for the outer shell. Then, the inner core granules of Reference Example 1 were placed in a rotating disk-type transfer granulator, and sprinkled with atomized water and the kneaded material for the outer shell to coat the inner core granules.

After being coated to a predetermined thickness, it is taken out, dried at 80 to 120°C, placed in a sagger pot, and gradually heated in a kiln for 25 minutes.
From 0°C to 600°C, heat slowly to 75°C.
The temperature is raised to 0°C, and the temperature is maintained at 750°C for 3 hours to make the outer shell strong and porous.

The functional material protection structure obtained in this way is spherical, the functional material in the inner core is powdered manganese oxide, and the outer shell is made of porous alumina glass with a thickness of 0.711 LIIL. The particle size is 6.4 mm.

This functional material protection structure was used in the same reaction as in Reference Example 1.

4 hours after the start of the reaction, the phenol conversion rate was 82.3%, 2.
6-xylenol yield 75.1%, 0-cresol yield 7
．． Obtained 2%.

The compressive strength before and after the reaction is shown below.

The following example shows an example in which the present functional material protection structure is used as a catalyst for purifying automobile exhaust gas.

Many catalysts have been known for the past as automobile exhaust gas purification catalysts, especially catalysts that completely burn carbon monoxide and hydrocarbons in exhaust gas, but most of them use silica-alumina, gamma-alumina, etc. as a carrier. It uses a porous material, and when used in an automobile, it has the disadvantage that its strength is significantly reduced due to vibrations, abrasion, etc.

By using the method of the present invention, the outer shell can be made into a strong structure, so it is possible to eliminate concerns about strength as much as possible.

Reference Example 3 Aqueous ammonia was added dropwise to a mixed aqueous solution of nitrates in an amount of 45 parts as Mn203 and 55 parts as Fe2O3, and 100 parts of the powder was prepared by co-precipitation and drying and then calcined at 500°C. Avicel powder (manufactured by Asahi Castle) 5
and a small amount of water, knead and form into spheres of a predetermined size in the same manner as in Reference Example 1.

This is the inner core. Next, fused alumina (120mes
h), 40 parts of boric acid-based glass powder (all 400 mesh) as a binder, 5 parts of wheat flour, and 15 parts of water are simultaneously kneaded, and this kneaded product is used as a kneaded product for the outer shell. .

In the same manner as in Reference Example 1, the inner core granules are placed in a rotating disk-type transfer granulator, and the inner core is coated with the outer shell mixture while sprinkling water in the form of a spray.

After being coated to a predetermined thickness, it was taken out, dried at 80 to 120°C, placed in a sagger pot and gradually heated in a kiln, and heated to 200°C.
From ℃ to 500℃, the temperature should be increased especially slowly to 500℃.
It is held at ℃ for 3 hours and fired to make the outer shell strong and porous.

In the functional material protection structure obtained in this manner, the functional material in the inner core is made of iron and manganese oxides with a particle size of about 5 mm, and the outer shell is made of alumina and glass with a thickness of 0.71 parts m. .

This functional material protection structure was used in a complete oxidation reaction of hexane as an example of an internal combustion engine exhaust gas oxidation reaction.

The reaction conditions are as follows.

Hexane 1%, air 99% 5V = 5000 (hours) -1 Carbon dioxide generation begins at normal pressure catalyst bed temperature 155℃, 23
At 0° C., 100% of the hexane fed was converted to carbon dioxide.

The compressive strength of this catalyst before and after the reaction is as follows.

Although the reaction was conducted intermittently for 500 hours, no decrease in strength was observed.

Next, this functional material protection structure was loaded into a car for 30 days (driving 974 km), and the compressive strength was 13.0.
kg, no decrease in strength was observed, and there was also a slight decrease in weight.

The following example is one that has a void between the inner core and the outer shell.

Example 1 The materials are the same as those in Reference Example 1, but before coating the raw material for the outer shell, 50 parts of walnut powder (through 100 mesh), 20 parts of wheat flour, 10 parts of cornstarch, and 3 parts of water were added to the surface of the inner core.
The material was kneaded with 0 parts, and was coated to a predetermined thickness in the same manner as for coating the raw material for the outer shell, and then the raw material for the outer shell was coated on this.

After drying, the three-layered structure obtained in this way was placed in a sagger pot, and fired at the same heating method and heating temperature as in Reference Example 1. .23 mr
A functional material protection structure having a void in the middle of tt, an outer shell thickness of 0.64 mm, and a total particle size of 7.24 mm was obtained.

When this product was used in the same reaction as in Reference Example 1, the phenol conversion rate was 98.0%, the 2.6-xylenol yield was 96.0%, and the O-cresol yield was 2.0% at a reaction temperature of 400°C.
I got %.

After 200 hours of reaction time, a decrease in activity was observed, so the catalyst was regenerated by passing air through the catalyst layer at a temperature of 500° C. and a space velocity of 3000 (hour) −1 for 3 hours.

Thereafter, it was used for a further 200 hours in the same reaction as in Reference Example 1,
The above catalyst regeneration was repeated seven times.

When the catalyst with a total reaction time of 1,600 hours was extracted, the catalyst was not destroyed at all and remained in its original shape.
The compressive strength also only increased from the initial 14.4 kg to 12.5 kg.

The following example describes the improved product selectivity achieved by the functional substance protection structure of the present invention.

In the reaction of phenol and methanol, O-cresol is first produced, which then becomes 2.6-xylenol, but when a functional material protection structure is used in this reaction,
The selectivity of 2.6 xylenol is improved.

This is probably due to the rate at which phenol that reaches the manganese oxide catalyst in the inner core reacts, becomes 0-cresol, leaves the manganese oxide catalyst and leaves the gas phase, and then re-adsorbs and reacts because the escape route is narrow. This seems to be because there are more.

This tendency is further exacerbated when the pore diameter of the outer shell is reduced or the thickness is increased.

This is shown by the magnitude of the 2.6-xylenol yield at the same phenol conversion rate when using a functional material protection structure and a regular shaped catalyst, and this effect is particularly noticeable at low conversion rates. be.

The functional material protection structure used in Reference Example 2 had a phenol conversion rate of 82.3%, a 2.6-xylenol yield of 75.1%, and an O-cresol yield of 7.2%. In the molded product of manganese oxide shown in the example, the reaction temperature was 4
00℃, LH8V=2.61゜MeOH/PhOH=1
Under conditions of 0 (molar ratio), when the phenol conversion rate is 82.0%, the yield of 2,6-xylenol is 50% and the yield of 0-cresol is 32%.

Next, we will show an example in which alumina cement is used as the raw material for the outer shell.

Reference example 4 Create an inner core of manganese oxide in the same manner as in reference example 1,
13 parts of water are sufficiently kneaded with 100 parts of alumina cement, and the mixture is coated on the inner core as in Reference Example 1.

This was left in the shade for two days and nights, and after making sure that the alumina cement in the outer shell was sufficiently hardened, it was placed in a sagger and heated to 620°C in a firing furnace at a rate of about 00°C/hour. After being held at 620° C. for 3 hours, it is cooled in the furnace.

The functional material protection structure thus created was spherical, the manganese oxide in the inner core was in the form of powder, and the outer shell was porous alumina cement with a thickness of 0.8 cm, and the overall particle size was 6.6 cm. .

The physical properties of this functional material protection structure are as follows.

When this functional substance protection structure was used in the same reaction as in Reference Example 1, the following results were obtained, and f was 31% in phenol conversion at a reaction temperature of 410°C, and a yield of 2.6-xylenol of 27%.
%, and the O-cresol yield was 4%.

Next, we will show an example of one with an outer shell made of diatomaceous earth.

Reference example 5 Create an inner core of manganese oxide in the same manner as in reference example 1,
70 parts of water are added to 100 parts of diatomaceous earth, thoroughly kneaded, and coated on the inner core in the same manner as in Reference Example 1.

This is sufficiently dried at 80 to 120°C, placed in a sagger, placed in a firing furnace, raised to 100°C at a rate of about 00°C/hour, held at 1000°C for 3 hours, and cooled in the furnace.

The functional material protection structure thus created is spherical, with an inner core made of manganese oxide with a particle size of 5 mm, and an outer shell with a thickness of 0.5 mm.
It is made of diatomaceous earth with 6mm pores.

The physical properties of this functional material protection structure are as follows.

When this functional material protection structure was used in the same reaction as in Reference Example 1, the reaction was as follows.

At a reaction temperature of 410°C, phenol conversion rate was 90%, 2.6
-Xylenol yield 83.0%, 0-cresol yield 7
%Met.

Next, an example will be shown in which the communicating pores in the outer shell have a large pore diameter.

Reference Example 6 In the same manner as Reference Example 1, an inner core of manganese oxide was made, and 85 parts of molten alumina (80 mesh) and 1 part of china clay were added.
2 parts of feldspar, 6 parts of walnut powder (60 to 100 meshO), 5 parts of wheat flour, 3 parts of Avicel powder (manufactured by Asahi Kasei), and 10 parts of water were sufficiently kneaded and coated as in Reference Example 1.

This was sufficiently dried at 80 to 120°C, placed in a sagger and heated to 1200°C at a heating rate of 100°C/hour in a firing furnace.
Hold at 1200°C for 3 hours and cool in the oven.

The functional material protection structure thus created is spherical, and the functional material in the inner core is manganese oxide with a particle size of 51rLrIL.
The outer shell is made of porous alumina and has a thickness of 1.01r111L.

The physical properties of this functional material protection structure are as follows.

When this functional substance protection structure was used in the same reaction as in Reference Example 1, the following results were obtained.

Phenol conversion rate 84.5% at reaction temperature 410°C, 2.
6-xylenol yield 73.5%, 0-cresol 11%
Met.

Comparative Example 2 The catalyst used in Reference Example 6 was used in the reaction in the same manner as in Example 1.
When the catalyst was taken out after a total reaction time of 1,600 hours after repeated use for 1,600 hours, it was found that the outer shell of 16.3% of the entire catalyst had been destroyed.

Example 2 An inner core of manganese oxide was made in the same manner as in Example 1,
Walnut powder (through 100 mesh) on the surface of this inner core
50 parts, 20 parts of wheat flour, 10 parts of cornstarch, 30 parts of water.
The material was kneaded in the same manner as in Reference Example 6, and was coated to a predetermined thickness in the same manner as the raw material for the outer shell was coated, and then the same outer shell material as in Reference Example 6 was coated in the same manner as in Reference Example 6, and fired. .

The functional substance protection structure thus obtained is porous alumina, which is made of manganese oxide with a particle size of 5 mm in the inner core, has a void of 0.2 mm, and has an outer shell thickness of 1.0 mm.

This catalyst was used in the same reaction as in Example 1, and the reaction and catalyst regeneration were repeated in the same manner as in Example 1. When the catalyst was taken out after a total reaction time of 1600 hours, no destruction of the outer shell was observed. The breaking strength of the catalyst was also the same as the initial 11.7 kg.
The weight was only 10.2 kg.

Next, we will show an example where metallic copper is used for the outer shell.

Reference example 7 Create an inner core of manganese oxide in the same manner as in reference example 1,
100 parts of copper powder (80-150 mesh), 3 parts of Avicel powder, and 10 parts of water were thoroughly kneaded and coated as in Reference Example 1.

After that, it is sufficiently dried at 80 to 120°C and placed in a non-porous porcelain crucible (inner diameter 800 mm, depth 150 mm, wall thickness 5
mm), put the lid on, and seal the gap between the lid and the crucible with clay. After the clay has dried sufficiently, heat it in an electric furnace at a heating rate of 100°C/hour to 1000°C.
Hold at 0° C. for 3 hours and cool in the furnace.

After cooling, remove the clay, remove the lid, take it out, and wash it with water to remove anything stuck to the surface.

After that, it is sufficiently dried at 80 to 120°C.

The functional material protection structure thus created is spherical, the functional material in the inner core is manganese oxide with a particle size of 51n11L, and the outer shell is porous copper with a thickness of 0.8mm.

The physical properties of this functional material protection structure are as follows.

When this functional material protection structure was used in the same reaction as in Reference Example 1, the reaction was as follows.

At a reaction temperature of 450°C, the phenol conversion rate was 39%, the 2.6-xylenol yield was 16%, and the O-cresol yield was 23%.

Claims (1)

[Claims] 1. A functional material protection structure in which voids are formed between an inner core of a functional material of a catalyst or adsorbent and a porous outer shell having communicating pores.