Zon-structured aluminum phosphate molecular sieve, synthesis method and application thereof

Abstract

The application discloses ZON structure aluminum phosphate molecular sieve and a synthesis method and application thereof. The synthesis method of the ZON structure aluminum phosphate molecular sieve comprises the following steps: S1, mixing an aluminum source, water, a phosphorus source, a main template agent TMA + , seed crystals and a co-template agent co-SDA to obtain an initial gel; TMA + is tetramethylammonium, and the co-SDA is an organic amine reagent different from the TMA + ; S2, crystallizing the initial gel in the step S1 under a closed condition to obtain ZON structure aluminum phosphate UiO-7 molecular sieve raw powder. The UiO-7 molecular sieve synthesized by the method has high crystallinity, and the yield reaches more than 70%. The molecular sieve can be used for adsorbing heat storage materials, heat pump materials, refrigeration materials or gas adsorption and separation, and the effect is good; the method is simple in operation, free of fluorine, low in cost, and raw materials are commercially available, and is suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, and particularly relates to a ZON structure aluminum phosphate molecular sieve, its synthesis method, and its application. Background Technology

[0002] Aluminum phosphate (AlPO) molecular sieves originated in 1982 and were first synthesized by Union Carbide Corp. As an important member of molecular sieve materials, AlPO molecular sieves, with their regular channels, abundant pore distribution, and excellent stability, have demonstrated outstanding performance in catalyst support, adsorption separation, and adsorption-based energy storage. For example, AlPO-11 (AEL) can support Pt for alkane isomerization reactions; AlPO-42 (LTA) and EMM-8 (SFO) show excellent performance in water adsorption energy storage; and ULM-6 achieved adsorption selectivity of 15.5 for CO2 / CH4 and 29.1 for CO2 / N2. The AlPO framework can be viewed as a three-dimensional framework formed by [AlO4] and [PO4] connected by shared oxygen bridges, with an Al / P ratio of approximately 1, classifying it as a neutral framework. Therefore, the performance of AlPO materials in adsorption applications typically depends on their structure.

[0003] Currently, in the field of CH4 / N2 adsorption and separation, small-pore UiO-7 (ZON structure, 8 / 6 / 4-membered rings) molecular sieves have shown considerable adsorption capacity and separation ratio. However, the synthesis of UiO-7 always requires the use of fluorides (tetramethylammonium fluoride or hydrofluoric acid) as mineralizing agents, and the template agent is usually tetramethylammonium hydroxide (TMAOH). Fluorides are highly corrosive to synthesis equipment. Summary of the Invention

[0004] In view of the above problems, the present invention provides a ZON structured aluminum phosphate molecular sieve, its synthesis method and application, which can solve the technical problem of the corrosiveness of fluorides in the molecular sieve synthesis process.

[0005] On one hand, the present invention provides a method for synthesizing ZON-structured aluminum phosphate molecular sieves, the method comprising the following steps:

[0006] S1: Combine aluminum source, water, phosphorus source, and main template agent TMA. + The seed crystals and co-templating agent co-SDA are mixed to obtain the initial gel;

[0007] Among them, TMA + It is a tetramethylammonium compound, and co-SDA is different from TMA. + Organic amine reagents;

[0008] S2: The initial gel in step S1 is crystallized under sealed conditions to obtain aluminum phosphate UiO-7 molecular sieve raw powder with ZON structure.

[0009] Optionally, in step S1, the aluminum source, water, phosphorus source, and master template agent TMA in the initial gel... + The molar ratio of co-templating agent co-SDA is:

[0010] Al2O3:H2O:P2O5:TMA + :co-SDA=0.5~1.5:10~100:0.5~1.5:0.5~2.0:0~2.0;

[0011] Wherein, the molar number of the aluminum source is calculated as the molar number of Al2O3, the molar number of water is calculated as the molar number of H2O itself, the molar number of the phosphorus source is calculated as the molar number of P2O5, and the main template agent TMA... + The number of moles in TMA + The number of moles of the cotemporal agent co-SDA is calculated based on its own molar number.

[0012] Optionally, in step S1, the aluminum source, water, phosphorus source, and master template agent TMA in the initial gel... + The molar ratio of co-templating agent co-SDA is:

[0013] Al2O3:H2O:P2O5:TMA + :co-SDA=0.8~1.2:20~100:0.8~1.2:0.8~2.0:0.5~2.0.

[0014] Optionally, in step S1, the aluminum source, water, phosphorus source, and master template agent TMA in the initial gel... + The molar ratio of co-templating agent co-SDA is:

[0015] Al2O3:H2O:P2O5:TMA + :co-SDA=1.0:40~60:1.0:0.5~1.0:1.0~1.5.

[0016] Optionally, in step S1, the amount of seed crystals added is 1 to 20 wt% of the total mass of Al2O3 and P2O5.

[0017] Optionally, in step S1, the amount of seed crystals added is 5 to 20 wt% of the total mass of Al2O3 and P2O5.

[0018] Optionally, in step S1, the amount of seed crystals added is selected from any value or a range between 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20%.

[0019] Optionally, the seed crystal is selected from UiO-7 seed crystal.

[0020] The UiO-7 seed crystal in step S1 of this invention can be synthesized using existing methods, or the molecular sieve powder synthesized in steps S1 and S2 can be used, or the molecular sieve powder can be calcined and used as a seed crystal.

[0021] Optionally, in step S1, the master template agent TMA + It is selected from at least one of tetramethylammonium hydroxide (TMAOH), tetramethylammonium chloride (TMACl), tetramethylammonium bromide (TMACl), and tetramethylammonium iodide (TMAI).

[0022] Optionally, in step S1, the co-templating agent co-SDA is selected from at least one of dimethylamine, trimethylamine, diethylamine, triethylamine, tetraethylammonium hydroxide, propylamine, dipropylamine, tripropylamine, diisopropylamine, n-butylamine, morpholine, piperazine, tetramethylethylenediamine, cyclohexylamine, cyclohexylimine, diethanolamine, and 1-[2-(2-hydroxyethoxy)ethyl]piperazine.

[0023] Preferably, the co-templating agent co-SDA is selected from at least one of diethylamine, morpholine, triethylamine, dipropylamine, and n-butylamine.

[0024] Optionally, in step S1, when the master template agent TMA + When selected from at least one of tetramethylammonium bromide, tetramethylammonium chloride, and tetramethylammonium iodide, the aluminum source, water, phosphorus source, and master template agent TMA in the initial gel are... + The molar ratio of co-templating agent co-SDA is:

[0025] Al2O3:H2O:P2O5:TMA + :co-SDA=0.5~1.5:10~100:0.5~1.5:0.5~2.0:0.5~2.0.

[0026] That is, when the TMA in the initial gel of the present invention + When using one or a combination of TMACl, TMACl and TMAI, the molar ratio of co-SDA in the initial gel must be no less than 0.5 (greater than or equal to 0.5) to synthesize molecular sieves.

[0027] This invention uses the master template agent TMA + The co-templating method, which combines co-SDA with seed crystals, typically yields UiO-7 in quantities greater than 70 wt%.

[0028] Optionally, in step S1, when the amount of the co-templating agent co-SDA added is 0, the main template agent TMA...+ It is tetramethylammonium hydroxide, and the molar ratio of each component in the initial gel is: Al2O3:H2O:P2O5:TMA + = 0.5~1.5:10~100:0.5~1.5:1.5~2.0, and the amount of the seed crystal added is 1~20wt% of the total mass of Al2O3 and P2O5; the seed crystal is selected from UiO-7 seed crystal.

[0029] That is, when the amount of co-SDA added to the initial gel of this invention is 0, TMA + When TMAOH is selected (TMAOH + seed crystals), the molar ratio of TMAOH in the initial gel is not less than 1.5 (greater than or equal to 1.5), and under the condition of seed crystal addition, UiO-7 can also be synthesized with a product yield of about 30 wt%.

[0030] Optionally, in step S1, the aluminum source is selected from at least one of boehmite, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum phosphate, and aluminum chloride.

[0031] Preferably, the aluminum source is selected from at least one of boehmite, aluminum hydroxide, aluminum isopropoxide, and aluminum oxide.

[0032] Optionally, in step S1, the phosphorus source is selected from at least one of orthophosphoric acid, phosphorous acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus oxides, organophosphorus reagents, and aluminum phosphate.

[0033] Preferably, the phosphorus source is orthophosphoric acid.

[0034] Optionally, in step S1, the aluminum source, the water, the phosphorus source, and the main template agent TMA are... + Premixing yields mixture I; mixture I is then mixed with the seed crystals and the co-templating agent co-SDA to obtain the initial gel.

[0035] Preferably, the premixing process involves stirring for 2 hours.

[0036] Optionally, in step S2, the initial gel is transferred to a self-pressurized reactor and crystallized at 140–200°C for 1–24 h. The product is then washed, centrifuged, and dried to obtain UiO-7 raw powder.

[0037] Optionally, the crystallization process can be dynamic or static.

[0038] Optionally, in step S2, the crystallization temperature is 150–200°C, the crystallization time is 2–12 hours, and the crystallization method is dynamic crystallization.

[0039] Optionally, the crystallization temperature is selected from any value of 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or a range between any two.

[0040] Optionally, the crystallization time is selected from any value among 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24h, or a range between any two.

[0041] Optionally, in step S2, the UiO-7 molecular sieve powder is calcined in an air atmosphere at a temperature of 450–800°C to remove the template agent.

[0042] Optionally, the UiO-7 molecular sieve is calcined at a temperature of 550-800℃ for 4-10 hours.

[0043] Optionally, the roasting temperature is selected from any value of 450, 500, 550, 600, 650, 700, 750, 800°C or a range between any two.

[0044] The present invention removes the template agent by calcining the UiO-7 molecular sieve prepared according to the above steps at 550-800℃ for 4-10 hours, which is then used for subsequent H2O / CH4 / N2 / CO2 adsorption performance testing.

[0045] Secondly, the present invention provides a ZON-structured aluminum phosphate molecular sieve, which is synthesized using the above-described method.

[0046] Thirdly, the present invention provides the application of the molecular sieve synthesized by the above method or the molecular sieve described above in adsorption heat storage materials, heat pump materials, refrigeration materials or gas adsorption and separation.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] 1) This invention successfully synthesized an aluminum phosphate molecular sieve UiO-7 with high purity and high crystallinity.

[0049] 2) This invention uses a seed crystal method to synthesize aluminum phosphate molecular sieve UiO-7 with a ZON structure. The yield of this method reaches 30-80%, it is simple to operate, fluorine-free, low in cost, and the raw materials are commercially available, making it suitable for industrial production.

[0050] 3) The ZON-structured aluminum phosphate molecular sieve UiO-7 synthesized in this invention can be used to adsorb heat storage materials, heat pump materials, refrigeration materials or adsorbents to separate gases, and has good adsorption capacity for CH4 and N2. Attached Figure Description

[0051] Figure 1 The XRD patterns of the products of Examples 1-3 of this invention are shown below.

[0052] Figure 2 This is an SEM image of the product of Example 1 of the present invention;

[0053] Figure 3 The N2 physical adsorption isotherms of the products of Examples 1-2 and Comparative Example 1 of this invention;

[0054] Figure 4 The static adsorption isotherms (25°C) of CH4 for the products of Examples 1-2 and Comparative Example 1 of this invention are shown.

[0055] Figure 5 The N2 static adsorption isotherm (25°C) of the products of Examples 1-2 and Comparative Example 1 of this invention;

[0056] Figure 6 This is an SEM image of the product of Example 2 of the present invention;

[0057] Figure 7 This is a SEM image of the product of Example 3 of the present invention;

[0058] Figure 8 The XRD patterns are of the products of Comparative Examples 1-3 of this invention;

[0059] Figure 9 This is a SEM image of the product of Comparative Example 1 of the present invention. Detailed Implementation

[0060] The present application is further illustrated below with reference to specific embodiments. The following descriptions are merely a few embodiments of the present application and are not intended to limit the present application in any way. Although the present application discloses preferred embodiments as follows, they are not intended to limit the present application. Any modifications or variations made by those skilled in the art without departing from the scope of the technical solution of the present application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

[0061] All chemical reagents used in the embodiments of this invention can be purchased commercially and do not require secondary purification. The English abbreviations of the chemical reagents used in the embodiments are as follows:

[0062] Morpholine, diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA), tetramethylammonium hydroxide (TMAOH), tetramethylammonium chloride (TMACl), tetramethylammonium bromide (TMABr), and tetramethylammonium iodide (TMAI).

[0063] The formula for calculating product yield in this embodiment is as follows:

[0064] Yield = 0.8 mproduct / (m Al2O3 +m P2O5 +m seed )×100%;

[0065] 0.8 — An empirical value for the inorganic content in the original powder solid obtained from thermogravimetric analysis;

[0066] m product —The solid mass of the product obtained after washing, separation, and drying;

[0067] m Al2O3 —The mass of Al2O3 corresponding to the aluminum source in the initial gel;

[0068] m P2O5 —The mass of P2O5 corresponding to the phosphorus source in the initial gel;

[0069] m seed —The quality of the seed crystals introduced into the initial gel;

[0070] The amount of seed crystals introduced in all embodiments of this invention is uniformly expressed as x·m (Al2O3+P2O5) Where x represents the proportion of added seed crystals to the total mass of Al2O3 and P2O5 in the initial gel, and m (Al2O3+P2O5) The sum of the masses of Al2O3 and P2O5 in the initial gel is given by x. The amount of seed introduced in the examples is represented by x only.

[0071] The crystal structure of the present invention was identified by powder X-ray diffraction (XRD) results. The XRD instrument was an X'Pert PRO X-ray diffractometer manufactured by PANalytical, Netherlands, with a Cu target, a Kα emission source (wavelength 0.15418 nm), and operating parameters of 40 kV voltage and 40 mA current.

[0072] The sample morphology in this embodiment of the invention was obtained by scanning electron microscopy (SEM). The testing instrument was a Hitachi SU8020 field emission scanning electron microscope (FE-SEM) with an accelerating voltage of 2KV.

[0073] The specific surface area, pore volume, and other parameters of the samples in this embodiment of the invention were obtained using an ASAP2020 physical adsorption instrument from Micromeritics, USA. The samples, after high-temperature calcination, were vacuum-treated at 350°C for 4 hours. The effective volume of the sample tube was determined by measuring He. N2 was used as the adsorbed gas. Physical adsorption and desorption experiments were conducted in a liquid nitrogen (77K) environment. The specific surface area of ​​the sample was calculated using the BET equation. The total pore volume of the sample was estimated using the amount of N2 adsorbed at a relative pressure (P / P0) of 0.99. A t-plot model was used to obtain the micropore surface area and volume. The cross-sectional area of ​​the N2 molecule was 0.162 nm. 2The surface area, volume, and diameter of the hole are obtained using the BET-BJH method.

[0074] The adsorption isotherm data of CH4 and N2 for the samples in this embodiment of the invention were obtained using a 3FLEX physical adsorption instrument from Micromeritics, USA, at a test temperature of 25°C. Before the test, approximately 0.2 g of the sample was treated in a vacuum environment at 350°C for 4 hours.

[0075] Example 1 (TMAOH + Mor + Seed Crystals)

[0076] The initial gel molar ratio of UiO-7 was Al2O3:H2O:P2O5:TMAOH:Mor = 1.0:40.0:1.0:0.5:1.0. Boehmite (77%), water, phosphoric acid (85% H3PO4), and TMAOH (25% aqueous solution) were added sequentially and stirred for approximately 2 hours. After homogeneous mixing, UiO-7 seed crystals with x = 0.15 were added, followed by Mor. Stirring continued for approximately 2 hours. The resulting initial gel was then transferred to a reaction vessel and dynamically crystallized at 180℃ for approximately 2 hours. The resulting product was washed, separated, and dried to obtain molecular sieve powder with a yield of 75%.

[0077] The product phase was identified by XRD. Figure 1 The diffraction peaks are obvious near 2θ = 10.7314°, 13.5538°, 19.9928°, 21.0599°, 23.3511°, and 30.0644°, with no other impurity peaks appearing. This is consistent with the SEM results. Figure 2 It can be proven to be a pure phase UiO-7, and SEM results show that its morphology is a bipyramidal shape of about 300 nm.

[0078] The N2 adsorption results were measured after the sample was calcined at 600℃ for 6 hours. Figure 3 ) is S BET =270.5m 2 / g, S micro =247.2m 2 / g, V total =0.2305cm 3 / g, V micro =0.1285cm 3 / g. At 25℃, the saturated adsorption capacity of CH4 reached 0.7 mmol / g, and the adsorption capacity of N2 also exceeded 0.2 mmol / g. Figure 4 and Figure 5 ).

[0079] Example 2 (TMABr+DEA+seed)

[0080] The initial gel molar ratio of UiO-7 was Al2O3:H2O:P2O5:TMABr:DEA = 1.0:60.0:1.0:0.5:1.0. Aluminum hydroxide (99%), water, phosphoric acid (85% H3PO4), and TMAOH (25% aqueous solution) were added sequentially. After the raw materials were mixed evenly, UiO-7 seed crystals with x = 0.10 were added, followed by DEA. After stirring for about 2 hours, the mixture was transferred to a reaction vessel and dynamically crystallized at 150℃ for about 4 hours. The resulting product was washed, separated, and dried to obtain molecular sieve powder with a yield of 72%.

[0081] The product phase was identified by XRD. Figure 1 The XRD peak shape is similar to that of the sample in Example 1, with no other impurity peaks appearing, combined with the SEM results ( Figure 6 It can be proven to be a pure phase UiO-7, and SEM results show that its morphology is a bipyramidal shape of about 300 nm.

[0082] N2 physical adsorption results of the sample after calcination at 600℃ for 6 hours ( Figure 3 ) is: S BET =268.7m 2 / g, S micro =247.8m 2 / g, V total =0.2126cm 3 / g, V micro =0.1288cm 3 / g. The adsorption results for CH4 and N2 were similar to those in Example 1, with the adsorption amounts of each component exceeding those of Comparative Example 1. Figure 4 and Figure 5 ).

[0083] Example 3 (TMAOH + Seeds)

[0084] The initial gel molar ratio of UiO-7 was Al2O3:H2O:P2O5:TMAOH = 1.0:40.0:1.0:1.5. Boehmite (67.5%), water, phosphoric acid (85% H3PO4), and TMAOH (25%) were added sequentially to a beaker, followed by seed crystals with x = 0.2. After thoroughly mixing all the raw materials, the mixture was transferred to a reaction vessel and dynamically crystallized at 180℃ for 5 hours. The product was then washed, separated, and dried to obtain the raw powder.

[0085] The sample was subjected to XRD ( Figure 1 Analysis showed that the product yield was similar to that of Examples 1-2, with a yield of 30%, which was lower than that of Examples 1 and 2. The SEM results of the sample are as follows... Figure 7 As shown, the product has a uniform morphology and a grain size of approximately 200-300 nm.

[0086] Examples 4-12 (TMA) + +co-SDA+seed crystals)

[0087] The initial gel was prepared according to the formulation method of Example 1. The types and proportions of raw materials and crystallization conditions are detailed in Table 1. After phase identification by XRD, the products were all UiO-7.

[0088] In this example, the molecular sieve powder synthesized in Example 1 was calcined and crystallized as UiO-7 seed crystal in Example 4. Example 4 adopted a static crystallization method. The seed crystals used in Examples 5 to 12 were all molecular sieve powder synthesized in Example 1.

[0089] Table 1. Molar ratio of raw materials and crystallization conditions for the synthesis of UiO-7 molecular sieve

[0090]

[0091]

[0092] Comparative Example 1 (TMAOH + HF)

[0093] The initial gel was prepared according to the molar ratio of Al2O3:H2O:P2O5:TMAOH:HF = 1.0:50.0:1.0:1.5:0.5. The raw materials were boehmite (67.5%), orthophosphoric acid (85% H3PO4), tetramethylammonium hydroxide (25% aqueous solution), and hydrofluoric acid (49% aqueous solution). The above raw materials were added sequentially and mixed evenly, and then transferred to a self-pressurized reactor. The mixture was dynamically crystallized at 150°C for 24 hours. After washing, separation, and drying, UiO-7 raw powder was obtained.

[0094] The XRD results of the product are as follows Figure 8 As shown, the SEM results are as follows: Figure 9 As shown, the XRD results of the product are consistent with those of Examples 1 and 2, but the morphology is significantly different.

[0095] N2 physical adsorption results of the sample after calcination at 600℃ for 6 hours ( Figure 3 ) is: S BET =302.2m 2 / g, S micro =242.0m 2 / g, V total =0.3355cm 3 / g, V micro =0.1232cm 3 / g. The adsorption capacity of this sample for CH4 and N2 is not as high as that of Examples 1 and 2 ( Figure 4 and Figure 5 ).

[0096] Comparative Example 2 (TMAOH + Mor)

[0097] Referring to the initial gel molar ratio, raw material type, and crystallization conditions of Example 1, without introducing seed crystals, the XRD results ( Figure 8 This demonstrates that the product synthesized in Comparative Example 2 contains both AFN and SOD structures, and no diffraction peaks of the ZON structure appeared, proving that the UiO-7 seed crystal is the key factor in achieving the fluorine-free synthesis of this molecular sieve.

[0098] Comparative Example 3 (TMAOH + Seed Crystals)

[0099] The synthesis gel formulation, ingredients, and crystallization method were the same as in Example 9, except that no co-SDA was added, and the product was washed, separated, and dried. XRD results showed that only the diffraction peak of the SOD structure appeared. Figure 8 The use of co-SDA template agent can promote the crystallization of UiO-7 molecular sieve. However, without co-SDA and with a TMAOH addition of less than or equal to 1.0, it is impossible to obtain the ideal UiO-7 molecular sieve product.

[0100] In Example 3 of this invention, UiO-7 molecular sieve in its ideal state was successfully synthesized without co-SDA and with a TMAOH addition amount of 1.5, but the yield was only 30%. This indicates that co-SDA can not only reduce the main template agent TMAOH, but also... + The dosage can also increase product yield.

[0101] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for synthesizing ZON-structured aluminum phosphate molecular sieves, characterized in that, The synthesis method includes the following steps: S1: Combine aluminum source, water, phosphorus source, and main template agent TMA. + The seed crystals and co-templating agent co-SDA are mixed to obtain the initial gel; Among them, TMA + It is a tetramethylammonium compound, and co-SDA is different from TMA. + Organic amine reagents; S2: The initial gel in step S1 is crystallized under closed conditions to obtain aluminum phosphate UiO-7 molecular sieve raw powder with ZON structure; In step S1, when the master template agent TMA + When selected from at least one of tetramethylammonium bromide, tetramethylammonium chloride, and tetramethylammonium iodide, the aluminum source, water, phosphorus source, and master template agent TMA in the initial gel are... + The molar ratio of co-templating agent co-SDA is: Al2O3 : H2O : P2O5 : TMA + : co-SDA = 0.5 ~ 1.5 : 10 ~ 100 : 0.5 ~ 1.5 : 0.5 ~ 2.0 : 0.5 ~ 2.0; In step S1, when the amount of co-templating agent co-SDA added is 0, the main template agent TMA... + The substance is tetramethylammonium hydroxide, and the molar ratio of each component in the initial gel is: Al2O3 : H2O : P2O5 : TMA. + = 0.5 ~ 1.5 : 10 ~ 100 : 0.5 ~ 1.5 : 1.5 ~ 2.

0.

2. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S1, the amount of seed crystal added is 1 to 20 wt% of the total mass of Al2O3 and P2O5, and the seed crystal is selected from UiO-7 seed crystal.

3. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S1, the co-templating agent co-SDA is selected from at least one of dimethylamine, trimethylamine, diethylamine, triethylamine, tetraethylammonium hydroxide, propylamine, dipropylamine, tripropylamine, diisopropylamine, n-butylamine, morpholine, piperazine, tetramethylethylenediamine, cyclohexylamine, cyclohexylimine, diethanolamine, and 1-[2-(2-hydroxyethoxy)ethyl]piperazine.

4. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S1, the aluminum source is selected from at least one of boehmite, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum phosphate, and aluminum chloride.

5. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S1, the phosphorus source is selected from at least one of orthophosphoric acid, phosphorous acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus oxides, organophosphorus reagents, and aluminum phosphate.

6. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S1, the aluminum source, the water, the phosphorus source, and the main template agent TMA are... + Premixing yields mixture I; mixture I is then mixed with the seed crystals and the co-templating agent co-SDA to obtain the initial gel.

7. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S2, the crystallization temperature is 140 ~ 200℃, the crystallization time is 1 ~ 24h, and the crystallization method is dynamic or static.

8. The method for synthesizing a ZON-structured aluminum phosphate molecular sieve according to claim 1, characterized in that, In step S2, the UiO-7 molecular sieve raw powder is calcined in an air atmosphere at a temperature of 450~800℃ to remove the template agent.

9. A ZON-structured aluminum phosphate molecular sieve, characterized in that, The molecular sieve is the UiO-7 molecular sieve synthesized using the method described in any one of claims 1 to 8.

10. The molecular sieve synthesized by the method according to any one of claims 1 to 8 or the molecular sieve according to claim 9, in the adsorption and heat storage materials, heat pump materials, refrigeration materials or gas adsorption and separation.

Images