JP4765244B2 - Method for producing aluminophosphates - Google Patents

Description

  The present invention relates to a method for producing aluminophosphates.

  Zeolite is widely used in various applications such as catalysts, adsorbents, separation materials, etc. As a method for synthesizing zeolite, hydrothermal synthesis is performed using a compound of a metal element capable of forming a framework structure of zeolite and a template. It is generally done.

  For example, Patent Document 1 discloses a method for producing a substituted aluminophosphate. The publication teaches hydrothermal synthesis at 90 ° C. or higher, heating at 90-120 ° C., and heating at 150-250 ° C. for up to 2 weeks. Details of hydrothermal synthesis conditions and effects thereof are taught. There is no mention about, and all the examples are heating at 200 ° C. for 24 hours, and there is no description about the temperature raising process.

Patent Document 2 discloses a method for synthesizing silicoaluminophosphate SAPO-37 having a FAU structure for the purpose of increasing yield and increasing cation exchange capacity. The reaction mixture is heated at a rate of 5 ° C./hr to 200 ° C./hr to 80-200 ° C. and held in that temperature range until SAPO-37 nucleation occurs, then 5 ° C./hr to 200 ° C. / It is taught to further heat to 100-300 ° C. for 5 to 500 hours at the rate of hr until crystals of SAPO-37 are formed. However, it is known that an aluminophosphate having a FAU structure with a low framework density of 12.7 T / nm ³ has low structural stability. That is, for example, according to Patent Document 3, it is known that SAPO-37 from which the template has been completely removed has its crystal structure destroyed by moisture in the atmosphere. The use of is considered extremely difficult.
JP 60-186409 A JP-A-61-151021 U.S. Pat. No. 4,681,864

  As described above, the conventional aluminophosphate production method has no description of the temperature raising process during hydrothermal synthesis, or the target aluminophosphate is essential even if the temperature raising process is disclosed. In particular, the structure is liable to break down and is not suitable for industrial use, particularly for repeated use.

  The present invention has been made to solve the above-mentioned problems, and its purpose is that there is little deterioration in its performance with repeated use or prolonged use, particularly when used as an adsorbent, It is an object of the present invention to provide a method for producing aluminophosphates having a sufficiently large adsorption capacity and which does not cause crystal structure breakage and accompanying adsorption capacity decrease due to repeated use. Another object of the present invention is to provide a method for producing template-containing aluminophosphates, which is advantageous for producing the above aluminophosphates.

As a result of intensive studies, the present inventors have used an aluminum source, a Me atom source, a phosphorus source, and a template as raw materials when producing aluminophosphates having a certain framework density by hydrothermal synthesis. The above-mentioned object can be achieved by placing the aqueous gel (material mixture) obtained by mixing them over a certain temperature range in the process of raising the temperature to the maximum temperature for aluminophosphate synthesis. As a result, the present invention has been completed.

Namely, the present invention provides a process for preparing aluminophosphate such manufacturing framework density by hydrothermal synthesis of the raw material mixture (FD) is 13T / nm ³ or more 20T / nm ³ or less of the template-containing aluminophosphate compound, In hydrothermal synthesis, 2 selected from the group consisting of (1) an alicyclic heterocyclic compound containing a nitrogen atom as a hetero atom, (2) an amine having a cycloalkyl group, and (3) an amine having an alkyl group. One or more compounds are used from each of the above groups, and the raw material mixture is linearly heated to the maximum temperature , and is placed in a temperature range of 75 ° C. to 115 ° C. for 1.3 hours or longer. And a method for producing template-containing aluminophosphates.

  Another gist lies in a method for producing aluminophosphates, characterized in that the template-containing aluminophosphates produced by the above method are fired.

  According to the method for producing aluminophosphates of the present invention, particularly when used as an adsorbent, the adsorption capacity is large, and the crystal structure is destroyed due to repeated use under severe conditions, and the adsorption capacity is reduced accordingly. It has an excellent effect that it can produce aluminophosphates that do not occur.

<Description of aluminophosphates of the present invention>
(Basic configuration of aluminophosphates)
In the present invention, aluminophosphates mean crystalline aluminophosphates defined by the International Zeolite Association (IZA), and the atoms constituting the skeletal structure are oxygen, aluminum and phosphorus, some of which are other May be substituted with an atom (Me). The other atom (Me) is at least one selected from the group consisting of Group 2A, Group 7A, Group 8, Group 1B, Group 2B, Group 3B (excluding Al) and Group 4B elements of the periodic table. Elemental atoms are mentioned. Among them, I) an aluminum atom is a heteroatom (Me1: where Me1 is at least one element selected from elements 2A, 7A, 8, 1B, 2B, 3B (excluding Al) of the periodic table) II) Me-aluminophosphate partially substituted with a), II) Me-aluminophosphate in which a phosphorus atom is substituted with a heteroatom (Me2: where Me2 is a group 4B element of the periodic table), Alternatively, III) Me-aluminophosphate in which both aluminum and phosphorus are substituted with heteroatoms (Me1 and Me2 respectively) is preferable from the viewpoint of adsorption characteristics and catalytic performance.

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

  Further, if y and z are out of the above ranges, synthesis tends to be difficult.

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

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

Further, the aluminophosphate compound, apart from the components constituting the skeleton structure may also include the an with other cations ion-exchangeable cationic species. Examples of cations in such a case include protons, alkaline elements such as Li, Na, and K, alkaline earth elements such as Ca, and rare earth elements such as La and Ce. Among these, protons, alkali elements, and alkaline earth elements are preferable.

Further, aluminophosphate compounds of the present invention, the framework density (hereinafter, sometimes abbreviated as FD.) Is, 13T / nm ³ or more 20T / nm ³ or less, preferably, 13.5T / nm ³ or more There, still more preferably 14T / nm ³ or more, whereas, preferably 19T / nm ³ or less, more preferably 17.5T / nm ³ or less. Where framework density (T
/ Nm ³ ) means the number of T atoms (atoms of elements other than oxygen constituting the skeleton of the zeolite) present per unit volume nm ³ of the zeolite, and this value is determined by the structure of the zeolite. If it is less than the above range, there is a problem that the structure becomes unstable and the durability is lowered. On the other hand, if it exceeds the above range, the adsorbed amount and the catalytic activity become small and it is not suitable for use as a catalyst or an adsorbent.

The structure of the aluminophosphate of the present invention is a code defined by the International Zeolite Association (IZA), and is AEI, AEL, AET, AFI, AFN.
, AFR, AFS, AFT, AFX, ATO, ATS, CHA, ERI, LEV, VFI, among them, AEI, AEL, AFI, C from the point of adsorption characteristics and catalytic activity
It is preferably any one selected from HA and LEV, and CHA is particularly preferable.
<Method for producing aluminophosphates>
Hereinafter, a method for producing aluminophosphates will be described.

(Constituent raw materials)
Aluminophosphates are produced by hydrothermal synthesis after mixing an aluminum source, a Me atom source (particularly preferably an iron source), a phosphorus source and a template as raw materials.

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

Me source: The Me source is not particularly limited, and usually, sulfate, nitrate, phosphate of the Me atom,
Inorganic acid salts such as chloride and bromide, organic acid salts such as acetate, oxalate and citrate, and organometallic compounds such as pentacarbonyl and ferrocene are used. Of these, inorganic acid salts and organic acid salts are preferred from the viewpoint of solubility in water. In some cases, a colloidal oxide or a fine powdered oxide may be used.

  Phosphorus source: The phosphorus source is usually phosphoric acid, but aluminum phosphate may be used.

Template: An amine, imine, or quaternary ammonium salt can be used as a template, but preferably (1) an alicyclic heterocyclic compound containing nitrogen as a hetero atom, (2) an amine having a cycloalkyl group, and (3 It is preferable to use at least one compound selected from the group consisting of amines having an alkyl group. They are easy to obtain and inexpensive, and also have the effect that the manufactured Me-aluminophosphate is easy to handle and structural destruction is not likely to occur.

  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 alone or in combination of two or more. When one of the above amines is used, from the viewpoint of ease of synthesis and durability of the zeolite, (1) morpholine in the alicyclic heterocyclic compound containing nitrogen as a hetero atom Or (2) A cyclohexylamine among amines having a cycloalkyl group is preferable, and morpholine is particularly preferable among them.

  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, a template includes (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 zeolite having a desired element ratio or having high crystallinity. In particular, (1) in the case of a combination of two or more containing an alicyclic heterocyclic compound containing nitrogen as a hetero atom, it is easy to synthesize a desired element ratio or highly crystalline aluminophosphates. cormorant from the viewpoint, more preferable. As a specific preferred combination, two or more kinds of morpholine, triethylamine or N, N-diethylethanolamine and cyclohexylamine, and more preferably a combination of two or more kinds including morpholine are more preferred.

  The mixing ratio of each group of these templates needs to be selected in a timely manner according to the conditions, but the molar ratio of the two types of templates to be mixed is in the range of 1:20 to 20: 1. From the viewpoint of easy synthesis of zeolite with high crystallinity, 1:10 to 10: 1 is preferable. Although other templates may be contained, in that case, the molar ratio is usually 20% or less, preferably 10% or less. These templates are advantageous in that they are inexpensive and easy to handle and less corrosive than conventional ones (for example, tetraethylammonium hydroxide).

(Hydrothermal synthesis)
Next, hydrothermal synthesis in the method for producing aluminophosphates will be described.

  First, an aqueous gel is prepared by mixing a Me source, an aluminum source, a phosphoric acid source, a template and water. The mixing order is not limited and may be appropriately selected depending on the conditions to be used. Usually, however, a phosphoric acid source and an aluminum source are first mixed with water, and then a Me source and a template are mixed therewith.

The composition of the aqueous gel affects the ease of synthesis of the desired one. When the aluminum source, Me source and phosphate source are expressed in terms of the molar ratio of the oxide, the value of MeO / Al ₂ O ₃ is usually greater than 0. 1.0 or less, preferably 0.02 or more, on the other hand, 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. The total amount of the template affects the ease of synthesis of the desired product and the economy, and the molar ratio of the template to P ₂ O ₅ is usually 0.2 or more, preferably 0.5 or more, more preferably 1 or more. Usually, it is 4 or less, preferably 3 or less, more preferably 2.5 or less. Also, the mixing ratio of two or more templates affects the ease of synthesis of the desired one, and should be selected as appropriate according to the conditions. For example, when using morpholine and triethylamine as described above, The molar ratio of morpholine / triethylamine is 0.03 to 20, preferably 0.05 to 5, more preferably 0.1 to 2, and most preferably 0.2 to 1.

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

The lower limit of the proportion of water, relative to Al ₂ O _3, is 3 or more in molar ratio, preferably 5 or more from the viewpoint of easiness of synthesis, and more preferably 10 or more. The upper limit of the ratio of water is preferably 200 or less, 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 templates or adding an acid such as hydrochloric acid or sulfuric acid.

In addition, components other than the above may be coexisted in the aqueous gel in order to improve the solubility of the raw material or to expect the effect of a mineralizer or the like. Examples of such components include hydrophilic organic solvents such as hydroxides and salts of alkali metals and alkaline earth metals, and alcohols. The coexistence ratio affects the ease of synthesis of the desired product. In the case of alkali metal or alkaline earth metal hydroxide or salt, the molar ratio with respect to Al ₂ O ₃ is usually 0.2 or less, preferably In the case of a hydrophilic organic solvent such as alcohol, the molar ratio with respect to water is usually 0.5 or less, preferably 0.3 or less.

  Hydrothermal synthesis is carried out by placing an aqueous gel prepared under the above conditions in a pressure resistant container and raising the temperature under a self-generated pressure or a gas pressure that does not inhibit crystallization and keeping it within a predetermined temperature range. The lower limit of this temperature range is usually 120 ° C or higher, preferably 130 ° C or higher, more preferably 140 ° C or higher. The upper limit is 200 ° C. or lower, preferably 195 ° C. or lower, more preferably 180 ° C. or lower, and most preferably 170 ° C. or lower. In the present invention, the highest temperature in this temperature range is referred to as the highest temperature, and this highest temperature affects the ease of synthesis of desired aluminophosphates and is selected from the above range.

  The important point in the method of the present invention is that the temperature is raised to the maximum temperature and the temperature is kept within a temperature range from 75 ° C. to 115 ° C. for 1.3 hours or more. This time (temperature rising time) is preferably 1.5 hours or longer, and more preferably 2 hours or longer. When the temperature raising time is less than 1.3 hours, the durability of the aluminophosphates obtained by firing the obtained template-containing aluminophosphates becomes insufficient. On the other hand, the upper limit of the time is not particularly limited, but if it is too long, it is not preferable in terms of production efficiency, and is usually 50 hours or less, preferably 24 hours or less.

  The temperature raising method between the temperature regions is not particularly limited. For example, various methods such as a method of increasing monotonously, a method of changing in a stepped manner, a method of changing up and down such as vibration, and a method of combining these methods. Can be used. In normal cases, for ease of control, a method of monotonically increasing the temperature while maintaining the temperature increase rate below a certain value is preferably used.

  Further, in the present invention, it is preferable to hold for a predetermined time in the vicinity of the highest temperature, and the vicinity of the highest temperature means a temperature 5 ° C. lower than the temperature or the highest temperature, and the time for holding at the highest temperature is: It affects the ease of synthesis of the desired product, and is usually 0.5 hours or more, preferably 3 hours or more, more preferably 5 hours or more, usually 30 days or less, preferably 10 days or less, more preferably 4 days. It is as follows.

  There are no particular restrictions on how to change the temperature after reaching the maximum temperature, a method that changes in a stepped manner, a method that changes the vibration below the maximum temperature, etc., and a method that combines these methods. Various schemes can be used. In normal cases, from the viewpoint of ease of control and durability of the obtained aluminophosphate, it is preferable to lower the temperature from 100 ° C. to room temperature after maintaining the maximum temperature.

After hydrothermal synthesis, the product is isolated. The method for separating the product is not particularly limited. Usually, it is separated by filtration, decantation or the like, washed with water, and dried at a temperature of room temperature to 150 ° C. or less to obtain aluminophosphates containing the product template.
<Manufacture of aluminophosphates>
In accordance with the above, the aluminophosphates containing the prepared template are usually activated by removing all or part of the organic template incorporated into the pore structure by firing, extraction or the like according to the purpose of use. It is used by making it.

The Me-aluminophosphate after firing can be obtained by firing Me-aluminophosphate under a flow of nitrogen, air or the like or under reduced pressure. 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 further preferable. The firing time is 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 near atmospheric pressure.
The firing gas can be an oxygen-containing gas such as air, or an inert gas such as nitrogen, but from the viewpoint of easy temperature control and easy template removal rate control, an inert gas having an oxygen concentration of 20 vol% or less. Diluted oxygen is preferably used.
As the gas other than oxygen, an inert gas such as nitrogen, argon, or helium is used. However, depending on the case, water vapor or nitrogen oxide may be mixed up to 10% by volume.

The firing gas may or may not be circulated in the processing apparatus. However, when it is circulated, it is preferable that the space velocity (GHSV) for the sample to be fired is within a range. 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, the 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 not economically preferable. As a baking apparatus, arbitrary heating apparatuses, such as a muffle furnace, a tubular furnace, and a kiln, are used, and it is performed in a fixed bed or fluidized bed format.

  The aluminophosphate obtained by the production method of the present invention is composed of an adsorbent, a catalyst for acid reaction and oxidation reaction, a separating material, an optical material such as quantum dots and quantum wires, semiconductor fine particles and phosphors serving as magnetic materials, Widely used as a host for dyes and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by the following example.

In the following Examples and Comparative Examples, the following physical property measurements and treatments were performed under the following conditions.
XRD measurement conditions X-ray source: Cu-Kα ray (λ = 1.54184Å),
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 to 50 degrees Scan speed: 0.05 ° (2θ / sec), continuous scan sample: about 100 mg of sample pulverized manually using an agate mortar
The sample amount was made constant by using a sample holder having the same shape.
Carbon and nitrogen analysis (CN analysis)
PERKIN ELMER 2400 SeriesII CHNS / O Analyzer was used.
Elemental analysis The sample was calcined at 550C for 6 hours under air flow, dissolved in hydrochloric acid, and then subjected to composition analysis by ICP method.
Adsorption characteristics (55 ° C)
The sample was evacuated at 120 ° C. for 5 hours, and then the water vapor adsorption isotherm at 55 ° C. was measured by a water vapor adsorption amount measuring device (Belsorb 18: Nippon Bell Co., Ltd.) by the following method.
Air bath temperature: 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
The operation of holding the durability test sample in a vacuum vessel maintained at 90 ° C. and exposing it to a 5 ° C. saturated water vapor atmosphere and a 90 ° C. saturated water vapor atmosphere for 90 seconds was repeated. Part of the water adsorbed on the sample when exposed to a 90 ° C. saturated water vapor atmosphere is desorbed in a 5 ° C. saturated water vapor atmosphere and moves to a water reservoir maintained at 5 ° C. From the m-th adsorption to the n-th desorption, the average amount of adsorption per time (Qn; m (g)) and the dry weight (W (g)) of the sample transferred to the 5 ° C. water sump Cn; m (g / g)) was determined as follows.
[Cn; m] = [Qn; m] / (n−m + 1) / W

The starting reactant was obtained in the following way:
To 210 g of water, 86.5 g of 85% phosphoric acid was added, and 40.8 g of pseudoboehmite (containing 25% water, manufactured by Condea) was slowly added thereto and stirred for 3 hours. To this was added a solution obtained by dissolving 41.7 g of ferrous sulfate heptahydrate in 218 g of water, 19.0 g of morpholine and 65.9 g of triethylamine were slowly added, and the mixture was further stirred for 3 hours. A gel-like starting reaction product having the following composition was obtained.
_{0.4FeSO 4: 0.8Al 2 O 3:} P 2 O 5: 0.5 morpholine: 1.5 triethyl amine: 70H ₂ O
The above starting materials were charged into a stainless steel autoclave (internal volume of about 1 L) having a Teflon (registered trademark) inner cylinder, and hydrothermal synthesis was performed as follows. While stirring at 100 rpm, the temperature was increased linearly from room temperature to 140 ° C. at a rate of temperature increase of 14 ° C./hr, and the reaction was allowed to proceed for 72 hours at a maximum temperature of 140 ° C. Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

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. As a result of elemental analysis, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ).
3 g of this iron aluminophosphate was sampled and placed in a vertical quartz fired tube, and a mixed gas (oxygen concentration 5 vol%) of 175 ml / min of air and 325 ml / min of nitrogen was circulated.
The temperature was raised to 315 ° C. at 35 ° C./min, and calcination was carried out at 315 ° C. for 6 hours to obtain an aluminophosphate baked product. As a result of CN analysis, the carbon and nitrogen contents were 3.16% by weight and 1.3% by weight, respectively. As a result of measuring the adsorption amount at 55 ° C., the adsorption amount at a relative vapor pressure of 0.3 was 0.23 g / g. This iron aluminophosphate baked product was subjected to an adsorption durability test. Table 1 shows the average adsorption amount [Q1; 1500 (g / g)] from the first time to 1500th time, and the average adsorption amount [Q1500; 2000 (g / g)] from the 1501st time to 2000th time. There was no significant decrease in the average adsorption amount. Further, the adsorption amount at 55 ° C. after the durability test was 0.2 g / g at a relative vapor pressure of 0.3, and there was no significant decrease in the water vapor adsorption amount. In addition, XRD measurement after the test confirmed a pure CHA structure, and no significant change in crystallinity was observed before and after the test.

  In Example 1, hydrothermal synthesis was carried out in the same manner as in Example 1 except that the temperature was raised almost linearly from room temperature to 140 ° C at a rate of 10.8 ° C / hr and reacted at 140 ° C for 96 hours. went. Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was It was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was set to 340 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate fired product was subjected to a durability test.

  Table 1 shows the average adsorption amount [Q1; 1000 (g / g)] from the first time to the 1000th time and the average adsorption amount [Q1001; 2000 (g / g)] from the 1001st time to the 2000th time. There was no significant decrease in the average adsorption amount. XRD measurement after the test confirmed a pure CHA structure, and no significant change in crystallinity was observed before and after the test.

  Example 1 is the same as Example 1 except that the highest temperature reached 130 ° C., the temperature was raised almost linearly from room temperature to 130 ° C. at a rate of 10 ° C./hr, and reacted at 130 ° C. for 96 hours. Similarly, hydrothermal synthesis was performed.

  Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was It was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was set to 340 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1.

There was no significant decrease in the average adsorption amount. Further, as a result of XRD measurement after the test, a pure CHA structure was confirmed, and a large change in crystallinity was not observed before and after the test.
[Reference Example 4]

  In the same manner as in Example 1, a gel-like starting reaction product was obtained. The starting reactant was charged into a stainless steel autoclave (internal volume of about 1 L) having a Teflon (registered trademark) inner cylinder, and hydrothermal synthesis was performed as follows. While stirring at 100 rpm, the temperature was raised almost linearly from room temperature to 100 ° C. with a temperature raising time of 25 ° C./hr and held at 100 ° C. for 1 hour. Thereafter, the temperature was raised linearly from 100 ° C. to 130 ° C. at 30 ° C./hr and reacted at 130 ° C. for 96 hours. Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was It was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was set to 300 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1. There was no significant decrease in the average adsorption amount. The XRD measurement results before and after the test are shown in FIGS. 1 and 2, respectively. No significant change in crystallinity was observed before and after the test.

In Example 1, the maximum temperature reached 140 ° C., the temperature was increased linearly from room temperature to 140 ° C. at a rate of 5.8 ° C./hr, and reacted at 140 ° C. for 96 hours. Hydrothermal synthesis was carried out in the same manner as above.
Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was It was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was 320 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1. There was no significant decrease in the average adsorption amount. Further, as a result of XRD measurement after the test, a pure CHA structure was confirmed, and no significant change in crystallinity was observed before and after the test.

A gel-like starting reaction product having the following composition was obtained in the same manner as in Example 1, except that the amount of morpholine was 38 g and the amount of triethylamine was 43.9 g.
_{0.4FeSO 4: 0.8Al 2 O 3:} P 2 O 5: 1.0 morpholine: 1.0 of triethylamine: 70H ₂ O
The above starting reactant was carried out except that the maximum temperature reached was 160 ° C., the temperature was raised from room temperature to 160 ° C. almost linearly at a temperature rising rate of 12.3 ° C./hr, and the reaction was carried out at 160 ° C. for 72 hours. Hydrothermal synthesis was performed as in Example 1. Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.
When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was It was as shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was set to 330 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1.
There was no significant decrease in the average adsorption amount. The XRD measurement results before and after the test are shown in FIGS. 3 and 4, respectively. No significant change in crystallinity was observed before and after the test.

  Hydrothermal synthesis was carried out in the same manner as in Example 1 except that the temperature was raised almost linearly from room temperature to 160 ° C. at a rate of 26.7 ° C./hr and reacted at 160 ° C. for 72 hours.

  Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was As shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was 320 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1. There was no significant decrease in the average adsorption amount. Further, as a result of XRD measurement after the test, a pure CHA structure was confirmed. No significant change in crystallinity was observed before and after the test.
(Comparative Example 1)
In Example 1, hydrothermal synthesis was carried out in the same manner as in Example 1 except that the temperature was increased substantially linearly from room temperature to 140 ° C. at a rate of 35 ° C./hr. Table 1 shows the time (temperature increase time) set in the range of 75 ° C to 115 ° C. When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was As shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ). This iron aluminophosphate was calcined in the same manner as in Example 1 except that the calcining temperature was set to 340 ° C. to obtain a calcined aluminophosphate. As a result of CN analysis, the carbon and nitrogen contents were 2.76 wt% and 1.1 wt%, respectively. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1.

A large decrease in average adsorption was observed. The XRD measurement results before and after the test are shown in FIGS. 5 and 6, respectively. A significant decrease in crystallinity was observed after the test. From this, it is clear that the durability is inferior when the temperature raising time is short.
(Comparative Example 2)
The hydrothermal synthesis was carried out in the same manner as in Example 6 except that the maximum temperature reached 140 ° C. was raised almost linearly from room temperature to 140 ° C. at a rate of 35 ° C./hr and reacted at 140 ° C. for 72 hours. . Table 1 shows the time (temperature increase time) set in the range of 75 ° C. to 115 ° C. in the process of increasing the temperature to the highest temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was As shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ).
This iron aluminophosphate was calcined in the same manner as in Example 6 except that the calcining temperature was 350 ° C. to obtain a calcined aluminophosphate. This iron aluminophosphate baked product was subjected to an adsorption durability test. The results of the durability test are shown in Table 1. A large decrease in average adsorption was observed. Further, as a result of XRD measurement after the test, a significant decrease in crystallinity was observed after the test. From this, it is clear that the durability is inferior when the temperature raising time is short.
(Comparative Example 3)
Hydrothermal synthesis was carried out in the same manner as in Example 6 except that the maximum temperature reached was 180 ° C., and the temperature was increased almost linearly from room temperature to 180 ° C. at a rate of 45 ° C./hr and reacted at 180 ° C. for 24 hours. . Table 1 shows the time in the range of 75 ° C. to 115 ° C. in the process of raising the temperature to the maximum temperature.

When the precipitate was separated, dried and analyzed in the same manner as in Example 1, the constituent ratio (mol%) of each element with respect to the total of aluminum (Al), iron (Fe) and phosphorus (P) in the precipitate was As shown in Table 1. As a result of XRD measurement of the precipitate, it was confirmed that the precipitate was an iron aluminophosphate having a CHA structure (FD: 14.5 T / nm ³ ).
This iron aluminophosphate was calcined in the same manner as in Example 6 except that the calcining temperature was 320 ° C., to obtain a calcined aluminophosphate. As a result of CN analysis, the carbon and nitrogen contents were 3.02% by weight and 1.23% by weight, respectively. This iron aluminophosphate fired product was subjected to a durability test. The results of the durability test are shown in Table 1. A large decrease in average adsorption was observed. Further, as a result of XRD measurement after the test, a significant decrease in crystallinity was observed after the test. The XRD patterns before and after the durability test are shown in FIGS. From this, it is clear that the durability is inferior when the temperature raising time is short.

It is an XRD pattern before the durability test of the iron aluminophosphate of Reference Example 4 . It is an XRD pattern after the durability test of the iron aluminophosphate of Reference Example 4 . It is an XRD pattern before the durability test of the iron aluminophosphate of Example 6. It is an XRD pattern after the durability test of the iron aluminophosphate of Example 6. It is an XRD pattern before the durability test of the iron aluminophosphate of the comparative example 1. It is an XRD pattern after the durability test of the iron aluminophosphate of Comparative Example 1. It is an XRD pattern before the durability test of the iron aluminophosphate of the comparative example 3. It is an XRD pattern after the durability test of the iron aluminophosphate of Comparative Example 3.

Claims (7)

A process for preparing aluminophosphate such a raw material for producing framework density by hydrothermal synthesis mixture (FD) is 13T / nm ³ or more 20T / nm ³ or less of the template-containing aluminophosphate such, upon hydrothermal synthesis, as a template ( 1) One or more kinds each selected from the group consisting of two or more groups selected from the group consisting of alicyclic heterocyclic compounds containing nitrogen atoms as heteroatoms, (2) amines having cycloalkyl groups, and (3) amines having alkyl groups using the compounds, and in the process of linearly raise the temperature of the raw material mixture to a maximum temperature, the template-containing aluminophosphate compound, characterized in that it is placed 75 ° C. or higher 115 ° C. 1.3 hours or more in the following temperature range Manufacturing method.   The method for producing template-containing aluminophosphates according to claim 1, wherein the maximum temperature reached is 200 ° C or lower. The manufacturing method of the template containing aluminophosphate of Claim 1 or 2 whose molar ratio of Me, Al, and P which comprises the frame | skeleton structure of aluminophosphate is the following formulas 1-3.
(However, Me represents at least one element selected from Group 2A, Group 7A, Group 8, Group 1B, Group 2B, Group 3B (excluding Al) and Group 4B elements of the periodic table.)
0 ≦ x ≦ 0.3… 1
(X represents the molar ratio of Me to the total of Me, Al, and P)
0.2 ≦ y ≦ 0.6 2
(Y represents the molar ratio of Al to the total of Me, Al, and P)
0.3 ≦ z ≦ 0.6 3
(Z represents the molar ratio of P to the sum of Me, Al, and P)   The method for producing template-containing aluminophosphates according to claim 3, wherein Me is Fe.   The structure of aluminophosphates is a code defined by IZA and is any one selected from AEI, AEL, AET, AFI, AFN, AFR, AFS, AFT, AFX, ATO, ATS, CHA, ERI, LEV, and VFI The method for producing a template-containing aluminophosphate according to any one of claims 1 to 4, wherein A method for producing an aluminophosphate, comprising firing the template-containing aluminophosphate produced by the method according to claim 1. The method for producing an aluminophosphate according to claim 6, wherein the baking is performed at 300 ° C to 450 ° C for 1 minute to 15 hours .

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