Utilization method of molecular sieve crystallization mother liquor, EMM-8 molecular sieve and application

Abstract

The invention discloses a utilization method of molecular sieve crystallization mother liquor, an EMM-8 molecular sieve and application. Comprising the following steps: S1, mixing an aluminum source, water, a phosphorus source, a main template agent and an EMM-8 seed crystal to obtain initial gel a; s2, heating and crystallizing the initial gel a under a closed condition to obtain a product I; s3, carrying out solid-liquid separation on the product I to obtain a solid-phase substance EMM-8 molecular sieve, so as to obtain a liquid-phase substance molecular sieve mother solution I; s4, mixing an aluminum source, the molecular sieve mother liquor I, a phosphorus source and an EMM-8 seed crystal to obtain initial gel b; s5, heating and crystallizing the initial gel b under a closed condition to obtain a product II; s6, washing the product II, and carrying out solid-liquid separation to obtain a solid-phase substance EMM-8 molecular sieve, so as to obtain a liquid-phase substance molecular sieve mother liquor II; the molecular sieve mother liquor II is recycled as a raw material for synthesizing the EMM-8 molecular sieve according to the steps S4 to S6. The method recycles the molecular sieve mother liquor, reduces the cost and is efficient.

Description

Technical Field

[0001] The invention belongs to the technical field of molecular sieves, and in particular relates to a method for utilizing molecular sieve crystallization mother liquor and an EMM-8 molecular sieve and its application. Background Art

[0002] The increasing energy consumption leads to CO 2 The emission of greenhouse gases such as carbon monoxide and other pollutants continues to increase, and the global warming situation continues to worsen, resulting in a continuous increase in demand for refrigeration. Traditional refrigeration materials such as Freon have been gradually eliminated due to their ability to damage the ozone layer. 2 O 3 The material has a limited adsorption capacity and the partial pressure of water vapor condensation is too high (P / P 0 >0.5); although metal organic frameworks (MOFs) have considerable adsorption capacity, their stability is poorer than that of zeolite materials and they are expensive; the desorption temperature of silica-alumina zeolites and small-pore aluminum phosphate materials is relatively high, resulting in a low coefficient of performance (COP) of the materials. Compared with the above-mentioned water adsorption heat pump and refrigeration materials, large-pore aluminum phosphate zeolites have considerable adsorption capacity and a lower desorption temperature. For example, the aluminum phosphate zeolite material EMM-8 can achieve regeneration and desorption at 65°C, and 30°C P / P 0 =0.17 when the water adsorption capacity reaches 0.28g·g -1 , used as a refrigerant at 63°C, the performance coefficient COP value reaches 0.85, far exceeding MOF and small-pore zeolite materials.

[0003] Aluminum phosphate (AlPO) zeolite was first invented by Union Carbide in the United States in 1982. The company has successively prepared a series of large-pore, medium-pore and small-pore aluminum phosphate molecular sieves. Unlike silica-aluminum zeolites, all synthesis systems of aluminum phosphate molecular sieves must involve template agents, and the template agents are mostly organic template agents. The synthesis methods of aluminum phosphate zeolites are mostly hydrothermal or solvent thermal methods. This type of method usually involves mixing aluminum source, phosphorus source, solvent and template agent and then crystallizing them in a closed container at high temperature and pressure. The crystallization time is long, and a large amount of waste liquid will be generated. The solvent is difficult to reuse and the utilization rate of the template agent is very low.

[0004] In addition, due to the limitation of the neutral skeleton of aluminum phosphate material itself, its application in fields such as catalysis and ion exchange is limited, and its performance in the common field of gas adsorption and separation is not as good as that of silicon aluminum, pure silicon and silicon aluminum phosphate materials. However, the neutral skeleton of aluminum phosphate material shows suitable affinity for water molecules. The four-coordinated skeleton aluminum element can combine with water molecules to form five-coordinated or six-coordinated aluminum. This force is not as strong as the force between Bronsted acid and water, so water molecules can be easily removed. There are hydrogen bonds between the adsorbed water molecules, which makes the water adsorption capacity of aluminum phosphate material considerable. Aluminum phosphate materials that have been industrially produced include AQSOATM -Z01 and AQSOA TM -Z05, these two materials have been successfully used as refrigerants in large compressors.

[0005] The above two excellent industrial refrigerants are macroporous molecular sieve materials with twelve-membered rings (12 / 6 / 4-membered rings) with AFI topological structure (framework density of 16.9T / ), EMM-8 molecular sieve also has twelve-membered ring (12 / 8 / 6 / 4-membered ring) channels, the topological structure is SFO, and the skeleton density is relatively low (15.2T / ) makes it have a more open pore volume and specific surface area, so the water adsorption capacity is larger than the previous two. However, the traditional EMM-8 synthesis requires a large amount of toxic and highly corrosive hydrofluoric acid, and the template agent is 4-dimethylaminopyridine (4-DMAPy), which is not only expensive but also highly toxic. The fluorine-containing synthesis system makes it difficult to achieve industrial scale-up of EMM-8, and the mother liquor after crystallization is difficult to reuse. Summary of the invention

[0006] In view of this, the present invention provides a method for utilizing molecular sieve crystallization mother liquor and EMM-8 molecular sieve and application, the main purpose of which is to solve the technical problems that EMM-8 molecular sieve crystallization mother liquor is difficult to reuse, hydrofluoric acid is required for synthesis, and a large amount of highly toxic template agents are used.

[0007] In one aspect, the present invention provides a method for utilizing a molecular sieve crystallization mother liquor, the method comprising the following steps:

[0008] S1: mixing aluminum source, water, phosphorus source, primary template 4-dimethylaminopyridine, and EMM-8 seed crystals to obtain initial gel a;

[0009] The molar ratio of aluminum source, water, phosphorus source and main template is:

[0010] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy=0.5~1.5:20~100:0.5~1.5:0.5~2.5;

[0011] Among them, the amount of EMM-8 seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1-20wt% of the total mass on dry basis;

[0012] S2: The initial gel a in step S1 is heated and crystallized under closed conditions, the crystallization temperature is 120-220° C., and the crystallization time is 0.1-48 h to obtain product I;

[0013] S3: The product I in step S2 is subjected to solid-liquid separation, and the obtained solid phase is EMM-8 molecular sieve, and the obtained liquid phase is molecular sieve mother liquid I;

[0014] S4: mixing the aluminum source, the molecular sieve mother solution I, the phosphorus source, and the EMM-8 seed crystals to obtain an initial gel b;

[0015] S5: The initial gel b in step S4 is heated and crystallized under closed conditions, the crystallization temperature is 120-220° C., and the crystallization time is 0.1-48 h to obtain product II;

[0016] S6: After washing and solid-liquid separation, the product II in step S5 obtains the EMM-8 molecular sieve as the solid phase and the molecular sieve mother liquor II as the liquid phase; the molecular sieve mother liquor II is recycled as the raw material for synthesizing the EMM-8 molecular sieve according to steps S4 to S6.

[0017] Optionally, in step S1, the molar ratio of the aluminum source, water, phosphorus source and primary template in the initial gel a is:

[0018] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy=0.5~1.5:20~100:0.5~1.5:0.5~2.5;

[0019] The amount of the seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1-20wt% of the total mass on dry basis;

[0020] The molar number of aluminum source is expressed as Al 2 O 3 The moles of water are measured in H 2 The molar number of the phosphorus source is P 2 O 5 The moles of the primary template are calculated based on the moles of 4-DMAPy itself.

[0021] Optionally, in step S1, the molar ratio of the aluminum source, water, phosphorus source and primary template in the initial gel a is:

[0022] Al 2 O3 :H 2 O:P 2 O 5 :4-DMAPy=0.5~1.5:20~100:0.5~1.5:1.5~2.5.

[0023] Preferably, in step S1, the molar ratio of the aluminum source, water, phosphorus source and primary template in the initial gel a is:

[0024] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy=1.0:40~60:1.0:1.5~2.5;

[0025] The amount of the seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 The seed crystal is selected from EMM-8, accounting for 1 to 10 wt% of the total dry basis mass.

[0026] Optionally, in step S1, the initial gel a further comprises a co-template agent;

[0027] The molar ratio of aluminum source, water, phosphorus source, main template and co-template is:

[0028] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=0.5~1.5:20~100:0.5~1.5:0.5~2.5:0.001~2.5.

[0030] Wherein, the molar number of the co-template agent is calculated based on the molar number of its own co-SDA;

[0031] The amount of seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1 to 20 wt% of the total dry mass.

[0032] Optionally, in step S1, the initial gel a further comprises a co-template agent;

[0033] The molar ratio of aluminum source, water, phosphorus source, main template and co-template is:

[0034] Al 2 O3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=0.8~1.2:40~80:0.8~1.2:0.5~1.0:1.0~1.5;

[0036] The amount of seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1 to 10 wt% of the total dry mass.

[0037] Optionally, in step S1, the initial gel a further comprises a co-template agent;

[0038] The molar ratio of aluminum source, water, phosphorus source, main template and co-template is:

[0039] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=1.0:40~60:1.0:0.5~1.0:1.0~1.5;

[0041] The amount of seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1 to 10 wt% of the total dry mass.

[0042] Optionally, the amount of the seed crystal added is selected from any value of 1%, 5%, 10%, 15%, 20%, or any range between the two.

[0043] The seed crystal in the present invention is selected from EMM-8 molecular sieve, which can be synthesized by existing methods, or the EMM-8 molecular sieve synthesized in steps S1-S6 can be used as the seed crystal, and can also be calcined.

[0044] Optionally, the co-template agent is selected from at least one of diethylamine, triethylamine, tetraethylammonium hydroxide, dipropylamine, tripropylamine, diisopropylamine, n-butylamine, morpholine, piperazine, cyclohexylamine, cycloheximide, diethanolamine and 1-[2-(2-hydroxyethoxy)ethyl]piperazine.

[0045] In step S1 of the present invention, the formula of the initial gel a can also be expressed as:

[0046] The molar ratio of aluminum source, water, phosphorus source, primary template, seed and co-template is:

[0047] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=0.5~1.5:20~100:0.5~1.5:

[0048] 0.5~2.5:0~2.5; the amount of seed added is the amount corresponding to Al in the initial gel a 2 O 3 With P 2 O 5 1 to 20 wt% of the total mass; the seed crystal is selected from EMM-8.

[0049] In the above initial gel a, the co-template agent (co-SDA) may be added or not; when the co-template agent is not added to the initial gel a, the amount of the main template agent is appropriately increased.

[0050] Optionally, in step S4, the raw material ratio of the initial gel b is:

[0051] The mass ratio of the aluminum source to the molecular sieve mother solution I is 0.001 to 0.400;

[0052] The mass ratio of the phosphorus source to the molecular sieve mother solution I is 0.001 to 0.750;

[0053] The amount of the seed added is the amount of Al in the initial gel b. 2 O 3 With P 2 O 5 1 to 20 wt% of the total mass on a dry basis, the seed crystals are selected from EMM-8;

[0054] Among them, the aluminum source is Al 2 O 3 The phosphorus source is P 2 O 5 count.

[0055] Optionally, the mass ratio of the aluminum source to the molecular sieve mother solution I is selected from any value among 0.001, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.400 or any range value between the two;

[0056] The mass ratio of the phosphorus source to the molecular sieve mother liquor I is selected from any value among 0.001, 0.01, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.750 or any range value between two thereof.

[0057] Optionally, in step S4, the raw material of the initial gel b further includes a primary template agent, and the primary template agent is selected from 4-dimethylaminopyridine;

[0058] The mass ratio of the main template agent to the molecular sieve mother solution I is 0.001 to 0.450;

[0059] The main template agent is calculated by the mass of its own 4-DMAPy pure substance.

[0060] Optionally, the mass ratio of the main template to the molecular sieve mother solution I is selected from any value among 0.001, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.400, 0.45 or any range value between two of them.

[0061] Optionally, in step S4, the raw material of the initial gel b also includes water;

[0062] The mass ratio of the water to the molecular sieve mother solution I is 0.001 to 10;

[0063] Wherein, the water is in the form of H 2 O self-counter.

[0064] Optionally, the mass ratio of the water to the molecular sieve mother liquor I is selected from any value among 0.001, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or any range value between two of them.

[0065] Optionally, the raw material of the initial gel b further includes a co-template agent;

[0066] The molar ratio of the co-template agent to the aluminum source is 0.001 to 2.0;

[0067] The molar number of the co-template is based on the molar number of its own co-SDA.

[0068] Optionally, the molar ratio of the co-template to the aluminum source is selected from any value of 0.001, 0.1, 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0 or any range between two values.

[0069] Optionally, the aluminum sources in step S1 and step S4 are each independently selected from at least one of pseudo-boehmite, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum phosphate and aluminum chloride.

[0070] Optionally, the phosphorus sources in step S1 and step S4 are each independently selected from at least one of orthophosphoric acid, phosphorous acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus oxides, organophosphorus reagents and aluminum phosphate.

[0071] Preferably, the aluminum source is selected from at least one of pseudo-boehmite, aluminum hydroxide, aluminum isopropoxide and aluminum oxide.

[0072] Preferably, the phosphorus source is selected from orthophosphoric acid.

[0073] Optionally, the co-template agent is selected from at least one of diethylamine, triethylamine, tetraethylammonium hydroxide, dipropylamine, tripropylamine, diisopropylamine, n-butylamine, morpholine, piperazine, cyclohexylamine, cycloheximide, diethanolamine and 1-[2-(2-hydroxyethoxy)ethyl]piperazine.

[0074] Optionally, the aluminum source, phosphorus source, and co-template in step S1 and step S4 are the same or different.

[0075] In step S1 of the present invention, the formula of the initial gel b can also be expressed as:

[0076] In step S4, the composition of the initial gel b is as follows:

[0077] The mass ratio of the aluminum source to the mother solution I is 0.001-0.400;

[0078] The mass ratio of the phosphorus source to the mother solution I is 0.001-0.750;

[0079] The mass ratio of water to mother liquor I is 0-10;

[0080] The mass ratio of the main template agent to the mother solution I is 0.000-0.450;

[0081] The molar ratio of the co-template to the aluminum source is 0-2.0;

[0082] Among them, the aluminum source is Al 2 O 3 Phosphorus source is H 3 PO 4 The main template is calculated as its own 4-DMAPy, and the co-template is calculated as its own co-SDA;

[0083] The amount of seed added is the amount of Al in the initial gel b. 2 O 3 With P 2 O 5 1 to 20 wt% of the total mass, the seed crystals are selected from EMM-8 molecular sieve.

[0084] In step S1 of the present invention, the formula of the initial gel b can also be expressed as:

[0085] Optionally, in step S4, the proportions of the raw materials in the initial gel b are as follows:

[0086] The mass ratio of the aluminum source to the mother solution I is 0.045-0.200;

[0087] The mass ratio of the phosphorus source to the mother solution I is 0.087-0.450;

[0088] The mass ratio of water to mother liquor I is 0-2;

[0089] The mass ratio of the main template (4-DMAPy) to the mother solution I is 0.055-0.264;

[0090] The molar ratio of the co-template agent (co-SDA) to the aluminum source is 0.01-2.0;

[0091] Among them, the aluminum source is Al 2 O 3 Phosphorus source is H 3 PO 4 The main template is calculated as its own 4-DMAPy, and the co-template is calculated as its own co-SDA;

[0092] The amount of seed added is the amount of Al in the initial gel b. 2 O 3 With P 2 O 5 The seed crystals are selected from EMM-8 molecular sieve, accounting for 1 to 10 wt% of the total mass.

[0093] In step S1 of the present invention, the formula of the initial gel b can also be expressed as:

[0094] Optionally, in step S4, the proportions of the raw materials in the initial gel b are as follows:

[0095] The mass ratio of the aluminum source to the mother solution I is 0.070-0.150;

[0096] The mass ratio of the phosphorus source to the mother solution I is 0.100-0.350;

[0097] The mass ratio of water to mother liquor I is 0;

[0098] The mass ratio of the main template (4-DMAPy) to the mother solution I is 0.055-0.150;

[0099] Among them, the aluminum source is Al 2 O 3 Phosphorus source is H 3 PO 4 The main template is calculated as its own 4-DMAPy, and the co-template is calculated as its own co-SDA;

[0100] The amount of seed added is the amount of Al in the initial gel b. 2 O 3 With P 2 O 5The seed crystals are selected from EMM-8 molecular sieve, accounting for 1 to 10 wt% of the total mass.

[0101] In step S1 of the present invention, the formula of the initial gel b can also be expressed as:

[0102] Preferably, in step S4, the ratio of each material in the initial gel b is:

[0103] The mass ratio of the aluminum source to the mother solution I is 0.070-0.120;

[0104] The mass ratio of the phosphorus source to the mother solution I is 0.120-0.230;

[0105] The mass ratio of phosphorus source to aluminum source II is 1.922;

[0106] The mass ratio of water to mother liquor I is 0;

[0107] The mass ratio of the main template (4-DMAPy) to the mother solution I is 0.055-0.100;

[0108] Among them, the aluminum source is Al 2 O 3 Phosphorus source is H 3 PO 4 The main template is calculated as its own 4-DMAPy, and the co-template is calculated as its own co-SDA;

[0109] The amount of seed added is the amount of Al in the initial gel b. 2 O 3 With P 2 O 5 The seed crystals are selected from EMM-8 molecular sieve, accounting for 1 to 10 wt% of the total mass.

[0110] Optionally, in step S4, when preparing the initial gel b, the amount of the co-template agent (co-SDA) may be 0; at this time, the molar ratio of the initial gel a needs to satisfy any one of the following two conditions:

[0111] 1. Add co-SDA to the initial gel a

[0112] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=1.0:40~60:1.0:0.5~1.0:

[0113] 1.0~2.0; the amount of seed added is the amount corresponding to Al in the initial gel a 2 O 3 With P 2 O 51 to 20 wt% of the total dry mass.

[0114] 2. No co-SDA was added to the initial gel a

[0115] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy=1.0:40~60:1.0:1.5~2.5;The amount of seed added is the amount corresponding to Al in the initial gel a 2 O 3 With P 2 O 5 1 to 20 wt% of the total dry mass.

[0116] Optionally, in step S4, the main template (4-DMAPy) in the initial gel b can be 0, but the molar ratio of the initial gel a in step S1 must satisfy any one of the following two conditions:

[0117] 1. No co-SDA was added to the initial gel a

[0118] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy=1.0:20~100:1.0:1.5~2.5;Addition of seed crystals

[0119] The amount of Al in the initial gel a 2 O 3 With P 2 O 5 1 to 20 wt% of the total dry mass.

[0120] 2. Add co-SDA to the initial gel a

[0121] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=1.0:20~100:1.0:1.5~2.5:

[0122] 1.0~2.0; the amount of seed added is the amount corresponding to Al in the initial gel a 2 O 3 With P 2 O 5 1 to 20 wt% of the total dry mass.

[0123] Optionally, in step S4, the ratio of co-SDA, water and 4-DMAPy can be 0 at the same time, or any combination of the two can be added.

[0124] Preferably, when co-SDA is added in step S1, no co-SDA is added in step S4.

[0125] Preferably, in step S4, H 2 The amount of O added is 0.

[0126] Preferably, in step S4, the amount of the primary template (4-DMAPy) added is not less than 0.001 (mass ratio of 4-DMAPy to mother liquor).

[0127] Optionally, in the step S1, the aluminum source, the water, the phosphorus source and the 4-DMAPy are pre-mixed to obtain a mixture; the mixture is then mixed with the seed crystal and the co-SDA to obtain an initial gel a.

[0128] Optionally, in the step S4, the aluminum source, the water, the mother liquor, the phosphorus source and the 4-DMAPy are pre-mixed to obtain a mixture; the mixture is then mixed with the seed crystal and the co-SDA to obtain an initial gel b.

[0129] Preferably, in the step S4, the aluminum source, the mother liquor, the phosphorus source and the 4-DMAPy are pre-mixed to obtain a mixture; and the mixture is then mixed with the seed crystal to obtain an initial gel b.

[0130] Preferably, the premixing is stirred for 1-2 hours.

[0131] Optionally, the crystallization method of the heating crystallization in step S2 and step S5 is dynamic or static.

[0132] Optionally, in step S2 or S5, the crystallization temperature is 150-200° C., the crystallization time is 0.5-8 h, and the crystallization method is dynamic crystallization.

[0133] Optionally, in step S2 or S5, the crystallization temperature is independently selected from any value among 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C and 220°C, or a range between any two of them.

[0134] Optionally, in step S2 or S5, the crystallization time is independently selected from any value of 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48 hours or any range between two of them.

[0135] Optionally, in steps S3 and S6, the product is washed, centrifuged and dried to obtain EMM-8 raw powder.

[0136] The solid yield of steps S1-S3 is usually 70-80%, and the solid yield of steps S4-S6 is 75-85%.

[0137] Optionally, in the steps S3 and S6, the EMM-8 molecular sieve having an SFO structure is calcined in an air atmosphere at a temperature of 450 to 800° C. to remove the template;

[0138] The EMM-8 molecular sieve raw powder with SFO structure is calcined in an air atmosphere at a temperature of 450-800° C. to remove the template agent.

[0139] Optionally, the calcination temperature is selected from any value of 450, 500, 550, 600, 650, 700, 750, 800° C. or any range between two thereof.

[0140] The EMM-8 molecular sieve prepared according to the above steps is calcined at 450-800°C for 4-10h to remove the template and to be used for the subsequent H 2 O / N 2 Adsorption performance test.

[0141] In a second aspect, the present invention provides a molecular sieve EMM-8 having an SFO structure, which is prepared by the above method.

[0142] Optionally, the molecular sieve has a particle size of 100 nm to 10 μm and a rod-like crystal morphology.

[0143] In a third aspect, the present invention provides a water adsorbent, wherein the material of the water adsorbent includes a molecular sieve EMM-8 having an SFO structure obtained by the above method.

[0144] In a fourth aspect, the present invention provides an application of a molecular sieve EMM-8 having an SFO structure in adsorption heat storage materials, heat pump materials, refrigeration materials or gas adsorption separation; the molecular sieve is a molecular sieve EMM-8 having an SFO structure obtained by the above method.

[0145] Compared with the prior art, the present invention has the following beneficial effects:

[0146] 1) The present invention successfully uses molecular sieve mother liquor to synthesize an aluminum phosphate molecular sieve EMM-8 with an SFO topological structure, and the product yield is high, which can reach 70-80%, and the crystallinity is high. The molecular sieve mother liquor is fully utilized, the amount of template agent used is reduced, and the production cost is reduced.

[0147] 2) The present invention adopts a seed crystal method to synthesize an aluminum phosphate molecular sieve EMM-8 with an SFO topological structure. The method is simple to operate, green, fluorine-free, low-cost, and suitable for industrial production.

[0148] 3) The aluminum phosphate molecular sieve EMM-8 with SFO topological structure synthesized by the present invention can be used for adsorption heat storage material, heat pump material, refrigeration material or adsorbent separation gas, and can be used for H 2 O adsorption capacity is good. BRIEF DESCRIPTION OF THE DRAWINGS

[0149] Figure 1 XRD diagrams of samples 1 to 3 provided in the embodiments of the present invention;

[0150] Figure 2 XRD diagrams of samples 4 to 6 provided in the embodiments of the present invention;

[0151] Figure 3 The SEM photo of sample 1 provided in the embodiment of the present invention;

[0152] Figure 4 SEM photos of 2 samples provided in the embodiments of the present invention;

[0153] Figure 5 SEM photos of 3 samples provided in the embodiments of the present invention;

[0154] Figure 6 SEM photos of 4 samples provided in the embodiments of the present invention;

[0155] Figure 7 SEM photos of 5 samples provided in the embodiments of the present invention;

[0156] Figure 8 SEM photos of 6 samples provided in the embodiments of the present invention;

[0157] Fig. 9 The nitrogen physical adsorption isotherms of samples 1 to 4 provided in the embodiments of the present invention;

[0158] Fig.10 The water adsorption isotherms of samples 1 to 4 provided in the embodiments of the present invention at 30°C;

[0159] Fig.11 XRD diagrams of samples 1 to 4 provided as comparative examples of the present invention;

[0160] Fig.12 This is a SEM photograph of the sample provided for Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0161] The present application is further described below in conjunction with specific embodiments. The following are only a few embodiments of the present application, and are not intended to limit the present application in any form. Although the present application discloses the following preferred embodiments, they are not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the above disclosed technical content to make some changes or modifications are equivalent to equivalent implementation cases and are within the scope of the technical solution.

[0162] The chemical reagents used in the embodiments of the present invention can be purchased through commercial channels without secondary purification. The English abbreviations of the chemical reagents used in the embodiments are as follows:

[0163] Morpholine (Mor), diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA), diisopropylamine (DIPA), 4-dimethylaminopyridine (4-DMAPy).

[0164] The calculation formula for product yield in the embodiment is as follows:

[0165] Yield=0.75·m product / (m Al2O3 +m P2O5 +m seed )×100%;

[0166] 0.75—The empirical value of inorganic content in the original powder solid obtained by thermogravimetric analysis;

[0167] m product —The solid mass of the product obtained after washing, separation and drying;

[0168] m Al2O3 —The aluminum source in the initial gel corresponds to Al 2 O 3 quality;

[0169] m P2O5 —Phosphorus source in initial gel corresponds to P 2 O 5 quality;

[0170] m seed —The mass of the seeds introduced into the initial gel;

[0171] The amount of seed crystal introduced in all embodiments of the present invention is uniformly expressed as x·m (Al2O3+P2O5) ; x represents the percentage of added seeds in the initial gel Al 2 O 3 and P 2 O 5 Ratio of total dry mass, m (Al2O3+P2O5) is the Al content in the initial gel 2 O 3and P 2 O 5 The dry basis mass and the seed introduction amount in the examples are represented by only x.

[0172] The crystal structure of the embodiment of the present invention is identified by powder X-ray diffraction (XRD) results. The XRD test instrument is an X'Pert PRO X-ray diffraction analyzer manufactured by PANalytical of the Netherlands, with a Cu target, a Kα emission source (wavelength 0.15418 nm), and operating parameters of 40 kV voltage and 40 mA current.

[0173] The sample morphology of the embodiment of the present invention is obtained by scanning electron microscopy (SEM), and the testing instrument is Hitachi SU8020 field emission scanning electron microscope (FE-SEM) with an acceleration voltage of 2KV.

[0174] The specific surface area, pore volume and other parameters of the samples in the embodiment of the present invention were obtained using the ASAP2020 physical adsorption instrument of Micromeritics, USA. The high-temperature calcined samples were vacuum treated at 350°C for 4 hours, and the effective volume of the sample tube was measured by He, N 2 To adsorb the gas, physical adsorption and desorption experiments were carried out in liquid nitrogen (77K) environment. The BET equation was used to calculate the specific surface area of ​​the sample. The relative pressure (P / P 0 ) is 0.99 2 The adsorption amount was used to estimate the total pore volume of the sample, and the t-plot model was used to obtain the micropore surface area and volume, N 2 The molecular cross-sectional area is 0.162nm 2 , the surface area, volume and diameter of the pores were obtained by the BET-BJH method.

[0175] The samples of the present invention are H 2 The adsorption isotherm data of O were obtained by the BSD-VVS&DVS (3H-2000PW) multi-station gravimetric gas vapor adsorption instrument of Beijing Bester Company, and the test temperature was 30°C. Before the test, about 0.1g of the sample was treated in a vacuum environment at 150°C for 3h.

[0176] Example 1 Preparation of molecular sieve mother liquor containing co-SDA

[0177] The molar ratio of each material in the initial gel a is as follows:

[0178] Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:DEA=1.0:60.0:1.0:0.8:1.0;

[0179] Pseudo-boehmite (77% Al 2 O 3 ), deionized water, phosphoric acid (85% H 3 PO 4 ) and 4-DMAPy (99%) are added in sequence and stirred for about 2 hours. Then, EMM-8 seed crystals with x=0.1 are added, and finally DEA is added and stirred for about 2 hours to obtain initial gel a. The initial gel a is transferred to a self-pressure reactor and crystallized at 170°C for 2 hours. The material in the reactor is directly filtered without washing, and the liquid phase is the molecular sieve mother liquor. The solid phase product is then washed with deionized water, centrifuged and dried to obtain EMM-8 molecular sieve raw powder with a yield of 75%, which can be used as a seed crystal.

[0180] The product was identified by XRD, and the spectrum showed Figure 1 It can be seen that there are obvious characteristic peaks of SFO structure at 2θ=8.336°, 12.717°, 14.019°, 14.250°, 19.720° and 25.988°, and no other impurity peaks, indicating that pure phase EMM-8 product was obtained. The SEM photo of the product is shown in Figure 2 As shown, the crystal size is between 200nm. After the product was calcined at 600℃ for 6h, the N 2 Adsorption results ( Figure 3 ) is: S BET =654.2m 2 / g,S micro =606.3m 2 / g,V total =0.3447cm 3 / g,V micro =0.3071cm 3 / g. The water adsorption test results of the product at 30°C are as follows Figure 4 As shown, showing P / P 0 =0.2 when the water adsorption is 0.28g·g -1 .

[0181] Example 2 Synthesis of EMM-8 using the molecular sieve crystallization mother liquor containing co-SDA in Example 1

[0182] The masses of the materials in the initial gel b are as follows: 5.000 g pseudo-boehmite (77% Al 2 O 3 )、8.110 g phosphoric acid (85% H 3 PO 4), 2.042 g 4-DMAPy, 37.034 g molecular sieve mother liquor (obtained in Example 1 without dilution) and 0.538 g seed crystals. Pseudo-boehmite was first added to the molecular sieve mother liquor, and then H 3 PO 4 and 4-DMAPy, stirred for about 2 hours, then added EMM-8 seed crystals, stirred for about 2 hours to obtain initial gel b. The initial gel b was transferred to a self-pressure reactor and dynamically crystallized at 170°C for 2 hours. The product was directly filtered without washing, and the liquid phase was the molecular sieve mother liquor. The solid phase was washed and dried to obtain the EMM-8 molecular sieve raw powder, with a yield of about 86%.

[0183] The product was identified by XRD. Figure 1 The characteristic peak position is consistent with the product obtained in Example 1, and there is no impurity peak. The SEM photo of the product is as follows Figure 2 As shown, the EMM-8 crystal size is between 500nm-1.00μm. After the product was calcined at 600℃ for 6h, the N 2 The adsorption results are shown in Figure 3 Shown: S BET =630.2m 2 / g,S micro =606.5m 2 / g,V total =0.3877cm 3 / g,V micro =0.3146cm 3 / g. The water adsorption test results of the product at 30°C are as follows Figure 4 As shown, P / P 0 =0.2 when the water adsorption is 0.32g·g -1 .

[0184] Water adsorption and N 2 Physical adsorption tests show that the EMM-8 molecular sieve synthesized from the mother liquor has better performance and higher yield than the EMM-8 synthesized from the pure reagent (Example 1 and Comparative Example 1). No co-SDA needs to be added to the initial gel b, which saves more raw materials in the preparation method compared to the initial gel a, and the mother liquor obtained in Example-2 can be recycled. The proportion of each material used in the recycling and the crystallization conditions can refer to this example.

[0185] Example 3 Preparation of molecular sieve mother liquor without co-SDA

[0186] The molar ratio of each material in the initial gel a is as follows:

[0187] Al 2 O 3 :H 2 O:P2 O 5 :4-DMAPy=1.0:40.0:1.0:2.4;

[0188] First, pseudo-boehmite (77% Al 2 O 3 ), water, phosphoric acid (85%), then add 4-DMAPy, stir for about 2h, then add EMM-8 seed crystals with x=0.05 (seed crystals come from comparative example-1), and stir for 1h. The uniformly mixed initial gel a is transferred to a self-pressure reactor and placed at 150°C for dynamic crystallization for 10h. The product after crystallization is not washed but directly centrifuged. The liquid phase obtained by separation is the molecular sieve mother liquor. The solid phase product is washed and dried to obtain the EMM-8 molecular sieve raw powder, and the solid yield is about 80%.

[0189] The product was subjected to XRD, showing Figure 1 After phase identification, it was confirmed to be EMM-8 pure phase product. SEM photos, such as Figure 2 As shown, the product morphology is a rod-like structure of 10-15 μm. After the sample was calcined at 600℃ for 6h, N 2 The adsorption results are shown in Figure 3 , is S BET =578.0m 2 / g,S micro =524.9m 2 / g,V total =0.3410cm 3 / g,V micro =0.2722cm 3 / g. Although the crystallinity of the EMM-8 product obtained in Example 3 is higher than that of Example 1-2, a large amount of 4-DMAPy is required for the synthesis, and this reagent has high toxicity. The water adsorption test results of the product at 30°C are as follows Figure 4 As shown, P / P 0 =0.2 when the water adsorption is 0.24 g·g -1 .

[0190] Example 4 Synthesis of EMM-8 using the molecular sieve mother liquor without co-SDA in Example 3

[0191] First, 5.000g of pseudo-boehmite (77% Al 2 O 3 ), 37.034 g molecular sieve mother liquor and 7.633 g H 3 PO 4(85%) were mixed and stirred for about 1 hour, and then 2.042g 4-DMAPy and 0.533g EMM-8 seed crystals were added and stirred for about 1 hour to prepare the initial gel b. The initial gel b was transferred to a self-pressure reactor and crystallized at 180°C for 2 hours. The product in the reactor was directly centrifuged without washing, and the obtained liquid phase was the molecular sieve mother liquor, which could be further recycled. The solid phase product was washed, separated and dried to obtain the EMM-8 molecular sieve raw powder, with a yield of about 80%.

[0192] The product was subjected to XRD, showing Figure 1 After phase identification, the signal peak position is consistent with that of Example 1-3, and there are no other impurity peaks. SEM photo Figure 2 The product was calcined at 600 °C for 6 h and then N 2 Physical adsorption test (, the results are shown in Figure 3 , S BET =630.7m 2 / g,S micro =604.9m 2 / g,V total =0.3308cm 3 / g,V micro =0.3090cm 3 / g. The mother liquor obtained in Example 3 was used to synthesize EMM-8 molecular sieve, which can make full use of 4-DMAPy in the mother liquor, avoiding the waste of template agent and unnecessary environmental pollution. The water adsorption test results of the product at 30°C ( Figure 4 ) shows that P / P 0 =0.2 when the water adsorption is 0.29 g·g -1 .

[0193] The EMM-8 product obtained in this example has higher crystallinity, larger micropore volume, and larger water adsorption capacity than that in Example 3, indicating that the effect of synthesizing EMM-8 using molecular sieve crystallization mother liquor is good.

[0194] Example 5: EMM-8 was synthesized using the molecular sieve mother liquor of Example 1. H was added to the initial gel b. 2 O and co-SDA

[0195] The mass of each material in the initial gel b is as follows: 15.733 g aluminum isopropoxide (98%), 8.110 g phosphoric acid (85% H 3 PO 4), 2.042 g 4-DMAPy, 37.034 g molecular sieve mother liquor (obtained in Example 1 without dilution), 37.000 g deionized water, 3.000 g morpholine (99%) and 0.538 g seed crystals. Deionized water was first added to the mother liquor for dilution, followed by addition of aluminum isopropoxide, H 3 PO 4 and 4-DMAPy, stirred for about 4 hours, and finally added seed crystals and morpholine, and stirred for about 2 hours to obtain the initial gel b. The initial gel b was transferred to a self-pressure reactor and dynamically crystallized at 160°C for 4 hours. The product was washed and dried to obtain EMM-8 molecular sieve raw powder, with a yield of about 70%.

[0196] The product was shown by XRD Figure 1 After phase identification, the signal peak position is consistent with that of Example 1-4, and there are no other impurity peaks. SEM photo Figure 2 There is no impurity crystal or amorphous material in the solution, which proves that EMM-8 is well crystallized. The molecular sieve crystallization mother liquor obtained in this embodiment can be recycled.

[0197] This example uses the molecular sieve mother liquor diluted with water for synthesis, and co-SDA is introduced into the initial gel b to adjust the pH, which ensures the smooth crystallization and proves the reusability of the diluted molecular sieve mother liquor. In this example, the supersaturation of the initial gel b is low, and the product yield is lower than that of the previous example.

[0198] Example 6: The mother solution of the molecular sieve crystallization of Example 3 was used, and H was not added to the initial gel b. 2 O, co-SDA and 4-DMAPy

[0199] First, 5.200g Al(OH) 3 (2-10 μm, 99%), 37.034 g molecular sieve mother liquor (mother liquor from Example-3) and 7.633 g H 3 PO 4 (85%) was mixed and stirred for about 2 hours, and then 0.533g of EMM-8 seed crystals were added and stirred for about 2 hours to prepare initial gel b. The initial gel b was transferred to a self-pressure reactor and crystallized at 180°C for 8 hours. The obtained product was washed, separated and dried to obtain EMM-8 molecular sieve raw powder with a yield of about 70%.

[0200] The product was identified by XRD. Figure 1 As shown, the diffraction peak positions of the samples are well matched with those of Examples 1-4, indicating that the sample is a pure phase EMM-8 product. Figure 2 It also showed that the product was well crystallized in the form of rod-shaped crystals 5.00 μm long.

[0201] Preparation of Molecular Sieve Mother Liquor of Examples 7a to 13a

[0202] Examples 7a to 13a mainly involve the preparation steps of the mother liquor. The molar ratio of each material in the initial gel a and the crystallization conditions refer to Table 1. The configuration of the initial gel a is similar to that of Examples 1 and 3, wherein Example 13a adopts a dynamic crystallization method, and Examples 7a to 12a adopt a dynamic crystallization method. Example 9a adds calcined seeds, and the seed calcination conditions are 600°C for 6h. After the crystallization of Examples 7a to 13a, the materials in the kettle are not washed temporarily, but directly filtered or centrifuged to obtain undiluted molecular sieve mother liquor for the synthesis of Examples 7b to 13b.

[0203] Table 1. Ratios of materials in initial gel a and crystallization conditions

[0204]

[0205]

[0206] Examples 7b to 13b correspond to Examples 7a to 13a (a corresponds to b, for example, 6a corresponds to 6b). The material ratios and crystallization conditions of the initial gel b are shown in Table 2, wherein the amount of mother liquor added is 10 g. Except for co-SDA, the other values ​​in Table 2 represent the ratio of the mother liquor mass (the aluminum source is expressed as Al 2 O 3 Phosphorus source is H 3 PO 4 4-DMAPy is calculated by the mass of its own pure substance), and the amount of co-SDA is calculated by the mass of co-SDA and Al 2 O 3 The molar ratio is expressed. Example 13b adopts a static crystallization method, and Examples 6b to 11b adopt a dynamic crystallization method. Example 9a adds calcined seed crystals, and the calcination conditions are 600°C for 6h. After the crystallization of Examples 7b to 13b is completed, the product is directly filtered or centrifuged without washing and dilution to obtain a molecular sieve mother liquor, which can be used for subsequent synthesis.

[0207] Table 2 Material ratios and crystallization conditions of initial gel b

[0208]

[0209] Comparative Example 1 Fluorine-containing synthesis method

[0210] The initial gel molar ratio is as follows:

[0211] Al 2 O 3 :H 2 O:P2 O 5 :4-DMAPy:HF=1.0:40.0:1.0:2.4:0.6;

[0212] Pseudo-boehmite (77% Al 2 O 3 ), water, phosphoric acid (85% H 3 PO 4 ) and 4-DMAPy (99%) were first mixed and stirred for about 1 hour, and then hydrofluoric acid (40% aqueous solution) was added and stirred for about 1 hour to obtain an initial gel. The initial gel was then transferred to a self-pressure reactor, placed in an oven at 180°C, and dynamically crystallized for 48 hours. The product was washed with deionized water, separated, and dried to obtain fluorine-containing EMM-8 molecular sieve raw powder, which was used as the seed of Example 1. Compared with the fluorine-free method in the present invention, the fluorine-containing method has a longer crystallization time and a higher amount of 4-DMAPy. Although the N 2 The physical adsorption performance is comparable to that of the above-mentioned embodiment, but the water adsorption performance of the product is inferior to that of the EMM-8 product synthesized from the mother liquor, and the yield is also slightly lower than that of the fluorine-free method and the method of synthesizing from the molecular sieve mother liquor.

[0213] XRD results of products Figure 5 It is proved that the fluorine-containing method can obtain pure phase EMM-8 products, and the products are small grains of about 200-300nm. Figure 2 Compared with the product obtained by the fluorine-free method, the grains are smaller.

[0214] Comparative Example 2: No Seed Crystals Were Added During Synthesis Using Mother Liquor

[0215] First, 5.000 g pseudo-boehmite (77%), 39.74 g molecular sieve mother liquor (obtained after solid-liquid separation after crystallization in Example 1), 8.110 g H 3 PO 4 (85%) and 2.040g 4-DMAPy (99%) were pre-mixed and stirred for about 2h to obtain the initial gel b. The initial gel b was transferred to an autoclave and crystallized at 170°C for 6h. The crystallized product was washed, separated and dried. The product phase was analyzed by XRD ( Figure 5 ) After identification, no characteristic peak of EMM-8 appeared, and AlPO-5 was the main product. By comparing with Example 2, it is proved that seed crystal is one of the key factors for resynthesizing EMM-8 using molecular sieve mother liquor.

[0216] Comparative Example 3: The mother liquor of Example 6 was used without adding 4-DMAPy

[0217] 1.000 g pseudo-boehmite (77%), 7.950 g molecular sieve mother liquor (obtained from solid-liquid separation after crystallization in Example 6) and 1.622 g H 3 PO 4 (85%) were added in sequence, stirred and mixed for about 2 hours, and then 0.108g of EMM-8 seed crystals were added, and stirring was continued for about 2 hours to obtain the initial gel b. The initial gel b was transferred to an autoclave and crystallized at 170°C for 6 hours. Only a small amount of EMM-8 diffraction peaks appeared ( Figure 5 ), the crystallization speed is slow, and AlPO-5 occupies the main crystal phase. Compared with the initial gel composition of Examples 2, 4, 5, and 6, it is proved that the addition of 4-DMAPy is one of the key factors for the recycling of the mother solution.

[0218] Comparative Example 4: EMM-8 was synthesized using the molecular sieve mother liquor of Example 1. H 2 O, the mass of each material in the initial gel b is as follows: 3.147 g aluminum isopropoxide (98%), 1.622 g phosphoric acid (85% H 3 PO 4 ), 0.408 g 4-DMAPy, 7.407 g molecular sieve mother liquor (obtained in Example 1 without dilution), 7.400 g deionized water and 0.107 g seed crystal. Deionized water was first added to the mother liquor for dilution, followed by addition of aluminum isopropoxide, H 3 PO 4 and 4-DMAPy, stirred for about 4 hours, and finally added seed crystals, and stirred for about 2 hours to obtain initial gel b. The initial gel b was transferred to a self-pressure reactor and dynamically crystallized at 160°C for 4 hours. The product was washed and dried to obtain molecular sieve raw powder.

[0219] Comparison between Example 4 and Example 5 shows that the reuse effect of the molecular sieve crystallization solution diluted with water without adding co-SDA is poor. Figure 5 , showing a mixed phase of AlPO-5 and EMM-8, with AlPO-5 accounting for a larger proportion. This indicates that co-SDA needs to be added to the diluted molecular sieve crystallization mother liquor in order to be better reused.

[0220] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for utilizing EMM-8 molecular sieve crystallization mother liquor, It is characterized in that The method comprises the following steps: S1: mixing aluminum source, water, phosphorus source, primary template 4-dimethylaminopyridine, and EMM-8 seed crystals to obtain initial gel a; The molar ratio of aluminum source, water, phosphorus source and main template is: Al 2 About 3 :H 2 O:P 2 About 5 :4-DMAPy=0.5~1.5:20~100:0.5~1.5:0.5~2.5; Among them, the amount of EMM-8 seed added is the amount of Al in the initial gel a. 2 O 3 With P 2 O 5 1-20wt% of the total mass on dry basis; S2: The initial gel a in step S1 is heated and crystallized under closed conditions, the crystallization temperature is 120-220° C., and the crystallization time is 0.1-48 h to obtain product I; S3: The product I in step S2 is subjected to solid-liquid separation, and the obtained solid phase is EMM-8 molecular sieve, and the obtained liquid phase is molecular sieve mother liquid I; S4: mixing the aluminum source, the molecular sieve mother solution I, the phosphorus source, and the EMM-8 seed crystals to obtain an initial gel b; S5: The initial gel b in step S4 is heated and crystallized under closed conditions, the crystallization temperature is 120-220° C., and the crystallization time is 0.1-48 h to obtain product II; S6: After washing and solid-liquid separation, the product II in step S5 obtains the EMM-8 molecular sieve as the solid phase and the molecular sieve mother liquor II as the liquid phase; the molecular sieve mother liquor II is recycled as the raw material for synthesizing the EMM-8 molecular sieve according to steps S4 to S6.

2. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 1, It is characterized in that In step S1, the molar ratio of the aluminum source, water, phosphorus source and primary template in the initial gel a is: Al 2 About 3 :H 2 O:P 2 About 5 :4-DMAPy=0.5~1.5:20~100:0.5~1.5:1.5~2.5。 3. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 1, It is characterized in that In step S1, the initial gel a also includes a co-template agent; The molar ratio of aluminum source, water, phosphorus source, main template, and co-template co-SDA is: Al 2 O 3 :H 2 O:P 2 O 5 :4-DMAPy:co-SDA=0.5~1.5:20~100:0.5~1.5:0.5~2.5:0.001~2.5。 4. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 1, It is characterized in that In step S4, the raw material ratio of the initial gel b is: The mass ratio of the aluminum source to the molecular sieve mother solution I is 0.001 to 0.400; The mass ratio of the phosphorus source to the molecular sieve mother solution I is 0.001 to 0.750; The amount of seed added is the Al content in the initial gel b. 2 O 3 With P 2 O 5 1-20wt% of the total mass on dry basis; The mass of aluminum source is expressed as Al 2 O 3 The mass of phosphorus source is P 2 O 5 count.

5. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 4, It is characterized in that In step S4, the raw materials of the initial gel b also include a primary template agent; The mass ratio of the main template agent to the molecular sieve mother solution I is 0.001 to 0.450; The mass of the primary template is calculated as 4-DMAPy.

6. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 4, It is characterized in that In step S4, the raw materials of the initial gel b also include water; The mass ratio of the water to the molecular sieve mother solution I is 0.001 to 10; The mass of water is expressed in H 2 O plan.

7. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 4, It is characterized in that The raw materials of the initial gel b also include a co-template agent; The molar ratio of the co-template agent to the aluminum source is 0.001 to 2.0; The co-template is expressed as the mole of co-SDA; the mole of the aluminum source is expressed as Al 2 O 3 count.

8. The method for utilizing the EMM-8 molecular sieve crystallization mother liquor according to claim 1, It is characterized in that The aluminum source is selected from at least one of pseudo-boehmite, alumina, aluminum hydroxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum phosphate and aluminum chloride; 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; Preferably, the co-template agent is selected from at least one of diethylamine, triethylamine, tetraethylammonium hydroxide, dipropylamine, tripropylamine, diisopropylamine, n-butylamine, morpholine, piperazine, cyclohexylamine, cycloheximide, diethanolamine and 1-[2-(2-hydroxyethoxy)ethyl]piperazine; Preferably, the aluminum source, phosphorus source and co-template in step S1 and step S4 are the same or different.

9. An EMM-8 molecular sieve, It is characterized in that The molecular sieve is synthesized by the method described in any one of claims 1 to 8; the synthesized EMM-8 molecular sieve raw powder is calcined in an air atmosphere at a temperature of 450 to 800° C. to remove the template.

10. Use of the EMM-8 molecular sieve synthesized by the method according to any one of claims 1 to 8 in adsorption heat storage materials, heat pump materials, refrigeration materials or gas adsorption separation.

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