Molecular sieve synthesis equipment and molecular sieve synthesis method

Abstract

The invention discloses molecular sieve synthesis equipment and a molecular sieve synthesis method. The molecular sieve synthesis equipment comprises a spherical rotary reactor with a thermal insulation layer and a steam heating layer. The spherical rotary reactor is heated by steam, is provided with a charging hole and a discharging hole, and is driven by a motor to rotate. And grinding materials with different materials and different shapes are added into the reaction kettle. In the process of synthesizing the molecular sieve, the grinding material exerts a mechanical force effect on the raw materials for synthesizing the molecular sieve. Different from a traditional rotary or stirring hydrothermal reaction kettle, the molecular sieve nucleation and crystallization growth process can be promoted by introducing mechanical force in the process, so that the range of synthesis formulas which can be used in the molecular sieve synthesis process is relatively wide, and the addition of a template agent can be effectively reduced; waste is reduced, energy consumption of chemical synthesis is reduced, equipment cost is low, and operation is easy.

Description

Technical Field

[0001] The present application relates to a molecular sieve synthesis device and a molecular sieve synthesis method, belonging to the field of chemistry and chemical engineering. Background Art

[0002] Molecular sieve is an advanced porous material composed of inorganic materials with a regular pore structure. It can be used in separation, purification, adsorption and catalysis. Molecular sieve can be used as an industrial catalyst in the preparation of catalyst carriers and reaction catalysts in the fields of petrochemicals, chemicals, fine chemicals, etc. It has the advantages of improving reaction efficiency and selectivity, reducing energy consumption, and reducing pollution. At the same time, the pore size of the molecular sieve can be adjusted as needed, so it can be used in the field of gas separation, such as air separation, hydrogen purification, natural gas liquefaction, etc., with the advantages of high efficiency, energy saving, and environmental protection. In addition, molecular sieves can selectively adsorb certain molecules, so they can be used in the field of adsorption separation, such as water treatment, removal of organic pollutants, etc. With the continuous advancement of technology and the expansion of application fields, the market prospects of molecular sieves are broad. At present, the global molecular sieve market has reached billions of dollars, mainly concentrated in Europe, North America and Asia. In the future, with the increasing demand in various fields and the continuous emergence of new technologies, the molecular sieve market will continue to expand. At the same time, with the rapid development of the domestic economy, the Chinese molecular sieve market is also showing a rapid growth trend. Therefore, the market prospects of molecular sieves in the future are very broad and have great development potential.

[0003] Traditional molecular sieve synthesis mainly uses intermittent hydrothermal reaction synthesis kettles, which have low efficiency, large heat loss, and high energy consumption. Intermittent hydrothermal reaction synthesis kettles usually use a stirring system for synthesis, so there are many restrictions on the selection of synthesis formulas. The feed liquid needs to have good fluidity. If the feed liquid is a slurry with high viscosity or even a solid state, it is difficult to synthesize. Therefore, more solvents and organic templates are usually used, resulting in high synthesis costs and subsequent wastewater treatment costs. At the same time, the synthesis speed of traditional molecular sieve hydrothermal synthesis kettles is slow and the synthesis efficiency is low. The product particle size distribution of traditional molecular sieve hydrothermal synthesis kettles is uneven, and there is a problem of large or small particle size. Therefore, the development of the molecular sieve synthesis industry is restricted. Summary of the invention

[0004] According to one aspect of the present application, a molecular sieve synthesis device is provided, which is simple and has a high degree of automation. The device synthesizes molecular sieves by mechanical force assistance, which is a new technology that uses mechanical force to assist molecules to self-assemble in solution to form crystals. This method can prepare high-quality, high-crystallization, and high-specific surface area molecular sieve materials in a relatively short time. The traditional synthesis method requires long-term solution immersion and high-temperature hydrothermal treatment, while the mechanical force-assisted synthesis method only takes a few hours to complete. Compared with the traditional synthesis method, the molecular sieve crystals prepared by the mechanical force-assisted synthesis method are more uniform, complete, and defect-free, and the crystals have a higher degree of crystallinity. The advantages of mechanical force-assisted synthesis of molecular sieves are that they can shorten the preparation time, improve product quality, and reduce chemical waste. The traditional synthesis method requires a large amount of organic solvents, template agents and other chemical reagents in the preparation process, generating a large amount of waste. The mechanical force-assisted synthesis method uses fewer chemical reagents in the preparation process, which can reduce the generation of waste and reduce environmental pollution. It is particularly suitable for systems with high viscosity, or even solid-phase synthesis processes, with low equipment cost and easy operation. Mechanical force-assisted synthesis of molecular sieves has the advantages of short preparation time, high crystal quality, large specific surface area, reduced waste and wider applicability. It will become an important development direction of molecular sieve preparation technology in the future.

[0005] This application adopts the following technical solutions:

[0006] A molecular sieve synthesis device, comprising a molecular sieve synthesis device and a heating device;

[0007] The molecular sieve synthesis device comprises a spherical rotating reactor (4), a feeding port (5), a discharging port (8), a rotating motor (7), and a reactor support (11);

[0008] The feed port (5) and the discharge port (8) are respectively arranged on opposite sides of the spherical rotating reactor (4); coaxial linkage shafts (12) are respectively arranged on both sides of the spherical rotating reactor (4) in the horizontal direction; the linkage shafts (12) are rotatably fixed on the upper end of the reactor support (11); and the rotating motor (7) is driven to connect one end of the linkage shaft (12);

[0009] The heating device comprises a steam inlet channel (6), a steam outlet channel (1), and a steam heating layer (3);

[0010] The steam heating layer (3) is wrapped around the periphery of the spherical rotating reactor (4), and the steam inlet channel (6) and the steam outlet channel (1) are respectively arranged inside the linkage rotating shaft (12) to connect the thermal insulation layer (2) and the external environment in an openable and closable manner;

[0011] The inner cavity of the spherical rotating reactor (4) is provided with movable grinding material (10).

[0012] Optionally, the controllable temperature of the steam heating layer (3) is 30-220°C.

[0013] The function of the heating device is to control the temperature during the molecular sieve synthesis process.

[0014] Optionally, the feed port (5) and the discharge port (8) are respectively arranged on the spherical rotating reactor (4) relative to each other in the vertical direction.

[0015] The discharge port is located on the opposite side of the feed port of the molecular sieve synthesis equipment. After the synthesis process is completed, the product is poured out from the discharge port. At the same time, the discharge port can be used as a cleaning port of the reactor to clean the internal cavity for next use.

[0016] The spherical rotating reactor (4) is driven to rotate by a rotating motor (7).

[0017] Optionally, the controllable rotation speed of the spherical rotating reactor (4) is 1 rpm to 80 rpm.

[0018] Grinding materials are added during the synthesis process, and this part of the grinding materials provides additional mechanical force for the molecular sieve raw materials during the synthesis process.

[0019] Optionally, the material of the grinding material is selected from at least one of agate, aluminum oxide, zirconium oxide, stainless steel, and synthetic resin.

[0020] Optionally, the grinding material has a shape selected from at least one of a sphere, a rod, a cube, a triangular pyramid, and a star.

[0021] Optionally, the heating device further comprises a drain port (9), wherein the drain port (9) penetrates the thermal insulation layer (2) and is connected to the external environment in an openable and closable manner.

[0022] Optionally, the heating device further comprises a heat-insulating layer (2), wherein the heat-insulating layer (2) is wrapped around the periphery of the steam heating layer (3).

[0023] According to another aspect of the application, the present application also proposes a molecular sieve synthesis method, and the molecular sieve synthesis method uses the above-mentioned molecular sieve synthesis equipment.

[0024] This method can shorten the preparation time, improve product quality and reduce chemical waste, etc. It can effectively reduce the amount of template used in the traditional hydrothermal synthesis process, and is particularly suitable for systems with high viscosity or even solid-phase synthesis processes.

[0025] Optionally, a molecular sieve synthesis method comprises the following steps:

[0026] The raw material of the molecular sieve to be synthesized is placed into the inner cavity of the spherical rotating reactor (4) through the feeding port (5), and the grinding material is added into the inner cavity of the spherical rotating reactor (4). After sealing, the spherical rotating reactor (4) is heated and rotated to synthesize the molecular sieve, which is then poured out from the discharge port (8).

[0027] In the present application, the spherical rotating reactor is sealed, heated and rotated, and the grinding material continuously applies mechanical force to the synthetic raw materials during the rotation process. After the reaction is completed, the molecular sieve generated by the reaction can be collected through the discharge port at the bottom of the molecular sieve synthesis device.

[0028] Optionally, the heating is as follows: steam of a set temperature is continuously passed through the steam inlet channel (6) into the steam heating layer (3), and excess steam in the steam heating layer (3) is discharged through the steam exhaust channel (1).

[0029] Optionally, the rotation is: driving one end of the linkage shaft (12) through a rotating motor (7) to drive the spherical rotating reactor (4) to rotate.

[0030] The molecular sieve synthesis method of the present application can heat the spherical rotating reactor (4) for molecular sieve synthesis by means of a steam heating device, thereby being able to perform molecular sieve synthesis at different temperatures.

[0031] The temperature of the spherical rotating reactor can be controlled to be 30-220° C. by means of the steam heating layer (3) in the heating device.

[0032] Optionally, the temperature for synthesizing the molecular sieve is selected from any value of 30°C, 40°C, 60°C, 90°C, 120°C, 150°C, 180°C, 200°C, 210°C, 220°C, or any range therebetween.

[0033] Optionally, the raw material is selected from at least one of X-type molecular sieve raw material, Y-type zeolite molecular sieve raw material, A-type zeolite molecular sieve raw material, mordenite molecular sieve raw material, ZSM-5 type zeolite molecular sieve raw material, TS-1 type zeolite molecular sieve raw material, EAB type zeolite molecular sieve raw material, β-type zeolite molecular sieve raw material and clinoptilolite molecular sieve raw material.

[0034] When the molecular sieve synthesis device of the present application is used with the above molecular sieve raw materials, the synthesis time of the molecular sieve is 0.5 to 168 hours and the rotation speed is 1 to 80 rpm.

[0035] Optionally, the time for synthesis of the molecular sieve is selected from any value among 0.5h, 1h, 6h, 12h, 24h, 48h, 72h, 96h, 120h, 144h, 168h, or any range value therebetween.

[0036] The spherical reactor in the molecular sieve synthesis device is driven to rotate by a motor, so that the spherical reactor can be controlled to perform molecular sieve synthesis under different rotation speed conditions.

[0037] Optionally, the rotation speed during the molecular sieve synthesis process is selected from any value of 1 rpm, 5 rpm, 10 rpm, 20 rpm, 30 rpm, 40 rpm, 50 rpm, 60 rpm, 70 rpm, 75 rpm, 80 rpm, or any range therebetween.

[0038] Optionally, the molecular sieve synthesized by the molecular sieve synthesis method is at least one of X-type molecular sieve, Y-type zeolite molecular sieve, A-type zeolite molecular sieve, mordenite molecular sieve, ZSM-5 type zeolite molecular sieve, TS-1 type zeolite molecular sieve, EAB type zeolite molecular sieve, β-type zeolite molecular sieve, and clinoptilolite molecular sieve.

[0039] Optionally, in the present method, the synthesis of molecular sieve adopts a mechanical force-assisted rotary reaction device. The device includes a molecular sieve synthesis device and a heating device, wherein the heating device mainly adopts a steam heating method, wherein the steam generator passes the steam of the set temperature from the entrance of the steam inlet channel (6) to the steam heating layer (3), and the excess steam is discharged from the outlet of the steam discharge channel (1) for circulation, and the heating device is provided with a drain port (9) to facilitate the discharge of the water condensed by the steam. To improve energy efficiency, the reactor is additionally provided with a heat preservation layer (2), which can effectively achieve the stability of the synthesis temperature. The synthesis process adds the raw material of the molecular sieve to be synthesized into a spherical rotary reactor (4) through a feed port (5), adds a grinding material (10) to the reactor, heats up after sealing, and drives the linkage shaft (12) to control its rotation through a rotary motor (7), wherein the grinding material continuously applies mechanical force to the synthetic raw material during the rotation process, and after the reaction is completed, pours out the molecular sieve product through a discharge port (8).

[0040] The beneficial effects of this application include:

[0041] 1) The molecular sieve synthesis equipment of the present application synthesizes molecular sieves by mechanical force assistance, which is a new technology that uses mechanical force to assist molecules to self-assemble in solution to form crystals. This method can prepare high-quality, high-crystallization, and high-specific surface area molecular sieve materials in a relatively short period of time. The method and equipment are simple and highly automated, and are particularly suitable for molecular sieve synthesis systems with high viscosity, or even solid-phase synthesis processes. The equipment cost is low and easy to operate;

[0042] 2) The molecular sieve synthesis method of the present application is a mechanical force-assisted synthesis method, and the prepared molecular sieve crystals are more uniform, complete, and defect-free, and the crystals have a higher degree of crystallinity. The advantages of mechanical force-assisted synthesis of molecular sieves are that it can shorten the preparation time, improve product quality, and reduce chemical waste. The mechanical force-assisted synthesis method uses less organic templates in the preparation process, which can reduce the generation of waste and reduce environmental pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a diagram of the molecular sieve synthesis equipment in this application.

[0044] Figure 2 This is a scanning electron microscope image of the product synthesized in Example 1 of this application.

[0045] Figure 3 This is the X-ray powder diffraction image of the product synthesized in Example 1 of the present application.

[0046] Figure ID

[0047] 1. Steam discharge channel; 2. Insulation layer; 3. Steam heating layer; 4. Spherical rotating reactor; 5. Feeding port; 6. Steam inlet channel; 7. Rotating motor; 8. Discharge port; 9. Drain port; 10. Grinding material; 11. Reactor bracket; 12. Linked rotating shaft. DETAILED DESCRIPTION

[0048] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0049] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0050] The analysis method in the examples of this application is as follows:

[0051] In the examples of the present application, the SEM morphology analysis of the product was performed using a Hitachi SU8020 scanning electron microscope.

[0052] In the examples of the present application, the X-ray powder diffraction phase analysis (XRD) of the product was performed using an X'Pert PRO X-ray diffractometer from PANalytical of the Netherlands, with a Cu target, a Kα radiation source (λ=0.15418 nm), a voltage of 40 KV, and a current of 40 mA.

[0053] According to one embodiment of the present application, the method of mechanical synthesis of molecular sieves is characterized in that the method comprises the following steps:

[0054] The raw material of the molecular sieve to be synthesized is added to the spherical rotating reactor (4) through the feed port (5), and the grinding material (10) is added to the reactor. The material of the grinding material includes one or more mixtures of materials such as agate, aluminum oxide, zirconium oxide, stainless steel or synthetic resin, and the shape of the grinding material includes one or more mixtures of different shapes such as sphere, rod, cube, triangular pyramid or star. After sealing, the temperature is increased and the reactor is rotated. During the reaction, the speed is between 1rpm and 80rpm, the temperature of the spherical rotating reactor is between 30°C and 220°C, and the molecular sieve synthesis time is between 0.5 hours and 168 hours. The grinding material continuously applies mechanical force to the synthetic raw material during the rotation process, and the molecular sieve product is poured out through the discharge port after the reaction is completed.

[0055] The molecular sieve synthesis equipment and molecular sieve synthesis method of the present application can synthesize molecular sieves such as X-type molecular sieve, Y-type zeolite molecular sieve, A-type zeolite molecular sieve, mordenite molecular sieve, ZSM-5 type zeolite molecular sieve, TS-1 type zeolite molecular sieve, EAB type zeolite molecular sieve, β-type zeolite molecular sieve or clinoptilolite molecular sieve.

[0056] Example 1

[0057] Molecular sieve synthesis equipment used in the molecular sieve synthesis process such as Figure 1 As shown. The molecular sieve synthesis equipment comprises a molecular sieve synthesis device and a heating device. The molecular sieve synthesis device comprises a spherical rotating reactor (4), a feeding port (5), a discharging port (8), a rotating motor (7), and a reactor support (11). The feeding port (5) and the discharging port (8) are respectively arranged on the spherical rotating reactor (4) in a vertical direction relative to each other. Coaxial linkage rotating shafts (12) are respectively arranged on both sides of the spherical rotating reactor (4) in a horizontal direction. The linkage rotating shaft (12) can be rotatably fixed on the upper end of the reactor support (11). The rotating motor (7) drives one end of the linkage rotating shaft (12).

[0058] The heating device mainly adopts steam heating, and the steam of set temperature is passed into the steam heating layer (3) through the steam inlet channel (6) through the external steam generator, and the excess steam is discharged from the steam discharge channel (1) for circulation. The heating device is also provided with a drain port (9) to facilitate the discharge of water condensed from the steam. In order to improve energy efficiency, the reactor is additionally provided with a heat preservation layer (2), which can effectively achieve the stability of the synthesis temperature. During the synthesis process, the raw material of the molecular sieve to be synthesized is added to the spherical rotating reactor (4) through the feed port (5), and the grinding material (10) is added to the reactor. After sealing, the temperature is increased and the rotation of the spherical rotating reactor (4) is controlled by the rotating motor (7) to drive the linkage shaft (12). The grinding material continuously applies mechanical force to the synthetic raw material during the rotation process. After the reaction is completed, the molecular sieve product is poured out through the discharge port (8).

[0059] In this embodiment, 60 g of ethyl orthosilicate, 5 g of tetrabutyl titanate, 15 g of tetrapropylammonium hydroxide and 60 g of deionized water are charged into the inner cavity of the molecular sieve synthesis device through the feed port (5), and agate grinding beads are added to the reaction system as grinding materials (10). The set temperature steam is passed from the steam inlet channel (6) to the steam heating layer (3) through an external steam generator, and the excess steam is discharged from the steam discharge channel (1) for circulation to provide a reaction temperature of 170° C. for the spherical rotary reactor (4). The reaction temperature is stabilized by the heat preservation layer (2). The rotation speed of the spherical rotary reactor (4) is controlled to be 40 rpm by driving the linkage shaft (12) through the rotary motor (7). At this reaction temperature and speed, the reaction time is 24 hours to synthesize the molecular sieve product. After the reaction is completed, the molecular sieve product is poured out through the discharge port (8). The scanning electron microscope picture is as shown in FIG. Figure 2 As shown, the X-ray powder diffraction image is as follows Figure 3 shown.

[0060] Example 2

[0061] The molecular sieve synthesis equipment and operation are the same as those in Example 1, and the molecular sieve product is synthesized. The difference is that the raw materials for the molecular sieve to be synthesized are 35g of aluminum hydroxide, 30g of sodium silicate, 15g of sodium hydroxide, and 20g of deionized water, the grinding material (10) is zirconium oxide and aluminum oxide grinding rods, the reaction temperature is 100°C, the reaction time is 6 hours, and the rotation speed is 70rpm.

[0062] Example 3

[0063] The molecular sieve synthesis equipment and operation are the same as those in Example 1, and the molecular sieve product is synthesized. The difference is that the raw materials for the molecular sieve to be synthesized are 75g of pseudo-boehmite, 60g of fumed silica, 25g of n-octylamine, and 220g of deionized water, and the grinding material (10) is added with stainless steel grinding triangular pyramids. The reaction temperature is 200°C, the reaction time is 72 hours, and the rotation speed is 20rpm.

[0064] Embodiments 4 to 13

[0065] The molecular sieve synthesis equipment and operation are the same as those in Example 1, and the molecular sieve product is synthesized. The difference lies in the type of molecular sieve raw material to be synthesized, the type of grinding material, the reaction temperature, the rotation speed, and the reaction time. The specific synthesis conditions are shown in Table 1 below.

[0066] Table 1 Molecular sieve synthesis conditions of Examples 4-13

[0067]

[0068] 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 molecular sieve synthesis device, characterized in that: It includes a molecular sieve synthesis device and a heating device; The molecular sieve synthesis device comprises a spherical rotating reactor (4), a feeding port (5), a discharging port (8), a rotating motor (7), and a reactor support (11); The feed port (5) and the discharge port (8) are respectively arranged on opposite sides of the spherical rotating reactor (4); coaxial linkage shafts (12) are respectively arranged on both sides of the spherical rotating reactor (4) in the horizontal direction; the linkage shafts (12) are rotatably fixed on the upper end of the reactor support (11); and the rotating motor (7) is driven to connect one end of the linkage shaft (12); The heating device comprises a steam inlet channel (6), a steam outlet channel (1), and a steam heating layer (3); The steam heating layer (3) is wrapped around the periphery of the spherical rotating reactor (4), and the steam inlet channel (6) and the steam outlet channel (1) are respectively arranged inside the linkage rotating shaft (12) to connect the thermal insulation layer (2) and the external environment in an openable and closable manner; The inner cavity of the spherical rotating reactor (4) is provided with movable grinding material (10).

2. The molecular sieve synthesis equipment according to claim 1, characterized in that: The controllable temperature of the steam heating layer (3) is 30-220°C.

3. The molecular sieve synthesis equipment according to claim 1, characterized in that: The feed port (5) and the discharge port (8) are arranged on the spherical rotating reactor (4) in a vertical direction relative to each other.

4. The molecular sieve synthesis equipment according to claim 1, characterized in that: The controllable rotation speed of the spherical rotating reactor (4) is 1 rpm to 80 rpm.

5. The molecular sieve synthesis equipment according to claim 1, characterized in that: The heating device also includes a drain port (9), which penetrates the thermal insulation layer (2) and is in openable and closable communication with the external environment.

6. The molecular sieve synthesis equipment according to claim 1, characterized in that: The heating device further comprises a heat-insulating layer (2), wherein the heat-insulating layer (2) is wrapped around the periphery of the steam heating layer (3).

7. A method for synthesizing a molecular sieve, characterized in that: The molecular sieve synthesis method uses the molecular sieve synthesis equipment according to any one of claims 1 to 6.

8. The method for synthesizing molecular sieve according to claim 7, characterized in that: The steps include: The raw material of the molecular sieve to be synthesized is placed into the inner cavity of the spherical rotating reactor (4) through the feeding port (5), and the grinding material is added into the inner cavity of the spherical rotating reactor (4). After sealing, the spherical rotating reactor (4) is heated and rotated to synthesize the molecular sieve, which is then poured out from the discharge port (8).

9. The method for synthesizing a molecular sieve according to claim 8, characterized in that: The heating comprises: continuously passing steam of a set temperature from a steam inlet channel (6) into the steam heating layer (3), and discharging excess steam in the steam heating layer (3) through a steam discharge channel (1); The rotation is: the rotating motor (7) drives one end of the linkage rotating shaft (12) to drive the spherical rotating reactor (4) to rotate.

10. The method for synthesizing a molecular sieve according to claim 8, characterized in that: The raw material is selected from at least one of X-type molecular sieve raw material, Y-type zeolite molecular sieve raw material, A-type zeolite molecular sieve raw material, mordenite molecular sieve raw material, ZSM-5 type zeolite molecular sieve raw material, TS-1 type zeolite molecular sieve raw material, EAB type zeolite molecular sieve raw material, β-type zeolite molecular sieve raw material and clinoptilolite molecular sieve raw material.

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