阅读说明：本技术 一种3d打印可组装整体式催化剂及其制备方法 (3D printing assemblable monolithic catalyst and preparation method thereof ) 是由 田小永 邱正平 霍存宝 于 2021-08-23 设计创作，主要内容包括：一种3D打印可组装整体式催化剂及其制备方法,可组装整体式催化剂包括安装在转子上的笼型催化剂保护架,笼型催化剂保护架上安装有整体式催化剂；制备方法先根据反应釜结构设计笼型催化剂保护架和整体式催化剂,再采用粉末床熔融技术3D打印笼型催化剂保护架；然后将催化活性剂、陶瓷载体材料机械搅拌混合为催化剂3D打印浆料并通过直写成型设备3D打印整体式催化剂初坯；再将整体式催化剂初坯自然干燥,然后进行高温烧结工艺,得到整体式催化剂；最后将多个整体式催化剂均匀地插在笼型催化剂保护架中,组装成为整体式催化剂结构；本发明增强整体式催化剂机械强度的功能,减少整体式催化剂在反应过程中的破损,充分发挥整体式催化剂的循环利用功能。(An assemblable monolithic catalyst for 3D printing and a preparation method thereof are disclosed, wherein the assemblable monolithic catalyst comprises a cage-type catalyst protection frame arranged on a rotor, and the cage-type catalyst protection frame is provided with a monolithic catalyst; the preparation method comprises the steps of designing a cage-type catalyst protection frame and an integral catalyst according to the structure of a reaction kettle, and then adopting a powder bed melting technology to print the cage-type catalyst protection frame in a 3D mode; then mechanically stirring and mixing the catalytic active agent and the ceramic carrier material to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment; naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst; finally, uniformly inserting a plurality of monolithic catalysts into a cage-type catalyst protection frame to assemble a monolithic catalyst structure; the invention enhances the function of the mechanical strength of the monolithic catalyst, reduces the damage of the monolithic catalyst in the reaction process and fully exerts the recycling function of the monolithic catalyst.)

1. The utility model provides a 3D prints and can assemble monolithic catalyst which characterized in that: the device comprises a cage-type catalyst protection frame (2) arranged on a rotor (3), wherein an integral catalyst (1) is arranged on the cage-type catalyst protection frame (2).

2. The 3D printed assemblable monolithic catalyst as recited in claim 1, wherein: the cage-type catalyst protection frame (2) adopts a frame structure, is similar to a stirring impeller structure, the central part of the impeller is a space for the rotor (3) to rotate, and the integral catalyst (1) is uniformly arranged at a fan blade; when in use, the inner wall of the reaction kettle is contacted with the peripheral surface of the cage-type catalyst protection frame (2).

3. The 3D printed assemblable monolithic catalyst as recited in claim 1, wherein: the cage-type catalyst protection frame (2) is made of a metal material of titanium alloy and aluminum alloy or a plastic material of PLA.

4. The 3D printed assemblable monolithic catalyst as recited in claim 1, wherein: the monolithic catalyst (1) is of a circular porous structure.

5. The 3D printed assemblable monolithic catalyst as recited in claim 1, wherein: the monolithic catalyst (1) is formed by 3D printing of catalyst slurry, the catalyst slurry is formed by mechanically stirring and mixing a catalytic active agent, a ceramic carrier material and an auxiliary material, the catalytic active agent is a titanium-silicon molecular sieve or a molecular sieve such as 13x, the ceramic carrier material is silicon dioxide spherical powder, silica sol or a mixture of the silicon dioxide spherical powder and the silica sol in any proportion, and the auxiliary material is polyethylene glycol, sesbania powder or a mixture of the silicon dioxide spherical powder and the silica sol in any proportion; the mass ratio of the catalytic active agent to the ceramic carrier material to the auxiliary material in the catalyst slurry is 0.5-1: 1: 0.05 to 0.1.

6. A preparation method of a 3D printing assemblable monolithic catalyst is characterized by comprising the following steps:

1) designing a cage-type catalyst protection frame (2) and an integral catalyst (1) according to the structure of a reaction kettle;

2) 3D printing a cage-type catalyst protection frame (2) by adopting a powder bed melting technology;

3) the method comprises the following steps of (1) mixing a catalytic active agent, a ceramic carrier material and an auxiliary material according to a mass ratio of 0.5-1: 1: mechanically stirring and mixing 0.05-0.1 to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment;

4) naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst (1);

5) a plurality of monolithic catalysts (1) are uniformly inserted into a cage-type catalyst protection frame (2) and assembled into a monolithic catalyst structure.

7. The method of claim 6, wherein: and in the step 1), simulation software is adopted as Fluent, and an optimal cage-type catalyst protection frame (2) and an integral catalyst (1) comprising pore canal directions and sizes are simulated to obtain optimal catalytic reaction efficiency.

8. The method of claim 6, wherein: the step 4) is specifically as follows: putting the integral catalyst blank into a constant temperature and humidity environment, drying for 24 hours at a constant temperature of 25 ℃ and a relative humidity selection range of 30%, then carrying out a high-temperature sintering process on the integral catalyst blank in a high-temperature sintering furnace, raising the temperature to 500-600 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 8 hours, and cooling to room temperature along with the furnace to obtain the integral catalyst 1.

9. The method of claim 6, wherein the step of removing the substrate comprises removing the substrate from the substrate: the crushing strength of the monolithic catalyst obtained in the step 4) is 195-332N/cm, and the specific surface area is 200-289 m²/g。

10. The method of claim 6, wherein: the monolithic catalyst structure finally obtained in the step 5) has good catalytic effect in the reaction from one-step oxidation of ethylene to ethylene glycol, the conversion rate of hydrogen peroxide is 96.9%, the utilization rate of hydrogen peroxide is 66.3%, and ethylene glycol (H) is obtained₂O₂) The yield was 64.21%, and the ethylene glycol selectivity was 92%.

Technical Field

The invention belongs to the technical field of monolithic catalysts in catalytic reaction, and particularly relates to a 3D printing assemblable monolithic catalyst and a preparation method thereof.

Background

The catalyst commonly used in industry at present mainly comprises a packed bed catalyst in a particle form, a supported catalyst, a monolithic catalyst and the like; the monolithic catalyst is prepared by mixing active components of the catalyst, a binder and the like according to a certain proportion to prepare slurry with a certain viscosity, and the catalyst with a specific structure is extruded, wherein the structure is mainly a honeycomb structure with regularly arranged parallel channels and has the advantages of high mass transfer and heat transfer and the like, but the traditional monolithic catalyst with the honeycomb structure does not have radial mass transfer and heat transfer and is possibly unfavorable for many applications; this requires the optimization of monolithic catalyst structures for optimum mass transfer and catalytic conversion efficiency, however some complex structures cannot be realized by conventional manufacturing processes.

The 3D printing technology thoroughly changes the limitation of the structural design of the monolithic catalyst, and the catalyst with a complex structure and excellent performance can be manufactured by relying on the 3D printing technology according to the requirements of mass transfer, heat transfer and the like, so that the manufacturing cost is reduced. The monolithic catalyst mainly adopts a direct write molding technology (DIW), which is one of 3D printing technologies and is a more advanced additive manufacturing technology, and can be used for quickly molding any complex 3D shape, and the working mode is that a platform controlled by a computer is used for moving a deposition nozzle to generate patterns with various sizes and shapes; this provides the possibility of designing a more optimal structure of the monolithic catalyst.

At present, some precedents of 3D printing monolithic catalysts exist, and Chinese patent (CN202011013321.7, name: a method for 3D printing monolithic catalysts) is closely combined with computer simulation and structural design according to a 3D printing technology, so that monolithic catalysts which need multiple materials to be integrally formed and have complex structures and optimized performance are accurately manufactured, which cannot be realized by the traditional manufacturing process. However, this technique has the following disadvantages: 1) the protection of the monolithic catalyst has the defects of insufficient mechanical strength, poor impact resistance and the like, and the phenomenon of fragmentation caused by liquid impact, collision of a stirring device and the like is occasionally generated in the experimental process; 2) poor controllability during catalytic reaction, incapability of fixing the position of the monolithic catalyst during catalytic reaction, incapability of realizing the expandability of the monolithic catalyst and the like.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a 3D printing assemblable monolithic catalyst and a preparation method thereof, which can enhance the mechanical strength of the monolithic catalyst, reduce the damage of the monolithic catalyst in the reaction process and fully exert the recycling function of the monolithic catalyst.

In order to achieve the purpose, the invention adopts the technical scheme that:

the utility model provides a 3D prints and to assemble monolithic catalyst, includes cage type catalyst fender bracket 2 of installing on rotor 3, installs monolithic catalyst 1 on the cage type catalyst fender bracket 2.

The cage-type catalyst protection frame 2 adopts a frame structure, is similar to a stirring impeller structure, the center part of the impeller is a space for the rotor 3 to rotate, and the integral catalyst 1 is uniformly arranged at a fan blade; when the device is used, the inner wall of the reaction kettle is contacted with the peripheral surface of the cage-type catalyst protection frame 2.

The cage type catalyst protection frame 2 is made of metal materials of titanium alloy and aluminum alloy or plastic materials of PLA.

The monolithic catalyst 1 is of a circular ring porous structure.

The monolithic catalyst 1 is formed by 3D printing of catalyst slurry, the catalyst slurry is formed by mechanically stirring and mixing a catalytic active agent, a ceramic carrier material and an auxiliary material, the catalytic active agent is a titanium-silicon molecular sieve or a molecular sieve such as 13x, the ceramic carrier material is silicon dioxide spherical powder, silica sol or a mixture of the silicon dioxide spherical powder and the silica sol in any proportion, and the auxiliary material is polyethylene glycol, sesbania powder or a mixture of the silicon dioxide spherical powder and the silica sol in any proportion; the mass ratio of the catalytic active agent to the ceramic carrier material to the auxiliary material in the catalyst slurry is 0.5-1: 1: 0.05 to 0.1.

A preparation method of a 3D printing assemblable monolithic catalyst comprises the following steps:

1) designing a cage-type catalyst protection frame 2 and an integral catalyst 1 according to the structure of a reaction kettle;

2) 3D printing a cage-type catalyst protection frame 2 by adopting a powder bed melting technology;

3) the method comprises the following steps of (1) mixing a catalytic active agent, a ceramic carrier material and an auxiliary material according to a mass ratio of 0.5-1: 1: mechanically stirring and mixing 0.05-0.1 to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment;

4) naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst 1;

5) a plurality of monolithic catalysts 1 are uniformly inserted into a cage-type catalyst protection frame 2 and assembled into a monolithic catalyst structure.

In the step 1), simulation software is adopted as Fluent, and an optimal cage-type catalyst protection frame 2 and an integral catalyst 1 containing pore canal directions and sizes are simulated to obtain optimal catalytic reaction efficiency.

The step 4) is specifically as follows: putting the integral catalyst blank into a constant temperature and humidity environment, drying for 24 hours at a constant temperature of 25 ℃ and a relative humidity selection range of 30%, then carrying out a high-temperature sintering process on the integral catalyst blank in a high-temperature sintering furnace, raising the temperature to 500-600 ℃ at a heating rate of 4 ℃/min, preserving the temperature for 8 hours, and cooling to room temperature along with the furnace to obtain the integral catalyst 1.

The crushing strength of the monolithic catalyst obtained in the step 4) is 195-332N/cm, and the specific surface area is 200-289 m²/g。

The monolithic catalyst structure finally obtained in the step 5) has good catalytic effect in the reaction from one-step oxidation of ethylene to ethylene glycol, the conversion rate of hydrogen peroxide is 96.9%, the utilization rate of hydrogen peroxide is 66.3%, and ethylene glycol (H) is obtained₂O₂) The yield was 64.21%, and the ethylene glycol selectivity was 92%.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1. according to the invention, the cage-type catalyst protection frame is matched with the monolithic catalyst for use, the cage-type catalyst protection frame has higher mechanical strength, the impact resistance and the mechanical strength of the monolithic catalyst are greatly enhanced, and the cage-type catalyst protection frame has a simple structure, is easy to design and manufacture, and reduces the manufacturing cost;

2. the cage-type catalyst protection frame adopted by the invention is of a frame structure, so that the influence on catalytic reaction is reduced; meanwhile, the catalytic reaction needs stirring to accelerate the reaction rate, the phenomenon that the rotor jumps or the rotor collides with the integral catalyst to cause the catalyst to be cracked frequently occurs, and the design and the use of the cage-type catalyst protection frame fix the rotating position of the rotor and the position of the integral catalyst, so that the collision of the integral catalyst and the rotor is avoided, the damage of the integral catalyst in the reaction process is reduced, the recycling frequency of the integral catalyst is improved, and the use cost is reduced.

3. The cage-type catalyst protective frame is used for assembling the integral catalyst in blocks, each part of the integral catalyst is independent, and the damaged or inactivated part of the integral catalyst can be replaced, so that the waste of materials is avoided.

Drawings

Fig. 1 is an assembly view of a 3D printed assemblable monolithic catalyst of the present invention.

FIG. 2 is a schematic diagram of the cage catalyst protector of the present invention.

Detailed Description

For a further understanding of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings, and it is to be understood that the description is intended to further illustrate the features and advantages of the present invention and not to limit the scope of the appended claims.

As shown in fig. 1, a 3D printed assemblable monolithic catalyst includes a cage-type catalyst support 2 mounted on a rotor 3, the cage-type catalyst support 2 having a monolithic catalyst 1 mounted thereon.

The magnetons rotate and stir liquid under the action of a magnetic field, the integral catalyst 1 is uniformly placed in the cage-type catalyst protection frame 2, the magnetic stirrer has the biggest characteristic that the magnetons are unstable in rotation and can jump or move left and right, the cage-type catalyst protection frame 2 not only fixes the rotation position of the magnetons 3, but also has the position fixing effect of the integral catalyst 1, the integral catalyst 1 has the characteristics of insufficient mechanical strength and insufficient impact resistance, the phenomenon that the integral catalyst 1 is damaged and dropped in liquid after each reaction and turbid liquid is caused is found through a plurality of experiments, and the cage-type catalyst protection frame 2 can reduce or even avoid the phenomenon.

As shown in fig. 2, the cage-type catalyst protection frame 2 adopts a frame structure, which is similar to a stirring impeller structure, the center part of the impeller is a space for the rotor 3 to rotate, and the monolithic catalyst 1 is uniformly arranged at the fan blades; when the device is used, the inner wall of the reaction kettle is contacted with the peripheral surface of the cage-type catalyst protection frame 2, so that the cage-type catalyst protection frame 2 is fixed, the position is prevented from moving in the fluid impact process, and the device can be used for fixing the assembled integral catalyst.

Example 1, a method of preparing a 3D printed assemblable monolithic catalyst, comprising the steps of:

1) designing a cage-type catalyst protection frame 2 and an integral catalyst 1 according to the structure of a reaction kettle;

in the embodiment, a three-dimensional model of an integral catalyst 1 is designed, and Fluent is used for simulation to obtain an integral catalyst 3 with an optimal structure (mass and heat transfer, conversion efficiency and the like) under theoretical conditions;

2) 3D printing a cage-type catalyst protection frame 2 by adopting a powder bed melting technology;

3) mechanically stirring and mixing a catalytic active agent, a ceramic carrier material and an auxiliary material to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment;

60g of titanium silicon powder, 10g of silicon dioxide powder and 50g of silica sol as a ceramic carrier material, and 2g of polyethylene glycol and 2g of sesbania powder as an auxiliary material are taken as a catalytic activator, and mechanically stirred at a speed of 50r/min for 40min to obtain catalyst slurry;

4) naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst 1;

in the embodiment, an integral catalyst blank is placed in a constant temperature and humidity environment, the constant temperature is 25 ℃, the relative humidity selection range is 30%, the integral catalyst blank is dried for 24 hours, then a high-temperature sintering process is carried out on the integral catalyst blank in a high-temperature sintering furnace, the temperature is increased to 550 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 8 hours, and the integral catalyst 1 is prepared after the integral catalyst blank is cooled to the room temperature along with the furnace;

5) uniformly inserting a plurality of monolithic catalysts 1 into a cage-type catalyst protection frame 2 to assemble a monolithic catalyst structure; and (3) putting the mixture into a reaction kettle for catalytic reaction, and setting the rotating speed of magnetons to be 600r/min to obtain the catalyst and the solution after the reaction.

Embodiment 2, a method for preparing a 3D printed assemblable monolithic catalyst, comprising the steps of:

1) designing a cage-type catalyst protection frame 2 and an integral catalyst 1 according to the structure of a reaction kettle;

in the embodiment, a three-dimensional model of an integral catalyst 1 is designed, and Fluent is used for simulation to obtain an integral catalyst 3 with an optimal structure (mass and heat transfer, conversion efficiency and the like) under theoretical conditions;

2) 3D printing a cage-type catalyst protection frame 2 by adopting a powder bed melting technology;

3) mechanically stirring and mixing a catalytic active agent, a ceramic carrier material and an auxiliary material to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment;

in the embodiment, 45g of titanium silicon powder, a ceramic carrier material which is a mixture of 10g of silicon dioxide powder and 50g of silica sol, and an auxiliary material which is a mixture of 2g of polyethylene glycol and 2g of sesbania powder are taken as a catalytic activator, and are mechanically stirred at a speed of 50r/min for 40min to obtain catalyst slurry;

4) naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst 1;

in the embodiment, an integral catalyst blank is placed in a constant temperature and humidity environment, the constant temperature is 25 ℃, the relative humidity selection range is 30%, the integral catalyst blank is dried for 24 hours, then a high-temperature sintering process is carried out on the integral catalyst blank in a high-temperature sintering furnace, the temperature is increased to 500 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 8 hours, and the integral catalyst 1 is prepared after the integral catalyst blank is cooled to the room temperature along with the furnace;

5) uniformly inserting a plurality of monolithic catalysts 1 into a cage-type catalyst protection frame 2 to assemble a monolithic catalyst structure; and (3) putting the mixture into a reaction kettle for catalytic reaction, and setting the rotating speed of magnetons to 900r/min to obtain the catalyst and the solution after the reaction.

Embodiment 3, a method for preparing a 3D printed assemblable monolithic catalyst, comprising the steps of:

1) designing a cage-type catalyst protection frame 2 and an integral catalyst 1 according to the structure of a reaction kettle;

in the embodiment, a three-dimensional model of an integral catalyst 1 is designed, and Fluent is used for simulation to obtain an integral catalyst 3 with an optimal structure (mass and heat transfer, conversion efficiency and the like) under theoretical conditions;

2) 3D printing a cage-type catalyst protection frame 2 by adopting a powder bed melting technology;

3) mechanically stirring and mixing a catalytic active agent, a ceramic carrier material and an auxiliary material to obtain catalyst 3D printing slurry, and 3D printing an integral catalyst primary blank by using direct-writing forming equipment;

in the embodiment, 30g of titanium silicon powder, 10g of silicon dioxide powder and 50g of silica sol as a ceramic carrier material, and 2g of polyethylene glycol and 2g of sesbania powder as an auxiliary material are taken as a catalytic activator, and mechanically stirred at a speed of 50r/min for 40min to obtain catalyst slurry;

4) naturally drying the integral catalyst primary blank, and then carrying out a high-temperature sintering process to obtain an integral catalyst 1;

in the embodiment, an integral catalyst blank is placed in a constant temperature and humidity environment, the constant temperature is 25 ℃, the relative humidity selection range is 30%, the integral catalyst blank is dried for 24 hours, then a high-temperature sintering process is carried out on the integral catalyst blank in a high-temperature sintering furnace, the temperature is increased to 600 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 8 hours, and the integral catalyst 1 is prepared after the integral catalyst blank is cooled to the room temperature along with the furnace;

5) uniformly inserting a plurality of monolithic catalysts 1 into a cage-type catalyst protection frame 2 to assemble a monolithic catalyst structure; and (3) putting the mixture into a reaction kettle for catalytic reaction, and setting the rotating speed of magnetons to be 1200r/min to obtain the catalyst and the solution after the reaction.

In the embodiment, the proportion of the catalytic active agent and the ceramic carrier material in the catalyst slurry and the rotating speed of the rotor 3 in the catalytic reaction are changed, the integral catalyst after the reaction is not damaged even under the condition that the rotating speed of the magnetons is increased, and the cage-type catalyst protection frame 2 has obvious effect.

The monolithic catalysts of examples 1, 2 and 3 were subjected to the crush strength and nitrogen adsorption tests, and the test results are shown in table 1, which satisfy the industrial requirements.

TABLE 1

The monolithic catalysts of example 1, example 2 and example 3 were respectively assembled on a cage-type catalyst protection frame 2, and the catalytic performance of one-step oxidation of ethylene to ethylene glycol was evaluated under the following reaction conditions: 6g of the prepared monolithic catalyst is put into a reaction kettle, 2.4MPa of ethylene is introduced, hydrogen peroxide (8%) is dropwise added at the dropping rate of 0.2moL/min for 60min at 70 ℃, the catalyst is used for oxidation reaction for 1H, then a sample is cooled to 20 ℃, clear solution is taken for chromatographic analysis, the test results are shown in Table 2, the monolithic catalyst in example 1 has good catalytic effect after being added with the cage-type catalyst protection frame 2, the hydrogen peroxide conversion rate is 96.9%, the hydrogen peroxide utilization rate is 66.3%, and ethylene glycol (H) is added₂O₂) The yield was 64.21%, and the ethylene glycol selectivity was 92%.

TABLE 2

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention, and the technical solution and the inventive concept thereof should be covered by the present invention.