JP4715230B2 - Aluminophosphate granule and method for producing the same - Google Patents

Description

The present invention relates to a granulated product containing aluminophosphates and a binder. The invention further relates to a method for producing such a granulate.

Zeolite includes crystalline silicates, crystalline aluminophosphates, and the like as defined by the International Zeolite Association (IZA). Zeolites are widely used as adsorbents, catalysts, separators, and detergent builders.
In recent years, from the viewpoint of energy saving, adsorption heat pumps using porous substances such as zeolite and mesoporous materials as adsorbents have been researched and developed.

As an adsorbent for an adsorption heat pump, for example, a zeolite containing at least aluminum, phosphorus, and heteroatoms in a skeleton structure has been proposed (Japanese Patent Laid-Open No. 2002-372332). However, details of granulation have not been studied.
As a method for producing an adsorbent, for example, a granulation method having a powdering step of raw material powder and a grinding step of crushing and polishing between grinders is known, and a particle size of 0.05-2 mm is suitable. (Japanese Patent Laid-Open No. 2001-38188). However, when an adsorbent is used in an adsorption heat pump, it is used by being fixed to a heat exchanger, but the adsorbent is not always satisfactory in terms of packing density and adsorption characteristics. Further, an adsorption heat pump using an adsorbent having a bulk density of 0.5 g / cc or more is known as an adsorbent for an adsorption heat pump from the viewpoint of miniaturization of the apparatus, and the particle size is 100 to 150 μm. The adsorbent is shown. However, the adsorbent is a high-density porous body mainly composed of silicon and oxygen, and is not necessarily satisfactory in terms of adsorption characteristics. (Japanese Patent Laid-Open No. 9-264633).

  On the other hand, aluminophosphates containing aluminum and phosphorus in the skeleton structure have been conventionally known to be mainly applied to the field of catalysts. Aluminophosphates are used as catalysts for chemical processes such as the conversion of methanol to light olefins. Among these, there is disclosed a catalyst obtained by granulating silicoaluminophosphate in which a part of phosphorus is substituted with silicon by spray drying together with binder components such as kaolin and silica sol (US Patent No. 1). No. 4973792 and US Pat. No. 5,095,163).

However, according to our study, these granulated materials used as a catalyst need to have an extremely high binder component ratio of 40% by weight or more in order to increase the strength. When applied to an adsorbent, there are problems such as insufficient strength and bulk density and practical problems, or insufficient adsorbing capacity and an increase in size of the apparatus.
JP 2002-372332 A JP 2001-38188 A JP-A-9-264633 U.S. Pat. No. 4,973,792 US Pat. No. 5,095,163

  The present invention has been made to solve the above-described problems, and its purpose is a granulated product substantially composed of an aluminophosphate and a binder, having excellent strength, and serving as an adsorbent. It is to provide a granulated product which can achieve a high packing density when used in a heat exchanger, and has a high adsorption capacity, and a method for producing the same.

As a result of intensive studies on the above problems, the inventors of the present invention include aluminophosphates and a binder, a granulated product having a specific particle size range, a specific pore volume, and a specific compression strength. The present inventors have found that the particles can solve the above-mentioned problems and have reached the present invention.
That is, the gist of the present invention for solving the above problems is a granulated product substantially composed of aluminophosphates and a binder and having a particle size range of 50 to 5000 μm, and having a pore size range of 0.1 to 5 μm. It exists in a granulated product having a pore volume of 0.05 cc / g or more and 0.5 cc / g or less and a compressive strength of 2 MPa or more.

  Another gist is a method for producing a granulated product of aluminophosphates using at least an aluminophosphate and a binder precursor, wherein the binder precursor contains a compound of the following formula (I) or a silicic acid solution. A method for producing a granulated product.

[In the formula (I), each R is independently an optionally substituted alkyl, aryl, alkenyl, alkynyl, alkoxy or phenoxy, and each R ′ is independently an optionally substituted alkyl. , Aryl, alkenyl or alkynyl, and n is a number from 1 to 100. ]

  Since the aluminophosphate granule of the present invention has high compressive strength, there is little deterioration such as crushing in an environment when used as an adsorbent for an adsorption heat pump, for example, and the bulk density is high, so the packing density is increased. It is possible to reduce the volume of the granulated material to be used, and the apparatus can be made compact. Furthermore, since the amount of adsorption by granulation is small and the adsorption capacity is large, it is extremely useful as an adsorbent for an adsorption heat pump. Moreover, according to the granulated material manufacturing method of this invention, said aluminophosphate granulated material can be manufactured with sufficient reproducibility.

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.
(Granulated product of the present invention)
The granulated product of the present invention is a granulated product substantially composed of an aluminophosphate and a binder, and has a particle size range of 50 to 5000 μm and a pore size range of 0.1 to 5 μm. A granulated product having a volume of 0.05 cc / g or more and 0.5 cc / g or less and a compressive strength of 2 MPa or more. Here, the measurement and calculation of the compressive strength are performed in accordance with the method described in JIS28841-1993 “Compressive strength”. Specifically, the stress at the time of crushing (unit: N or gf) obtained by compressing the particles at a constant speed is converted into a compressive strength (unit: MPa) according to the “Hiramatsu method”. Hiramatsu's method is described in “Japan Mining Association Vol. 81, No. 932, p. 1024 (1965)”.

  In the present invention, the shape of the granulated product is not limited as long as it is granular. Therefore, the particle size means the average when there is a major axis or minor axis, and is measured by laser diffraction, microscopic observation, or the like. . The particle size of the granulated product of the present invention is preferably 60 μm or more, on the other hand, preferably 3000 μm or less, more preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 600 μm or less.

  If the particle size is too small, it becomes difficult to fill the heat exchanger or the diffusion of the adsorbate in the adsorbent layer is inhibited, and if the particle size is too large, the particulate matter is filled and used. Density decreases and particle strength decreases. In addition, the granulated material having the above-mentioned particle size can usually be obtained in a desired particle size range by controlling the granulation conditions and, if necessary, pulverizing and sieving.

  The granulated product of the present invention has a pore volume in the range of 0.1 to 5 μm in pore diameter of 0.05 cc / g or more and 0.5 cc / g or less, preferably 0.1 cc / g or more, .45cc / g or less is preferable, and more preferably 0.4cc / g or less. When the pore volume is too small, the diffusion of the adsorbate into the pores is slow, and the adsorption rate is unfavorable. On the other hand, if it is too large, the bulk density becomes small, so that the packing density decreases, which is not preferable. In addition, the pore volume in the pore diameter range of 0.1 to 5 μm is measured by a mercury intrusion method. The granulated product of the present invention has a compressive strength of 2 MPa or more, more preferably 2.5 MPa or more, particularly preferably 3 MPa or more. Higher compressive strength is preferable, but it is usually about 4 MPa or less. If the compressive strength is too small, there are problems such as powdering by repeated use. The bulk density is usually 0.5 g / cc or more, preferably 0.6 g / cc or more. If the bulk density is too low, the heat exchanger is undesirably large.

  The granulated product of the present invention has a water adsorption amount of 0 when the relative vapor pressure changes by 0.15 in the range of the relative vapor pressure of 0.01 to 0.30 on the water vapor adsorption isotherm measured at 25 ° C. Those that change by .12 g / g or more are preferable, those that change in adsorption amount by 0.15 g / g or more are more preferable, and those by 0.17 g / g or more are more preferable. When the adsorption amount change is large, the amount of adsorbent when used in an adsorption heat pump or the like can be reduced, and there is an advantage that the apparatus can be made compact. In the water vapor adsorption isotherm, the adsorption amount at a relative vapor pressure of 0.01 is preferably 0.15 g / g or less, more preferably 0.12 g / g or less, and particularly preferably 0.10 g / g or less.

  The granulation method of the present invention is not particularly limited as long as the above physical properties are satisfied. In particular, as described later, aluminophosphates are silicon-containing binders, more specifically, silicones or silicic acid solutions are used. And is preferably obtained by adjusting the particle size by sieving if necessary. Furthermore, it is preferable that the molar ratio of Si, P, Al, and Me (heteroatom) in the granulated product of the present invention satisfies the following formula derived from the binder precursor.

1.02 ≦ (Si + P) / (Al + Me) ≦ 1.4
Me is a heteroatom that can be substituted for a part of Al in the aluminophosphate skeleton, and its content may be zero.
When the aluminophosphate contains Si and / or Me in its skeleton structure, a part of Al is replaced by Me and a part of P is replaced by Si. Therefore, the composition formula of such aluminophosphates is Al _{1− x} Me _x P _1-y Si _y O _4, and as is apparent from this composition formula, (P + Si) /
The molar ratio of (Al + Me) is 1. Here, if the binder precursor is mainly composed of silicon, silicon is introduced from other than the aluminophosphate skeleton component, and therefore, the molar ratio of (P + Si) / (Al + Me) is larger than 1. In the granulated product of the present invention, the molar ratio of (P + Si) / (Al + Me) is preferably 1.02 or more, and more preferably 1.05 or more. If this value is too small, the strength tends to decrease. On the other hand, it is preferably 1.4 or less, and more preferably 1.2 or less. If this value is too large, the ratio of the binder to the aluminophosphate increases, and the adsorption capacity tends to decrease. The proportion of these elements in the granulated product is determined by conducting the elemental analysis such as ICP method after the granulated product is fired at 550 ° C. in an oxygen-containing atmosphere and then dissolved in hydrochloric acid / hydrofluoric acid. It is determined. Furthermore, since silica contained in the binder in the granulated product does not dissolve in hydrochloric acid in which aluminophosphates containing silicon as a skeleton component dissolve, it can be quantified separately from silicoaluminophosphates.

(Aluminophosphates)
In the present invention, aluminophosphates mean crystalline aluminophosphates defined by International Zeolite Association (IZA), and the atoms constituting the skeletal structure are aluminum and phosphorus, some of which are other atoms. It may be substituted with (Me: heteroatom). Above all,
(I) A heteroatom in which aluminum is represented by Me1 (provided that Me1 belongs to the third or fourth period of the periodic table, and belongs to groups 2A, 7A, 8, 1B, 2B, 3B (except for Al). Me-aluminophosphate partially substituted with at least one element selected from elements), (II) heteroatom in which phosphorus is represented by Me2 (where Me2 is the third or fourth period of the periodic table) Me-aluminophosphate substituted with a 4B group element belonging to
(III) Me-aluminophosphate in which both aluminum and phosphorus are respectively substituted with heteroatoms Me1 and Me2 is preferable from the viewpoint of adsorption characteristics.

  Here, the constituent ratio (molar ratio) of Me, Al, and P constituting the skeleton structure is usually a molar ratio of the following formulas 1-1 to 3-1, preferably the following formulas 1-2 to 3-2. If x is smaller than the above range, the amount of adsorption in the region where the adsorbate pressure is low tends to be small or the synthesis tends to be difficult, and if it is larger than the above range, impurities tend to be mixed during synthesis. Further, if y and z are out of the above ranges, synthesis is difficult.

0 ≦ x ≦ 0.3… 1-1
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.2 ≦ y ≦ 0.6… 2-1
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.3 ≦ z ≦ 0.6… 3-1
(Z represents the molar ratio of P to the sum of Me, Al, and P)
0.01 ≦ x ≦ 0.3… 1-2
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.3 ≦ y ≦ 0.5… 2-2
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.4 ≦ z ≦ 0.5 ... 3-2
(Z represents the molar ratio of P to the sum of Me, Al, and P)

Me may be contained alone or in combination of two or more. Preferable Me (Me1, Me2) is an element belonging to the third and fourth periods of the periodic table. Me1 is preferably a divalent state having an ionic radius of 0.3 or more and 0.8 Å or less, more preferably a divalent or tetracoordinate state having an ionic radius of 0.4 or more and 0.7 Å or less. is there. Among these, at least one element selected from Fe, Co, Mg, and Zn is preferable from the viewpoint of ease of synthesis and adsorption characteristics, and Fe is particularly preferable. Me2 is a group 4B element belonging to the third or fourth period of the periodic table, and is preferably Si.

Further, aluminophosphate compounds of the present invention, the framework density (FD) is usually, 13T / nm ³ or more 20T / nm ³ or less, preferably, 13.5T / nm ³ or more, more preferably 14T / nm ³ or more, whereas, preferably 19T / nm ³ or less, more preferably 17.5T / nm ³ or less. Here, T / nm ³ means T atoms present per unit volume nm ³ (the number of elements constituting a skeleton other than oxygen per 1 nm ^{3 of} zeolite), and is a unit indicating framework density: FD. . If the amount is less than the above range, the structure tends to be unstable and the durability is lowered. On the other hand, if the range is exceeded, the adsorption capacity tends to be small and the adsorbent tends not to be used.

  The aluminophosphates of the present invention have a structure defined by the International Zeolite Association (IZA) and are AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA , ERI, LEV, and VFI. Among them, from the viewpoint of adsorption characteristics and durability, any one selected from AEI, AEL, AFI, CHA, and LEV is preferable, and CHA and AFI are particularly preferable.

(binder)
The binder of the present invention is a component that binds aluminophosphates in the granulated product. Since the granulated product of the present invention is obtained by granulating and heating a mixture containing at least aluminophosphates and a binder precursor, the binder is usually one in which the binder precursor described below is modified by cross-linking or the like. It is. However, a binder also includes the component, when the component added as needed at the time of granulation or shaping | molding remains in the granulated material.

As the binder precursor of the present invention, inorganic binders such as silicones, silicic acid liquid, specific silica sol or alumina sol are used. Here, the silicones refer to oligomers having a polysiloxane bond in the main chain, and include those in which a part of the substituents of the main chain of the polysiloxane bond is subjected to hydrolysis to become an OH group. Among them, a binder precursor that is a silicon-containing compound in which condensation proceeds at a low temperature of room temperature to 300 ° C. is preferable. Silicate and silicic acid solutions undergo a condensation reaction at a low temperature of room temperature to about 300 ° C. The above-mentioned “specific silica gel” means that the condensation reaction proceeds at such a low temperature. On the other hand, ordinary silica sols on the market are not preferable as the binder precursor of the present invention because the condensation proceeds only at a high temperature of several hundred degrees Celsius. Moreover, silicones or a silicic acid liquid is preferable from the viewpoint of the compressive strength of the granulated product. Among these, a silicic acid solution is most preferable because an organic compound such as alcohol is not generated by hydrolysis in the granulation step.
Silicones are compounds having a polysiloxane bond, and examples thereof include compounds having the following structure or partial hydrolysates thereof.

[In the formula (I), each R is independently an optionally substituted alkyl, aryl, alkenyl, alkynyl, alkoxy, or aryloxy, and each R ′ is independently substituted. Alkyl, aryl, alkenyl or alkynyl, where n is a number from 1 to 100; ]
R is preferably an alkyl group of _{C 1 ~C 6, C 6 ~C} 12 aryl group, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, an alkoxy group having C ₁ -C _6, or C ₆ include an aryloxy group -C _12, which may be optionally substituted. More preferably, each independently includes an unsubstituted alkoxy group, an alkyl group, and an aryloxy group, particularly preferably an alkoxy group, particularly preferably an ethoxy group or a methoxy group, and most preferably a methoxy group.

R ′ is preferably a C ₁ -C ₆ alkyl group, a C ₆ -C ₁₂ aryl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group, which are optionally substituted May be. Preferably it is an unsubstituted C1-C5 alkyl group, more preferably methyl or ethyl, and most preferably methyl.

The partial hydrolyzate of the above formula (I) is a product in which at least a part of R and R ′ is converted to an OH group by hydrolysis.
The repeating unit n is usually 2 to 100, preferably 2 to 50, more preferably 3 to 30.
Depending on the value of n, the compounds of the formula (I) are present here in the form of monomers or in the form of long chains, optionally in the form of long branched oligomers.
The silicones of the present invention include alkyl silicates conventionally referred to as methyl silicate and ethyl silicate.

The silicic acid solution in the present invention is obtained by removing alkali metal ions from an alkali silicate solution.
For the removal of alkali metal ions, for example, a known method such as ion exchange can be adopted. For example, as described in Japanese Patent No. 3540040 and Japanese Patent Application Laid-Open No. 2003-26417, a sodium silicate solution is converted into an H ⁺ type. It is prepared by contacting with a cation exchange resin.

As the alkali silicate, potassium silicate or a mixture thereof can be used in addition to sodium silicate, but sodium silicate is preferable from the viewpoint of availability. As the H ⁺ -type cation exchange resin, a commercially available product such as Diaion SKT-20L, Amberlite IR-120B or the like is used after ion-exchanged into the H ⁺ type by a conventional method.
The required amount of the cation exchange resin to be used is selected based on known knowledge, but is usually an amount that provides at least a cation exchange capacity equal to or greater than the amount of alkali metal ions in the alkali silicate. The ion exchange can be either a flow type or a batch type, but a flow type is usually adopted.

The SiO ₂ concentration in the silicic acid solution is usually 1 to 10% by weight, preferably 2 to 8% by weight. If the concentration is lower than this range, the strength of the granulated product tends to decrease. On the other hand, if the concentration is too high, the stability of the silicic acid solution tends to decrease.
The silicic acid solution may contain a small amount of an alkali base ion, an organic amine, or an organic base such as quaternary ammonium as a stabilizer. The concentration of these stabilizers is usually 1% by weight or less, preferably 0.2% by weight or less, particularly preferably 0.0005 to 0.15% by weight, taking alkali metal ions as an example.

  If the alkali metal ion concentration is too higher than this range, the adsorption capacity tends to decrease. The alkali metal ion concentration can be controlled by adding a soluble salt such as alkali metal hydroxide, hydroxide, sodium silicate or the like to the silicic acid solution from which alkali metal ions have been removed to about 100 ppm or less. The alkali metal ion concentration to be controlled may be controlled.

In order to obtain the granulated product of the present invention, it is particularly preferable to use a silicone or silicic acid solution as a binder precursor and to select a firing temperature in the third step described later from a preferred range.
(Granulation method)
The granulated product of the present invention is produced by a process including the following three processes.
(1) First step of preparing a reaction mixture by mixing at least aluminophosphates and a binder precursor (2) The reaction mixture obtained in the first step is extruded, stirred granulated or spray granulated, Second step (3) to obtain a granule precursor by pulverization and / or sieving if necessary The granule precursor obtained in the second step is calcined at a temperature in the range of 150 ° C to 700 ° C. Third step

(First step)
In the first step, at least an aluminophosphate and a binder precursor are mixed to prepare a reaction mixture.
The blending ratio of the aluminophosphates and the binder precursor in the reaction mixture is usually 2 to 40 parts by weight, preferably 5 to 30 parts by weight in terms of oxide of the binder precursor with respect to 100 parts by weight of the aluminophosphate. Use at a rate of. If the amount is less than this range, the compressive strength tends to decrease, and if the amount is too large, the adsorption capacity tends to decrease.

Usually, water is added to the reaction mixture. The blending ratio is usually 10 to 500% by weight with respect to the aluminophosphates although it depends on the molding method. For example, in the case of extrusion molding or stirring granulation, it is 10 to 50 parts by weight, preferably 10 to 30 parts by weight, and in the case of spray drying, 30 parts by weight to 400 parts by weight, preferably 40 parts by weight to 220 parts by weight. is there.
Moreover, according to the characteristic at the time of kneading | mixing and extrusion, you may add plasticizers, such as celluloses, such as methylcellulose, starch, and polyvinyl alcohol, in order to improve fluidity | liquidity to this reaction mixture. The blending ratio is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of aluminophosphate. When there is too much addition amount, it exists in the tendency for the intensity | strength of a granulated material to fall.
In addition, the average particle diameter of the raw material aluminophosphate used for granulation is usually 15 μm or less, preferably 10 μm or less, and the lower limit is usually 1 μm. If necessary, dry pulverization such as a jet mill or wet pulverization such as a ball mill may be performed.

(Second step)
In the second step, the reaction mixture obtained in the first step is subjected to extrusion molding, stirring granulation or spray granulation, and if necessary, pulverized and / or sieved to obtain a granule precursor.
As an apparatus used for extrusion molding, stirring granulation, or spray granulation, a known extrusion molding machine, stirring granulator, or spray dryer can be used. Spray granulation is suitable for a particle size range of 50 to 200 μm, and rolling granulation or stirring granulation is suitable for 200 to 5000 μm, particularly 500 to 5000 μm.

In the case of stirring granulation, aluminophosphates, a binder precursor and a plasticizer are usually mixed at room temperature, and then a predetermined amount of water is added to perform granulation (stirring). The granulation time is not particularly limited, but is usually 1 minute to 120 minutes, preferably 2 minutes to 30 minutes. If the granulation time is too short, the granulation is insufficient and the particle size distribution of the granulated product becomes wide. If the granulation time is too long, the moisture in the system volatilizes during granulation, making moisture management difficult. After granulation, the granule precursor is obtained by drying at 50 to 150 ° C. as necessary.

  By adopting rolling granulation, even if the binder is about 10% by weight in terms of oxide, after firing, for example, the particle size is about 1 mm and the compressive strength is as high as 6-10 MPa, 0.1- A spherical granulated product having a pore volume in the 5 μm range of 0.2 to 0.4 ml / g can also be obtained. When the particle size is about 1 mm, if necessary, particles such as silica, alumina, silica-alumina, etc. may be used as a nucleus, and a binder and an aluminophosphate may be adhered around the particles.

In the case of extrusion molding, usually, aluminophosphates, a binder precursor, a plasticizer and water are added and kneaded, and then molded by an extrusion molding machine. Although there is no restriction | limiting in particular in the pressure in the case of shaping | molding, Usually, it is about 5-500 kgf / cm < ² >. After granulation, usually from 50 ° C to 15
Dry at a temperature of about 0 ° C., pulverize and classify to obtain the desired granule precursor.
In the case of spray drying, a slurry obtained by adding aluminophosphates, a binder precursor, a plasticizer and water and mixing them is introduced into a spray dryer. As conditions, the solid concentration of the raw slurry is usually about 20 to 70% by weight, the inlet temperature of the spray dryer is preferably about 150 to 450 ° C., and the outlet temperature is preferably about 60 to 225 ° C. The particle size of the granule precursor depends on the size of the sprayed droplets, and also on the slurry feed rate, slurry concentration, and spray type. In addition, the strength of the granulated product tends to increase and the bulk density tends to increase as the spray drying temperature is lowered. However, if the spray drying temperature is too low, the proportion of particles reaching the wall surface before drying increases. Since the rate decreases, it is preferable to set a relatively high value within the above range.
In addition, it is preferable to select the above conditions so that the aluminophosphates in the granulated product are subjected to the second step in a state containing a template (template) used for the synthesis.

(Third step)
In the third step, the granule precursor obtained in the second step is fired at a temperature in the range of 150 ° C to 900 ° C. The temperature is preferably 200 ° C. or higher, more preferably 250 ° C.
As described above, the temperature is particularly preferably 300 ° C. or higher. On the other hand, it is preferably 800 ° C. or lower, more preferably 700 ° C. or lower. By calcination in the above temperature range, the binder precursor is substantially cross-linked and a high compression strength of the granulated product is obtained, and the adsorption and catalytic properties of the produced granulated product are also improved. If the firing temperature is too high, the structure of the aluminophosphate is destroyed and the adsorption capacity decreases. On the other hand, if the firing temperature is too low, crosslinking of the binder precursor, preferably alkyl silicate, does not proceed sufficiently, and the template is not sufficiently removed, and the adsorption capacity tends to decrease.

  In the firing step, known firing methods such as a fixed bed, a fluidized bed, and a rotary furnace can be applied, but a fluidized bed and a rotary furnace are preferred from the viewpoint of uniformity of firing and ease of temperature control. The firing gas is preferably circulated in order to quickly remove volatile substances and moisture generated by firing. As the firing gas, an oxygen-containing gas such as air or an inert gas such as nitrogen can be used, but in order to control the heat generated by the combustion of the organic template or the like that is derived from the aluminophosphate synthetic raw material, air is used. Diluted oxygen-containing gas obtained by diluting with an inert gas such as nitrogen is preferably used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by the following examples.
In the following examples, each physical property was measured by the following method.
(Measurement of macropore volume)
The pore volume was determined from the pore distribution curve by the mercury intrusion method. Specifically, an Autopore 9200 type pore distribution measuring apparatus manufactured by Micrometrics was used, and the measurement conditions were an equilibration time of 10 seconds, a contact angle of 130 degrees, a surface tension of 484 dyne / cm, and a measurement pressure range of 20 to 59500 psi.

(Measurement of water vapor adsorption)
The water vapor adsorption amount was measured using BELSORP18 manufactured by Bell Japan. About 0.1 g of the sample was used for measurement, and evacuation was performed at 120 ° C. for 5 hours as a pretreatment. The measurement was performed at 25 ° C.
(Measurement of compressive strength)
Based on JIS28841-1993, it measured by the following method.
(I) When the particle size is 500 μm or less:
A micro compression tester MCTM500 manufactured by Shimadzu Corporation was used. Specifically, the measurement was automatically performed at room temperature under the following conditions.
Sample shape Particle Flat indenter 500μm
Load speed 0.79gf / sec
In addition, in order to reduce the measurement error due to the difference of each particle, 10 points were measured per one type of sample, and the average value was adopted as the measured value.

(Ii) When the particle diameter exceeds 500 μm:
A Shimadzu autogram automatic load-strain controller AGS-500B manufactured by Shimadzu Corporation was used. Specifically, the measurement was automatically performed at room temperature under the following conditions.
Sample shape Particle Displacement speed 2mm / min
In addition, in order to reduce the measurement error due to the difference of each particle, 10 points were measured per one type of sample, and the average value was adopted as the measured value.

(Measurement of bulk density)
About 25 ml of sample is put into a 25 ml graduated cylinder and the sample weight (W) is measured. Next, the graduated cylinder was vibrated for 3 minutes, and after that, the volume (V) was measured by striking about 100 times with a hammer. The bulk density was measured in a dry state. (Bulk density = W ÷ V)
(Measurement of particle size distribution)
The particle size distribution was measured using LASER MICRON SIZER LMS-24 manufactured by Seishin Enterprise Co., Ltd. A small amount of sample was dispersed in water and introduced into the measuring section, and automatic measurement was performed under the following conditions.
Dispersion time 60 seconds Number of washings 2 times Uptake number 100 times Density 1.000 g / cm ³
Refractive index 1.33
Shape factor 1

(Elemental analysis)
A sample calcined at 550 ° C. for 6 hours was dissolved by heating with hydrochloric acid, and the filtrate obtained by filtration was subjected to a constant volume, followed by ICP analysis. The filter paper was ashed with a platinum crucible, melted with sodium carbonate, dissolved in water, and analyzed by ICP. Binder-derived silica was contained in the insoluble material when dissolved in hydrochloric acid. (Si + P) / (Al + Fe) was determined from the results of elemental analysis.

Example 1
(Preparation of iron aluminophosphate)
To a mixture of 126.0 parts by weight of water and 51.9 parts by weight of 85% phosphoric acid, 24.6 parts by weight of pseudoboehmite (containing 25% by weight of water, PURAL SB manufactured by Condea) was slowly added and stirred for 3 hours. To this was added a solution prepared by dissolving 25.02 parts by weight of ferrous sulfate heptahydrate in 130.2 parts by weight of water, and then a mixture of 19.56 parts by weight of morpholine and 22.74 parts by weight of triethylamine was added to add 3 Stirring for a time gave a starting reactant having the following composition:

0.4FeSO ₄ /0.8Al ₂ O ₃ / P ₂ O ₅ / morpholine / triethylamine / 70H ₂ O
The above starting reaction product was charged in a stainless steel autoclave and reacted at 160 ° C. for 2 days with stirring. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed with water three times by decantation, filtered, and dried at 120 ° C.

(Manufacture of granules)
The aluminophosphate thus obtained was pulverized with a microjet mill CPN-04 type manufactured by Seishin Enterprise Co., Ltd. under a supply rate of 1140 g / Hr using 5 kg / cm ² of pressure nitrogen. The average particle size after pulverization was 5.3 μm. 500 parts by weight of the pulverized product and 5 parts by weight of Shin-Etsu Chemical Co., Ltd. Metroze (SM-100) were charged into a stirring granulator (Neigra Machine SEG-200 manufactured by Seishin Enterprise Co., Ltd.) and mixed with stirring. Next, 50 parts by weight of methyl silicate (MKS silicate (registered trademark) MS51, manufactured by Mitsubishi Chemical Co., Ltd., average value of n in the general formula (I): about 5) was added as a binder precursor and mixed with stirring. . Further, 100 parts by weight of water was added at a rotation speed of 600 rpm in about 30 seconds, and the mixture was stirred for 10 minutes for granulation. The obtained granulated product was dried at 120 ° C. and then sieved with a sieve having openings of 106 μm and 250 μm to obtain a granulated product precursor having a desired particle size of 106 to 250 μm. The granule precursor thus granulated was calcined at 300 ° C. for 8 hours in a fluidized bed calciner in a 5% oxygen atmosphere. Table 1 shows the results of various evaluations after cooling.
Table 1 shows the compressive strength, bulk density, and pore volume in the range of 0.1 to 5 μm of the obtained granulated product. As a result of elemental analysis, the results were Si 6.5 mol%, Al 33.4 mol%, P 46.6 mol%, Fe 13.4 mol%, and (Si + P) / (Al + Fe) was 1.13 mol / mol.
Moreover, the water vapor adsorption isotherm at 25 ° C. is shown in FIG.

(Reference example)
FIG. 2 shows a water vapor adsorption isotherm of the aluminophosphate obtained by firing at 300 ° C. without granulating the aluminophosphate obtained in Example 1.
As apparent from the comparison between FIG. 1 and FIG. 2, it can be seen that the granulated product of this example hardly shows a decrease in adsorption characteristics due to granulation, and maintains the adsorption characteristics of aluminophosphate.

(Example 2)
In 146 parts by weight of the same aluminophosphate pulverized product as in Example 1, methyl silicate (MKS silicate (registered trademark) MS60 manufactured by Mitsubishi Chemical Corporation) as a binder precursor, average value of n in the above general formula (I): About 28) 29.2 parts by weight and 324.8 parts by weight of water were added and stirred and mixed. The obtained mixture was introduced into a spray granulator (Okawahara Chemical Industries, Ltd .: L-8 type spray granulator) for granulation. The granulation conditions were an atomizer rotation speed of 10,000 rpm, a liquid supply speed of 0.86 L / Hr, a hot air outlet temperature of about 140 ° C. (hot air inlet temperature of 200 to 220 ° C.), and an air volume of 72 m ² / Hr. This obtained granulated product is classified to a particle size of 63 μm or more and 150 μm.
The following granules were obtained. The obtained granulated material was fired in the same manner as in Example 1, and the results of various evaluations are shown in Table 1.

(Example 3)
2.5 parts by weight of the same aluminophosphate pulverized product as in Example 1, methyl silicate (MKS silicate MS56S manufactured by Mitsubishi Chemical Co., Ltd., average value of n in the above general formula (I): about 16 as a binder precursor ) 0.5 parts by weight and 2.5 parts by weight of water were added and mixed with stirring. The obtained mixture was introduced into a spray granulator (pressure nozzle type) and granulated. The granulation conditions were a spray pressure of about 0.5 mPa, a feed rate of 29.5 kg / Hr, and a hot air outlet temperature of about 95 ° C. (hot air inlet temperature of 200 to 220 ° C.). The obtained granulated product was classified to obtain a granulated product precursor having a particle size of 100 to 250 μm. The obtained granule precursor was fired in the same manner as in Example 1, and the results of various evaluations are shown in Table 1.

Example 4
50 parts by weight of the same aluminophosphate pulverized product as in Example 1, 0.5 parts by weight of Shin-Etsu Chemical Co., Ltd. Metroze (SM-100), 10 parts by weight of methyl silicate (MKS silicate MS51) as a binder, and water 22 parts by weight were added and kneaded in a mortar. The obtained mixture is molded by a hydraulic extrusion molding machine (manufactured by ENERPAC: hydraulic molding machine), dried at 120 ° C., and then pulverized and classified to obtain a granule precursor having a desired particle size of 100 to 250 μm. It was. Table 1 shows the results of baking and various evaluations as in Example 1. The water vapor adsorption isotherm at 25 ° C. is shown in FIG.

(Example 5)
(Preparation of silicoaluminophosphate)
To a mixture of 210.5 parts by weight of water and 83.7 parts by weight of 85% phosphoric acid, 56.4 parts by weight of pseudoboehmite (containing 25% by weight of water, CATAPAL C1 manufactured by SASOL) was slowly added and stirred for 3 hours. To this was added a slurry in which 6.2 parts by weight of fumed silica (Aerosil 200) was suspended in 210.5 parts by weight of water, then 32.5 parts by weight of morpholine and 41.5 parts by weight of triethylamine were added and stirred for 3 hours. Thus, a starting reactant having the following composition was obtained.
0.25 SiO ₂ / Al ₂ O ₃ /0.875 P ₂ O ₅ /0.9 morpholine / 0.99 triethylamine / 60H ₂ O
The above starting reactants were charged into a stainless steel autoclave and reacted at 185 ° C. for 2 days with stirring. After the reaction, the reaction mixture was cooled, the supernatant was removed by decantation, and the precipitate was collected. The precipitate was washed with water three times by decantation, filtered, and dried at 100 ° C. As a result of XRD measurement, a pure CHA structure was confirmed.

(Manufacture of silicic acid solution)
Cation exchange resin (10+ parts by weight of sodium silicate solution (No. 3: SiO ₂ : 29% by weight, Na ₂ O: 9.5% by weight) diluted to 100 parts by weight with water to make H ⁺ type in advance. Diaion SKT-20L) was passed through a column packed with 20 parts by weight to exchange ions with the H ⁺ type, and the silicic acid solution was recovered. The silicic acid solution had a pH of 4.5, an Na content of 50 ppm, and an SiO ₂ content of 3% by weight.

(Manufacture of granules)
To 120.75 parts by weight of a pulverized product obtained by pulverizing silicoaluminophosphate in the same manner as in Example 1, 403 parts by weight of silicic acid solution was added and stirred and mixed. The obtained mixture was introduced into a spray granulator (Okawahara Chemical Industries, Ltd .: L-8 type spray granulator) for granulation. The granulation conditions were an atomizer rotational speed of 8000 rpm, a liquid supply speed of 1.00 L / Hr, a hot air outlet temperature of about 110 ° C. (hot air inlet temperature 160 to 165 ° C.), and an air volume of 72 m ² / Hr. The obtained granulated product was classified to obtain a granulated product having a particle size of 63 μm or more and 250 μm or less. The obtained granulated product was fired at 700 ° C. for 6 hours in a batch rotary kiln under a flow of 5% oxygen of the granulated product precursor. Table 1 shows the results of various evaluations. The water vapor adsorption isotherm at 25 ° C. is shown in FIG.

(Example 6)
Add 644 parts by weight of the silicic acid solution obtained in Example 5, 12.5 parts by weight of water glass No. 3 and 62.5 parts by weight of water to 120.75 parts by weight of the pulverized silicoaluminophosphate of Example 5. Mixed. The concentration of Na in the silicic acid solution was 0.12% by weight. The obtained mixture was introduced into a spray granulator (Okawahara Chemical Industries, Ltd .: L-8 type spray granulator) for granulation. The granulation conditions were an atomizer rotational speed of 8000 rpm, a liquid supply speed of 1.00 L / Hr, a hot air outlet temperature of about 110 ° C. (hot air inlet temperature 160 to 165 ° C.), and an air volume of 72 m ² / Hr. The obtained granulated product was classified to obtain a granulated product having a particle size of 63 μm or more. The obtained granulated product was fired in the same manner as in Example 5, and the results of various evaluations are shown in Table 1. In addition, in the water vapor adsorption isotherm measured at 25 ° C., the amount of water adsorbed when the relative vapor pressure changes by 0.15 in the range of the relative vapor pressure of 0.01 to 0.30 is 0.19 g / g. Met.

(Example 7)
Agitation granulation was performed by the following method to obtain a 1-2 mm granulated product. Using a Newgramachine NGIS-200 type manufactured by Seishin Enterprise Co., Ltd., 500 parts by weight of a pulverized silicoaluminophosphate product of Example 5 and 5 parts by weight of a plasticizer: Metrose (SM-100), methyl silicate (MS51) as a binder precursor 50 parts by weight were added with stirring, and 190 parts by weight of water was added with stirring at a rotation speed of 900 rpm. The stirring time was 10 minutes. The temperature at that time was 50 ° C. The granulated product was taken out and dried at 100 ° C. for 4 hours under reduced pressure. Among the obtained granulated materials, those having a particle size of about 1-2 mm were obtained by sieving. The average particle size was 1.2 mm. The obtained granulated product was fired in the same manner as in Example 5, and the results of various evaluations are shown in Table 1. In the water vapor adsorption isotherm measured at 25 ° C., the adsorption amount at a relative vapor pressure of 0.05 is 0.095 g / g, the adsorption amount at a relative vapor pressure of 0.2 is 0.28 g / g, and the relative vapor pressure is The adsorption amount change was 0.185 g / g when 0.15 changed from 0.05 to 0.20.

(Example 8)
Rolling granulation was performed by the following method to obtain a 1-2 mm granulated product. Silica aluminophosphate pulverized product of Example 5: 20 parts by weight, Metrose SM-100: 0.2 part by weight and silicate MS51: 2 parts by weight were mixed with a kneader for 30 minutes. While adding this to a pot mixer charged with 0.7 parts by weight of silica particles R5 (manufactured by Mikawa Silica Co., Ltd., diameter 0.5 mm) while rotating at 30 rpm, water was sprayed to grow the particles to 1-2 mm. It was. Then, after taking out the granulated material from the mixer and air-drying, it dried similarly to Example 7, sieved, and baked. The average particle diameter was 1.2 mm. Table 1 shows the results of various evaluations. In the water vapor adsorption isotherm measured at 25 ° C., the adsorption amount at a relative vapor pressure of 0.05 is 0.095 g / g, the adsorption amount at a relative vapor pressure of 0.2 is 0.28 g / g, and the relative vapor pressure is The adsorption amount change was 0.185 g / g when 0.15 changed from 0.05 to 0.20.

(Comparative Example 1)
50 parts by weight of the same aluminophosphate pulverized product as in Example 1, 0.5 parts by weight of San Nopco's SN thickener (A-812: urethane-modified polyether) as a plasticizer, and Silica sol (S-20L) by Catalysts Kasei as a binder 38.5 parts by weight were added and kneaded. The obtained mixture was molded with a hydraulic extrusion molding machine (manufactured by ENERPAC: hydraulic molding machine), dried at 120 ° C., and then pulverized and classified to obtain a granulated precursor having a desired particle size of 100 to 250 μm. . Table 1 shows the results of baking and various evaluations as in Example 1.

(Comparative Example 2)
To 111 parts by weight of the same aluminophosphate pulverized product as in Example 1, 14.6 parts by weight of phenol resin (Resitop XPL manufactured by Gunei Chemical Industry Co., Ltd.) and 324.8 parts by weight of water were added as a binder precursor and mixed with stirring. The obtained mixture was introduced into a spray granulator (Okawahara Chemical Industries, Ltd .: L-8 type spray granulator) for granulation. The granulation conditions were an atomizer rotation speed of 10,000 rpm, a liquid supply speed of 0.86 L / Hr, a hot air outlet temperature of about 140 ° C. (hot air inlet temperature of 200 to 220 ° C.), and an air volume of 72 m ² / Hr. Due to the pulverization of the granulated product, the compression strength and bulk density could not be measured.

2 is a water vapor adsorption isotherm of the granulated product of Example 1. FIG. 4 is a water vapor adsorption isotherm of the granulated product of Reference Example 1. 4 is a water vapor adsorption isotherm of the granulated product of Example 3. 6 is a water vapor adsorption isotherm of the granulated product of Example 5.

Claims (9)

  It consists essentially of an aluminophosphate and a binder, and is a granulated product having a particle size range of 50 to 5000 μm, and a pore volume in a pore size range of 0.1 to 5 μm is 0.05 cc / g or more. A granulated product having 5 cc / g or less and a compressive strength of 2 MPa or more.   In the water vapor adsorption isotherm measured at 25 ° C., when the relative vapor pressure changes by 0.15 in the range of the relative vapor pressure of 0.01 or more and 0.30 or less, the change in the adsorption amount of water is 0.12 g / g or more. The granulated product according to claim 1, which has a relative vapor pressure region. The molar ratio of Si, P, Al, and Me in the granulated product (where Me represents a hetero atom that can be substituted for a part of Al in the aluminophosphate skeleton) satisfies the following formula: The granulated product according to claim 1 or 2 .
1.02 ≦ (Si + P) / (Al + Me) ≦ 1.4 A granulated product obtained from a reaction mixture containing at least an aluminophosphate and a binder precursor, wherein the binder precursor contains a compound of the following formula (I): Granules described in 1.

[In the formula (I), each R is independently an optionally substituted alkyl, aryl, alkenyl, alkynyl, alkoxy or phenoxy, and each R ′ is independently an optionally substituted alkyl. , Aryl, alkenyl or alkynyl, and n is a number from 1 to 100. ]   The granulated product obtained from a reaction mixture containing at least aluminophosphates and a binder precursor, wherein the binder precursor contains a silicic acid solution. object. In a method for producing an aluminophosphate granule using at least an aluminophosphate and a binder precursor, the binder precursor contains a compound of the following formula (I) or a silicic acid solution. Manufacturing method.

[In the formula (I), each R is independently an optionally substituted alkyl, aryl, alkenyl, alkynyl, alkoxy or phenoxy, and each R ′ is independently an optionally substituted alkyl. , Aryl, alkenyl or alkynyl, and n is a number from 1 to 100. ]   The method for producing a granulated product according to claim 6, wherein the binder precursor is used in an amount of 2 to 40 parts by weight in terms of oxide with respect to 100 parts by weight of the aluminophosphate. (1) a first step of preparing a reaction mixture by mixing at least aluminophosphates and a binder precursor;
(2) a second step of obtaining a granule precursor by extruding, stirring granulation or spray granulation, and if necessary, pulverizing and / or sieving the reaction mixture obtained in the first step;
(3) A method for producing a granulated product according to claim 6 or 7, comprising a third step of firing the granulated product precursor obtained in the second step at a temperature in the range of 150 ° C to 800 ° C. .   The method for producing a granulated product according to any one of claims 6 to 8, wherein the granulated product is the granulated product according to claim 1.

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