CN111229231A - 3D printing monolithic alloy catalyst and preparation method and application thereof - Google Patents

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

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CN111229231A
CN111229231A CN202010167139.0A CN202010167139A CN111229231A CN 111229231 A CN111229231 A CN 111229231A CN 202010167139 A CN202010167139 A CN 202010167139A CN 111229231 A CN111229231 A CN 111229231A
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alloy catalyst
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CN111229231B (en
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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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    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract

The invention discloses a 3D printing monolithic alloy 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 alloy catalyst. The method has simple preparation process, can be customized and produced according to the complex structure, can quickly and stably prepare the integral alloy catalyst, saves materials and improves the production speed, and the structure can be formed at one time without assembly and secondary processing; the catalyst formula can be randomly adjusted according to the active metal component powder and the carrier powder, and the flexibility is high; the activation method is simple and convenient to use on site. The obtained integral alloy 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, macromolecular compound synthesis, oxidative dehydrogenation, hydrodesulfurization and the like.

Description

3D printing monolithic alloy 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 alloy 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 areas＜1m2/g), the specific surface area is generally increased by applying a catalyst coating. 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 alloy catalyst and a preparation method and application thereof, 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 alloy 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) preparing metal powder A with catalytic activity and metal powder B capable of being dissolved by alkaline solution 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: 3D printing is carried out on metal powder A serving as active component powder and metal powder B serving as carrier powder in an inert atmosphere; and dissolving the carrier of the obtained product by using an alkali solution to obtain the integral alloy catalyst.
Preferably, the particle size of metal powder A and metal powder B is < 100 μm.
Preferably, the metal powder a is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium.
Preferably, the metal powder B is aluminum, zinc or beryllium.
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 structural outline in the programming software, planning a printing path, selecting and switching the printing positions of the metal powder A and the metal powder B according to the formula of the integral alloy 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 alloy catalyst prepared by the preparation method.
The invention discloses an application of the 3D printing monolithic alloy catalyst in methanation reaction, denitration reaction and methanol synthesis reaction, wherein during the methanation reaction, metal powder A is nickel, metal powder B is aluminum, and the mass ratio of the metal powder A to the metal powder B is 1: 2; during denitration reaction, the metal powder A is vanadium, the metal powder B is aluminum, and the mass ratio of the metal powder A to the metal powder B is 1: 3; during the methanol synthesis reaction, the metal powder A is copper, the metal powder B is zinc, and the mass ratio of the metal powder A to the metal powder B 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 alloy catalyst, which comprises the steps of printing active component powder with catalytic activity and carrier powder into a three-dimensional monolithic structure at one time, and then treating with an alkali solution to dissolve and remove part of the carrier, so that the catalytic activity of metal can be activated, and the monolithic alloy catalyst is obtained. The method has simple preparation process, and can be produced nearby and processed in a portable way; the integral alloy catalyst can be produced in a customized manner according to the required complex structure, and the obtained integral alloy catalyst has high structural precision and high strength; the integral alloy catalyst can be quickly and stably prepared, materials are saved, the production speed is improved, and the structure can be formed at one time without assembly and secondary processing; the catalyst formula can be randomly adjusted according to the active metal component powder and the carrier powder, and the flexibility is high; the activation method is simple and convenient to use on site.
Furthermore, the grain diameters of the metal powder A and the metal powder B are less than 100 mu m, so that the powder is convenient to convey and process.
Furthermore, the metal powder A is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium, and has good catalytic activity.
Furthermore, the metal powder B is aluminum, zinc or beryllium, can provide enough strength for the carrier, and is easily activated by alkali solution, thereby being convenient for field operation.
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, a part of metal powder B in the printing model can be quickly dissolved, more metal powder A with catalytic activity is exposed, and the effective specific surface area is increased.
The invention also discloses the 3D printing integral alloy catalyst prepared by the preparation method, which has strong strength and activity, and the performance of the alloy, so that the integral alloy catalyst is suitable for high-temperature and high-pressure reaction.
The invention also discloses application of the 3D printing integral alloy 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 3D printed monolithic alloy catalyst made according to the present invention;
FIG. 2 is a schematic illustration of the principle of the 3D printed monolithic alloy catalyst of the present invention;
fig. 3 is a schematic structural diagram of the grid type three-dimensional model 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 alloy 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 can be selected from metal elements such as aluminum, zinc, beryllium and the like which are easily dissolved by alkali liquor. The particle size of the powder is required to be less than 100 microns so as to facilitate powder transportation.
And step 3: designing a printing formula of the catalyst, and adjusting the proportion of the active component powder A and the carrier powder B to obtain the catalysts with different formulas. The active component powder A can be a combination of one or more metal elements with catalytic activity, and the carrier powder B can be a combination of one or more metal elements which are easily dissolved by alkali liquor.
For example, the ratio of active component powder nickel to carrier powder aluminum 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 proportion of aluminum is 1: 2, the catalyst formula is particularly suitable for methanation reaction.
For example, the ratio of active component powder vanadium to carrier powder aluminum 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 proportion of aluminum is 1: 3, the catalyst formula is particularly suitable for denitration reaction.
For example, the ratio of active component powder copper to carrier powder zinc 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 proportion of zinc 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. 2, a coaxial powder feeding type laser 3D printer is used for preparing an integral alloy model, metal 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 powders 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 of the printed integral alloy model through alkali solution dissolution treatment, and recovering the catalytic activity of the active component metal to obtain the integral alloy catalyst.
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:
examples
Step 1: a corresponding three-dimensional model with a pore structure is manufactured through 3D model design software, as shown in figure 3, a grid type form is adopted, each grid is 3 mm long, 2 mm high and 1 mm thick, 6x4 grids are arranged on a section, the width is 70 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 adopts nickel metal elements with catalytic activity, and the carrier powder adopts aluminum metal elements which are easily dissolved by alkali liquor. The particle size of the powder is required to be less than 100 microns so as to facilitate powder transportation.
And step 3: selecting nickel: the proportion of aluminum 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 coaxial powder feeding type laser 3D printer is used for preparing the integral alloy model, metal powder is conveyed to a set position through the powder feeder in the preparation process and is solidified under the melting of the laser, the printing process can be switched among different powders according to the program on a printing path, and the model is always printed under the argon atmosphere.
Step 6: and (3) removing part of the carrier of the printed integral alloy 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 alloy catalyst is shown in figure 1.
As can be seen from FIG. 1, the 3D printing monolithic alloy catalyst realizes the precision machining of a complex structure, the mechanical strength of the machined monolithic module is high, and a large amount of specific surface with reaction activity is obtained after the processing of alkali solution.
Monolithic body prepared in example 1The alloy catalyst is subjected to mechanical strength, physical adsorption specific surface area and methanation reaction activity evaluation (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 BDA0002407848160000071
the data in the table show that the prepared monolithic alloy 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 alloy catalyst is characterized by comprising the following steps:
step 1: weighing the following components in a mass ratio of (1-3): (1-6) preparing metal powder A with catalytic activity and metal powder B capable of being dissolved by alkaline solution 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: 3D printing is carried out on metal powder A serving as active component powder and metal powder B serving as carrier powder in an inert atmosphere; and dissolving the carrier of the obtained product by using an alkali solution to obtain the integral alloy catalyst.
2. The method for preparing a 3D printing monolithic alloy catalyst as claimed in claim 1, wherein the particle size of the metal powder A and the metal powder B is less than 100 μm.
3. The preparation method of the 3D printing monolithic alloy catalyst according to claim 1, wherein the metal powder A is nickel, copper, cobalt, iron, titanium, vanadium, cerium or zirconium.
4. The preparation method of the 3D printing monolithic alloy catalyst as claimed in claim 1, wherein the metal powder B is aluminum, zinc or beryllium.
5. The method for preparing a 3D printing monolithic alloy catalyst according to claim 1, wherein the three-dimensional model is porous, circular, honeycomb or grid.
6. The preparation method of the 3D printing monolithic alloy 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 structural outline in the programming software, planning a printing path, selecting and switching the printing positions of the metal powder A and the metal powder B according to the formula of the integral alloy catalyst, and obtaining a numerical control program of the 3D printer.
7. The method for preparing a 3D-printed monolithic alloy catalyst as recited in claim 1, wherein in step 3, the alkali solution is a sodium hydroxide solution.
8. The preparation method of the 3D printing monolithic alloy catalyst as claimed in 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 alloy catalyst prepared by the preparation method of any one of claims 1-8.
10. The application of the 3D printing monolithic alloy catalyst in methanation reaction, denitration reaction and methanol synthesis reaction as claimed in claim 9, wherein during the methanation reaction, the metal powder A is nickel, the metal powder B is aluminum, and the mass ratio of the metal powder A to the metal powder B is 1: 2; during denitration reaction, the metal powder A is vanadium, the metal powder B is aluminum, and the mass ratio of the metal powder A to the metal powder B is 1: 3; during the methanol synthesis reaction, the metal powder A is copper, the metal powder B is zinc, and the mass ratio of the metal powder A to the metal powder B is 1: 1.
CN202010167139.0A 2020-03-11 2020-03-11 3D printing monolithic alloy catalyst and preparation method and application thereof Active CN111229231B (en)

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