JP4886178B2 - Carbon-containing silicoaluminophosphate, production method thereof, adsorbent containing carbon-containing silicoaluminophosphate, heat utilization system, adsorption heat pump, and cold storage heat system - Google Patents

Description

  The present invention relates to a carbon-containing silicoaluminophosphate, a method for producing the same, an adsorbent containing the carbon-containing silicoaluminophosphate, a heat utilization system, an adsorption heat pump, and a cold storage heat system, and more specifically, containing carbon having a specific content. The present invention relates to silicoaluminophosphate, a production method thereof, an adsorbent containing the same, and the like.

  Zeolites are widely used as adsorbents, catalysts for acid reactions and oxidation reactions, separation materials, optical materials such as quantum dots and quantum wires, and host materials such as semiconductor fine particles, phosphors, and dyes used as magnetic materials. . Zeolite includes crystalline silicates, crystalline aluminophosphates, and the like according to the provisions of the International Zeolite Association (referred to herein as IZA).

  Zeolite is usually produced by hydrothermal synthesis using a zeolite raw material and a structure-directing agent (also referred to as an organic template), and then removing the organic template by a method such as calcination or extraction. In general, zeolite from which an organic template has been removed as much as possible is used as an industrially useful zeolite for a catalyst, an adsorbent, or the like. The reason for removing the organic template as much as possible is that the zeolite before removal of the organic template obtained by hydrothermal synthesis or the like (referred to as a zeolite precursor in this application) has the space in the pores occupied by the organic template. This is because the reaction substrate or the adsorbed substance cannot enter the pores and the function as a catalyst or an adsorbent is not exhibited. Therefore, industrially useful zeolite is usually in a form in which the organic template is removed from the zeolite precursor as much as possible.

Among the zeolites, in particular, as a method for producing silicoaluminophosphate using silicon as a heteroatom, the following Patent Document 1 discloses that when an organic template is removed from a silicoaluminophosphate zeolite precursor, A method is described in which the body is heated to decompose and remove the organic template (firing). Further, it is described that SAPO-5 (framework density (FD): 17.3 T / nm ³ ) having a carbon content before firing of 6.9 wt% was manufactured. However, the SAPO-5 obtained here has a relatively large framework density, and according to our study, the amount of adsorption when used as an adsorbent is insufficient.

  In addition, in Patent Document 2 below, when a part of the pore structure of zeolite is occupied by an organic template or a decomposition product of the organic template, adsorption of moisture in the atmosphere is prevented during storage or transportation, so that the catalytic activity Does not decrease, and the examples show examples where 8.20% by weight or more of carbon atoms remain. On the other hand, when using zeolite as a catalyst, it is taught that as an activation treatment, firing or combustion treatment is performed in an oxygen-containing atmosphere to completely remove the organic template and the like from the pore structure of the zeolite.

Non-Patent Document 1 below describes a silicoaluminophosphate having a GIS structure in which carbon atoms are 3.99 wt% to 6.09 wt% and nitrogen atoms are remaining 4.83 wt% to 6.09 wt%. (SAPO-43) _has, CO _2, H 2 O, are reported to exhibit a selective adsorbability, such as _{H 2} S. However, the zeolite is essentially unstable when the organic template is completely removed, and the crystal structure collapses as the organic template is removed, and the adsorption capacity is almost completely removed when the organic template is completely removed. Has been shown to lose. Further, in the zeolite, the adsorption capacity of the zeolite obtained while maintaining the structure by leaving the organic template was as low as 8% by weight when the adsorbed water was water.
JP 59-35018 A US Pat. No. 6,395,674 (Example) RTYang et al., Langmuir, 2003, 19, 2193-2200

  As described above, conventional zeolites have a relatively large amount of organic template or a substance derived from the zeolite remaining in the zeolite, removed as much as possible, or stable when the organic template is completely removed. In the zeolite that cannot be present in the above, the organic template is removed to such an extent that the crystal structure is not completely destroyed, or the framework density is relatively large, that is, the pore volume is relatively small. Therefore, the conventional zeolite has insufficient adsorption capacity when used as an adsorbent, or if the adsorption capacity is sufficient, the durability when repeatedly used as an adsorbent is insufficient. .

  In contrast, even if the zeolite is stable with the organic template in the zeolite completely removed, the initial adsorption capacity or catalytic activity is high when the organic template in the pores is completely removed. However, it has been found that the powdering of the particles and the destruction of the crystal structure occur with use, and the adsorption performance may be lowered accordingly. It has been found that such a problem is significant in zeolites having a relatively small framework density (that is, a relatively large pore volume). On the other hand, if a part of the organic template remains in the pores of the zeolite above a certain content, it is effective to prevent the catalyst activity from being reduced by moisture in the atmosphere during storage. However, it has been found that the adsorption capacity and the like cannot be sufficiently obtained from the initial stage.

  The present invention has been made to solve the above-mentioned problems, and its purpose is to produce a zeolite with little performance deterioration during use under conditions exposed to high temperatures, repeated use, or long-term use, and production thereof. Providing a method, especially when used as an adsorbent, the adsorption capacity is sufficiently large, and the zeolite particles are pulverized, the crystal structure is destroyed, and the adsorption capacity associated with the use at high temperature and repeated use is increased. An object of the present invention is to provide a zeolite that does not deteriorate and a method for producing the same. Another object of the present invention is to provide an adsorbent containing such zeolite, a heat utilization system using the adsorbent, an adsorption heat pump, and a cold storage heat system.

  As a result of intensive studies on the above problems, the present inventors have found that when the zeolite is a silicoaluminophosphate having a specific framework density and whose structure is maintained by calcination, the organic template remaining therein or derived therefrom It has been found that a silicoaluminophosphate that controls the amount of the substance to be controlled and, as a result, controls the carbon content in the silicoaluminophosphate to a specific amount solves the above-mentioned problems. Furthermore, the present inventors have found that the adsorbent using the silicoaluminophosphate having an adjusted carbon content has little change in adsorption characteristics even when exposed to hydrothermal conditions, and is excellent in durability. . Furthermore, the present inventors are effective in using the adsorbent in a heat utilization system or a cold storage heat system, specifically, a cold storage heat system, an adsorption heat pump, a dehumidification or humidification humidity control air conditioner. It has been found that it can be effectively used as an adsorbent for general purpose.

That is, in the present invention for solving the above-mentioned problems, the carbon content is 0.8 wt% or more and 6 wt% or less, and each molar ratio of Me, Al, P and Si constituting the skeleton structure is represented by the following formulas 1 to 4. a silicoaluminophosphate phosphate satisfying the, if the framework density is 10T / nm ³ or more 16T / nm ³ or less, that by calcining the silicoaluminophosphate phosphate and carbon content less than 0.3 wt% The skeleton structure before firing is maintained. Here, Me is at least one element selected from elements of Groups 2A, 7A, 8, 1B, and 2B of the periodic table.

0 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Me to the sum of Me, Al, P and Si)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the sum of Me, Al, P and Si)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the sum of Me, Al, P and Si)
0.001 ≦ w ≦ 0.3 4
(W represents the molar ratio of Si to the sum of Me, Al, P and Si)

  According to this invention, the silicoaluminophosphate containing carbon in the above range has a large adsorption capacity and excellent hydrothermal stability when used as, for example, an adsorbent, and the destruction of the crystal structure associated with repeated use. It has an excellent effect that the adsorption capacity is not reduced accordingly.

  In the carbon-containing silicoaluminophosphate of the present invention, the carbon content is preferably 1.8 wt% or more and 6 wt% or less. The skeleton structure is preferably a structure selected from AEI, AFR, AFS, AFT, AFX, ATS, CHA, ERI, LEV, LTA and VFI represented by a code defined by IZA, and particularly AEI, CHA. And a structure selected from LEV. In addition, Me is preferably at least one element selected from Fe, Ni, Co, Mg and Zn, and particularly preferably Fe.

  Moreover, in the carbon-containing silicoaluminophosphate of the present invention, when a repeated durability test of the carbon-containing silicoaluminophosphate is performed according to the following, it is preferable that the crystal structure before the test is retained. In the present application, the “repetitive durability test” is an operation in which a carbon-containing silicoaluminophosphate is held in a vacuum vessel maintained at 90 ° C. and exposed to a vacuum state and a saturated steam atmosphere at 90 ° C. for 90 seconds. It is a test repeated twice. “Crystal structure is retained” means that the strongest peak intensity after repeated endurance test is repeated endurance when XRD measurement is performed with the same equipment, the same measurement conditions, the same sample holder and the same sample weight. It means 50% or more of the strongest peak intensity before the property test. The peak intensity is the peak height and is defined by subtracting the background count from the peak top count.

  In addition, the method for producing a carbon-containing silicoaluminophosphate of the present invention that solves the above-mentioned problems is obtained by hydrothermally synthesizing a compound of a metal element constituting the silicoaluminophosphate in the presence of a structure indicating material, and obtaining the obtained silicoalumino The phosphate precursor is calcined in an atmosphere having an oxygen concentration of 20 vol% or less.

  In the invention of this production method, the temperature for firing the silicoaluminophosphate precursor is preferably 300 ° C. or higher and 450 ° C. or lower. Further, the silicoaluminophosphate precursor is hydrothermally synthesized in the presence of two or more kinds of structure indicating materials, and the structure indicating materials are (1) an alicyclic heterocyclic compound containing nitrogen, (2 It is desirable to be selected from two or more of the group consisting of :)) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. Silicoaluminophosphate precursors are morpholine, cyclohexylamine, triethylamine, isopropylamine, N, N-diisopropylethylamine, N-methyl-n-butylamine, isobutylamine, hexamethyleneimine, N, N-diethylethanolamine and It is preferably synthesized in the presence of at least one nitrogen-containing organic compound selected from N, N-dimethylethanolamine as a structure indicating material.

  According to the inventions of these production methods, the carbon-containing silicoaluminophosphate of the present invention that exhibits the above effects can be produced stably.

  Moreover, the adsorbent of the present invention that solves the above-described problems includes the above-described carbon-containing silicoaluminophosphate of the present invention.

In the invention of the adsorbent, (i) the carbon-containing silicoaluminophosphate has a relative vapor pressure change of 0.15 in the range of the relative vapor pressure of 0.01 to 0.5 on the adsorption isotherm measured at 25 ° C. It is preferable that the adsorption amount change of the adsorbed material has a relative vapor pressure range of 0.1 g / g or more. Further, the adsorbent of the present invention is (ii) a heat utilization system that uses adsorption heat generated by adsorption of the adsorbent on the adsorbent, and / or latent heat of vaporization that is generated when the adsorbent evaporates from the adsorbent. preferably used in the heat utilization system, utilizing, (iii) the heat utilization system, the configuration for desorbing the adsorbed material was supplied to the adsorbent: (a) waste heat, (b -1 ) Configuration to supply the heat of adsorption generated when the adsorbed material is adsorbed to the adsorbent, and / or (b-2) Generated when the adsorbed material evaporates from the adsorbent is preferably a cooling refrigeration machine the evaporation latent heat you are cold storage heat system having a configuration for supplying the cooling medium circulates. Further, the adsorbent of the present invention is (iv) an adsorbent used in the cold storage heat system, wherein the carbon-containing silicoaluminophosphate contained in the adsorbent is an adsorption isotherm measured at 55 ° C. The adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is 0.12 g / g or less, the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.13 g / g or more, and the relative vapor pressure It has an adsorption characteristic having a relative vapor pressure region in which the adsorption amount change of the adsorbed material is 0.05 g / g or more when the relative vapor pressure is changed by 0.05 in the range of 0.02 to 0.1. It is desirable. In the present invention, (v) the heat utilization system is preferably an adsorption heat pump, and (vi) the carbon-containing silicoaluminophosphate contained in the adsorbent used in the adsorption heat pump is measured at 25 ° C. In the adsorption isotherm, the relative vapor pressure range where the adsorption amount change of the adsorbed material is 0.1 g / g or more when the relative vapor pressure changes 0.15 in the range of relative vapor pressure 0.05 or more and 0.30 or less. It is desirable to have adsorption characteristics having

  According to the invention of these adsorbents, the carbon-containing silicoaluminophosphate constituting the adsorbent has a large adsorption capacity and excellent hydrothermal stability, the destruction of the crystal structure accompanying repeated use, and the adsorption capacity associated therewith. The adsorbent itself has excellent durability because it has a suitable characteristic that no deterioration occurs. Therefore, this adsorbent can be preferably used in a heat utilization system, an adsorption heat pump, or a cold storage heat system.

  Moreover, this invention which solves the said subject consists of a heat utilization system, an adsorption heat pump, and a cool storage heat system using the adsorbent mentioned above.

  According to this invention, since the adsorbent excellent in durability containing the carbon-containing silicoaluminophosphate of the present invention described above is used, the durability of the system is excellent.

  As described above, according to the carbon-containing silicoaluminophosphate of the present invention, since it contains the predetermined amount of carbon, particularly when used as an adsorbent, the adsorption capacity is large and the hydrothermal stability is excellent. It has an excellent effect that the crystal structure is not broken and the adsorption capacity is not lowered by repeated use.

  In addition, the heat utilization system using the adsorbent containing the carbon-containing silicoaluminophosphate of the present invention has an effect that the system has excellent durability by using the adsorbent containing the zeolite of the present invention. Have.

  Hereinafter, the carbon-containing silicoaluminophosphate of the present invention, a production method thereof, an adsorbent including the carbon-containing silicoaluminophosphate, a heat utilization system, an adsorption heat pump, and a cold storage heat system will be sequentially described.

(Carbon-containing silicoaluminophosphate)
The silicoaluminophosphate according to the present invention is a silicoaluminophosphate containing carbon in an amount of 0.8 wt% or more and 6 wt% or less, and Me, Al, P and the like constituting the skeletal structure of the silicoaluminophosphate. Each molar ratio of Si satisfies the following formulas 1 to 4, and when the silicoaluminophosphate is fired to make the carbon content less than 0.3% by weight, the skeletal structure before firing is maintained. There is a special feature. Here, Me is at least one element selected from elements of Groups 2A, 7A, 8, 1B, and 2B of the periodic table.

0 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Me to the sum of Me, Al, P and Si)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the sum of Me, Al, P and Si)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the sum of Me, Al, P and Si)
0.001 ≦ w ≦ 0.3 4
(W represents the molar ratio of Si to the sum of Me, Al, P and Si)

  For each molar ratio, when x indicating the molar ratio of Me is larger than the above range, synthesis of the carbon-containing silicoaluminophosphate according to the present invention tends to be difficult. Note that x may be 0, and in that case, Me is not included in the silicoaluminophosphate. However, the inclusion of x makes it easy to control the adsorption characteristics (relationship between relative humidity and adsorption amount) when the carbon-containing silicoaluminophosphate of the present invention is used as an adsorbent. It is preferable to satisfy Formula 1 ′.

0.01 ≦ x ≦ 0.3 1 ′
(X represents the molar ratio of Me to the sum of Me, Al, P and Si)

  Further, if y indicating the molar ratio of Al is smaller than the above range, the synthesis tends to be difficult as described above, and if larger than the above range, impurities tend to be mixed. Further, when z indicating the molar ratio of P is smaller than the above range, the synthesis tends to be difficult as described above, and when larger than the above range, impurities tend to be mixed. Further, when w indicating the molar ratio of Si is smaller than the above range, the synthesis tends to be difficult as described above, and when it is larger than the above range, desired adsorption characteristics tend to be difficult to obtain.

  About each molar ratio of Me, Al, P, and Si, it is more preferable to satisfy the following formulas 5 to 8, which makes it easier to synthesize the carbon-containing silicoaluminophosphate of the present invention and suppresses the contamination of impurities. Furthermore, it becomes easier to obtain desired adsorption characteristics.

0 ≦ x ≦ 0.3 ... 5
(X represents the molar ratio of Me to the sum of Me, Al, P and Si)
0.3 ≦ y ≦ 0.5 6
(Y represents the molar ratio of Al to the sum of Me, Al, P and Si)
0.4 ≦ z ≦ 0.5… 7
(Z represents the molar ratio of P to the sum of Me, Al, P and Si)
0.01 ≦ w ≦ 0.25… 8
(W represents the molar ratio of Si to the sum of Me, Al, P and Si)

  Me may be at least one element selected from the elements of Group 2A, Group 7A, Group 8, Group 1B, and Group 2B of the periodic table, and may be included in two or more. Preferable Me is an element (Mg) belonging to the third period of the periodic table and an element (Ca, Mn, Fe, Co, Ni, Cu, Zn) belonging to the fourth period. Among these, those having an ionic radius of 0.3 to 0.8 in the divalent state (Mn, Fe, Co, Ni, Cu, Zn, Mg) are preferable, and more preferably, they are divalent. In addition, in the four-coordinate state, the ion radius is 0.4 to 0.7 (Fe, Co, Cu, Zn, Mg). Among these, from the viewpoint of easy synthesis and adsorption characteristics, one or two elements selected from Fe, Co, Mg, and Zn are preferable, and Fe is particularly preferable. 1Å is a unit converted to 10 nm.

  The silicoaluminophosphate according to the present invention may include those having a cation species capable of ion exchange with other cations, in addition to the components constituting the skeleton structure. Examples of such cationic species include protons, alkaline elements such as Li, Na, and K, alkaline earth elements such as Mg and Ca, rare earth elements such as La and Ce, and transition metal elements such as Fe, Co, and Ni. . Among these, protons, alkali elements, and alkaline earth elements are preferable.

  The silicoaluminophosphate of the present invention is such that when it is fired to have a carbon content of less than 0.3% by weight, the skeletal structure before firing is maintained. Here, when the carbon content is less than 0.3% by weight, the skeleton structure before firing means that the skeleton structure unique to the silicoaluminophosphate is maintained, and the following ( When satisfying 1) or (2), it is considered that the inherent skeleton structure is retained, and preferably both of the following (1) and (2) are satisfied. Hereinafter, (1) and (2) will be described.

  (1) The ideal water vapor adsorption amount assuming that an ideal skeleton structure is maintained is Qi, and the water vapor adsorption amount after firing until the carbon content is less than 0.3% by weight (25 ° C. When the relative vapor pressure 0.5) is Qc, Qc / Qi is 0.4 or more. However, Qi is determined according to the following (1-1) or (1-2). Note that the structural skeleton here refers to a code defined by IZA, and even if the elements constituting the skeleton are different, those described with the same code are regarded as the same skeleton structure.

  (1-1) When structural analysis of the framework structure of zeolite in a hydrated state has been made; the ratio of the contained water to the formula weight of the crystal in the hydrated state is defined as Qi.

  (1-2) If the skeletal structure of the hydrated zeolite has not been analyzed; DWBreck, "ZEOLITE MOLECULAR SIEVES: STRCTURE, CHEMISTRY, AND USE", A WILEY-INTERSCIENCE PUBLICATION, 1974- In page 50 and Table 2.4, the Void Fraction of the zeolite having the corresponding structure is defined as Qi.

  (2) In the powder X-ray diffraction pattern, among the peaks measured in the state before firing, at least one of the three peaks having a large intensity ratio derived from the corresponding crystal structure has a carbon content of 0.3 by firing. Even after less than% by weight, it has a peak height of 50% or more before firing. In addition, the measurement of peak intensity shall be performed with the same sample weight using the same sample holder.

  The peak intensity is measured by the following method (A) or (B) from the viewpoint of measurement accuracy.

  (A) When an internal standard is not used: Measure under the same conditions and compare the absolute values of the peak intensities of the samples to be measured. When the same sample is measured before and after measuring the peak intensity of the sample to be measured, the change in absolute value of the peak intensity is preferably 10% or less.

  (B) When using an internal standard substance: Mix the internal standard substance at a certain weight ratio, measure the peak intensity of the sample to be measured and the peak intensity of the internal standard substance (peak intensity ratio), Compare peak intensity ratios.

  More specifically, for example, the following methods can be mentioned.

  (A) Using the same apparatus, the sample is pulverized well manually with a mortar or the like, the measurement sample amounts are the same, and the measurement is performed under the same conditions. At this time, it is desirable that the measurements of the samples for comparing the intensities are as close as possible in time. In addition, in order to keep the state of the X-ray source as constant as possible, a well-known consideration shall be given to those who perform general XRD measurements. In addition, the same sample is measured before and after the comparative measurement to confirm that the change in diffraction intensity is 10% or less.

  (B) If the same device cannot be used, or if the X-ray source state may change significantly even in the same device, add the same internal standard substance to the measurement sample at a constant weight ratio, and mortar After mixing well, etc., XRD measurement is performed. Comparison of peak intensities between samples is performed by a ratio of the intensity of a diffraction peak derived from an internal standard substance and the diffraction peak intensity derived from zeolite. The internal standard substance is selected with knowledge known to those skilled in the art, such as not having a diffraction peak at the diffraction peak position derived from the zeolite whose intensity is to be compared.

  The indicator that the carbon content is less than 0.3% by weight after firing is an indicator that indicates the state in which the organic template used for the production of silicoaluminophosphate has been removed, and was determined by the detection limit. Value.

  Moreover, as a baking condition in the case of baking and making carbon content less than 0.3 weight%, it can be 450 degreeC or more and 2 hours in an oxygen-containing atmosphere, for example.

  In the silicoaluminophosphate of the present invention, the skeletal structure before firing is maintained after the carbon content is less than 0.3% by weight by firing. In the case of silicoaluminophosphate that does not retain the pre-firing skeletal structure after firing, due to the skeletal structure, for example, when used repeatedly as an adsorbent, the crystal structure is very easy to break and quickly absorb Tends to decrease.

Silicoaluminophosphate phosphate according to the present invention, the framework density is 10T / nm ³ or more 16T / nm ³ or less. If the framework density is less than the above range, the structure of the silicoaluminophosphate tends to be unstable. On the other hand, if the framework density exceeds the above range, the adsorption amount becomes small. Such framework density, more preferably 12T / nm ³ or more, more preferably 13T / nm ³ or more. On the other hand, the framework density is preferably 15 T / nm ³ or less. Here, T is an atom other than oxygen atoms constituting the skeleton of the silicoaluminophosphate, and T / nm ³ is a unit indicating the number of T atoms (framework density) present per nm ³ .

  The framework structure of the silicoaluminophosphate according to the present invention is a code defined by the International Zeolite Association (International Zeolite Association; referred to as “IZA”). AEI, AFR, AFS, AFT, AFX, ATS, CHA, ERI, LEV, It is a structure selected from LTA and VFI. Among these, from the viewpoint of adsorption characteristics and structural stability, a structure selected from AEI, CHA, and LEV is preferable, and CHA is particularly preferable.

  As described above, the silicoaluminophosphate according to the present invention contains 0.8 wt% or more and 6 wt% or less of carbon. Silicoaluminophosphate containing carbon in this range, for example, when used as an adsorbent, has a large adsorption capacity and excellent hydrothermal stability, destruction of the crystal structure associated with repeated use and a decrease in adsorption capacity associated therewith It has an excellent effect that does not occur. In particular, the crystal structure is hardly broken and the durability is improved. Therefore, it can be preferably applied to various practical uses. Examples of practical applications include a heat utilization system, an adsorption heat pump, and a cold storage heat system described later.

  When carbon content exceeds the said range, especially when using as an adsorbent, the amount of adsorption will fall and the performance as an adsorbent will become inadequate. On the other hand, when the carbon content is less than the above, particularly when used as an adsorbent, durability when the adsorbent is exposed to high temperature in the presence of water vapor (this durability is referred to as “hydrothermal stability”). The same) and durability against repeated adsorption / desorption may occur. The carbon content is preferably 1.8% by weight or more, and more preferably 2% by weight or more. The carbon content is preferably 5% by weight or less. The reason why the durability of silicoaluminophosphate containing carbon in such a range is improved is not clear enough, but it is considered that the change in crystal structure, lattice constant, and bonding state during adsorption / desorption is small. It is done.

  The silicoaluminophosphate according to the present invention does not need to contain nitrogen as long as the carbon content is in the above range, but may contain nitrogen. In the case of containing nitrogen, the nitrogen content has little influence on the hydrothermal stability, but if it is too much, the adsorption performance is lowered. Therefore, even when nitrogen is contained, it is usually preferably 2% by weight or less, and more preferably 1% by weight or less.

  In the silicoaluminophosphate according to the present invention, the proportion of the pore structure in which the adsorbed substance (sometimes referred to as adsorbate) can enter and exit (the pore utilization rate defined by the following formula 9 or the following formula 10). (Pore utilization rate 1 or pore utilization rate 2) is preferably 0.6 or more and 0.99 or less. The pore utilization rate is more preferably 0.7 or more, and particularly preferably 0.8 or more. On the other hand, the pore utilization rate is more preferably 0.95 or less, and particularly preferably 0.93 or less. In the present invention, the pore utilization rate is defined by the pore utilization factor 2 of the following formula 10 even if it is defined by the pore utilization factor 1 of the following equation 9. Also good.

Pore utilization factor 1 = Q1 / Qs ... 9
Here, Qs is the water vapor adsorption amount when the structure indicating material is completely removed, and Q1 is the water vapor adsorption amount of the silicoaluminophosphate according to the present invention. However, this water vapor adsorption amount represents the water vapor adsorption capacity per unit weight at a relative vapor pressure of 0.5 and room temperature (25 ° C.).

Pore utilization factor 2 = W1 / Ws ... 10
Here, Ws is an effective water adsorption amount when the structure indicating material is completely removed, and W1 is an effective water adsorption amount of the silicoaluminophosphate according to the present invention. The amount of effective water adsorbed here refers to the weight of the sample before the temperature rise when the sample saturated and adsorbed in a saturated water vapor atmosphere at 25 ° C. for one day is heated at a rate of 10 ° C./min under a circulation of dry air. This is the weight of water desorbed from 25 ° C to 100 ° C.

  When the carbon-containing silicoaluminophosphate of the present invention is subjected to a repeated durability test according to the following, it is preferable that the crystal structure before the repeated durability test is retained.

  In the present application, the “repetitive durability test” is an operation in which a carbon-containing silicoaluminophosphate is held in a vacuum vessel maintained at 90 ° C. and exposed to a vacuum state and a saturated steam atmosphere at 90 ° C. for 90 seconds. It is a test repeated several times. Here, “the crystal structure is retained” means that the strongest peak intensity after the repeated durability test is performed when the XRD measurement is performed with the same apparatus, the same measurement conditions, the same sample holder and the same sample weight. It means that it is 50% or more of the strongest peak intensity before the repeated durability test. The peak intensity is the peak height, and is defined by subtracting the background count from the peak top count.

  In addition, when the carbon-containing silicoaluminophosphate of the present invention is subjected to repeated durability tests in the same manner as described above, the water vapor adsorption amount at 25 ° C. and a relative vapor pressure of 0.5 is 80% or more before the test. It is preferable.

  The carbon-containing silicoaluminophosphate of the present invention preferably has a weight reduction rate (g1) of 0 to 3 wt% when heated from 200 ° C. to 350 ° C. The smaller weight loss rate (g1) is preferred, and the upper limit thereof is preferably 2% by weight, more preferably 1.5% by weight. When the weight reduction rate (g1) is too large, the thermal stability becomes insufficient.

  On the other hand, the weight reduction rate (g2) when the carbon-containing silicoaluminophosphate of the present invention is heated from 350 ° C. to 700 ° C. is preferably 2% by weight or more and 6% by weight or less. The weight loss rate (g2) is preferably 2.5% by weight or more, more preferably 3% by weight or more, and preferably 5.5% by weight or less. If the weight reduction rate (g2) is too small, the durability tends to be inferior. If the weight reduction rate (g2) is too large, the adsorbed amount is increased when the carbon-containing silicoaluminophosphate of the present invention is used as an adsorbent. There is a tendency to become insufficient.

  The weight reduction rate is calculated by the following equations 11 and 12, where w1 at 200 ° C., w2 at 350 ° C., and w3 at 700 ° C.

Weight reduction rate (g1) = (w1-w2) / w1 × 100 ... 11
Weight reduction rate (g2) = (w2-w3) / w1 × 100 ... 12

(Method for producing carbon-containing silicoaluminophosphate)
Next, the manufacturing method of the carbon containing silicoaluminophosphate of this invention is demonstrated.

  A method for producing a carbon-containing silicoaluminophosphate according to the present invention is a method for producing a carbon-containing silicoaluminophosphate according to the present invention having the above-mentioned composition and structural characteristics. It is manufactured by hydrothermally synthesizing a constituent metal element compound in the presence of a structure indicating material and firing the resulting silicoaluminophosphate precursor in an atmosphere having an oxygen concentration of 20 vol% or less.

  First, constituent materials for producing the silicoaluminophosphate according to the present invention will be described. As the constituent materials used, an aluminum source, a Me source (particularly preferably an iron source), a phosphorus source, a silicon source, and an organic template as a structure indicating material are used. And after mixing each of these raw materials, a silicoaluminophosphate precursor is obtained by carrying out hydrothermal synthesis.

  Aluminum source: The aluminum source is not particularly limited, and aluminum alkoxides such as pseudoboehmite, aluminum isopropoxide, aluminum triethoxide, aluminum hydroxide, alumina sol, sodium aluminate and the like are usually used. Among these, pseudoboehmite is preferably used from the viewpoint of ease of handling and reactivity.

  Me source; Me source is not particularly limited, usually, inorganic acid salts such as sulfates, nitrates, phosphates, chlorides and bromides, organic acid salts such as acetates, oxalates and citrates, pentacarbonyl Organic metal compounds such as ferrocene are used. Of these, inorganic acid salts or organic acid salts are preferably used from the viewpoint of solubility in water. In some cases, a colloidal oxide may be used. As the Me source, those having a valence of Me of 2 are preferred. The type of Me is as described above.

  Phosphorus source: Phosphoric acid is usually used as the phosphorus source, but aluminum phosphate may be used.

  Silicon source: As the silicon source, an organosilicon compound such as silica sol, fumed silica, ethyl silicate or the like is used. Among these, silica sol or fumed silica is preferably used because of easy handling.

  Organic template: As an organic template having a role as a structure indicating material in hydrothermal synthesis, amine, imine, and quaternary ammonium salt can be used. Preferably, (1) an alicyclic heterocycle containing nitrogen as a hetero atom It is preferable to use at least one compound selected from the group consisting of a compound, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. They are easy to obtain and inexpensive, and also have the effect that the manufactured silicoaluminophosphate is easy to handle and structural destruction is unlikely to occur.

  Here, each said amines preferably used as an organic template is demonstrated in detail.

  An alicyclic heterocyclic compound containing nitrogen as a heteroatom; The alicyclic heterocyclic compound containing nitrogen as a heteroatom is usually a 5- to 7-membered ring, preferably a 6-membered ring. The number of heteroatoms contained in the heterocycle is usually 3 or less, preferably 2 or less. The type of heteroatoms contained is not particularly limited except for nitrogen, but those containing oxygen in addition to nitrogen are preferred from the viewpoint of ease of synthesis. The positions of the heteroatoms are not particularly limited, but those in which the heteroatoms are not adjacent to each other are preferable from the viewpoint of ease of synthesis. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of such alicyclic heterocyclic compounds containing nitrogen as a heteroatom include morpholine, N-methylmorpholine, piperidine, piperazine, N, N′-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane. , N-methylpiperidine, 3-methylpiperidine, quinuclidine, pyrrolidine, N-methylpyrrolidone, hexamethyleneimine and the like. Of these, morpholine, hexamethyleneimine, and piperidine are preferred from the viewpoint of ease of synthesis, and morpholine is particularly preferred.

  An amine having a cycloalkyl group; In an amine having a cycloalkyl group, the number of cycloalkyl groups is preferably 2 or less, more preferably 1 per amine molecule. The cycloalkyl group usually has 5 to 7 carbon atoms, preferably 6 carbon atoms. The number of cycloalkyl cyclo rings is not particularly limited, but usually one is preferred. Moreover, it is preferable from the point of easiness of a synthesis | combination that the cycloalkyl group has couple | bonded with the nitrogen atom of the amine compound. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of the amine having such a cycloalkyl group include cyclohexylamine, dicyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, and cyclopentylamine, and cyclohexylamine is particularly preferable.

  An amine having an alkyl group; in an amine having an alkyl group, any number of alkyl groups may be contained in one amine molecule, but preferably three. The number of carbon atoms of the alkyl group is preferably 4 or less, and more preferably the total number of carbon atoms of all alkyl groups in one molecule is 10 or less. The molecular weight is 250 or less, preferably 200 or less, more preferably 150 or less from the viewpoint of ease of synthesis.

  Examples of amines having such alkyl groups include di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, triethanolamine, N, N-diethylethanolamine, N, N-dimethylethanol. Amine, N-methyldiethanolamine, N-methylethanolamine, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl-ethylamine, N-methyl-n -Butylamine and the like, di-n-propylamine, tri-n-propylamine, tri-isopropylamine, triethylamine, di-n-butylamine, isopropylamine, t-butylamine, ethylenediamine, di-isopropyl Le - ethylamine, preferably in that N- methyl -n- butylamine synthetic ease, N, N- diethylethanolamine, N, N- dimethylethanolamine, triethylamine is more preferable. Most preferred are N, N-diethylethanolamine and triethylamine.

  The (1) alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group are preferably used in combination of two or more. You may use together. When one of the amines is used, from the viewpoint of ease of synthesis, (1) a morpholine in an alicyclic heterocyclic compound containing nitrogen as a hetero atom or (2) a cycloalkyl group Of the amines, cyclohexylamine is preferable, and morpholine is particularly preferable.

  On the other hand, in order to synthesize a desired composition with high purity, it is preferable to use a combination of two or more amines. Among these, as a preferable combination, as an organic template, (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group, It is preferable to use one or more compounds from two or more groups. By combining in this way, there is an advantage that it is easy to synthesize a silicon aluminophosphate having a desired element ratio and high crystallinity. Among them, (1) in the case of a combination of two or more containing an alicyclic heterocyclic compound containing nitrogen as a heteroatom, it is easy to synthesize a desired element ratio or highly crystalline silicoaluminophosphate. More preferred. As a specific preferred combination, a combination of two or more of morpholine, triethylamine or N, N-diethylethanolamine and cyclohexylamine, more preferably a combination of two or more containing morpholine is more preferable.

  The mixing ratio of each group of these organic templates needs to be selected as appropriate according to the conditions, but the molar ratio of the two organic templates to be mixed is in the range of 1:20 to 20: 1, and the desired element ratio From the viewpoint of easy synthesis of silicoaluminophosphate having high crystallinity and 1:10 to 10: 1. In addition, although other organic templates may be contained, in that case, the molar ratio is usually preferably 20% or less, and more preferably 10% or less. These organic templates are advantageous in that they are inexpensive and easy to handle and less corrosive than conventional organic templates (eg, tetraethylammonium hydroxide).

  In the method for producing silicoaluminophosphate according to the present invention, (i) the crystallization speed in the synthesis process of silicoaluminophosphate is improved by simultaneously producing a plurality of organic templates and selecting the production conditions. (Ii) it is possible to easily produce silicoaluminophosphate having a desired structure while suppressing the generation of impurities, and (iii) to produce silicoaluminophosphate having a stable structure that is hard to break. The effect of being able to be obtained can be obtained.

  In the method for producing silicoaluminophosphate of the present invention, an organic template in which a plurality of types of compounds selected from the above-mentioned (1) to (3) are combined is preferably used, and the organic template exhibits a synergistic action alone. There is an advantage that the effects (i) to (iii) that cannot be obtained with the organic template can be obtained.

  Next, hydrothermal synthesis in the method for producing silicoaluminophosphate according to the present invention will be described.

  First, an aqueous gel is prepared by mixing constituent materials consisting of a Me source, an aluminum source, a phosphate source, a silicon source, an organic template and water. The order of mixing the constituent raw materials is not limited and may be appropriately selected depending on the conditions to be used. Usually, however, a phosphoric acid source, an aluminum source and a silicon source are first mixed in water, and then a Me source and an organic template are mixed. To do.

The composition of the aqueous gel affects the ease of synthesis of the desired one. When the aluminum source, the Me source, and the phosphate source are expressed by the molar ratio of the oxide, the value of MeO / Al ₂ O ₃ is usually larger than 0. 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less. The ratio of P ₂ O ₅ / Al ₂ O ₃ affects the ease of synthesis of the desired product, and is usually 0.6 or more, preferably 0.8 or more, more preferably 1 or more. It is 8 or less, preferably 1.7 or less, more preferably 1.6 or less.

In the silicoaluminophosphate of the present invention, the ratio of SiO ₂ / Al ₂ O ₃ is 0.0001 ≦ SiO ₂ / Al ₂ O ₃ ≦ 2, and from the viewpoint of easy synthesis, 0.005 ≦ SiO ₂ / Al ₂ O ₃ ≦ 1.8 is preferable, and 0.05 ≦ SiO ₂ / Al ₂ O ₃ ≦ 1.5 is more preferable.

The total amount of the organic template, the synthesis and affects the ease and _economy, in a molar ratio of organic templates for P 2 _{O 5} (organic template _/ P 2 _{O 5),} usually 0.2 or more, preferably 0.5 or more, More preferably, it is 1 or more, usually 4 or less, preferably 3 or less, more preferably 2.5 or less. In addition, the mixing ratio of two or more organic templates affects the ease of synthesis of the desired one and needs to be appropriately selected according to the conditions. As described above, for example, when morpholine and triethylamine are used, morpholine / Triethylamine molar ratio is 0.03 to 20, preferably 0.05 to 10, more preferably 0.1 to 9, and most preferably 0.2 to 4.

  The order of mixing one or more organic templates selected from each of the two or more groups is not particularly limited, and may be mixed with other substances after preparing the organic template. The mixture may be formulated after mixing with other substances.

The lower limit of the proportion of water, relative to _Al 2 _{O 3,} and at at least 3 molar ratio (water / _Al 2 _{O 3),} preferably 5 or more from the viewpoint of ease of synthesis, more than 10 Is more preferable. The upper limit of the ratio of water is 200 or less in terms of molar ratio (water / Al ₂ O ₃ ), preferably 150 or less, and more preferably 120 or less from the viewpoint of ease of synthesis and high productivity.

The pH of the aqueous gel is 4 to 10, preferably 5 to 9 and more preferably 5.5 to 7.5 from the viewpoint of ease of synthesis. The pH is adjusted by adjusting the amount of organic template added or by adding an acid such as hydrochloric acid or sulfuric acid. In addition, in order to improve the solubility of a raw material or the role of a mineralizer etc., you may coexist components other than the above in aqueous gel. Examples of such components include hydrophilic organic solvents such as hydroxides and salts of alkali metals and alkaline earth metals, and alcohols. The ratio of the coexisting component affects the ease of synthesis of the desired compound. In the case of a hydroxide or salt of an alkali metal or alkaline earth metal, the molar ratio with respect to Al ₂ O ₃ (coexisting component / Al ₂ O ₃ ) is usually 0.2 or less, preferably 0.1 or less, and in the case of a hydrophilic organic solvent such as alcohol, it is usually 0.5 or less, preferably 0.3 or less, in molar ratio to water. .

  Under such conditions, hydrothermal synthesis is performed by placing the aqueous gel in a pressure-resistant container and maintaining a predetermined temperature under stirring or standing under self-generated pressure or gas pressure that does not inhibit crystallization.

  The reaction temperature of hydrothermal synthesis affects the ease of synthesis of the desired product, and is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower. More preferably, it is 180 ° C. or lower.

  The reaction time affects the ease of synthesis of the desired product, and is usually 2 hours or more, preferably 3 hours or more, more preferably 5 hours or more, and usually 30 days or less, preferably 10 days or less, more preferably 4 days or less. The reaction temperature may be constant during the reaction for this time or may be changed stepwise.

  After the hydrothermal synthesis, the product is separated. The method for separating the product is not particularly limited. Usually, the product is separated by filtration or decantation, washed with water, dried at a temperature of room temperature (25 ° C.) to 150 ° C., and the product containing the organic template as a product. The aluminophosphate precursor can be separated.

  Next, the firing step in the method for producing silicoaluminophosphate according to the present invention will be described.

  The firing step is a process in which the silicoaluminophosphate precursor hydrothermally synthesized and separated as described above is heat-treated under predetermined conditions under a flow of nitrogen, air, or the like or under reduced pressure. The silicoaluminophosphate of the present invention containing the following carbon is produced.

  In this firing step, silicoaluminophosphate containing a predetermined amount of carbon is produced by controlling the firing conditions and controlling the removal of the organic template. In addition, after completely removing the organic template by firing, a silicoaluminophosphate containing a predetermined amount of carbon may be produced by adsorbing organic compounds such as organic amines such as methylamine and ethylamine. . At this time, the organic template molecule may remain in the silicoaluminophosphate while maintaining its structure, but the organic template has a structure in which at least a part of carbon, hydrogen or nitrogen is removed by causing a chemical reaction. Preferably it remains. Whether or not the organic template remains can be confirmed by an analysis means such as CHN elemental analysis, thermogravimetric-mass spectrometry (TG-MASS), or the like.

  The firing temperature is usually 200 ° C. or higher and 800 ° C. or lower, preferably 250 ° C. or higher, more preferably 280 ° C. or higher, and particularly preferably 300 ° C. or higher. On the other hand, 700 ° C. or lower is preferable, 500 ° C. or lower is more preferable, and 450 ° C. or lower is still more preferable. By setting the firing temperature to 300 ° C. or higher and 450 ° C. or lower, there is an effect that the carbon content can be easily controlled. The firing time is a maximum temperature holding time of 1 minute to 15 hours, preferably 2 minutes to 10 hours, and more preferably 5 minutes to 8 hours. The pressure at the time of firing may be reduced pressure or increased pressure, but is usually performed at or near atmospheric pressure.

  Firing may be performed in a gas not containing oxygen or in a gas containing oxygen in an inert gas. The upper limit of the oxygen concentration when oxygen is contained in the gas is 20 vol%, preferably 15 vol% or less, and more preferably 10 vol% or less. By containing oxygen in the gas and controlling the oxygen concentration in the gas within this range, there is an effect of suppressing the heat generation of the organic template during firing and facilitating the control of firing. Moreover, in order to avoid the rapid heat_generation | fever accompanying the oxidative decomposition | disassembly of an organic template, after baking in inert gas flow, such as nitrogen, it can also bake in oxygen-containing gas flow. In this case, since a part of the organic template is removed during firing in the inert gas, heat generation during firing in the second stage oxygen-containing gas can be suppressed. It becomes easy to control. As the gas other than oxygen, an inert gas such as nitrogen, argon, or helium is used, but in some cases, water vapor or nitrogen oxide may be mixed up to 10% by volume.

  In determining the firing conditions for obtaining the silicoaluminophosphate according to the present invention, the thermal decomposability of the silicoaluminophosphate precursor is verified in advance, and the firing is performed at a temperature close to and lower than the temperature at which thermal decomposition starts. Is preferably performed. Therefore, in the above temperature range, it is preferable from the viewpoint of improving durability that a relatively low temperature is employed and the reaction is performed in the presence of an inert gas not containing oxygen or a relatively low oxygen content.

  The silicoaluminophosphate having the characteristics of the present invention is produced by selecting from the above firing conditions based on the type, composition ratio, framework density, and the like of the constituent elements of the desired silicoaluminophosphate. Among these, the preferable structure indicating material is used, the baking temperature is 300 to 450 ° C., the baking time is 2 to 8 hours, oxygen is not contained, or the inert gas atmosphere is contained at a ratio described in the preferred range. There is a tendency to be obtained by selecting these conditions. As preferable baking conditions for producing the silicoaluminophosphate having the characteristics of the present invention, for example, reaction conditions of 300 to 450 ° C. and 4 to 8 hours in an inert gas can be mentioned as preferable baking conditions. .

  Furthermore, when the silicoaluminophosphate having the characteristics of the present invention contains Me as an essential constituent element, by performing in an inert gas atmosphere containing oxygen in a ratio described in the above preferred range as the firing condition. There is a tendency to be obtained, and furthermore, firing at a relatively low temperature (for example, 300 to 400 ° C.) in the above-mentioned firing temperature range is performed in an inert gas atmosphere containing oxygen in a proportion described in the above preferred range. There is a tendency to be obtained by doing.

The calcining gas may or may not be circulated in the calcining apparatus. However, when it is circulated, the space velocity (GHSV) relative to the silicoaluminophosphate precursor to be calcined is a predetermined value. A range is preferable. As the space velocity (GHSV), 10 hr ^-1 or more, preferably 10000 hr ^-1 or less, 20 hr ^-1 or more, 3000 hr ^-1 or less is more preferable. If the GHSV is too small, removal of the organic template is delayed, and if the GHSV is too high, the gas flow rate required for firing is too large, which is economically undesirable. As a baking apparatus, arbitrary heating apparatuses, such as a muffle furnace, a tubular furnace, and a kiln, can be used, and it carries out in a fixed bed or a fluidized bed format. Here, GHSV is expressed as “gas flow capacity / silicoaluminophosphate precursor capacity” per unit time.

  With the above method, the carbon-containing silicoaluminophosphate according to the present invention is produced.

(Use of carbon-containing silicoaluminophosphate)
The silicoaluminophosphate according to the present invention is an adsorbent, a catalyst for acid reaction or oxidation reaction, a separation material, an optical material such as a quantum dot or a quantum wire, a host such as a semiconductor fine particle, a phosphor, or a dye as a magnetic material. Can be widely used. In particular, it is suitably used as an adsorbent because the crystal structure is hardly destroyed by repeated use and the deterioration of adsorption characteristics is small.

(Use as adsorbent)
The silicoaluminophosphate according to the present invention is preferably used as an adsorbent that is repeatedly used because it is excellent in durability, such as being less susceptible to structural destruction.

  In particular, it is preferably used as an adsorbent for a heat utilization system. For example, the adsorption heat generated by adsorption of an adsorbent on the adsorbent and / or the latent heat of vaporization of the adsorbent generated by evaporation of the adsorbent It can be suitably used as an adsorbent for the heat utilization system to be utilized. Note that the heat utilization system here refers to the use of thermal energy recovered as adsorption heat as a heat source for heating other substances and / or other thermal energy (cold heat) recovered as latent heat of evaporation. This means a system that is used as a heat source for cooling the substance, and specifically includes a cold storage heat system, an adsorption heat pump, a humidity control air conditioner for dehumidification and humidification, and the like.

  The silicoaluminophosphate of the present invention itself has an adsorption performance, but when used in the above heat utilization system, as its adsorption characteristic, a relative vapor pressure of 0.01 or more in an adsorption isotherm measured at 25 ° C. It is preferable that the adsorption amount change of the adsorbing substance (for example, water) when the relative vapor pressure changes by 0.15 in a range of 0.5 or less has a relative vapor pressure region of 0.1 g / g or more. That is, a relatively hydrophilic material that can be desorbed at a relative vapor pressure of 0.01 or more and can be adsorbed at a relative vapor pressure of 0.5 or less is suitable. In the heat utilization system, a heat source having a high temperature of 150 ° C. or higher can be used depending on the system, and the relative humidity required for desorption can be sufficiently reduced. However, in the case of adsorption, since it is affected by the environment such as the outside air temperature, it is difficult to make the relative humidity larger than 0.5 necessary for the adsorption.

  Here, the operating vapor pressure range of the heat utilization system is determined by the desorption side relative vapor pressure (φ1a) and the adsorption side relative vapor pressure (φ2a). φ1 and φ2 can be calculated by the following formulas 13 and 14, and the range between φ1a and φ2a is an operable relative vapor pressure range.

Desorption side relative vapor pressure (φ1a) = Equilibrium vapor pressure (Tlow1) / Equilibrium vapor pressure (Thigh)… 13
Adsorption side relative vapor pressure (φ2a) = Equilibrium vapor pressure (Tcool) / Equilibrium vapor pressure (Tlow2)… 14

  Here, the equilibrium vapor pressure (Tlow1), the equilibrium vapor pressure (Thigh), the equilibrium vapor pressure (Tcool) and the equilibrium vapor pressure (Tlow2) mean the equilibrium vapor pressure at the temperature of Tlow1, Thigh, Tcool and Tlow2, respectively. . In this equation, Thigh (high temperature heat source temperature) is the temperature of the heating medium that is heated when the adsorbent is desorbed from the adsorbent and regenerated, and Tlow1 (low temperature heat source temperature) is the adsorbent of the condenser. Tlow2 (low temperature heat source temperature) is the temperature of the heat medium that cools the regenerated adsorbent when it is subjected to adsorption, and Tcool (cold heat generation temperature) is the temperature of the adsorbed material in the evaporator, that is, the generation The temperature of the cold. The equilibrium vapor pressure can be obtained from the temperature using the equilibrium vapor pressure curve of the adsorbed substance.

  In the adsorption process of the heat utilization system described above, the lower the low-temperature heat source temperature Tlow2, the greater the relative humidity necessary for adsorption and the wider the relative humidity that can be used. However, in practice, it is difficult to completely remove the heat of adsorption generated when the adsorbent adsorbs the adsorbed material, and it is also affected by environmental factors such as outside temperature. It is difficult to keep the temperature Tlow2 below 20 ° C. That is, when the adsorbed material is water, for example, when trying to obtain a cold heat generation temperature Tcool of 10 ° C., an operating relative water vapor pressure range greater than a relative humidity of 0.52 when the low temperature heat source temperature Tlow 2 is 20 ° C. It is not suitable for a heat utilization system.

  On the other hand, in the desorption process of the heat utilization system described above, the higher the high temperature heat source temperature Thigh, the smaller the relative humidity necessary for desorption and the wider the relative humidity that can be used. Depending on the system, it is possible to obtain a heat source having a high temperature heat source temperature Thigh of 100 ° C. or higher, and in some cases 120 ° C. or higher, or near 200 ° C. In this case, for example, when the low-temperature heat source temperature Thigh is 200 ° C. even if it is assumed that the low-temperature heat source temperature Tlow1 rises due to heat removal failure or environmental factors, and the low-temperature heat source temperature Tlow1 becomes 50 ° C. The relative humidity is about 0.01.

  From the above, in the heat utilization system of the present invention, the silicoaluminophosphate according to the present invention having the adsorption characteristic that the adsorption amount changes in the range of relative humidity of 0.01 to 0.5 is used as the adsorbent. It is preferable.

  When the relative vapor pressure changes by 0.15, the change in the amount of adsorption of the adsorbed material is 0.1 or more. ) Changes in the adsorption amount. This amount of change means that the change in adsorption amount is large in a relatively narrow relative vapor pressure range, so the amount of adsorbent required to obtain an equivalent adsorption amount under the same conditions can be reduced, and the cooling heat source Even if the temperature difference between the heat source and the heating heat source is small, the heat utilization system can be driven.

Such adsorption characteristics are provided in the silicoaluminophosphate of the present invention having a relatively low framework density, preferably 16 T / nm ³ or less.

  When the silicoaluminophosphate of the present invention is used as an adsorbent, it may be used as a molded body. In the case of forming a molded body, care should be taken not to reduce the adsorption characteristics of the silicoaluminophosphate of the present invention as much as possible, and other components such as binders such as known adsorbent binders and the present invention can be used as necessary. It is possible to mold with a mixture in which other adsorbents other than silicoaluminophosphate are mixed. Examples of the binder include inorganic binders such as alumina, silica, and clay. The mixture is granulated by agitation granulation, granulation by spray granulation or the like, or a molding method (CIP) by hydrostatic pressure, and processed into a molded body. Moreover, you may crush a molded object as needed.

  The content of the silicoaluminophosphate of the present invention contained in the adsorbent is 60% by weight or more, preferably 70% by weight or more, and may be 100%. The case of 100% is a case where the adsorbent is composed only of the silicoaluminophosphate of the present invention.

(Application to cold storage system)
Next, the aspect which applied the adsorbent which consists of or contains the silicoaluminophosphate of this invention to the cool storage heat system is demonstrated.

  FIG. 1 is a conceptual diagram showing an example of a cold storage heat system of the present invention. The regenerative heat storage system 11 of the present invention includes an adsorption regenerative heat storage device that mainly includes a circulating water supply device 12, an adsorption / desorption device 13, and an evaporator / condenser 14. Here, the adsorption / desorption device 13 is an apparatus that includes an adsorbent and is supplied with an adsorbing substance (for example, water) from the evaporator / condenser 14 or supplies the adsorbing substance to the evaporator / condenser 14. The evaporator / condenser 14 is an apparatus that combines an evaporator for evaporating the adsorbed material and supplying it to the adsorption / desorption device 13, and a condenser for condensing the adsorbed material supplied from the adsorption / desorption device 13. . The circulating water supply device 12 is a device that supplies high temperature water A or low temperature water B to the adsorption / desorption device 13.

  The cold storage heat system 11 is configured to desorb an adsorbed substance (for example, water) from the adsorbent by supplying (configuration a) waste heat (circulated water of the circulating water supply device 12) to the adsorbent (in the adsorption / desorption device 13). And (configuration b-1) a configuration for supplying heat (adsorption heat) generated when the adsorbed material supplied from the evaporator / condenser 14 is adsorbed to the adsorbent to a device that requires a warm-up operation, And / or (configuration b-2) The latent heat of vaporization of the adsorbed material generated when the adsorbed material supplied from the evaporator / condenser 14 is adsorbed to the adsorbent is supplied to the cooling medium circulating in the cooling refrigerator. And a system.

  The adsorption-type regenerative heat storage device using the function of the adsorbent uses the ability of the adsorbent to adsorb and desorb the adsorbed material as a drive source. In the adsorption-type regenerative heat storage device, water, ethanol, acetone, or the like can be used as an adsorbent, but water is most preferable from the viewpoint of safety, price, and latent heat of vaporization, and the adsorbent is adsorbent as water vapor. To be adsorbed.

  As described above, the adsorbent comprising the silicoaluminophosphate itself of the present invention or the adsorbent containing the same has mechanical characteristics and adsorption characteristics with excellent structural strength during repeated use. It can be suitably used as an adsorbent for a cold storage heat system. Among them, an adsorbent having an adsorption characteristic with a large change in adsorption amount in a narrow relative vapor pressure range is particularly preferable because it can reduce the amount of adsorbent necessary to obtain an equivalent adsorption amount under the same conditions, and cooling. Even if the temperature difference between the heat source and the heating heat source is small, there is an advantage that the cold storage heat device can be driven.

(Application to adsorption heat pump)
Next, the aspect which applied the adsorption material which consists of or contains the silicoaluminophosphate of this invention to the adsorption heat pump is demonstrated.

  FIG. 2 is a conceptual diagram showing an example of the adsorption heat pump of the present invention. The adsorption heat pump 21 of the present invention includes an adsorbent, an adsorbent that adsorbs and desorbs the adsorbent, and adsorbers 22 and 23 that are filled with the adsorbent and transmit heat generated by the adsorption and desorption of the adsorbent to the heat medium. The evaporator 24 is mainly composed of an evaporator 24 for taking out the cold heat obtained by the evaporation of the adsorbing substance, and a condenser 25 for releasing the hot heat obtained by the condensation of the adsorbing substance to the outside. High-temperature water or low-temperature water is supplied to the adsorption / desorption devices 22 and 23 from the circulating water supply devices 26 and 27, and open / close valves 28 to 28 are provided between the adsorption / desorption devices 22 and 23, the evaporator 24, and the condenser 25. 31 is attached.

  The operating principle of the adsorption heat pump is, for example, (1) Open / close valves 29 and 30 are open, low temperature water is supplied to the adsorption / desorption device 22 from the circulating water supply device 26, and circulating water is supplied to the adsorption / desorption device 23. When high-temperature water is supplied from the vessel 27, (i) in the adsorption / desorption device 22, the adsorbent adsorbs the adsorbed substance (for example, water) supplied from the evaporator 24, and the adsorption heat generated during the adsorption is used. Hot water is obtained, and (ii) in the adsorber / desorber 23, the adsorbent desorbs the adsorbed material, and cold water is obtained by the latent heat of evaporation generated during the desorption. On the other hand, (2) the open / close valves 28 and 31 are open, high temperature water is supplied to the adsorption / desorption device 22 from the circulating water supply device 26, and low temperature water is supplied to the adsorption / desorption device 23 from the circulation water supply device 27. (I) in the adsorption / desorption device 22, the adsorbent desorbs the adsorbed material, and cold water is obtained by the latent heat of evaporation generated during the desorption, and (ii) in the adsorption / desorption device 23, the adsorbent is evaporated. The adsorbing substance (for example, water) supplied from the vessel 24 is adsorbed, and hot water is obtained by the adsorption heat generated during the adsorption.

  The adsorption heat pump 21 is a heat utilization system that can always obtain cooling water by repeating these two operations by operating an on-off valve. More detailed contents about the configuration and operating principle of such an adsorption heat pump are described in, for example, JP-A-2002-372332.

  The adsorption heat pump of the present invention is an adsorption heat pump to which the adsorbent comprising the silicoaluminophosphate of the present invention or an adsorbent containing the adsorbent is applied, and the adsorbent has an excellent structure when used repeatedly as described above. Since it has mechanical properties and adsorption properties with strength, it can be suitably used as an adsorbent for adsorption heat pumps. Among them, an adsorbent having an adsorption characteristic with a large change in adsorption amount in a narrow relative vapor pressure range is particularly preferable because it can reduce the amount of adsorbent necessary to obtain an equivalent adsorption amount under the same conditions, and cooling. There is an advantage that the adsorption heat pump can be driven even if the temperature difference between the heat source and the heating heat source is small.

(Application to dehumidifying air conditioner)
Next, the aspect which applied the adsorbent which consists of or contains the silicoaluminophosphate of this invention to a dehumidification air conditioner is demonstrated.

  FIG. 3 is a conceptual diagram showing an example of the dehumidifying air conditioner of the present invention. The dehumidifying air conditioner 61 of the present invention includes an adsorbent capable of adsorbing and desorbing an adsorbing substance (for example, water), an adsorption / desorption device 61 provided with the adsorbent, and a mechanism 63 for regenerating the adsorbent. It is. The dehumidifying air conditioner 61 is supplied with an air path (not shown) for circulating air 62 (also referred to as humidity conditioning air) for conditioning the humidity if necessary, or air after humidity conditioning. A device (not shown) for forced exhaust may be provided.

  The adsorber / desorber 61 only needs to have a shape that allows the adsorbent and the humidity control air 62 to be in sufficient contact. Examples of the shape include a rotor shape having a honeycomb structure.

  The mechanism 63 for regenerating the adsorbent may be any heat supply mechanism that can supply heat of about 80 ° C. necessary for the regeneration of the adsorbent to the adsorption / desorption device 61 in the case of (i) dehumidifying use. . Further, (ii) when heat is generated by electric heating or the like inside the apparatus, a heat source such as a heater or a heating coil, or a mechanism such as a blower for sufficiently transferring the heat to the adsorption / desorption device 61 may be used. Further, (iii) when a heat source is obtained from the outside of the apparatus, a mechanism such as a pipe for supplying the high-temperature gas may be used. The heat source from the outside at this time is not particularly limited like the adsorption heat pump, and examples thereof include cogeneration equipment such as a gas engine and a gas turbine, and a fuel cell. In the case of (iv) humidification applications, any route may be used as long as high-humidity air for reabsorption is circulated.

  An example of the humidity control method using the dehumidifying air conditioner will be specifically described with reference to FIG. 4, but is not limited thereto.

  FIG. 4 is a conceptual diagram of an example of a desiccant air conditioner that is a dehumidifying air conditioner. The desiccant air conditioner 70 includes a processing air path 71, a regeneration air path 72, a desiccant rotor 73 with adsorbent attached thereto, two sensible heat exchangers 74 and 75, a heat supply mechanism 76 from a heating source, The humidifier 77 is a main component. The processing air is dehumidified by the desiccant rotor 73 and the temperature rises due to the moisture adsorption heat of the desiccant. Thereafter, the treated air is cooled by exchanging heat with the regenerated air in the first sensible heat exchanger 74, then humidified by the humidifier 77, and supplied to the conditioned space 78. On the other hand, the regenerative air is taken in from the external space, heat-exchanged with the processing air in the first sensible heat exchanger 74 and heated, and then heated by the heat supply mechanism 76 to reduce the relative humidity. Passing through the desiccant rotor 73, the moisture of the desiccant rotor 73 is desorbed and regenerated. The sensible heat of the regenerated air after regeneration is recovered by exchanging heat with the regenerated air before heating by the second sensible heat exchanger 75 and then discharged to the outside 79.

  By applying the adsorbent comprising the silicoaluminophosphate of the present invention or an adsorbent containing the adsorbent to the dehumidifying air conditioner, the adsorbent has excellent structural strength during repeated use as described above. Since it has mechanical characteristics and adsorption characteristics, it can be suitably used as an adsorbent for a dehumidifying air conditioner.

  In accordance with the above principle, for example, it is possible to perform humidification by supplying air after regeneration in which moisture has been adsorbed from an adsorbent into the room.

(Application and adsorption properties)
The heat utilization system using the silicoaluminophosphate of the present invention as an adsorbent uses heat energy recovered as adsorption heat as a heat source for heating other substances and / or is recovered as latent heat of evaporation. This is a system that uses thermal energy (cold heat) as a heat source for cooling other substances. Specifically, as described above, a cold storage heat system, an adsorption heat pump, a humidity control air conditioner for dehumidification and humidification, etc. It is done.

  In such a heat utilization system, an adsorbent (for example, water) is adsorbed on the adsorbent as a vapor, and the adsorbent is preferably a material having a large change in the amount of adsorbent adsorbed in a narrow relative vapor pressure range. This adsorption characteristic differs somewhat depending on the application for which the adsorbent is used.

  First, preferable adsorption characteristics when the adsorbent of the present invention is applied to an adsorption heat pump will be described.

  The adsorbent applied to the adsorption heat pump is such that the carbon-containing silicoaluminophosphate of the present invention contained in the adsorbent has a relative vapor pressure of 0.05 to 0.30 on an adsorption isotherm measured at 25 ° C. When the relative vapor pressure changes by 0.15 in the range, it is desirable that the adsorption amount change of water as an adsorbent has a relative vapor pressure region of 0.1 g / g or more. At this time, the change in the amount of water adsorbed is preferably 0.12 g / g or more, more preferably 0.15 g / g or more, and still more preferably 0.18 g / g or more.

  The reason why such adsorption characteristics are preferable will be described in the case where the adsorption heat pump is driven by utilizing the relatively low temperature gas engine cogeneration at 100 ° C. or lower, the solid polymer fuel cell, or the exhaust heat of the automobile engine. The operation vapor pressure range when water is used as an adsorbent will be described.

  When an adsorption heat pump is driven using exhaust heat from a relatively low temperature gas engine cogeneration of 100 ° C. or lower, a polymer electrolyte fuel cell or an automobile engine, for example, the high temperature heat source temperature is 80 ° C. and the low temperature heat source temperature is In the case of 30 ° C., the operating vapor pressure range (φ1a to φ2a) is 0.09 to 0.29. Similarly, when the high temperature heat source temperature is 60 ° C. and the low temperature heat source temperature is 30 ° C., the operating relative water vapor pressure range (φ1a to φ2a) is 0.21 to 0.29. Further, when the case where an adsorption heat pump is driven using exhaust heat of an automobile engine based on the description in JP-A-2000-140625, the high-temperature heat source temperature is about 90 ° C. and the low-temperature heat source temperature is 30 ° C. In this case, the operation relative water vapor pressure range (φ1a to φ2a) is 0.06 to 0.29.

  Accordingly, when the adsorption heat pump is driven using the exhaust heat, the operation relative water vapor pressure range (φ1a to φ2a) is 0.05 to 0.30, more preferably 0.06 to 0.29. Become. Therefore, when regenerating the adsorbent by lowering the relative water vapor pressure by heating, use an adsorbent having an adsorption characteristic that completes desorption when the relative water vapor pressure is in the range of 0.05, preferably 0.06 or more. Is preferred. On the other hand, in terms of adsorption, it is preferable to use an adsorbent having an adsorption characteristic capable of obtaining a sufficient adsorption amount within a relative water vapor pressure of 0.30, preferably 0.29 or less.

  In view of the above, a material having a large change in the adsorption amount in the applied operating humidity range is preferred, and the relative water vapor pressure is generally 0.05 to 0.30, preferably 0.06 to 0.29. Thus, a material whose adsorption amount varies greatly is preferable.

  The adsorbent having the adsorption characteristics may be selected from adsorbents comprising or including the silicoaluminophosphate of the present invention, and particularly contains at least one Me element selected from Fe, Co, Mg and Zn. A carbon-containing silicoaluminophosphate is preferable, and among them, a carbon-containing iron silicoaluminophosphate in which Me is Fe is particularly preferable. Note that the skeleton structure is preferably a structure selected from AEI, CHA, and LEV, and the ratio of the Me metal contained is the molar ratio of “Me + Si” to the entire elements other than oxygen forming the skeleton structure ((Me + Si ) / (Me + Si + Al + P)) is from 0.01 to 0.15, preferably from 0.02 to 0.1.

  Next, preferable adsorption characteristics when the adsorbent of the present invention is applied to a cold storage heat system will be described.

  The adsorbent applied to the cold storage heat system is the adsorption of adsorbed material at a relative vapor pressure of 0.02 on the adsorption isotherm measured by the carbon-containing silicoaluminophosphate of the present invention contained in the adsorbent at 55 ° C. The amount of the adsorbed material at an amount of 0.15 g / g or less, the relative vapor pressure at 0.1 is 0.10 g / g or more, and the relative vapor pressure is 0.02 or more and 0.1 or less. It is desirable to have a relative vapor pressure region in which the amount of adsorption of the adsorbed material when the pressure changes by 0.05 is 0.05 g / g or more. Further, in the adsorption isotherm measured at 55 ° C., the adsorption amount of the adsorbent at a relative vapor pressure of 0.02 is 0.12 g / g or less, and the adsorption amount of the adsorbent at a relative vapor pressure of 0.1 is 0. .13 g / g or more, and relative vapor pressure in which the adsorption amount change of the adsorbed material is 0.05 g / g or more when the relative vapor pressure is changed by 0.05 in the range of relative vapor pressure of 0.02 or more and 0.1 or less. It is more desirable to have a pressure region. Further, the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.02 is 0.04 g / g or less, and the adsorption amount of the adsorbing substance at a relative vapor pressure of 0.1 is 0.15 g / g or more. It is particularly desirable to have a relative vapor pressure region in which the adsorption amount change of the adsorbed material is 0.10 g / g or more when the relative vapor pressure is changed by 0.05 within a pressure range of 0.02 to 0.1.

  The reason why such an adsorption characteristic is preferable will be described with reference to a cold storage system installed in an automobile.

  In a cold storage heat system mounted on an automobile, the adsorption / desorption device is heated to about 90 ° C. by hot water heated at about 90 ° C., and the adsorbent in the heated adsorption / desorption device desorbs the adsorbed substance, The refrigerant circulating in the cooler is cooled by the latent heat of evaporation generated at that time, and the condenser is cooled to about 10 ° C. At this time, since the relative vapor pressure between them is about 0.02, it is preferable that the adsorption amount of the adsorbed substance at the relative vapor pressure 0.02 is small. When the temperature of the adsorption / desorption device is a low temperature of 90 ° C. or lower (for example, about 60 to 85 ° C.), or the temperature of the condenser is higher than 10 ° C. (for example, about 15 to 30 ° C.). Since the relative vapor pressure between them becomes larger than 0.02, it is necessary that sufficient desorption is performed at a relative vapor pressure higher than 0.02. Therefore, it is preferable that the adsorption amount of the adsorbed material under the condition of the relative vapor pressure of 0.02 is smaller.

  In automobiles and the like, the temperature of the adsorption / desorption device may be about 45 to 60 ° C. by the cooling water cooled by the radiator, and the temperature of the evaporator may be about 10 ° C. by the heat exchanger. In this case, since the relative vapor pressure between the adsorption / desorption device and the evaporator is about 0.10, it is preferable that the adsorption amount of the adsorbed substance at the relative vapor pressure 0.10 is large. That is, it is preferable to use an adsorbent having a large change in the amount of adsorption within this operating humidity range.

  The adsorbent having the adsorption characteristics may be selected from adsorbents composed of or including the carbon-containing silicoaluminophosphate according to the present invention, and is particularly preferably a carbon-containing iron silicoaluminophosphate including Fe. . The skeleton structure is preferably a CHA structure, and the ratio of the Me metal contained is 0.00 in terms of the molar ratio of “Me + Si” to the entire elements other than oxygen forming the skeleton structure ((Me + Si) / (Me + Si + Al + P)). It is desirable that it is 03 or more and 0.25 or less, preferably 0.04 or more and 0.20 or less.

  As described above, the relationship between the heat utilization system and the adsorption characteristic taking the adsorption heat pump and the cold storage heat system as an example has been described, but the silicoaluminophosphate exhibiting the preferred adsorption characteristic is selected, and the adsorbent containing the same is used. In some cases, the adsorbing process occurs under lower relative vapor pressure conditions than the conventional adsorbing material, as well as the durability of the adsorbing material due to the performance of the silicoaluminophosphate of the present invention. Will occur under higher relative vapor pressure conditions. As a result, the adsorption amount changes due to a slight change in relative humidity, so an adsorption heat pump mounted on a car that has a problem that waste heat is generated and the fuel consumption further decreases by using an air conditioner, It can be preferably applied as an adsorbent for a cold storage heat system.

  As described above, the silicoaluminophosphate of the present invention and the adsorbent containing the same are excellent in durability when left at a high temperature in the presence of water vapor because the carbon content is within a predetermined range. In particular, when it is used as an adsorbent that repeatedly adsorbs and desorbs an adsorbed substance, it has a desirable characteristic that there is little deterioration in adsorption performance due to repeated use. Therefore, a heat utilization system that uses the adsorption heat generated by adsorption of the adsorbed substance on the adsorbent and / or the latent heat of vaporization of the adsorbed substance generated by evaporation of the adsorbed substance, specifically, a cold storage heat system, It has a beneficial effect of being able to withstand use under severe conditions such as adsorption heat pumps and dehumidifying air conditioners that perform adsorption and desorption, for example, several hundred thousand times or more.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited at all by the following examples.

  First, each physical property in Examples and Comparative Examples was performed under the following measurement conditions.

<Powder X-ray diffraction (XRD) measurement conditions>
X-ray source: Cu-Kα ray (λ = 1.54Å)
Output setting: 40 kV, 30 mA
Optical conditions during measurement: Divergent slit = 1 °
Scattering slit: 1 °
Receiving slit: 0.2mm
Diffraction peak position: 2θ (diffraction angle)
Measurement range: 2θ = 4-50 °
Sample: About 100 mg of a sample pulverized manually using an agate mortar, and using a sample holder of the same shape, the amount of the sample was made almost constant.

<CN analysis>
PERKIN ELMER 2400 SeriesII CHNS / O Analyzer was used.

<Elemental analysis>
The sample was calcined at 550 ° C. for 6 hours under air flow, dissolved in hydrochloric acid, and then subjected to composition analysis by the ICP method.

<Weight reduction rate measurement>
The sample was subjected to thermogravimetric analysis under the conditions of a heating rate of 10 ° C./min and a sample of about 10 mg under a flow of air of 10 ml / min. From the weights of 200 ° C., 350 ° C. and 700 ° C., the weight reduction rate (g1) The weight reduction rate (g2) was determined.

<Measurement of effective water adsorption amount>
About 10 mg of a sample that was allowed to stand in a saturated water vapor atmosphere at room temperature (25 ° C.) in a vacuum desiccator for one day using a thermogravimetric analyzer (manufactured by Shimadzu Corporation: TGA-50) under a flow of dry air of 10 ml / min at room temperature (25 The temperature was increased to 250 ° C. at a temperature increase rate of 10 ° C./min. The weight percent of water desorbed from room temperature (25 ° C.) to 100 ° C. relative to the sample weight in the saturated water vapor adsorption state at room temperature (25 ° C.) was defined as the effective water adsorption amount.

<Adsorption characteristics (25 ° C.)>
The water vapor adsorption amount at 25 ° C. was measured with a water vapor adsorption amount measuring device (Belsorb 18: manufactured by Nippon Bell Co., Ltd.).

Air temperature chamber: 50 ° C
Adsorption temperature: 25 ° C
Initial introduction pressure: 3.0 torr
Introduced pressure setting points: 0
Saturated vapor pressure: 23.755 torr
Equilibrium time: 500 seconds Sample: Measured after evacuation at 120 ° C. for 5 hours.

<Adsorption characteristics (55 ° C.)>
The water vapor adsorption amount at 55 ° C. was measured by a water vapor adsorption amount measuring device (Belsorb 18: manufactured by Nippon Bell Co., Ltd.) by the following method.

Air temperature chamber: 60 ° C
Adsorption temperature: 55 ° C
Initial introduction pressure: 3.0 torr
Introduced pressure setting points: 0
Saturated vapor pressure: 118.11 torr
Equilibrium time: 500 seconds Sample: Measured after evacuation at 120 ° C. for 5 hours.

<Durability test # 1: Hydrothermal test>
0.2 g of pure water was added to the bottom of a stainless steel autoclave (internal volume of about 100 ml (inner diameter: 42 mm)) lined with Teflon (registered trademark). In order to avoid contact between the liquid water and the sample during the test, 0.2 g of the sample was placed in a Teflon (registered trademark) sample pan (outer diameter: 40 mm) with a foot of about 20 mm in length and placed in the autoclave. Sealed. The autoclave was kept for 24 hours in a constant temperature drier kept at 100 ° C. and then taken out and allowed to cool to room temperature (25 ° C.).

<Durability test # 2: Repeat test>
The operation of holding the sample in a vacuum vessel maintained at 90 ° C. and exposing it to a vacuum state and a saturated steam atmosphere at 90 ° C. for 90 seconds was repeated 500 times.

Example 1
Hydrothermal synthesis and firing were carried out to produce a carbon-containing silicoaluminophosphate as follows.

  First, 87.1 g of 85% phosphoric acid was added to 180 g of water, and 57.2 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. This was designated as liquid A. Separately from the liquid A, a liquid prepared by mixing 5.04 g of fumed silica (Aerosil 200), 36.6 g of morpholine, and 240 g of water was prepared. This was slowly added to solution A. Further, 47.0 g of triethylamine was added and stirred for 3 hours to obtain a gel-like starting reaction product having the following composition.

0.2SiO ₂ : Al ₂ O ₃ : 0.9P ₂ O ₅ : 1 morpholine: 1.1 triethylamine: 60H ₂ O

  The obtained starting reaction product was charged into a 1 L stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, and reacted at 190 ° C. for 60 hours while stirring at 100 rpm. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Elemental analysis of the dried solid (silicoaluminophosphate precursor) was performed. As a result, the constituent ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus and silicon was 7.9% for silicon, 48.7% for aluminum, and 43.3% for phosphorus.

Next, the obtained solid (silicoaluminophosphate precursor) was heated from room temperature (25 ° C.) to 350 ° C. under an air flow of GHSV = about 6000 hr ⁻¹ at about 1 ° C./min. Firing was performed for 6 hours under air flow to obtain a fired product.

An XRD pattern showing a CHA structure (framework density 14.5 T / nm ³ ) as shown in FIG. 5 was obtained by XRD measurement of the fired product. The pore utilization factor 2 obtained from the formula 10 was 0.89. The adsorption isotherm as shown in FIG. 6 was obtained by measuring the adsorption characteristics (25 ° C.) of the fired product. CN analysis of the fired product confirmed that it contained 3.5% by weight of carbon and 1.0% by weight of nitrogen. The effective water adsorption amount of the fired product was 20.4% by weight. An XRD pattern showing a CHA structure as shown in FIG. 7 was obtained by XRD measurement performed after durability test # 1 of the fired product. The effective water adsorption amount after the durability test # 1 of the fired product was 18.4% by weight. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

  Further, when the fired product was subjected to durability test # 2, sufficient durability was confirmed. This fired product showed sufficient durability even when the number of repetitions was several thousand in the durability test # 2. Furthermore, the fired product has durability against repeated adsorption and desorption of several hundred thousand times when applied to an adsorption heat pump and a humidity control system.

(Example 2)
Hydrothermal synthesis and firing were carried out to produce a carbon-containing iron silicoaluminophosphate as follows.

  First, 11.5 g of 85% phosphoric acid was added to 28.05 g of water, and 6.26 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this, 2.78 g of ferrous sulfate heptahydrate was dissolved in 29 g of water, 1.2 g of fumed silica (Aerosil 200) was added thereto, and 4.35 g of morpholine and 5.64 g of triethylamine were further mixed. The solution was added slowly and stirred for an additional 3 hours. A gel-like starting reaction product having the following composition was obtained.

_{0.2FeSO 4: 0.4SiO 2: 0.92Al 2} O 3: P 2 O 5: 1.0 morpholine: 1.0 triethyl amine: 60H ₂ O

  The obtained starting reaction product was charged into a 0.2 L stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and allowed to react at 180 ° C. for 1 day in a stationary state. After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Elemental analysis of the dried solid (iron silicoaluminophosphate precursor) was performed. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, iron, and silicon was Al: 43.9 mol%, P: 40.3 mol%, Fe: 6.1 mol%, Si: 9.7 mol %Met.

  Thermogravimetric analysis was performed using a part of the dried solid (12.7 mg). Thermogravimetric analysis was performed at 10 ° C from room temperature (25 ° C) to 700 ° C while circulating air (oxygen concentration 7 vol%) diluted with helium at 30 mL / min using a thermogravimetric analyzer (Shimadzu Corporation TGA-50). The temperature was raised at / min. The result is shown in FIG.

Next, the obtained solid (iron silicoaluminophosphate precursor) was passed through nitrogen-diluted air having an oxygen concentration of 7% at a rate of about 0.000 from room temperature (25 ° C.) to 420 ° C. with GHSV = about 6000 hr ⁻¹ . The temperature was raised at 5 ° C./min and fired at 420 ° C. (this temperature is around the decomposition temperature by thermogravimetric analysis shown in FIG. 8) for 6 hours to obtain a fired product.

By XRD measurement of the fired product, an XRD pattern showing a CHA structure (framework density 14.5 T / nm ³ ) as shown in FIG. 9 was obtained. The pore utilization rate 1 obtained from the equation 9 was 0.77, and the pore utilization rate 2 obtained from the equation 10 was 0.91. The adsorption isotherm as shown in FIG. 10 was obtained by measuring the adsorption characteristics (55 ° C.) of the fired product. CN analysis of the fired product confirmed that it contained 3.2% by weight of carbon and 1.1% by weight of nitrogen. The effective water adsorption amount of the fired product was 16.7% by weight. By XRD measurement performed after durability test # 1 of the fired product, an XRD pattern having a CHA structure as shown in FIG. 11 was obtained. The effective water adsorption amount after the durability test # 1 of the fired product was 15.5% by weight. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Example 3)
In Example 2, except that the firing gas was nitrogen and the firing temperature was 450 ° C., firing was performed in the same manner as in Example 2 to obtain a carbon-containing iron silicoaluminophosphate.

  An XRD pattern showing a CHA structure as shown in FIG. 12 was obtained by XRD measurement of the fired product. The pore utilization factor 2 obtained from the formula 10 was 0.85. CN analysis of the fired product confirmed that it contained 5.0% by weight of carbon, but nitrogen was below the lower limit of detection (0.3% by weight). The effective water adsorption amount of the fired product was 15.7% by weight. An XRD pattern showing a CHA structure as shown in FIG. 13 was obtained by XRD measurement performed after durability test # 1 of the fired product. The effective water adsorption amount after the durability test # 1 of the fired product was 15.7% by weight. By XRD measurement performed after durability test # 2 of the fired product, an XRD pattern showing a CHA structure as shown in FIG. 14 was obtained. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

  In addition, in any of the silicoaluminophosphates of Examples 1 to 3, when the carbon content is less than 0.3% by weight, the skeleton structure before firing is maintained. is there. The silicoaluminophosphate obtained in Examples 1 to 3 retains the crystal structure before the repeated durability test when the repeated durability test is performed according to the following.

  <Repetitive Durability Test>: The operation of holding the silicoaluminophosphate in a vacuum vessel maintained at 90 ° C. and exposing it to a vacuum state and a saturated water vapor atmosphere at 90 ° C. for 90 seconds is repeated 500 times.

  Further, when the repeated durability test is performed according to the above, the water vapor adsorption amount at 25 ° C. and the relative vapor pressure of 0.5 is 80% or more before the repeated durability test.

(Comparative Example 1)
A silicoaluminophosphate containing no carbon is calcined in the same manner as in Example 1 except that hydrothermal synthesis is performed in the same manner as in Example 1 and the dried solid is circulated in the air and the calcining temperature is 550 ° C. Got.

By XRD measurement of the fired product, an XRD pattern showing a CHA structure (framework density 14.5 T / nm ³ ) as shown in FIG. 15 was obtained. The pore utilization factors 1 and 2 determined from the above formulas 9 and 10 were all 1. According to CN analysis of the fired product, both carbon and nitrogen were below the lower limit of detection (0.3% by weight). The effective water adsorption amount of the fired product was 22.8% by weight. An XRD pattern showing an amorphous state as shown in FIG. 16 was obtained by XRD measurement performed after durability test # 1 of the fired product. From this, it is considered that the pore structure of the fired product is destroyed and the adsorption capacity is remarkably reduced. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Comparative Example 2)
Except for hydrothermal synthesis by the same method as in Example 2 and air circulation (oxygen concentration 7 vol%, GHSV = about 6000 hr ⁻¹ ) in which the dried solid was diluted with nitrogen, the firing temperature was set to 550 ° C. Firing was conducted in the same manner as in No. 2 to obtain an iron silicoaluminophosphate containing no carbon.

By XRD measurement of the fired product, an XRD pattern showing a CHA structure (framework density 14.5 T / nm ³ ) as shown in FIG. 17 was obtained. The pore utilization factors 1 and 2 determined from the above formulas 9 and 10 were all 1. According to CN analysis of the fired product, both carbon and nitrogen were below the lower limit of detection (0.3% by weight). The effective water adsorption amount of the fired product was 18.3% by weight. The XRD pattern which shows the amorphous state as shown in FIG. 18 was obtained by the XRD measurement performed after the durability test # 1 of the fired product. The effective water adsorption amount after the durability test # 1 of the fired product was 6.8% by weight. By XRD measurement performed after durability test # 2 of the fired product, an XRD pattern showing an amorphous state as shown in FIG. 19 was obtained. From this, it is considered that the pore structure of the fired product is destroyed and the adsorption capacity is remarkably reduced. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Comparative Example 3)
The solid which was hydrothermally synthesized and dried in the same manner as in Example 2 was calcined in the same manner as in Example 2 except that the calcining temperature was 325 ° C. under a nitrogen stream, and contained carbon beyond the scope of the present invention. To obtain iron silicoaluminophosphate.

The CHA structure (framework density 14.5 T / nm ³ ) was confirmed by XRD measurement of the fired product. The pore utilization factor 2 determined from the equation 10 was 0.57. CN analysis of the fired product confirmed that it contained 8.9% by weight of carbon and 1.9% by weight of nitrogen. The effective water adsorption amount of the fired product was 10.5% by weight. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. Table 1 shows the results. From this, it is clear that the amount of adsorption is small when carbon is contained beyond the scope of the present invention.

(Comparative Example 4)
According to Example 5 of US Pat. No. 6,395,674, the SAPO-34 precursor was calcined to obtain SAPO-34. That is, 15.4 g of 85% phosphoric acid and 9.2 g of pseudo boehmite (containing 25% by weight of water) were slowly added to 18 g of water and stirred. Further, 10 g of water was added and stirred for 1 hour, and this was designated as solution A. Separately from the liquid A, a liquid in which 4.1 g of fumed silica (Aerosil 200), 11.6 g of morpholine, and 15 g of water were mixed and slowly added to the liquid A, and then 24 g of water was further added to the liquid 3 Stir for hours. The obtained mixture was charged into a 200 ml stainless steel autoclave containing a Teflon (registered trademark) inner cylinder and reacted at 200 ° C. for 24 hours. After the reaction, the mixture was cooled and the supernatant was removed by decantation, and the precipitate was collected. The obtained precipitate was washed with water three times, filtered, and dried at 120 ° C. for 12 hours. The obtained solid was confirmed to have a pure CHA structure (framework density: 14.5 T / nm ³ ) by powder X-ray diffraction measurement. As described in Example 5 of US Pat. No. 6,395,674, the SAPO-34 having a carbon content of 8.5% by weight was calcined at 450 ° C. for 1 hour in a He stream. Got. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Comparative Example 5)
SAPO-34 described in Example 5 of US Pat. No. 6,395,674 was obtained in the same manner as in Comparative Example 4 except that the calcination temperature in He was changed to 625 ° C. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Comparative Example 6)
Silicoaluminophosphate was synthesized according to the description of RTYang et al., Langmuir, 2003, 19, 2193-2200. That is, 5 g of 85% phosphoric acid was added to 52 g of water, and 8.9 g of aluminum isopropoxide was slowly added with stirring, followed by stirring for 3 hours. To this, 4.55 g of colloidal silica (LUDOX-AS, 40 wt% SiO ₂ ) was added. Further, 25.6 g of isopropylamine (i-PrNH ₂ ) was added dropwise with stirring to obtain a starting mixture having the following composition.

Al ₂ O ₃ : P ₂ O ₅ : 0.7SiO ₂ : 10i-PrNH ₂ : 50H ₂ O

  The starting mixture thus obtained was charged into a stainless steel autoclave having an internal volume of 150 ml containing a Teflon (registered trademark) inner cylinder, and reacted at 160 ° C. for 120 hours. After the reaction, the mixture was cooled to room temperature, and the precipitate was separated by decantation, filtered and washed with water to recover the product.

When the obtained product was subjected to powder X-ray diffraction measurement, a pure GIS structure (framework density: 15.3 T / nm ³ ) was confirmed. The result is shown in FIG.

  The obtained product was calcined according to the conditions shown in Table-2 of the above-mentioned document (R.T.Yang et al.) And subjected to thermogravimetric analysis. That is, about 10 mg of the obtained product was heated to 325 ° C. at 5 ° C./min in a He stream (30 cc / min) using a thermogravimetric analyzer (Shimadzu Corporation; TGA-50), at 325 ° C. After treating for 1 hour, it was cooled to room temperature. Thereafter, the He air flow was switched to the Air air flow (30 cc / min), the temperature was raised to 700 ° C. at 10 ° C./min, and the obtained calcined product was subjected to thermogravimetric analysis. These results are shown in Table 1.

(Comparative Example 7)
In accordance with the conditions in Table-2 of the above-mentioned document (RTYang et al.), Firing was performed in a He stream as in Comparative Example 6 except that the temperature rising rate in the He stream was 40 ° C./min. The product was subjected to thermogravimetric analysis in an air stream. These results are shown in Table 1.

(Comparative Example 8)
Hydrothermal synthesis and firing were carried out to produce a carbon-containing silicoaluminophosphate as follows.

  First, 16.1 g of 85% phosphoric acid and 9.52 g of pseudo boehmite (containing 25% water, manufactured by Condea) were slowly added to 30 g of water and stirred. This was designated as solution B. Separately from Liquid B, a liquid in which 2.52 g of fumed silica (Aerosil 200), 6.1 g of morpholine, 7.1 g of triethylamine, and 40 g of water were prepared. This was slowly added to the B liquid and stirred for 3 hours to obtain a starting reaction product having the following composition.

_{0.6SiO 2: Al 2 O 3:} 1P 2 O 5: 1 Morpholine: 1 triethylamine: 60H ₂ O

  The obtained starting reaction product was charged into a 200 cc stainless steel autoclave containing a Teflon (registered trademark) inner cylinder, reacted at 190 ° C. for 24 hours while rotating, then heated to 200 ° C. and reacted for 24 hours. . After the reaction, the reaction mixture was cooled and the supernatant was removed by decantation to collect a precipitate. The precipitate was washed with water three times, filtered off and dried at 120 ° C. Elemental analysis of the dried solid (silicoaluminophosphate precursor) was performed. As a result, the composition ratio (molar ratio) of each component with respect to the total of aluminum, phosphorus, and silicon was 11.6% for silicon, 49.0% for aluminum, and 39.4% for phosphorus.

  Next, the obtained solid (silicoaluminophosphate precursor) was subjected to a calcination treatment in the same manner as in Example 1 except that nitrogen was used as a calcination gas and the calcination temperature was 450 ° C. to obtain a baked product.

The XRD measurement of the fired product confirmed that it had a CHA structure (framework density 14.5 T / nm ³ ). The pore utilization factor 1 determined from the equation 9 was 0.83, and the pore utilization factor 2 determined from the equation 10 was 0.77. It was. CN analysis of the fired product confirmed that it contained 7.5% by weight of carbon and 0.6% by weight of nitrogen. The effective water adsorption amount of the fired product was 14.0% by weight. The XRD measurement performed after durability test # 1 of the fired product confirmed the CHA structure. The effective water adsorption amount after the durability test # 1 of the fired product was 12.0% by weight. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

(Comparative Example 9)
According to US Pat. No. 4,440,871, silicoaluminophosphate having an AFI structure was synthesized. That is, 7.69 g of 85 wt% phosphoric acid and 33.29 g of water were mixed, 4.58 g of pseudoboehmite was added, mixed until homogeneous, and stirring was continued for 3 hours. Next, 1.08 g of 37 wt% HCl was added to the mixture, and then 2.16 g of fumed silica (Aerosil 200) was added and mixed until homogeneous. Finally, 18.6 g of 35 wt% tetraethylammonium hydroxide (TEAOH) aqueous solution was added and stirred until homogeneous. A part of this reaction mixture was sealed in a stainless steel autoclave lined with Teflon (registered trademark) and heated in an oven at 150 ° C. for 168 hours. The solid reaction product was recovered by decantation, water washing and filtration, and washed with water. The obtained solid was dried in air at room temperature. XRD measurement confirmed that the structure was almost pure (FI framework density 17.3 T / nm ³ ). The obtained fired product had a nitrogen content of 1.0% by weight, a carbon content of 7.2% by weight, and a C / N weight ratio of 7.20. Further, the weight reduction rate (g1) and the weight reduction rate (g2) of the fired product were measured. These results are shown in Table 1.

It is a conceptual diagram which shows an example of the cool storage heat system of this invention. It is a conceptual diagram which shows an example of the adsorption heat pump of this invention. It is a conceptual diagram which shows an example of the dehumidification air conditioner of this invention. It is a conceptual diagram of an example of the desiccant air conditioner which is a dehumidification air conditioner. 2 is an XRD pattern of a fired product obtained in Example 1. FIG. 2 is a water vapor adsorption isotherm at 25 ° C. of the fired product obtained in Example 1. FIG. It is an XRD pattern after durability test # 1 of the fired product obtained in Example 1. 2 is a thermogravimetric analysis result of the iron aluminophosphate precursor obtained in Example 2. FIG. 3 is an XRD pattern of a fired product obtained in Example 2. FIG. 3 is a water vapor adsorption isotherm at 55 ° C. of the fired product obtained in Example 2. FIG. It is an XRD pattern after durability test # 1 of the fired product obtained in Example 2. 4 is an XRD pattern of a fired product obtained in Example 4. It is an XRD pattern after durability test # 1 of the fired product obtained in Example 4. It is an XRD pattern after durability test # 2 of the fired product obtained in Example 4. 3 is an XRD pattern of a fired product obtained in Comparative Example 1. It is an XRD pattern after durability test # 1 of the fired product obtained in Comparative Example 1. 3 is an XRD pattern of a fired product obtained in Comparative Example 2. It is an XRD pattern after durability test # 1 of the fired product obtained in Comparative Example 2. It is an XRD pattern after durability test # 2 of the fired product obtained in Comparative Example 2. 7 is an XRD pattern of a product obtained by hydrothermal synthesis of Comparative Example 6.

Explanation of symbols

11 Cold storage heat system 12, 26, 27 Circulating water supply 13, 22, 23 Adsorption / desorption device 14 Evaporator / condenser 21 Adsorption heat pump 24 Evaporator 25 Condenser 28, 29, 30, 31 Open / close valve 61 Dehumidifying air conditioner 62 Air 63 Adsorbent regeneration mechanism 70 Desiccant air conditioner 71 Processing air path 72 Regeneration air path 73 Desiccant rotor 74, 75 Sensible heat exchanger 76 Heat supply mechanism 77 Humidifier 78 Air conditioning space 79 External

Claims (21)

Silicoaluminophosphate having a carbon content of 0.8 wt% or more and 6 wt% or less, and each molar ratio of Me, Al, P and Si constituting the skeleton structure satisfies the following formulas 1 to 4, framework density 10T / nm ³ or more 16T / nm ³ or less, the skeleton structure before firing when the carbon content by firing the silicoaluminophosphate phosphate and less than 0.3% by weight is maintained (Wherein Me is at least one element selected from elements of groups 2A, 7A, 8, 1B, and 2B of the periodic table).
0 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Me to the sum of Me, Al, P and Si)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the sum of Me, Al, P and Si)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the sum of Me, Al, P and Si)
0.001 ≦ w ≦ 0.3 4
(W represents the molar ratio of Si to the sum of Me, Al, P and Si)   The carbon-containing silicoaluminophosphate according to claim 1, wherein the carbon content is 1.8 wt% or more and 6 wt% or less. The skeleton structure is a structure selected from AEI, AFR, AFS, AFT, AFX, ATS, CHA, ERI , LEV, LTA and VFI represented by a code defined by IZA. The carbon-containing silicoaluminophosphate described.   The carbon-containing silicoaluminophosphate according to claim 1 or 2, wherein the skeleton structure is a structure selected from AEI, CHA, and LEV represented by a code defined by IZA.   The carbon-containing silicoaluminophosphate according to any one of claims 1 to 4, wherein Me is at least one element selected from Fe, Ni, Co, Mg and Zn.   The carbon-containing silicoaluminophosphate according to any one of claims 1 to 4, wherein Me is Fe. The carbon-containing silico according to any one of claims 1 to 6, wherein when a repeated durability test of the carbon-containing silicoaluminophosphate is performed according to the following, the crystal structure before the test is retained. Aluminophosphate.
“Repeated durability test” is a test in which a carbon-containing silicoaluminophosphate is held in a vacuum vessel maintained at 90 ° C., and exposed to a vacuum state and a saturated water vapor atmosphere at 90 ° C. for 90 seconds each, 500 times. It is. “Crystal structure is retained” means that when XRD measurement is performed with the same equipment, the same measurement conditions, the same sample holder and the same sample weight, the strongest peak intensity after the repeated durability test is the repeated durability test. It means 50% or more of the previous strongest peak intensity. However, the peak intensity is the peak height, and is obtained by subtracting the background count from the peak top count. A method for producing a carbon-containing silicoaluminophosphate according to any one of claims 1 to 7,
A carbon characterized by hydrothermally synthesizing a compound of a metal element constituting a silicoaluminophosphate in the presence of a structure indicating material, and firing the resulting silicoaluminophosphate precursor in an atmosphere having an oxygen concentration of 20 vol% or less. A method for producing a silicoaluminophosphate.   The method for producing a carbon-containing silicoaluminophosphate according to claim 8, wherein the temperature for firing the silicoaluminophosphate precursor is 300 ° C or higher and 450 ° C or lower.   The silicoaluminophosphate precursor is hydrothermally synthesized in the presence of two or more structure indicators, and the structure indicator is (1) an alicyclic heterocyclic compound containing nitrogen, (2) cyclo The carbon-containing silicoaluminophosphate according to claim 8 or 9, wherein the carbon-containing silicoaluminophosphate is selected from two or more groups selected from the group consisting of an amine having an alkyl group and (3) an amine having an alkyl group. Manufacturing method.   Silicoaluminophosphate precursors are morpholine, cyclohexylamine, triethylamine, isopropylamine, N, N-diisopropylethylamine, N-methyl-n-butylamine, isobutylamine, hexamethyleneimine, N, N-diethylethanolamine and N The carbon-containing silicoaluminophos according to claim 8 or 9, which is synthesized in the presence of at least one nitrogen-containing organic compound selected from N, dimethylethanolamine as a structure indicating material. Fate manufacturing method.   An adsorbent comprising the carbon-containing silicoaluminophosphate according to any one of claims 1 to 7.   The adsorption amount of the adsorbed material when the relative vapor pressure is changed by 0.15 in the range of the relative vapor pressure of 0.01 or more and 0.5 or less in the adsorption isotherm of the carbon-containing silicoaluminophosphate measured at 25 ° C. The adsorbent according to claim 12, which has a relative vapor pressure range of 0.1 g / g or more.   To be used in a heat utilization system that uses adsorption heat generated by adsorption of an adsorbent on the adsorbent and / or a heat utilization system that uses latent heat of evaporation generated when the adsorbent evaporates from the adsorbent. The adsorbent according to claim 12 or 13, characterized in that:   The heat utilization system includes (a) a structure for supplying waste heat to the adsorbent and desorbing the adsorbent, and (b-1) warming up the adsorption heat generated when the adsorbent is adsorbed on the adsorbent. A configuration for supplying equipment that needs operation, and / or (b-2) a configuration for supplying latent heat of evaporation generated when the adsorbed material evaporates from the adsorbent to a cooling medium circulating in the cooling refrigerator; The adsorbent according to claim 14, wherein the adsorbent is a cold storage heat system.   An adsorbent used in the cold storage heat system, wherein the carbon-containing silicoaluminophosphate contained in the adsorbent is adsorbed on the adsorption isotherm measured at 55 ° C. at a relative vapor pressure of 0.02. The amount of the adsorbed substance at a relative vapor pressure of 0.1 is 0.13 g / g or more, and the relative vapor pressure is 0.02 or more and 0.1 or less. The adsorbent according to claim 15, wherein the adsorbent has a relative vapor pressure region in which a change in the amount of adsorption of the adsorbent when the pressure changes by 0.05 is 0.05 g / g or more.   The adsorbent according to claim 14, wherein the heat utilization system is an adsorption heat pump.   An adsorbent used in the adsorption heat pump, wherein the carbon-containing silicoaluminophosphate contained in the adsorbent has a relative vapor pressure of 0.05 to 0.30 on an adsorption isotherm measured at 25 ° C. 18. The adsorbent according to claim 17, wherein the adsorbent has a relative vapor pressure range of 0.1 g / g or more when the relative vapor pressure changes by 0.15 in a range.   The heat utilization system using the adsorbent according to claim 12 or 13, wherein the heat utilization system using adsorption heat generated by adsorption of the adsorbent on the adsorbent and / or the adsorbent evaporates from the adsorbent. A heat utilization system that utilizes latent heat of vaporization generated at the time.   An adsorption heat pump using the adsorbent according to claim 12 or 13.   A cold storage heat system using the adsorbent according to claim 12 or 13.

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