JP4287295B2 - Microsphere zeolite fuel treatment agent - Google Patents

Description

  The present invention relates to a microspherical zeolite fuel treatment agent having a high compressive strength even when the pore volume is large or the particle diameter is small, and having excellent fluidity and wear resistance.

In recent years, fuel cells have attracted attention as power generation systems that use clean hydrogen as an energy source and do not generate greenhouse gases such as CO _{2 with} no pollution. Such fuel cells have been fully developed and researched for use in fixed facilities such as homes and offices, and mobile facilities such as automobiles.

  Examples of the fuel used in the fuel cell include hydrocarbon fuels such as natural gas, LP gas, city gas, alcohol, gasoline, kerosene, light oil, and other biomass.

  Such hydrocarbon fuel is first converted into hydrogen gas and CO gas by reactions such as steam reforming and partial oxidation, and the hydrogen gas is removed by poisoning the anode described later to remove the CO gas that lowers the power generation performance. Get. This hydrogen is supplied to the anode, dissociated into hydrogen ions and electrons by the metal catalyst of the anode, the electrons flow to the cathode while working through an external circuit, and the hydrogen ions diffuse to the cathode and flow to the cathode. The electrons, hydrogen ions, and oxygen supplied to the cathode are converted into water and diffused into the electrolyte membrane. That is, it is a mechanism for taking out an electric current in the process of supplying water with oxygen and hydrogen derived from fuel gas.

  In the CO gas removal step, a noble metal such as Ru, Pt, Ni, or Fe or a metal catalyst is usually used. However, if the sulfur component is present even in the order of ppm in the fuel, the CO removal catalyst is poisoned, the activity is lowered, and the performance of the fuel cell is lowered.

  For this reason, when the sulfur component is contained in the fuel used for a fuel cell, it is desired to remove sulfur by a hydrodesulfurization method (usually under high temperature and hydrogen pressure). However, this method requires a separate step of removing by-produced hydrogen sulfide. Further, the lower the sulfur content in the fuel oil, the higher the hydrodesulfurization cost (equipment, running cost, etc.) for removing the sulfur content to a predetermined level, and there is a problem in economy.

When using LP gas, city gas, etc. for the fuel cell, sulfur compounds such as sulfides, thiophenes, or mercaptans are added as odorants from the viewpoint of safety in use as ordinary fuel. ing. Specifically, as sulfides, dimethyl sulfide (abbreviated as DMS in the present specification), ethyl methyl sulfide or diethyl sulfide, etc., thiophenes as tetrahydrothiophene (THT), etc., mercaptans as tertiary butyl mercaptan (same as above) , Abbreviated as TBM), isopropyl mercaptan, normal propyl mercaptan, tertiary amyl mercaptan, tertiary hebutyl mercaptan, methyl mercaptan, ethyl mercaptan and the like. DMS, THT and TBM are often used as odorants that are generally added.
Not limited to species, two or more species are added (for example, most of the city gas in the metropolitan area currently has DMS and TBM added), and their concentrations are several ppm.

  Therefore, even when LP gas, city gas, or the like is used for a fuel cell, it is necessary to remove this sulfur compound or the sulfur compound contained therein before use.

As such an adsorbent for removing sulfur compounds in fuel gas, Japanese Patent Application Laid-Open No. 2002-66313 (Patent Document 1) discloses a material in which silver is supported on Na-Y zeolite by ion exchange. .

  By the way, as a sulfur compound remover for such fuel cells, a pellet-like treatment agent has been studied, but the pellet may be damaged and worn and pulverized, and the activity and adsorption performance of the treatment agent. However, there are problems such as insufficient durability, damage or abrasion during filling, powdering, difficulty in uniformly filling, and low filling efficiency and packing density.

  It is well known that zeolite (crystalline aluminosilicate) itself is industrially used as an adsorbent, a catalyst, a catalyst carrier and the like. Synthetic zeolite is usually obtained as particles having a particle size on the order of submicron to several tens of microns. The fine powder zeolite is rarely used as it is, and in many cases, it is formed into a pellet shape, a spherical shape or the like.

  However, it is often difficult to form zeolite alone, and it is usually formed by adding a binder (binding material). For example, in patent document 1, it shape | molds into a pellet using an alumina binder.

  The size and shape of the zeolite compact is appropriately selected depending on the purpose of use, conditions, etc., but the pellets may be crushed due to breakage or abrasion of the pellets, and it may be difficult to uniformly fill them. There were cases where there were problems such as low filling efficiency.

  For this reason, if a spherical shape with rounded pellets is used as a shape that changes into a pellet shape, the edge will not be damaged or worn and powdered, and the filling efficiency can be increased. It was thought.

As a method for forming millimeter-order spherical particles using zeolite, a method disclosed in JP-A-6-64916 (Patent Document 2) is known. In this publication, a) granulation core particles composed of a zeolite and an inorganic binder are charged into a rolling granulator, and the moisture is adjusted in advance. B) a zeolite fine powder and an inorganic binder. A method of obtaining a spherical zeolite compact by supplying granulated fine powder at a constant rate and adhering the fine powder for granulation to core particles as a granulating medium is disclosed.
JP 2002-66313 A JP-A-6-64916

  However, it has been difficult to obtain a zeolite molded body that is a spherical molded body and has sufficient strength, wearability, high bulk specific gravity, and the like. In particular, a fine zeolite compact excellent in diffusibility and the like is difficult to obtain, and even if it is obtained, there is a problem in economical efficiency such as low yield and production capacity.

In the method disclosed in Patent Document 2,
1) It is necessary to prepare and use dense particles as core particles,
2) If the ratio of the desired product particle size to the core particle is too large, the particle size distribution will be broadened.
3) For this reason, the yield decreases when classified,
4) In order to obtain the desired large particles when the ratio of the size of the product particles to the core particles is small, the particles are originally excellent in sphericity, uniform particle size distribution, etc. It is required to produce core particles having other particle sizes and other performances.

  However, it has been difficult to obtain such core particles.

  Further, even when a spherical molded body is obtained as described above, the extrusion granulation method or the compression molding method is used because the fine powder for granulation is attached to the granulation core particles as a granulation medium. If the particle strength is not obtained, and the pore volume is increased or the size of the molded product is reduced, the compressive strength and wear resistance of the particles are reduced, and there are restrictions on applications and use conditions. .

  As a result of intensive studies on a processing agent such as a fuel gas composed of a spherical molded body, the present inventors have determined that the average particle diameter of the molded body, the pore volume of specific pores, and the index defined by the average compressive strength ( By controlling the compressive strength index to a specific range, it is possible to obtain a microspherical zeolite molded article excellent in compressive strength, wear resistance, etc. If this molded article is used as a fuel processing agent, pellets with a high bulk specific gravity are obtained. The filling amount can be larger than that of the shape. In addition, the inventors have found that the differential pressure of the filling container does not increase, and have completed the present invention. Further, when producing a fuel treatment agent, a powder mixture of zeolite having a predetermined amount of water, a binder and water is prepared, and formed into pellets with an extrusion molding machine. As a result, it was found that the fuel treatment agent was obtained in the previous period, and the present invention was completed.

That is, the microspherical zeolite fuel treatment agent according to the present invention is
It consists of a zeolite and a binder, the average particle diameter (D) is in the range of 0.3 to 5 mm, and the pore volume (PV) in the range of the pore diameter of 30 to 500 nm is 0.1 to 0.6 ml / g. Zeolite compacts in the range, the average compressive strength (N) is in the range of 2 to 30 N (Newton), and the average compressive strength index (C) represented by the following formula is in the range of 1.0 to 5,
It is characterized in that any one of ions, metals, and metal oxides of one or more elements selected from the IB group, VIII group, and lanthanide group of the periodic table are supported.
C = N x PV / D
The zeolite content is preferably in the range of 60 to 98% by weight, and the binder content is preferably in the range of 2 to 40% by weight.

  As the binder, alumina is preferable.

The spherical coefficient (D _L ) / (D _S ) is preferably in the range of 1 to 1.5. (D _L : major axis, D _S : minor axis)

  According to the present invention, it comprises zeolite and a binder, and has a high compressive strength and excellent wear resistance even when the pore volume is large or the particle size is small, and the spherical coefficient is close to 1, and the particle size distribution is To provide a microsphere zeolite fuel treatment agent that is uniform and has a large effective treatment surface of zeolite, further suppresses pulverization, is excellent in fluidity, and can be packed at high density, and thus has excellent treatment capacity. Can do.

  First, each component which comprises the fuel processing agent of this invention is demonstrated.

Zeolite There are no particular limitations on the type of zeolite used in the present invention, and zeolites that are usually used as adsorbents, catalysts, catalyst carriers, and the like can be used. For example, A type zeolite, faujasite type zeolite (X type, Y type zeolite), L type zeolite, mordenite type zeolite, MFI type zeolite (ZSM-5 type zeolite), β type zeolite and the like can be used.

  Such a zeolite preferably has a particle size in the range of 0.01 to 30 μm, preferably 0.1 to 20 μm. If the particle diameter is in the above range, even aggregated particles (that is, secondary particles) can be used. However, it is preferable to use as monodispersed (dispersed in primary particles) as much as possible.

Note that it is difficult to obtain a zeolite having a particle size of less than 0.01 μm, and if the particle size of the zeolite exceeds 30 μm, the compressive strength and wear resistance may be insufficient.

  The zeolite used in the present invention is preferably a faujasite type zeolite.

Binder The fuel treating agent of the present invention contains a binder together with zeolite.

  The binder is present between the zeolite particles to increase the plasticity at the time of molding to improve the moldability, and to increase the compressive strength and abrasion resistance of the obtained microspherical zeolite fuel treatment agent.

  Examples of the binder include clay minerals such as kaolin, montmorillonite, bentonite, allophane, and sepiolite, oxide fine particles such as alumina, silica, zirconia, titania, silica / alumina, silica / zirconia, and composite oxide fine particles.

  Such a binder preferably has a particle size in the range of about 10 nm to 5 μm, and preferably smaller than the particle size of the zeolite used. Further, the shape is not particularly limited, and may be any of spherical, fibrous, and irregular shapes.

  Further, for alumina, silica, silica / alumina, etc., it is desirable that these fine particles are used as a sol dispersed in an appropriate dispersion medium because they can be uniformly dispersed.

  Among the binders used in the present invention, fibrous binders such as bentonite and alumina are excellent in moldability. Therefore, they have a uniform particle size distribution, are spherical, and are microspherical zeolite fuel treated with excellent strength and wear. An agent can be obtained. In particular, the fibrous alumina binder has a large pore volume, excellent wear resistance, and a microspherical zeolite fuel treating agent having excellent compressive strength even when the particle diameter is small.

  When a fibrous alumina binder is used as the binder, the alumina fine particles preferably have a particle diameter (here, the length of fibrous primary particles) in the range of about 3 to 100 nm, more preferably 5 to 50 nm. . At this time, it is preferable to use a sol in which alumina fine particles are dispersed as the alumina fine particles.

Metal component In the fuel treatment agent according to the present invention, one or more elements selected from the group IB, group VIII, and lanthanide group of the periodic table are supported on the zeolite mainly in the zeolite. Has been. Specific examples include Cu, Ag, Au, Co, Rh, Ni, Pd, Pt, La, and Ce.

These function as processing components for removing sulfur components in the fuel. Among these, faujasite type zeolite containing any of Ag ions, metals, and oxides is suitable for removing sulfur in fuel.

  The supported substance may be an ion, a simple metal, an oxide, or any of them. If ion exchange is performed with a salt, ions are supported, and if the salt is reduced, a simple metal or oxide is supported. Examples of the metal salt include copper nitrate, silver nitrate, chloroauric acid, ferrous chloride, ferric chloride, cobalt chloride, nickel nitrate, palladium chloride, chloroplatinic acid, lanthanum chloride, cerium nitrate and the like.

Microspherical zeolite fuel treating agent The microspherical zeolite fuel treating agent according to the present invention comprises the above zeolite and a binder, and has an average particle diameter (D) in the range of 0.3 to 5 mm and a pore diameter of 30 to 500 nm. The range of pore volume (PV) is in the range of 0.1 to 0.6 ml / g, the average compressive strength (N) is in the range of 2 to 30 N (Newton), and the average compressive strength represented by the following formula Zeolite compacts having an index (C) in the range of 1.0 to 5,
Any one of ions, metals, and metal oxides of one or more elements selected from the IB group, VIII group, and lanthanide group of the periodic table are supported.
C = N x PV / D
The zeolite content in the microspherical zeolite fuel treatment agent of the present invention is preferably in the range of 60 to 98% by weight, more preferably 75 to 95% by weight, and the binder content is 2 to 40% by weight, Is preferably in the range of 5 to 25% by weight.

  When the content of the zeolite in the microspherical zeolite fuel treatment agent is less than 60% by weight, the amount of zeolite is small and the sulfur removal performance is insufficient.

  When the content of zeolite in the microspherical zeolite fuel treatment agent exceeds 98% by weight, sufficient compressive strength and wear resistance cannot be obtained due to the small amount of binder.

  Moreover, when the content of the binder in the microspherical zeolite fuel treatment agent is less than 2% by weight, sufficient compression strength and wear resistance cannot be obtained because the binder is small.

  If the content of the binder in the microspherical zeolite fuel treatment agent exceeds 60% by weight, the effect as a treatment agent may be hindered due to too much binder depending on the type of binder, and the compressive strength There is no further improvement in wear resistance.

  The microspherical zeolite fuel treating agent according to the present invention preferably has an average particle diameter (D) of 0.3 to 5 mm, more preferably 0.5 to 3 mm.

When the average particle diameter (D) of the microspherical zeolite fuel treatment agent is less than the above range, the pore diameter of the die of the extrusion molding machine is small, so that it cannot be extruded, and thus it is difficult to produce.

When the average particle diameter (D) of the microspherical zeolite fuel treatment agent exceeds 5 mm, such a large spherical molded body can be formed by other methods without depending on the method of the present invention, or the packing density of the treatment agent Therefore, the ability to know is inferior to that of the microspherical zeolite fuel treating agent having a particle diameter in the above range.

  The microspherical zeolite fuel treatment agent has a pore volume (PV) in the range of 30 to 500 nm in the range of 0.1 to 0.6 ml / g, and further in the range of 0.2 to 0.5 ml / g. Is preferred.

When the pore volume (PV) in the range of the pore diameter of the microspherical zeolite fuel treatment agent in the range of 30 to 500 nm is less than the above range, the zeolite is not effectively used and the treatment capacity tends to be insufficient.

  When the pore volume (PV) in which the pore diameter of the microspherical zeolite fuel treating agent is in the range of 30 to 500 nm exceeds the above range, the compressive strength of the treating agent may be lowered and the wear resistance may be lowered.

The above pore volume in the present invention is measured by a pore distribution measuring device (manufactured by QUANTA CHROME: AUTOSCAN-60 POROSOMETER, mercury contact angle 130 ° C., mercury surface tension 473 Dyn / cm ² , measurement range “high pressure”). Can be measured.

  The microspherical zeolite fuel treatment agent preferably has a bulk specific gravity (CBD) in the range of 0.5 to 1.5 g / cc, more preferably in the range of 0.6 to 1.2 g / cc.

  When the bulk specific gravity (CBD) is less than the above lower limit, the pore volume is large and the particle strength may be insufficient, and the amount of processing agent that can be packed in a fixed-volume processing tower during processing cannot be increased. In some cases, the processing capacity may decrease.

  If the bulk specific gravity (CBD) exceeds the above upper limit, the pore volume becomes small, and the processing capacity becomes insufficient.

  The bulk specific gravity in the present invention is the weight (g) of the filled processing agent after filling the 100 cc graduated cylinder with about 100 cc of the microspherical zeolite fuel processing agent, measuring the volume of the processing agent after moderately vibrating. Is divided by the volume of the treatment agent.

The microspherical zeolite fuel treatment agent preferably has an abrasion resistance of 0.6% by weight or less, more preferably 0.3% by weight or less. Abrasion resistance can be measured based on a wear strength measurement method (JIS K1464).

  When the amount is large, the wear resistance is small, and powder may be pulverized when the processing agent is transported or filled, resulting in a differential pressure in the filled container, which may result in insufficient fuel processing.

The average compressive strength (N) of the microspherical zeolite fuel treatment agent according to the present invention is preferably in the range of 2 to 30 N (Newton), more preferably 4 to 20 N.

If the average compressive strength (N) of the microspherical zeolite fuel treatment agent is less than 2N, it will break when it is filled or withdrawn when used, and depending on the conditions of use, a differential pressure may occur in the filled container, resulting in a reaction result. It becomes difficult to use repeatedly.

It is difficult to obtain a fine spherical zeolite fuel treating agent having a high compressive strength when the average compressive strength (N) of the fine spherical zeolite fuel treating agent exceeds 30N.

The average compressive strength (N) used in the present invention was determined by measuring the compressive strength of 20 microspherical zeolite fuel treatment agents using a Kiyama hardness tester (manufactured by Fujiwara Seisakusho).

The microspherical zeolite fuel treating agent according to the present invention has N, PV, D in the above-described range, and a compressive strength index (C) represented by the following formula is 1.0 to 5, preferably 1.5. It is in the range of 5.
C = N x PV / D
This compressive strength index (C) is obtained by calculating the average compressive strength (N) of the microspherical zeolite fuel treating agent, multiplying this by the pore volume (PV), and dividing by the average particle diameter (D).

  Usually, since the compressive strength is proportional to the particle diameter and inversely proportional to the pore volume, the compressive strength index (C) means a compressive strength independent of the particle diameter and pore volume.

  A molded article having such a compressive strength index in the above range has high compressive strength and excellent wear resistance even when the pore volume is large or the particle diameter is small, and the particle size distribution is uniform. Therefore, the effective area of the microspherical zeolite fuel treatment agent is high, pulverization is suppressed, fluidity is excellent, and high density packing can be performed. For this reason, the treatment capacity of the fuel treatment agent is very high.

  If the compressive strength index (C) of the microspherical zeolite fuel treatment agent is less than 1.0, it will be easily damaged when filled or withdrawn regardless of the particle size. A differential pressure is generated in the container, resulting in a decrease in reaction results or difficulty in repeated use.

It is difficult to obtain a microspherical zeolite fuel treating agent having a high compressive strength index when the compressive strength index (C) of the microspherical zeolite fuel treating agent exceeds 5.

  The ratio of the major axis (DL) to the minor axis (DS) of the microspherical zeolite fuel treatment agent (spherical coefficient (DL) / (DS) is 1 to 2, further 1 to 1.5, especially 1 to 1.2. Those in this range have a high sphericity and can be filled with a high degree of filling.The spherical shape referred to in the present invention does not necessarily need to be a true spherical shape, and has moderate fluidity. It is sufficient that the shape has no curvature and a curvature so that powdering does not occur.

  When the sphericity coefficient exceeds 2, the packing density is lowered and the reproducibility of the filling may be inferior. For this reason, the performance may not be sufficiently exhibited or the reproducibility may be inferior. The body effect may not be obtained sufficiently.

  The average particle diameter and spherical coefficient in the present invention are obtained by taking an optical photograph of particles, obtaining the long and short diameters of the particles with a caliper, and determining the average value as the particle diameter. The value was defined as the average particle diameter (D), and the average value of the ratio between the long diameter and the short diameter was defined as the spherical coefficient (DL) / (DS).

  In the microspherical zeolite fuel treatment agent according to the present invention, the proportion of particles having a particle size in the range of (D) × (1 ± 0.3) is preferably 80% by weight or more, more preferably 90% by weight or more. . Those having such a particle size distribution have the same size, so that high filling is possible and the sizes are equal, so there is no difference in activity and selectivity, and it is easy to obtain optimum performance. There is no differential pressure.

  In the particle size distribution of the microspherical zeolite fuel treatment agent, when the proportion of particles with a particle size in the range of (D) x (1 ± 0.3) is less than 80% by weight, the particle size varies depending on the type of reaction. Because of differences in activity and selectivity, it may be difficult to obtain optimal performance or cause differential pressure.

  Such a microspherical zeolite fuel treating agent according to the present invention can be specifically produced as follows.

Method for Producing Microspherical Zeolite Fuel Treatment Agent The microspherical zeolite fuel treatment agent is not particularly limited as long as the above-described microspherical zeolite fuel treatment agent is obtained, but the microspheres comprising the following steps (a) to (e) A method for producing a spherical zeolite fuel treatment agent is preferred.
(A) Step of preparing a powder mixture of zeolite, binder and water so as to have a predetermined water content (b) Molding with an extruder, the diameter (D) is in the range of 0.3 to 5 mm A step of forming a pellet-shaped formed body (c) A step of forming a spherical formed body with a spherical machine (d) A step of drying and / or firing (e) A step of supporting a metal component.

  Such a production method makes it possible to produce the above-described microspherical zeolite fuel treatment agent, which has heretofore been difficult to produce.

Step (a): moisture adjustment
Zeolite and binder The above-mentioned zeolite and binder are mixed with water by adjusting the amount of water so as to have a specific value depending on the type of zeolite. The mixing method is not particularly limited. For example, zeolite and binder may be mixed with individual powders to adjust the moisture, and each slurry may be mixed and dried, and if necessary moisture You may adjust.

  In the present invention, it is particularly preferable to use a mixture powder obtained by spray-drying a slurry in which zeolite and a binder are dispersed and adjusting the moisture as necessary.

  The amount of water varies depending on the type of zeolite, and specifically, it is prepared to be in the range of K ± 4% by weight. K is a numerical value that varies depending on the type of zeolite, and represents an appropriate amount of moisture that can be extruded when the binder content is in the range of 2 to 40% by weight of the total solid content. That is, it is the amount of water that enables extrusion molding when the binder content is in the range of 2 to 40% by weight of the total solid content.

  Specifically, the K value is determined by performing an extrusion test while changing the water content.

  When the water content is less than K-4% by weight, extrusion molding is difficult, and even if extrusion molding is possible, it may be easily pulverized during granulation.

  If the water content exceeds K + 4% by weight, the length of the extruded pellet tends to be non-uniform or long, making it difficult to form spherical particles in the granulation process, and will be described later. It is necessary to cut the pellet length (L). In addition, pellets may adhere to each other and form a molded body.

K value is 47% by weight of A type zeolite, 46% by weight of faujasite type zeolite (X type, Y type zeolite, for example, Na-Y type containing Na ions), 42% by weight of mordenite type zeolite, 41% by weight of MFI type zeolite (ZSM-5 type zeolite),
β-type zeolite 52% by weight or the like.

  In the present invention, in the step (a), the zeolite and the binder can be used as individual powders and individual slurries, but the powder obtained by spray drying the mixed slurry in which the zeolite and the binder are dispersed is used. It is preferable to use and prepare moisture within the above range.

  In the method for producing spray-dried powder, a slurry is prepared in advance by dispersing zeolite and a binder in water.

  The concentration of the slurry at this time is preferably in the range of 1 to 40% by weight, more preferably 2 to 35% by weight as the solid content.

  When the concentration of the slurry is less than 1% by weight as the solid content, not only the spray drying thermal efficiency is low, but also a spray dried powder having a desired particle size described later may not be obtained.

  When the concentration of the slurry exceeds 40% by weight as the solid content, the viscosity of the slurry becomes high and stable spray drying may not be possible.

  In particular, when alumina is used as a binder, the pH of the slurry in which zeolite and alumina fine particles are dispersed is preferably in the range of 3.5 to 11.5, more preferably 4 to 11.

  When the pH of the slurry in which zeolite and alumina fine particles are dispersed is less than 3.5, depending on the type of zeolite, the crystallinity of the zeolite may be impaired, or the pore volume of the resulting microspherical zeolite fuel treatment agent, particularly the pore diameter, Since the pore volume of 100 to 10,000 nm is small, the zeolite may not be used sufficiently effectively.

  When the pH of the slurry in which zeolite and alumina fine particles are dispersed exceeds 11.5, the strength and wear resistance of the resulting microspherical zeolite fuel treatment agent may be insufficient.

  When the pH of the slurry in which zeolite and alumina fine particles are dispersed is in the above range, the pore volume of the pores having relatively large pore diameters (mesopores) is large, so that the performance of the zeolite can be sufficiently exhibited, In addition, although the pore volume is large, a microspherical zeolite fuel treatment agent having sufficient strength and wear resistance and having a uniform particle size distribution can be obtained.

  The method for adjusting the pH of the slurry in which zeolite and alumina fine particles are dispersed to the above range is not particularly limited and can be adjusted by a conventionally known method. For example, it can be adjusted by adding an alkaline aqueous solution to a slurry in which zeolite and alumina fine particles are dispersed. At this time, an aqueous ammonia solution is preferably used as the alkali. Moreover, it can adjust also by adding ammonia water to a zeolite dispersion | distribution slurry, and mixing an alumina fine particle or alumina sol with this. In addition, when ammonia water is added to alumina sol and mixed with zeolite slurry, the alumina sol may be gelled. For this reason, a microspherical zeolite fuel treatment agent having excellent strength and wear resistance may not be obtained. .

  Note that the pH of the slurry in which ordinary zeolite and ordinary alumina fine particles are dispersed is usually less than 3.5. If the pH is not adjusted to the above range, the pore volume of the pores having relatively large pore diameters (mesopores) is small, so that the performance of the zeolite cannot be fully exhibited, and depending on the type of the zeolite, In some cases, the performance of the zeolite cannot be fully exhibited because the crystallinity of the zeolite is impaired.

  At this time, the reason why the pH of the slurry is usually less than 3.5 is due to mineral acids such as sulfuric acid and organic acids such as acetic acid used when producing alumina fine particles (alumina sol) used as a binder. .

  Next, the slurry in which zeolite and alumina fine particles adjusted in pH are dispersed is heated as it is or concentrated under reduced pressure, and then the slurry is spray-dried.

  The spray drying method is not particularly limited as long as particles having an average particle size in the range of 20 to 150 μm, preferably 30 to 120 μm are obtained, and conventionally known spray drying methods can be employed.

  For example, although it depends on the solid content concentration of the slurry, a method of spraying the slurry using a disk or a nozzle in a hot air stream usually at 70 to 500 ° C. can be suitably employed.

  When the average particle size of the particles obtained by spray drying is less than 20 μm, the particles obtained by spray drying are aggregated when water is added to adjust the moisture for extrusion molding, and uniform moisture adjustment cannot be performed. Extrusion molding is difficult, or when the granulation is performed, the pellets may adhere to each other and agglomerate, and a microsphere zeolite fuel treating agent having a uniform particle size may not be obtained.

  When the average particle size of the spray-dried particles exceeds 150 μm, it is necessary to increase the pressure at the time of extrusion molding, and when the extrusion molding is performed at the same pressure as that of particles having an average particle size in the above range, the resulting microspherical zeolite The strength and wear resistance of the fuel treatment agent may be insufficient.

  In the present invention, the fine spherical zeolite fuel treatment agent obtained in the steps (a) to (d) of the present invention is pulverized (or pulverized and then calcined) as the above-mentioned mixture powder for spray drying. A product (consisting of zeolite and binder) may be used by mixing with a mixture powder.

  At this time, the average particle size of the pulverized fine spherical zeolite fuel treatment agent is preferably in the range of 10 to 100 μm, more preferably 20 to 80 μm. The content is preferably 2 to 40% by weight, more preferably 5 to 30% by weight.

  When the content in the total solid content of the pulverized product obtained by pulverizing the microspherical zeolite fuel treatment agent is less than 2% by weight, the effect of mixing the pulverized product, that is, improving the formability, the microspherical zeolite fuel treatment agent The strength and wear resistance may not be sufficiently improved. When the content in the total solid content of the pulverized product obtained by pulverizing the microspherical zeolite fuel treatment agent exceeds 40% by weight, the extrusion molding becomes difficult or the powder tends to be pulverized when spheroidized. .

  In addition, when the average particle size of the powder obtained by pulverizing the microspherical zeolite fuel treatment agent is less than 10 μm, the effect of mixing the pulverized product, that is, (improving moldability, strength of the microspherical zeolite fuel treatment agent, (Improved wear resistance) may not be obtained sufficiently.

  When the average particle diameter of the pulverized fine spherical zeolite fuel treatment agent exceeds 100 μm, although it depends on the content, extrusion molding becomes difficult or the powder tends to be pulverized when spheroidized.

  Such pulverized powder may be simply mixed with the zeolite and binder used as raw materials, and may further be mixed with the mixed slurry so as to be in the above weight range when the mixed slurry is spray-dried. Further, it may be mixed with the mixed powder that has been spray-dried.

  In the present invention, in addition to the pulverized product obtained by pulverizing the microspherical zeolite fuel treatment agent, the pulverized product obtained by firing the powder obtained by spray drying described above and pulverizing as necessary may be used. it can. The average particle size and calcination temperature of the pulverized product at this time are the same as those of the pulverized product obtained by pulverizing the microspherical zeolite fuel treatment agent.

Furthermore, a molding aid (sometimes referred to as a plasticizer) may be added to the mixture powder thus prepared as necessary. Examples of the molding aid include crystalline cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, starch, and lignin. Such a molding aid is preferably added in a range of 10 wt% or less, more preferably 1 to 6 wt% of the solid content.

  When such a molding aid is added, it is possible to widen the range of water content during extrusion molding described later. For this reason, it is possible to obtain a microspherical zeolite fuel treating agent that has good moldability, does not adhere dies or the like during granulation, and has sufficient compressive strength and wear resistance. Furthermore, although the reason is not clear, when the extrusion molding described later, the pellet is folded so that the ratio L / D of the length (L) and the diameter (D) of the pellet is approximately in the range of 1-2. In particular, a push roll type extruder can perform granulation without artificially cutting.

  The amount of the molding aid added at this time is preferably in the range of 0.5 to 15% by weight, more preferably 1 to 10% by weight of the total solid content (zeolite, binder, pulverized powder).

When the addition amount of the molding aid is less than 0.5% by weight of the total solid content, the effect of adding the molding aid cannot be sufficiently obtained, and the addition amount of the molding aid is 15% of the total solid content. If it exceeds wt%, it tends to be pulverized during granulation, and the strength and wear resistance of the resulting microspherical zeolite fuel treatment agent tend to decrease.

  The mixture powder whose water content is adjusted to a predetermined range can be formed by adding a molding aid as necessary, kneading as necessary, and immediately extruding, but for an appropriate time, Extrusion may be carried out after standing and aging while maintaining the water content. When such aging is performed, the strength and wear resistance of the obtained microspherical zeolite fuel treatment agent may be improved.

Step (b): Preparation of pellet-shaped molded body Next, the mixture powder obtained in the step (a) is extruded with a molding machine, and the diameter (D) is in the range of 0.5 to 5 mm. A molded body.

When the diameter (D) of the pellet-shaped molded body is less than 0.5 mm, it cannot be extruded because the hole diameter of the die is small, and if the diameter (D) of the pellet-shaped molded body exceeds 5 mm, the final The particle diameter of the spherical molded body obtained in this way also exceeds 5 mm, and when used as a catalyst, the effectiveness factor may decrease, and the activity may be inferior to that of the microspherical zeolite fuel treatment agent.

  As the extrusion molding machine, there is no particular limitation as long as the diameter (D) of the pellet is in the above range and it can be spheroidized in the step (c) described later, and a conventionally known extrusion molding machine can be adopted. For example, molding machines such as a front push screw type, a side push screw type, a front push ram type, a side push roll type, a bottom push roll type, a side push basket type, and a bottom push screen type can be mentioned. Among them, the lower pressing roll type can extrude the mixture powder with less moisture compared to other molding machines, and therefore, the pellets do not adhere to each other when spheroidizing, so that the yield is uniform. A microspherical zeolite fuel treating agent having a particle size distribution can be obtained.

The length (L) of the pellet varies depending on the hole diameter of the die of the extrusion molding machine (or the diameter (D) of the obtained pellet, but is in the range of 0.5 to 10 mm, preferably 0.6 to 7.5 mm. The pellet diameter (D) is preferably approximately the particle diameter of the desired microspherical zeolite fuel treating agent, where the ratio L / D of the pellet length (L) to the pellet diameter (D) Is preferably in the range of 1 to 2, and more preferably in the range of 1 to 1.5 The L / D is difficult to be less than 1, and even if it is possible, it tends not to be spherical. If D exceeds 2, the resulting particles are less likely to be spherical, and even if it can be produced, it takes a long time to spheroidize, so the production efficiency may be reduced, and for L / D exceeding 2, Can be cut to 2 or less, but still raw There is a problem that the production efficiency decreases.

  As described above, in the present invention, the fine spherical zeolite fuel treating agent having a very uniform particle size distribution adjusted to a specific pellet diameter by extrusion molding the mixture powder adjusted to a specific water content as described above. Can be obtained.

Step (c): Molding of spherical molded body Next, the pellet prepared in the above step (b) is formed into a spherical molded body with a high-speed rolling spherical granulator.

As the high-speed rolling spherical granulator, a conventionally known one can be used without particular limitation, and such a high-speed rolling spherical granulator is widely marketed as a malmerizer. When using a rolling type granulator, the pellets obtained in step (b) are filled and the granulator is rotated, or the rotated rolling granulator is filled with pellets to obtain a spherical shape. The spheroidizing conditions at this time, for example, rotation speed, peripheral speed, granulation time, etc.

It depends on the size, the degree of spherical shape, etc., and is preferably selected and set appropriately. In the present invention, the water content is adjusted to a predetermined value in the step (a) and is extruded to a predetermined size in the step (b), so that the pellets do not adhere to each other and agglomerate. It is not necessary to dry the pellets to prevent aggregation before spheroidization or at the time of spheroidization, and there is no deterioration in moldability due to drying.

  The pellet forming and spheronization in the steps (b) and (c) can also be performed with the same apparatus.

Step (d): The dried and / or fired spherical molded body is then dried and / or fired.

  When drying the obtained molded body, the degree of drying may be appropriately set depending on the use, but particles having a small particle diameter can be set at a relatively high drying speed, but particles having a large particle diameter can be dried slowly. preferable. The drying temperature is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. Moreover, although drying time changes also with drying temperature, it is preferable that it exists in the range of 10 minutes-48 hours, Furthermore, 30 minutes-24 hours.

  When firing, the temperature is preferably in the range of 200 to 1000 ° C, more preferably 300 to 800 ° C. When the firing temperature is less than 200 ° C., the strength of the obtained particles may be insufficient, or powdering due to wear may be remarkable. Even if the calcination temperature exceeds 1000 ° C., the strength of the particles is not further improved, and depending on the type of zeolite, the crystallinity may be greatly reduced and the function of the zeolite may not be exhibited.

  In the present invention, either drying or baking may be performed, or both may be performed.

Step (e): Supporting Metal Component In the present invention, a metal component as a processing component is supported on the microspherical zeolite molded body obtained in the step (d).

  The supporting method is not particularly limited. For example, a desired metal salt or an aqueous solution thereof is mixed in the dispersion of the microspherical zeolite compact, and the pH of the dispersion is adjusted and heated as necessary. A metal component is supported on the zeolite in the compact by ion exchange or the like. In this case, the ion exchange operation of the same type of metal may be repeated, or the ion exchange operation of different types of metal may be sequentially performed.

  After the ion exchange, the target microspherical zeolite fuel treating agent is obtained by filtering, washing and drying by an ordinary method and then calcining as necessary.

  In the present invention, instead of the method for supporting the metal component in the step (e), a metal salt or an aqueous solution of a desired metal component is mixed with the dispersion of the zeolite powder before molding, and the pH of the dispersion is adjusted as necessary. And after obtaining a zeolite in which the metal component is ion-exchanged by heating, a zeolite fuel treatment agent is obtained according to the steps (a) to (d) using the zeolite on which the metal component is previously supported. You can also.

Furthermore, after supporting a predetermined amount or less of the metal component on the zeolite powder before molding,
By preparing a spherical zeolite compact according to a) to (d) and then supporting the metal component according to step (e), a microspherical zeolite fuel treatment agent supporting a predetermined amount of the metal component can also be obtained. .

  The amount of the metal component supported is preferably in the range of 3 to 35% by weight, more preferably 5 to 30% by weight, in terms of the metal oxide in the ion exchange zeolite. If it is less than 3% by weight, the treatment capacity (adsorption capacity) may be insufficient, and if it exceeds 35% by weight, the loading itself is difficult, and even if it can be carried, the treatment capacity may not be improved further.

  In the present invention, as a method for supporting the metal component, a molded body may be obtained by using a zeolite on which a treatment component is previously supported, but it is prepared according to the steps (a) to (e) using a zeolite before supporting. It is preferable to increase the utilization rate of the ion exchange component (metal component), which can improve the properties such as particle strength. It may be a method of supporting the rest after production).

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example by these.

Example 1
Preparation of microspherical zeolite fuel treatment agent (1) Na-Y type zeolite slurry (solid content concentration 36.4 wt%) 17.6 as zeolite
Kg and powdered alumina as a binder (Catalyst Kasei Kogyo Co., Ltd .: Cataloid-AP, solid content (Al ₂ O ₃ ) concentration 70.3 wt%, CH ₃ COOH content 10.8 wt%, moisture 18.9 (Wt%) 2.28 Kg and water 43 Kg were mixed to obtain a slurry having a solid content concentration of 12.7 wt%. Next, 465 g of 15% by weight ammonia water was added to adjust the pH to 9.4.
Aging was performed at 5 ° C. for 3 hours.

  The aged slurry was spray-dried with a spray dryer (hot air inlet temperature 300 to 320 ° C., outlet temperature 120 to 130 ° C.) to be powdered. The average particle size of the obtained powder was 65 μm, and the water content was 24.5% by weight.

  1.32 kg of this powder is put into a high speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C / I type), and 0.47 kg of water in which 30 g of crystalline cellulose is dissolved in advance is added and mixed well. The water content was adjusted to 44.2% by weight.

The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Powdal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. At this time, the length of the pellet was relatively uniform, and the average length was 1.8 mm.

The obtained pellets having a diameter of 1.5 mmφ were formed into spherical particles with a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400 type). At this time, the rotation speed of the Malmerizer was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes. The obtained spherical molded body was dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel treatment agent precursor (1).

Disperse 1000 g of the fuel processing agent precursor (1) in 10 L of water, and adjust the pH of the dispersion with nitric acid to 7.
To this, 870 g of an aqueous silver nitrate solution having a concentration of 10% by weight was added, and the mixture was gently stirred at 40 ° C. for 4 hours, filtered, dried, and then calcined at 400 ° C. for 3 hours to produce a microspherical zeolite fuel. A treating agent (1) was obtained. The composition was analyzed and the content converted to silver oxide in the zeolite was shown in the table.

The average short diameter, average long diameter, average particle diameter, spherical coefficient of microspherical zeolite fuel treatment agent (1),
The compressive strength was measured, the average compressive strength index was determined, and the results are shown in Table 1.

  Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

  The compressive strength was measured with a compressive strength meter (manufactured by Fujiwara Seisakusho: Kiya-type hardness meter, max 5 kg).

  The wear resistance was measured as follows based on the wear strength measurement method (JIS K1464).

  A micromesh sieve with an opening of 800 μm and 355 μm and a tray at the bottom are sequentially stacked, 50 g of fuel treatment agent and five 10-yen coins are placed on the top micromesh sieve, and after 30 minutes of vibration, the tray The powder was weighed, divided by 50 g, and shown as a wear rate (%) in the table.

  The average minor axis and the average major axis were measured with respect to 100 particles by taking an optical micrograph, and the average particle diameter was expressed as (average minor axis + average major axis) / 2.

Adsorption performance evaluation A stainless steel reaction tube having an inner diameter of 20 mmΦ was filled with 6 cm ³ of microspherical zeolite fuel treatment agent (1) (filling amount: 4.3 g).

City gas (13A) was used as the test gas. The sulfur compound concentration in the test gas is 4.4 mg-S / Nm ³ (DMS = 50 wt%, TBM = 50 wt%, which corresponds to DMS = 1.8 ppm, TBM = 1.2 ppm). About 380 ppm (dew point -30 ° C) was added (by underwater bubbling of the test gas in a thermostatic bath). The gas flow rate is 4000 cm ³ / min [Lv (linear velocity of gas) = 21 cm / sec, SV (space velocity = 40000 h ^-1 ), temperature is room temperature (20-30 ° C), and pressure is normal pressure. went.

The amount of sulfur compound adsorbed by the microspherical zeolite fuel treatment agent (1) was determined as follows. The test gas was introduced from the inlet of the reaction tube, the gas discharged from the outlet of the reaction tube was sampled over time, and the sulfur concentration was determined by GC-FPD (gas chromatograph with a flame photometric detector). The sulfur compound adsorption amount was calculated by integrating the total sulfur compound adsorption amount up to the point when each sulfur compound concentration at the outlet of the reaction tube reached 0.1 ppm, and calculating the sulfur adsorption amount by the following formula. The results are shown in Table 1. .

  In addition, Table 1 shows the time required for the sulfur compound concentration to reach 0.1 ppm (breakthrough time).

Examples 2-5
Preparation of microspherical zeolite fuel treatment agents (2) to (5) In the same manner as in Example 1, except that 1740 g, 2610 g, 3480 g and 4350 g of an aqueous silver nitrate solution having a concentration of 10% by weight were added, respectively. Treatment agents (2) to (5) were prepared.

  Measure the content, average minor axis, average major axis, average particle size, spherical coefficient, compressive strength of the microspherical zeolite fuel treatment agent (2) to (5) in terms of silver oxide in the zeolite, and measure the average compressive strength. The index was determined and the results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

In the performance evaluation example 1, each of the microspherical zeolite fuel treatment agents (2) to (5) was evaluated in the same manner except that 4.4 g, 4.6 g, 4.7 g, and 4.7 g were sequentially filled. The results are shown in Table 1.

Example 6
Preparation of microspherical zeolite fuel treatment agent (6) In Example 1, except that 0.47 Kg of water in which 50 g of crystalline cellulose was dissolved was used, the water-adjusted powder was obtained in the same manner as an extruding machine of a lower roll type. (Fuji Powdal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type) was formed into pellets. At this time, first, extrusion was performed once with an extruder nozzle diameter of 3 mmφ, and then extrusion was performed once with a nozzle diameter of 0.7 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 0.9 mm.

The obtained pellets having a diameter of 0.7 mmφ were formed into spherical particles with a sphere machine (manufactured by Fuji Powder Co., Ltd .: Malmerizer, QJ-400 type). At this time, the rotation speed of the Malmerizer was 600 rpm, the external heat temperature was 60 ° C., and the treatment time was 3.5 minutes. The obtained spherical molded body was dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel treatment agent precursor (6).

A microspherical zeolite fuel treatment agent (6) was obtained in the same manner as in Example 1, except that the fuel treatment agent precursor (6) was used.

The content, average short diameter, average long diameter, average particle diameter, spherical coefficient, compressive strength measured in terms of silver oxide in the zeolite of the microspherical zeolite fuel treatment agent (6) were determined, and the average compressive strength index was obtained. The results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance Evaluation In Example 1, the evaluation was performed in the same manner except that 4.6 g of the microspherical zeolite fuel treatment agent (6) was charged. The results are shown in Table 1.

Example 7
Preparation of microspherical zeolite fuel treatment agent (7) Aqueous dispersion (SiO ₂ · Al ₂ O ₃ concentration of zeolite (manufactured by Catalysts & Chemicals Co., Ltd .: Na-Y zeolite: T-90, average particle size 1 μm) While adjusting the pH of the dispersion to 7.2 with 10% by weight of nitric acid, add 2.6 kg of silver nitrate aqueous solution with a concentration of 10% by weight.
Ion exchange was performed at 0 ° C. for 3 hours. The zeolite was then filtered and washed, dried, and calcined at 400 ° C. for 3 hours to prepare a silver exchanged zeolite. The content of silver oxide in the zeolite is shown in the table.

950 g of silver exchanged zeolite and powdered alumina (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Cataloid-AP,
Solid content (Al ₂ O ₃ ) concentration 70.3% by weight, CH ₃ COOH content 10.8% by weight, moisture 18.
9% by weight) 320 g, 1300 g of water, and 40 g of crystalline cellulose were placed in a high-speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C / I type) and mixed well to obtain a moisture content of 44.
Adjusted to 9% by weight.

The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Powdal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. At this time, the length of the pellet was relatively uniform, and the average length was 1.7 mm.

The obtained pellets having a diameter of 1.5 mmφ were formed into spherical particles with a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400 type). At this time, the rotation speed of the Malmerizer was 600 rpm, the external heat temperature was 65 ° C., and the treatment time was 2.5 minutes. The obtained spherical molded body was dried at 130 ° C. for 24 hours and then calcined at 400 ° C. for 3 hours to obtain a microspherical zeolite fuel treatment agent (7).

The average short diameter, average long diameter, average particle diameter, spherical coefficient of microspherical zeolite fuel treatment agent (7),
The compressive strength was measured, the average compressive strength index was determined, and the results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance evaluation In Example 1, the evaluation was performed in the same manner except that 4.7 g of the microspherical zeolite fuel treatment agent (7) was charged, and the results are shown in Table 1.

Example 8
Preparation of microsphere-forming zeolite fuel treatment agent (8) 1600 g of β-zeolite which was calcined and made into H type and powdered alumina (Cataloid-AP, manufactured by Catalyst Chemical Industry Co., Ltd., solid content (Al ₂ O ₃ ) concentration 70. 570 g (3 wt%, CH ₃ COOH content 10.8 wt%, moisture 18.9 wt%) was dispersed in 10200 g water and mixed well to prepare a slurry with a solid content concentration of 16.2 wt%.

  This slurry was spray-dried with a spray dryer (hot air inlet temperature 250 to 300 ° C., outlet temperature 120 to 130 ° C.) to be powdered. The average particle diameter of the obtained powder was 65 μm, and the water content was 26.3% by weight.

1360 g of this powder and 50 g of crystalline cellulose are placed in a high-speed stirring powder mixer (Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C / I type) and mixed thoroughly to adjust the water content to 52.5% by weight. did.

The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Powdal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. The length of the pellet at this time was relatively uniform, and the average length was 1.6 mm.

The obtained pellets having a diameter of 1.5 mmφ were formed into spherical particles with a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400 type). At this time, the rotation speed of the Malmerizer was 600 rpm, the external heat temperature was 65 ° C., and the treatment time was 5 minutes. The obtained spherical molded body was dried at 130 ° C. for 24 hours and then calcined at 650 ° C. for 3 hours to obtain a fuel treatment agent precursor (8).

Disperse 1000 g of the fuel processing agent precursor (8) in 10 L of water, and adjust the pH of the dispersion with nitric acid to 7.
While adjusting to 1, 1530 g of a 10% strength by weight aqueous silver nitrate solution was added thereto, stirred gently at 40 ° C. for 4 hours, filtered, dried, and then calcined at 400 ° C. for 3 hours to produce a microspherical zeolite fuel A treating agent (8) was obtained. The composition was analyzed and the content converted to silver oxide in the zeolite was shown in Table 1.

The average short diameter, average long diameter, average particle diameter, spherical coefficient of microspherical zeolite fuel treatment agent (8),
The compressive strength was measured, the average compressive strength index was determined, and the results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance Evaluation In Example 1, evaluation was performed in the same manner except that 4.2 g of the microspherical zeolite fuel treatment agent (8) was charged. The results are shown in Table 1.

Example 9
Preparation of microspherical zeolite fuel treatment agent (9) Na-Y type zeolite slurry (solid content concentration 36.4% by weight) 18.7 as zeolite
As a binder, 1.26 kg of powdered bentonite (manufactured by Nippon Bentonite Co., Ltd .: solid content 95 wt%) and 30 kg of water were mixed as a binder to obtain a slurry having a solid content concentration of 16 wt%. Then, it was aged at 95 ° C. for 3 hours.

  The aged slurry was spray-dried with a spray dryer (hot air inlet temperature 290 to 320 ° C., outlet temperature 130 to 140 ° C.) to be powdered. The average particle size of the obtained powder was 65 μm, and the water content was 25.8% by weight.

1.32 kg of this powder, 470 g of water and 30 g of crystalline cellulose were mixed with a high-speed stirring powder mixer (
Mitsui Mining Co., Ltd .: Henschel mixer, FM-20C / I type)
Adjusted to 1% by weight.

  The moisture-adjusted powder was formed into pellets using a down roll type extruder (Fuji Powdal Co., Ltd .: Disc pelleter, F-5 (PV-S) / 11-175 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. At this time, the length of the pellet was relatively uniform, and the average length was 1.8 mm.

The obtained pellets having a diameter of 1.5 mmφ were formed into spherical particles with a spherical machine (Fuji Paudal Co., Ltd .: Malmerizer, QJ-400 type). At this time, the rotational speed of the Malmerizer was 600 rpm, the external heat temperature was 65 ° C., and the treatment time was 3 minutes. The obtained spherical molded body was dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel treatment agent precursor (9).

6. Disperse 1000 g of the fuel treatment agent precursor (9) in 10 L of water and adjust the pH of the dispersion to 7 with nitric acid.
2800 g of an aqueous silver nitrate solution having a concentration of 10% by weight was added to the solution.
After stirring gently for a period of time, the mixture was filtered, dried, and then calcined at 400 ° C. for 3 hours to obtain a microspherical zeolite fuel treatment agent (9). The composition was analyzed and the content converted to silver oxide in the zeolite was shown in Table 1.

The average short diameter, average long diameter, average particle diameter, spherical coefficient of microspherical zeolite fuel treatment agent (9),
The compressive strength was measured, the average compressive strength index was determined, and the results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance evaluation In Example 1, evaluation was performed in the same manner except that 4.1 g of the microspherical zeolite fuel treatment agent (9) was charged. The results are shown in Table 1.

Comparative Example 1
Preparation of fine zeolite fuel treatment agent (R1) Na-Y type zeolite slurry (solid content concentration 36.4% by weight) 17.6 as zeolite
Kg and powdered alumina as a binder (Catalyst Kasei Kogyo Co., Ltd .: Cataloid-AP, solid content (Al ₂ O ₃ ) concentration 70.3 wt%, CH ₃ COOH content 10.8 wt%, moisture 18.9 (Wt%) 2.28 Kg and water 43 Kg were mixed to obtain a slurry having a solid content concentration of 12.7 wt%. Next, 465 g of 15% by weight ammonia water was added to adjust the pH to 9.4.
Aging was performed at 5 ° C. for 3 hours.

The aged slurry was concentrated with a kneader while using a heating element. At this time, the water content was 49.8% by weight. Next, 30 g of crystalline cellulose was added and sufficiently kneaded.

This kneaded product was formed into pellets with a front screw type extruder (Honda Iron Works, Ltd .: DE-75 type). At this time, first, extrusion was performed once with a nozzle diameter of 3 mmφ of the extruder, and then extrusion was performed once with a nozzle diameter of 1.5 mmφ to form pellets. The average length of the pellets at this time was 2.2 mm. The obtained pellet-shaped molded body was dried at 130 ° C. for 24 hours and then calcined at 650 ° C. for 3 hours to obtain a fuel treatment agent precursor (R1).

  Disperse 1000 g of the fuel processing agent precursor (R1) in 10 L of water, and adjust the pH of the dispersion to 7.2 with nitric acid. After gently stirring, the mixture was filtered, dried, and then calcined at 400 ° C. for 3 hours to obtain a fine zeolite fuel treating agent (R1). The composition was analyzed and the content converted to silver oxide in the zeolite was shown in Table 1.

  The diameter, length, and compressive strength of the microzeolite fuel treating agent (R1) were measured, the average compressive strength index was determined, and the results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance evaluation In Example 1, evaluation was performed in the same manner except that 3.8 g of the microspherical zeolite fuel treatment agent (10) was charged. The results are shown in Table 1.

Comparative Example 2
Preparation of Fine Zeolite Fuel Treatment Agent (R2) In Comparative Example 1, kneading was carried out in the same manner except that concentration with a kneader was carried out until the water content became 44.0% by weight.

The kneaded product was tried to be extruded with a front screw type extruder (Honda Iron Works Co., Ltd .: DE-75 type), but it was difficult to extrude.

Comparative Example 3
Preparation of microspherical zeolite fuel treatment agent (R3) Na-Y type zeolite slurry (solid content concentration 32% by weight) 12.5 kg as zeolite
Further, 1.42 kg of powdery alumina (manufactured by Catalyst Kasei Kogyo Co., Ltd .: alumina sol, Cataloid-AP, solid content concentration of 70.3 wt%) and 6.1 kg of water were mixed as a binder.

  Subsequently, it was dried to a moisture content of 26% by weight in a dryer, and pulverized to obtain a powder having a particle size of 300 μm or less and an average particle size of 180 μm. A spherical shaped product was obtained from this powder using a bread type rolling granulator (Kurimoto Iron Works Co., Ltd .: KG10 type). The obtained molded body was dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel treatment agent precursor (R3).

  Disperse 1000 g of the fuel processing agent precursor (R3) in 10 L of water, adjust the pH of the dispersion to 7.2 with nitric acid, add 870 g of a 10% by weight aqueous silver nitrate solution, and add it at 40 ° C. for 4 hours. After gently stirring, the mixture was filtered, dried, and then calcined at 400 ° C. for 3 hours to obtain a microspherical zeolite fuel treatment agent (R3). The composition was analyzed and the content converted to silver oxide in the zeolite was shown in Table 1.

  The average short diameter, average long diameter, average particle diameter, spherical coefficient, and compressive strength of the microspherical zeolite fuel treatment agent (R1) were measured to determine the average compressive strength index. The results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance evaluation In Example 1, evaluation was performed in the same manner except that 2.8 g of the microspherical zeolite fuel treatment agent (R3) was charged. The results are shown in Table 1.

Comparative Example 4
Preparation of microzeolite fuel treatment agent (R4) In the same manner as in Example 1, pellets having a diameter of 1.5 mmφ and an average length of 1.8 mm were prepared. The pellets were dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel processing agent precursor (R4).

  Subsequently, a fine zeolite fuel treating agent (R4) was obtained in the same manner as in Example 3 except that the fuel treating agent precursor (R4) was used. The composition was analyzed and the content converted to silver oxide in the zeolite was shown in Table 1.

  The diameter, major axis, and compressive strength of the fine zeolite fuel treating agent (R4) were measured to obtain an average compressive strength index. The results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance Evaluation In Example 1, evaluation was performed in the same manner except that 3.9 g of the fine zeolite fuel treatment agent (R4) was charged. The results are shown in Table 1.

Comparative Example 5
Preparation of microzeolite fuel treatment agent (R5) In the same manner as in Example 6, pellets having a diameter of 0.7 mmφ and an average length of 0.9 mm were prepared. The pellets were dried at 130 ° C. for 24 hours and then calcined at 670 ° C. for 3 hours to obtain a fuel processing agent precursor (R5).

  Subsequently, a fine zeolite fuel treating agent (R5) was obtained in the same manner as in Example 6 except that the fuel treating agent precursor (R5) was used. The composition was analyzed and the content converted to silver oxide in zeolite was shown in Table 1.

  The diameter, length, and compressive strength of the microzeolite fuel treating agent (R5) were measured to determine the average compressive strength index. The results are shown in Table 1. Further, the wear resistance and bulk specific gravity were measured, and the results are shown in Table 1.

Performance evaluation In Example 1, evaluation was performed in the same manner except that 4.3 g of the fine zeolite fuel treatment agent (R5) was charged. The results are shown in Table 1.

Claims (8)

It consists of a zeolite and a binder, the average particle diameter (D) is in the range of 0.3 to 5 mm, and the pore volume (PV) in the range of the pore diameter of 30 to 500 nm is 0.1 to 0.6 ml / g. Zeolite compacts in the range, the average compressive strength (N) is in the range of 2 to 30 N (Newton), and the average compressive strength index (C) represented by the following formula is in the range of 1.0 to 5,
A microspherical zeolite fuel treatment agent characterized by carrying one or more elements selected from the group IB, group VIII, and lanthanide of the periodic table, a metal, or a metal oxide.
C = N x PV / D   2. The microspherical zeolite fuel treatment agent according to claim 1, wherein the zeolite content is in the range of 60 to 98 wt% and the binder content is in the range of 2 to 40 wt%.   The microsphere zeolite fuel treatment agent according to claim 1 or 2, wherein the binder is alumina. The microspherical zeolite fuel treatment agent according to any one of claims 1 to 3, wherein the spherical coefficient (D _L ) / (D _S ) is in the range of 1 to 1.5. (D _L : major axis, D _S : minor axis) The microspherical zeolite fuel treating agent according to any one of claims 1 to 4, wherein the microspherical zeolite fuel treating agent is produced from the following steps (a) to (e):
(A) Moisture content is K ± 4 wt% (where K value is 47 wt% A-type zeolite, Forge
Zeolite and binder so that it becomes 46% by weight zeolite (X type, Y type zeolite), 42% by weight mordenite type zeolite, 41% by weight MFI type zeolite (ZSM-5 type zeolite) and 52% by weight β type zeolite) (B) Step of preparing a mixture powder of water and water (b) Step of forming with a molding machine and forming a pellet-shaped molded body having a diameter (D) in the range of 0.3 to 5 mm (c) With a spherical machine A step of forming a spherical molded body (d) A step of drying and / or firing (e) A step of supporting a metal component. The microspherical zeolite fuel treating agent according to any one of claims 1 to 4, wherein the microspherical zeolite fuel treating agent is produced from the following steps (a) to (d):
(A) Preliminarily containing a metal component-supported zeolite, a binder, and water with a water content of K ± 4% by weight (where K value is 47% by weight of type A zeolite, faujasite type Zeora
Ito (X-type, Y-type zeolite) 46% by weight, mordenite-type zeolite 42% by weight, MFI
(B) A mixture powder is prepared so as to be a zeolite (ZSM-5 type zeolite 41 wt%, β type zeolite 52 wt%), and the diameter (D) is 0. A step of forming a pellet-shaped formed body in a range of 3 to 5 mm (c) a step of forming a spherical formed body with a spherical machine (d) a step of drying and / or firing;   7. In the step (a), a powder mixture is prepared by spray-drying and adjusting the water content of a water-dispersed slurry prepared so that the binder and zeolite are 1 to 40% by weight. The microspherical zeolite fuel treatment agent according to 1. The microspherical zeolite fuel treating agent according to claim 7, wherein the binder is alumina and the pH of the water-dispersed slurry is in the range of 3.5 to 11.5.