CN111250093A - 3D printing monolithic composite structure catalyst and preparation method and application thereof - Google Patents

3D printing monolithic composite structure catalyst and preparation method and application thereof Download PDF

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CN111250093A
CN111250093A CN202010167140.3A CN202010167140A CN111250093A CN 111250093 A CN111250093 A CN 111250093A CN 202010167140 A CN202010167140 A CN 202010167140A CN 111250093 A CN111250093 A CN 111250093A
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王晓龙
郜时旺
许世森
刘练波
王绍民
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Huaneng Clean Energy Research Institute
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    • C07C2523/74—Iron group metals
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Abstract

The invention discloses a 3D printing monolithic composite structure catalyst and a preparation method and application thereof, and belongs to the technical field of 3D printing and catalyst intersection. Printing active component powder with catalytic activity and carrier powder into a three-dimensional integral structure at one time, dissolving with an alkali solution to remove part of the carrier, and activating the catalytic activity of the metal to obtain the integral composite structure catalyst. The method has simple preparation process, can be customized and produced according to the complex structure, can quickly and stably prepare the integral composite structure catalyst, saves materials and improves the production speed, and has one-step structure molding without assembly and secondary processing; the catalyst formula can be adjusted randomly according to the active metal component powder, and the flexibility is high; the activation method is simple and convenient to use on site. The obtained integral composite structure catalyst has high structural precision, high strength and long service life, and can be widely applied to the fields of tail gas denitration, synthesis gas methanation, high molecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and the like.

Description

3D printing monolithic composite structure catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of 3D printing and catalyst intersection, and particularly relates to a 3D printing monolithic composite structure catalyst and a preparation method and application thereof.
Background
The monolithic catalyst is mainly suitable for high-flux rapid reaction occasions, such as tail gas denitration, synthesis gas methanation, macromolecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and other processes. Taking synthesis gas methanation as an example, the methanation reactor is a fixed bed reactor which is widely used at present, and the fixed bed reactor has the advantages of simple design and operation and small catalyst abrasion. However, in practical production processes, conventional particulate catalysts suffer from some significant disadvantages: low porosity, large pressure drop of the catalyst bed layer, large temperature gradient of each point of the catalyst bed layer, serious carbon deposition of the catalyst and the like. In order to overcome the disadvantages of the conventional granular catalysts and to optimize the reaction performance of heterogeneous catalysts, researchers have designed monolithic catalysts. At present, the most used monolithic carriers are honeycomb ceramics, and the specific surface areas of the honeycomb ceramics are all small (the specific surface area is less than 1 m)2Per g), usually by application of a catalystA layer to increase its specific surface area. CN104998645A discloses a preparation method of methanation catalyst using cordierite honeycomb ceramic as carrier, which comprises immersing active component precursor on the surface of cordierite honeycomb ceramic, and processing by microwave calcination method to obtain the required catalyst, but limited by the manufacturing process and technology, the through holes of ceramic carrier are straight-hole channels, further limiting the effective reaction area and reaction time.
3D printing technology is gaining increasing attention worldwide as an emerging manufacturing technology. By adopting the 3D printing technology, the catalyst molding with different structures, particularly the catalyst molding with a complex structure can be easily realized through fewer steps. In addition, the 3D printing technology is adopted, so that the utilization rate of raw materials can be obviously improved. At present, some reports of directly preparing monolithic catalysts by using 3D printing equipment exist, and the methods are divided into two methods. In the first method, as reported in patent CN201810319113, a printing paste containing an active component, a rheological agent and a thickening agent is prepared, then a gel is used for 3D printing to obtain a blank, and then the blank is cured, dried, calcined and molded to obtain the catalyst. Second, as reported in patents CN201910718129.9 and CN201710689261.2, a three-dimensional model is made by using a photo-curing 3D printing apparatus with photo-curing resin as a carrier, and then the model is dried and calcined to obtain a structured carbon carrier, and finally the catalyst is obtained by loading and impregnating the catalyst active component on the surface of the carbon carrier, and drying and calcining the catalyst. The catalyst carrier prepared by the two methods has low strength, is not beneficial to high-pressure reaction, and is easy to fall off.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention discloses a 3D printing monolithic composite structure catalyst, and a preparation method and application thereof, wherein the preparation process is simple, the structure precision is high, and the catalyst is strong in strength and activity, and can be widely applied to the fields of tail gas denitration, synthesis gas methanation, high molecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and the like.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of a 3D printing monolithic composite structure catalyst, which comprises the following steps:
the method comprises the following steps:
step 1: weighing the following components in a mass ratio of (1-3): (1-6) the metal powder with catalytic activity and the silicon powder are used;
step 2: designing a three-dimensional model with a pore structure, and setting a numerical control program of the 3D printer according to the three-dimensional model;
and step 3: performing 3D printing in an inert atmosphere by using metal powder as active component powder and silicon powder as carrier powder; and dissolving the carrier of the obtained product by using an alkali solution to obtain the integral composite structure catalyst.
Preferably, the particle size of the metal powder and the silicon powder is less than 100 μm.
Preferably, the metal powder is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium.
Preferably, the three-dimensional volumetric model is porous, toroidal, cellular or mesh.
Preferably, step 2 is specifically: manufacturing a corresponding three-dimensional model with a pore structure through 3D model design software, converting the format of the 3D model into a binary format, programming the information of the binary format, determining a structure outline in the programming software, planning a printing path, selecting and switching the printing positions of the metal powder and the silicon powder according to the formula of the integral composite structure catalyst, and obtaining a numerical control program of the 3D printer.
Preferably, in step 3, the alkali solution is a sodium hydroxide solution.
Preferably, the concentration of the sodium hydroxide solution is 1-8 mol/L, and the time of the dissolving treatment is 0.5-24 hours.
The invention discloses a 3D printing integral composite structure catalyst prepared by the preparation method.
The invention discloses an application of the 3D printing monolithic composite structure catalyst in methanation reaction, denitration reaction and methanol synthesis reaction, wherein during the methanation reaction, metal powder is nickel, and the mass ratio of the metal powder to silicon powder is 1: 2; during denitration reaction, the metal powder is vanadium, and the mass ratio of the metal powder to the silicon powder is 1: 3; during the methanol synthesis reaction, the metal powder is copper, and the mass ratio of the metal powder to the silicon powder is 1: 1.
compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a 3D printing monolithic composite structure catalyst, which comprises the steps of printing active component powder with catalytic activity and carrier powder silicon powder into a three-dimensional monolithic structure at one time, and activating the catalytic activity of metal by dissolving and removing part of carriers through alkali solution treatment to obtain the monolithic composite structure catalyst. The method has simple preparation process, and can be produced nearby and processed in a portable way; the catalyst can be produced according to the required complex structure in a customized manner, and the obtained integral composite structure catalyst has high structural precision and high strength; the catalyst with the integral composite structure can be quickly and stably prepared, materials are saved, the production speed is improved, and the structure can be formed in one step without assembly and secondary processing; the catalyst formula can be adjusted randomly according to the active metal component powder, and the flexibility is high; the carrier powder has the advantages of three aspects, firstly, the melting point of silicon is closer to that of active metals such as nickel and the like, so that laser cladding forming is facilitated during 3D printing, the printed product has higher precision, and various complex structures can be manufactured; secondly, the silicon as a carrier has high solubility in an alkaline solution, so that more specific surfaces can be easily manufactured, and the reaction activity of the catalyst is improved; thirdly, the silicon powder is cheap and easy to obtain, and the cost of the raw materials can be saved. The activation method is simple and convenient to use on site.
Furthermore, the grain diameter of the metal powder and the silicon powder is less than 100 μm, which is convenient for the transportation and processing of the powder.
Furthermore, the metal powder is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium, and has good catalytic activity.
Furthermore, the three-dimensional model is porous, circular, honeycomb or grid type, and has flexible structure and wide application range.
Furthermore, the alkali solution adopts a sodium hydroxide solution, so that the cost is low, part of silicon powder in the printing model can be quickly dissolved, more metal powder with catalytic activity is exposed, and the effective specific surface area is increased.
The invention also discloses the 3D printing monolithic composite structure catalyst prepared by the preparation method, the catalyst has strong strength and activity, the performance of alloy and silicon element is high, the monolithic composite structure catalyst is suitable for high-temperature and high-pressure reaction, the specific surface of silicon powder as carrier powder after alkaline dissolution is more, and the reaction activity of the catalyst is obviously improved.
The invention also discloses application of the 3D printing monolithic composite structure catalyst in methanation reaction, denitration reaction and methanol synthesis reaction, can effectively solve the problems that the existing catalyst is insufficient in mechanical strength, easy to pulverize and break to block a reaction channel after long-term use, and easy to lose reaction activity due to falling of surface components, and has the advantages of high strength and long service life.
Drawings
FIG. 1 is a product diagram of a lattice composite structure catalyst prepared by the present invention;
FIG. 2 is a product diagram of a round honeycomb composite structure catalyst prepared by the present invention;
fig. 3 is a schematic diagram of the 3D printed monolithic composite structure catalyst of the present invention.
Detailed Description
The invention will now be described in further detail with reference to the following figures and examples, which are given by way of illustration and not of limitation.
The preparation method of the 3D printing monolithic composite structure catalyst comprises the following steps:
step 1: the corresponding three-dimensional model with the pore structure is manufactured through 3D model design software, and can adopt various forms such as a porous form, a ring form, a honeycomb form and a grid form, and the format of the 3D model is converted into a binary format.
Step 2: preparing powder for metal 3D printing, wherein the powder is divided into active component powder and carrier powder, the active component powder can be selected from metal elements with catalytic activity such as nickel, copper, cobalt, iron, titanium, vanadium, cerium, zirconium and the like, and the carrier powder is silicon powder, and the particle size of the powder is required to be less than 100 micrometers so as to be convenient for powder conveying.
And step 3: designing a printing formula of the catalyst, and adjusting the proportion of the active component metal powder and the carrier powder to obtain the catalysts with different formulas. The active component metal powder A can be one or a combination of several metal elements with catalytic activity, and the carrier powder is silicon powder.
If the ratio of active component powder nickel to carrier silicon powder is M: n, the value range of M is 1-3, the value range of N is 1-6, and particularly, nickel is preferred: the ratio of silicon is 1: 2, the catalyst formula is particularly suitable for methanation reaction.
If the ratio of active component powder vanadium to carrier silicon powder is M: n, the value range of M is 1-3, the value range of N is 1-6, and vanadium is particularly preferred: the ratio of silicon is 1: 3, the catalyst formula is particularly suitable for denitration reaction.
If the ratio of the active component powder copper to the carrier silicon powder is M: n, the value range of M is 1-3, the value range of N is 1-6, and copper is particularly preferred: the ratio of silicon is 1: 1, the catalyst formula is particularly suitable for methanol synthesis reaction.
And 4, step 4: and (3) programming the binary information, determining a structural outline in programming software, planning a printing path, selecting and switching printing positions of active component powder and carrier powder according to the catalyst formula determined in the step (3), and finally generating a numerical control program.
And 5: referring to fig. 3, a coaxial powder feeding type laser 3D printer is used for preparing an integral composite structure model, raw material powder is fed to a set position through a powder feeder in the preparation process and is solidified under the melting of a laser, different powder bodies can be selected and switched on a printing path according to a program in the printing process, and the model is always printed under an inert atmosphere (such as argon).
Step 6: and (3) removing part of the carrier from the printed integral composite structure model through alkali solution dissolution treatment, so that the catalytic activity of the active component metal can be recovered, and the integral composite structure catalyst is obtained.
The alkali solution is preferably sodium hydroxide, the concentration is 1-8 mol/L, and the dissolving time is 0.5-24 hours.
The following is a specific example:
example 1
Step 1: the method comprises the steps of manufacturing a corresponding three-dimensional model with a pore structure through 3D model design software, adopting a dot matrix form, enabling the diameter of each point to be 0.5 mm, enabling the distance between each point and each point to be 2 mm, enabling the diameter of a connecting line between each point and each point to be 0.5 mm, enabling the three-dimensional structure to be an 8 x 8 matrix, and converting the format of the 3D model into a binary format.
Step 2: preparing powder for metal 3D printing, wherein the powder is divided into active component powder and carrier powder, the active component powder is nickel metal element powder with catalytic activity, and the carrier powder is silicon powder which is easily dissolved by alkali liquor. The particle size of the powder is required to be less than 100 microns so as to facilitate the powder transportation.
And step 3: selecting nickel: the ratio of silicon is 1: 2, the catalyst formula is particularly suitable for methanation reaction.
And 4, step 4: and (3) programming the binary information, determining a structural outline in programming software, planning a printing path, selecting and switching printing positions of active component powder and carrier powder according to the catalyst formula determined in the step (3), and finally generating a numerical control program.
And 5: the preparation that uses coaxial powder formula laser 3D printer that send to carry out integral composite structure model, raw materials powder sends the establishment position through the powder feeder and solidifies under the laser instrument melting in the preparation process, and the printing in-process can select for use to switch between different powders on printing the route according to the procedure, and the model is printed under argon atmosphere all the time.
Step 6: and (3) removing part of the carrier from the printed integral composite structure model by using an alkali solution to recover the catalytic activity of the active component metal, wherein the alkali solution is a sodium hydroxide solution with the concentration of 2mol/L, the dissolving time is 2 hours, and the obtained integral composite structure catalyst is shown in figure 1.
Example 2
Step 1: a corresponding three-dimensional model with a pore channel structure is manufactured through 3D model design software, a circular honeycomb type form is adopted, the diameter of an outer circular ring is 10 mm, the diameter of an inner circular ring is 1.5 mm, pore channels with the diameter of 1 mm are arranged in the inner circular ring and the outer circular ring, the thickness of the pore channels is 8 mm, and the format of the 3D model is converted into a binary format.
Step 2: preparing powder for metal 3D printing, wherein the powder is divided into active component powder and carrier powder, the active component powder is nickel metal element powder with catalytic activity, and the carrier powder is silicon powder which is easily dissolved by alkali liquor. The particle size of the powder is required to be less than 100 microns so as to facilitate the powder transportation.
And step 3: selecting nickel: the ratio of silicon is 1: 2, the catalyst formula is particularly suitable for methanation reaction.
And 4, step 4: and (3) programming the binary information, determining a structural outline in programming software, planning a printing path, selecting and switching printing positions of active component powder and carrier powder according to the catalyst formula determined in the step (3), and finally generating a numerical control program.
And 5: the preparation that uses coaxial powder formula laser 3D printer that send to carry out integral composite structure model, raw materials powder sends the establishment position through the powder feeder and solidifies under the laser instrument melting in the preparation process, and the printing in-process can select for use to switch between different powders on printing the route according to the procedure, and the model is printed under argon atmosphere all the time.
Step 6: and (3) removing part of the carrier from the printed integral composite structure model by using an alkali solution to recover the catalytic activity of the active component metal, wherein the alkali solution is a sodium hydroxide solution with the concentration of 2mol/L, the dissolving time is 2 hours, and the obtained integral composite structure catalyst is shown in figure 2.
As can be seen from fig. 1 and 2, the 3D printed monolithic composite structure catalyst realizes precision machining of a complex structure, the mechanical strength of the machined monolithic module is high, and a large amount of specific surface with reactivity is obtained after alkali solution treatment.
The monolithic composite structure catalyst prepared in example 1 was subjected to evaluations of mechanical strength, physical adsorption specific surface area, and methanation reaction activity, respectively (CO: H)2The molar ratio is 3: 1, the temperature is 300 ℃, the pressure is 3Mpa, and the space velocity is 8000h-1) The results are given in the following table:
Figure BDA0002407857140000071
Figure BDA0002407857140000081
the data in the table show that the prepared monolithic composite structure catalyst has excellent mechanical strength and can be applied to the working conditions of high temperature and high pressure; the physical adsorption specific surface area and methanation catalytic activity are good, and the catalyst can be widely applied to the fields of tail gas denitration, synthesis gas methanation, macromolecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and the like.
While the invention has been described in detail by way of the general description and the specific examples set forth above, it will be apparent to those skilled in the art that certain changes and modifications may be made thereto without departing from the scope of the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A preparation method of a 3D printing monolithic composite structure catalyst is characterized by comprising the following steps:
step 1: weighing the following components in a mass ratio of (1-6): the silicon powder and the metal powder with catalytic activity in the step (1-3) are used for later use;
step 2: designing a three-dimensional model with a pore structure, and setting a numerical control program of the 3D printer according to the three-dimensional model;
and step 3: performing 3D printing in an inert atmosphere by using metal powder as active component powder and silicon powder as carrier powder; and dissolving the carrier of the obtained product by using an alkali solution to obtain the integral composite structure catalyst.
2. The method of preparing a 3D printed monolithic composite structured catalyst as claimed in claim 1, wherein the metal powder particle size is < 100 μm.
3. The method of preparing a 3D printed monolithic composite structure catalyst according to claim 1, wherein the particle size of the silicon powder is < 100 μ ι η.
4. The method for preparing a 3D printing monolithic composite structure catalyst according to claim 1, wherein the metal powder is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium.
5. The method of preparing a 3D printed monolithic composite structure catalyst according to claim 1, wherein the three-dimensional solid model is porous, circular, honeycomb or mesh.
6. The preparation method of the 3D printing monolithic composite structure catalyst according to claim 1, wherein the step 2 specifically comprises: manufacturing a corresponding three-dimensional model with a pore structure through 3D model design software, converting the format of the 3D model into a binary format, programming the information of the binary format, determining a structure outline in the programming software, planning a printing path, selecting and switching the printing positions of the metal powder and the silicon powder according to the formula of the integral composite structure catalyst, and obtaining a numerical control program of the 3D printer.
7. The method for preparing a 3D printed monolithic composite structured catalyst according to claim 1, wherein in step 3, the alkali solution is a sodium hydroxide solution.
8. The preparation method of the 3D printing monolithic composite structure catalyst according to claim 7, wherein the concentration of the sodium hydroxide solution is 1-8 mol/L, and the time of the dissolving treatment is 0.5-24 hours.
9. The 3D printing monolithic composite structure catalyst prepared by the preparation method of any one of claims 1-8.
10. The application of the 3D printing monolithic composite structure catalyst in methanation reaction, denitration reaction and methanol synthesis reaction, which is characterized in that during the methanation reaction, the metal powder is nickel, and the mass ratio of the metal powder to the silicon powder is 1: 2; during denitration reaction, the metal powder is vanadium, and the mass ratio of the metal powder to the silicon powder is 1: 3; during the methanol synthesis reaction, the metal powder is copper, and the mass ratio of the metal powder to the silicon powder is 1: 1.
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CN112058317A (en) * 2020-09-24 2020-12-11 西安交通大学 Method for 3D printing of monolithic catalyst
CN112536027A (en) * 2020-11-23 2021-03-23 河钢承德钒钛新材料有限公司 Spherical denitration catalyst with lattice structure prepared by 3D printing and preparation method thereof
WO2023035712A1 (en) * 2021-09-09 2023-03-16 中国华能集团清洁能源技术研究院有限公司 Fuel cell hydrogen purification pipeline, method, and system
CN116459843A (en) * 2023-04-27 2023-07-21 江苏大学 3D prints NiMo/Al 2 O 3 MMT composite integral hydrogenation catalyst and preparation method and application thereof

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