KR20200128235A - 3D printing Ink Composition for Preparing Catalyst Structure and Method for Preparing Catalyst Structure Using Same - Google Patents

Abstract

The present invention relates to a 3D printing ink composition for producing a catalyst structure and a method for producing a catalyst structure using the same. More particularly, the present invention relates to a 3D printing ink composition for producing a catalyst structure, which, when producing the catalyst structure, does not cause shrinkage after firing, and can further improve the strength of the catalyst structure without deteriorating catalyst properties, and a method for producing the catalyst structure using the same.

Description

3D printing ink composition for preparing catalyst structure and method for preparing catalyst structure using same {3D printing ink composition for preparing catalyst structure and method for preparing catalyst structure using same}

The present invention relates to a 3D printing ink composition for producing a catalyst structure and a method for producing a catalyst structure using the same, and in more detail, a 3D printing ink composition for producing a catalyst structure capable of further improving the strength of the catalyst structure as well as printing properties and using the same. It relates to a method for producing a catalyst structure.

As catalyst technology development can be applied as a base technology for a number of various industries, its importance is very great, and related research is being actively conducted both at home and abroad. In particular, catalysts are substances that play a central role in chemical reactions, and various catalysts are used in processes such as pharmaceuticals, fine chemistry, polymers, and dye industries, and the importance of developing catalysts to solve energy and environmental problems is increasing day by day. There is a trend.

In recent years, research on technology development for manufacturing a catalyst structure applying 3D printing technology is underway. 3D printing is the concept of printing in 3D (3D) space, and printing materials in space going a step further from two-dimensional printing concepts such as inkjet printers or laser printers that print documents at home or office. It refers to a technology that prints out 3D objects. 3D printing technology refers to a manufacturing technology that uses an additive manufacturing method in which new layers are stacked one after another, instead of cutting or cutting materials, which are traditional processing methods.

As such, the reason that interest is focused on 3D printing technology is that, unlike the existing manufacturing process, assembly cost can be significantly reduced, and since direct production from digital data is possible, it is very effective in using customized small-scale products, and consumers can directly produce products. This is because it has the advantage that it is possible to make it.

Representatively, the 3D printing process is classified by material shape: adhesive jetting method using powder as a raw material, powder bed fusion method, direct energy deposition method, and filament or paste form. There are a material extrusion method for printing with a material, a photo polymerization method for printing in a slurry form, and a sheet lamination method for printing in a thin film form. Among these, many attempts have been made to manufacture a catalyst structure by a photopolymerization method and a material extrusion method.

The photo polymerization method is a method of producing a three-dimensional shape by selectively irradiating a photocurable material or a mixture containing a photocurable material with light in the UV or visible region, and is a catalyst in the tray where the light is irradiated. A raw material containing a ceramic and a polymer material and an organic photocuring agent forming the structure is supplied, and the printed structure is irradiated with light to form a desired structure. Here, as the photocuring agent, a hydroxy ketone-based, phenylglyoxylate-based, bisacylphosphine-based, α-amino ketone-based, or the like may be used.

This photopolymerization method is advantageous in that the shape of the structure can be precisely controlled by forming the structure using a photocuring agent. In particular, although it has the advantage of being able to manufacture PPI (pore per inch) at a high level, It is necessary to remove organic substances such as polymers and photocuring agents, which may cause unpredictable pores or cracks in the structure, resulting in lower strength, as well as distortion of the structure and shrinkage of the structure. There is a problem in that unremoved organic substances remain in the structure and may affect the catalytic reaction occurring in the catalyst structure in the future.

On the other hand, in the material extrusion method, a 3D structure is formed at a desired location by continuously pushing a material with secured flowability by using pressure through a method such as applying high temperature or energy, or without applying energy. In this way, in order to manufacture the catalyst structure, ink or paste containing a ceramic material and an inorganic binder is used, and since the catalyst structure is formed and fired, the strength of the structure is not only high, but also due to distortion and firing of the structure. No shrinkage of the structure occurs. However, the material extrusion method has a high technical barrier to accurately control the viscosity and printing conditions of the ink for 3D printing, and due to it, the structure cannot be maintained and collapsed during printing, and the structure of the structure can be precisely controlled. Can't.

Accordingly, Korean Patent No. 1551255 discloses a low viscosity ceramic slurry composition for 3D printing that lowers the viscosity of the ceramic slurry composition by adding a reactive diluent to adjust the viscosity of the ceramic slurry composition. No. 0093730 discloses an ink composition for 3D printing in which a solid content is contained in an amount of 80 to 90 parts by weight based on 100 parts by weight of a solvent so as to have a viscosity applicable to 3D printing.

However, these prior technologies also use organic binders and photocuring agents, so that they remain in the structure without being carbonized at the time of manufacture, the fragility of the structure strength due to the structural deformation mentioned above, shrinkage during curing, and carbonization during firing. Therefore, there is still a problem affecting the properties of the catalyst.

Korean Patent Registration No. 1551255 (Publication date: 2015.07.08) Korean Patent Publication No. 2018-0093730 (Publication date: 2018.08.22)

The main object of the present invention is to solve the above-described problems, and a 3D printing ink composition for manufacturing a catalyst structure capable of further improving the mechanical properties of the catalyst structure without deteriorating the catalyst properties, and using the same. It is to provide a method for producing a catalyst structure.

In order to achieve the above object, an embodiment of the present invention provides a 3D printing ink composition for producing a catalyst structure, comprising a catalyst carrier powder, an inorganic binder, an acid additive, and a solvent.

In a preferred embodiment of the present invention, the 3D printing ink composition comprises 10 parts by weight to 90 parts by weight of an inorganic binder, 0.5 parts by weight to 70 parts by weight of an acid additive, and 50 parts by weight to 100 parts by weight of a solvent based on 100 parts by weight of the catalyst carrier powder. It may be characterized by including parts by weight.

In a preferred embodiment of the present invention, the catalyst carrier powder is from alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium diboride, yttria, silicon nitride, titanium nitride, tungsten carbide and boron carbide. It may be characterized by including carbides, oxides, nitrides, sulfides or mixtures of selected metals.

In a preferred embodiment of the present invention, the catalyst carrier powder may be characterized in that zeolite.

In a preferred embodiment of the present invention, the catalyst carrier powder may have an average particle diameter of 0.1 µm to 50 µm.

In a preferred embodiment of the present invention, the inorganic binder is characterized in that at least one selected from the group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite. I can.

In a preferred embodiment of the present invention, the acid additive may be characterized in that it is at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid, and perchloric acid.

In a preferred embodiment of the present invention, the solvent may be selected from the group consisting of water, C1 to C4 alcohols and mixtures thereof.

Another embodiment of the present invention includes the steps of: (a) injecting the 3D printing ink composition into a 3D printer, and printing a structure having a predetermined shape; And (b) it provides a method of manufacturing a catalyst structure using a 3D printing ink composition comprising the step of drying and firing the printed structure.

In another preferred embodiment of the present invention, the 3D printer of step (a) may be an extrusion type 3D printer.

In another preferred embodiment of the present invention, the sintering of step (b) may be characterized in that it is performed at 400° C. to 2,000° C. for 1 hour to 24 hours.

The 3D printing ink composition for producing a catalyst structure according to the present invention does not cause shrinkage even after firing, and it is possible to improve the strength of the catalyst structure without deteriorating the catalyst properties.

In addition, the method of manufacturing a catalyst structure according to the present invention has an economic advantage in terms of time and cost because it is possible to easily manufacture a catalyst structure desired by a user using 3D printing.

1 is a graph for measuring strength of a catalyst structure according to an embodiment of the present invention.
2 is a graph for measuring strength of a catalyst structure according to another embodiment of the present invention.
3 is a graph of measuring CO conversion of a catalyst structure according to an embodiment of the present invention.
4 is a graph of measuring CO conversion of a catalyst structure according to another embodiment of the present invention.
5 is a photographed image of a catalyst structure according to an embodiment of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.

Throughout the specification of the present application, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In one aspect, the present invention relates to a 3D printing ink composition for producing a catalyst structure comprising a catalyst carrier powder, an inorganic binder, an acid additive, and a solvent.

More specifically, the 3D printing ink composition for producing a catalyst structure according to the present invention contains a catalyst carrier powder, an inorganic binder, an acid additive and a solvent in a specific amount without a photocuring agent and an organic binder, Problems can be solved, shrinkage after firing can be prevented, and desired strength can be maintained, so that various geometrical structures of the catalyst structure can be precisely controlled, and uniform mechanical properties can be realized.

The 3D printing ink composition for preparing a catalyst structure according to the present invention includes a catalyst carrier powder, an inorganic binder, an acid additive, and a solvent.

The catalyst carrier powder may be used without limitation as long as it is a material applicable as a catalyst carrier, and alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium diboride, yttria, silicon nitride, titanium nitride, tungsten carbide and It may include carbides, oxides, nitrides, sulfides of metals selected from boron carbide, or a mixture thereof, preferably zeolite, which is an aluminum silicate hydrate having good affinity with an inorganic binder described below, and more preferably Si/ Al ZSM-5 with a ratio of 10 to 200 can be used.

The catalyst carrier powder according to the present invention is a porous material and contains many pores, so it can effectively improve the reactivity by supporting the catalytically active ingredient in the pores, sufficiently support the catalytically active ingredient, and have a high reactivity with the catalytically active ingredient. No, it can be selected as a material that is not sensitive to temperature changes.

The catalyst carrier powder has an average particle diameter of 0.1 μm to 50 μm, preferably 0.5 to 30 μm, and if the average particle diameter of the catalyst carrier powder is less than 0.1 μm, the mechanical properties of the catalyst structure may be degraded, while the pore size is small. The supporting rate of the catalytically active component may be lowered, and if it exceeds 50 µm, the fluidity in the composition is small and the printing characteristics may be deteriorated, and the surface area may be reduced, resulting in a decrease in the reactivity of the catalytically active component.

On the other hand, the inorganic binder bonds the catalyst carrier powder to each other to impart cohesion and viscosity, while imparting fluidity and flow properties to the composition to facilitate extrusion.

The inorganic binder may be at least one selected from the group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite, preferably having properties suitable for acidity. You can use boehmite.

In particular, boehmite used as the inorganic binder is a monovalent γ-AlO(OH) having one hydroxyl group (-OH), and has various Al ₂ O ₃ forms depending on the heat treatment conditions and methods. This boehmite is high strength, high acidity, high crystallization, high growth Al ₂ O ₃ compared to Al ₂ O ₃ and has excellent thermal/structural properties as a starting material for gamma/delta/theta/alpha Al ₂ O ₃ . The mechanical properties of the catalyst structure can be improved without a binder and a photocuring agent.

The inorganic binder according to the present invention contains 10 parts by weight to 90 parts by weight, preferably 10 parts by weight to 80 parts by weight, more preferably 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the catalyst carrier powder, If the inorganic binder is mixed with less than 10 parts by weight with respect to 100 parts by weight of the catalyst carrier powder, the bonding strength of the catalyst carrier powder may be lowered to weaken the strength of the catalyst structure, and if it exceeds 90 parts by weight, the porosity in the catalyst structure may be reduced. Can be reduced.

On the other hand, the acid additive serves to gelatinize the 3D printing ink composition, and if it is less than 0.5 parts by weight based on 100 parts by weight of the catalyst carrier powder, the composition may not be properly gelled, resulting in poor mechanical properties of the catalyst structure. In addition, when it exceeds 70 parts by weight, the viscosity of the composition is high, so that printing characteristics are deteriorated, and the catalytic activity of the prepared catalyst structure may be deteriorated. Accordingly, the acid additive is preferably 0.5 parts by weight to 70 parts by weight, preferably 3 parts by weight to 20 parts by weight, based on 100 parts by weight of the catalyst carrier powder.

At this time, the acid additive may be at least one or more selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid and perchloric acid, and preferably nitric acid.

In addition, the solvent is to uniformly mix the components contained in the 3D printing ink composition and control the viscosity to increase the strength, and may be selected from the group consisting of water, C1 to C4 alcohols, and mixtures thereof. From the side, it may be preferably water.

The solvent includes 50 parts by weight to 100 parts by weight based on 100 parts by weight of the catalyst carrier powder. If the solvent is mixed with less than 50 parts by weight based on 100 parts by weight of the catalyst carrier powder, the viscosity of the 3D printing ink composition increases, making it difficult to quantitatively discharge from the tip when extruding, and if it exceeds 100 parts by weight, 3D printing ink The viscosity of the composition may be too low to cause a problem in that molding is not properly performed.

The 3D printing ink composition according to the present invention may have a viscosity (room temperature) of 100 cps to 5,000 cps, preferably 100 cps to 1,000 cps or less. If the viscosity of the 3D printing ink composition is less than 100 cps, it is difficult to maintain its shape after printing, making it difficult to manufacture a high-precision, high-quality catalyst structure. If it exceeds 5000 cps, it is difficult to precisely control the structure, and shrinkage and cracking during firing. Can occur.

In another aspect, the present invention includes the steps of: (a) injecting the 3D printing ink composition into a 3D printer and printing a structure having a predetermined shape; And (b) it relates to a method for producing a catalyst structure using a 3D printing ink composition comprising the step of firing the printed structure.

In the method of manufacturing a catalyst structure according to the present invention, a 3D printing ink composition is added to a 3D printer, a structure having a predetermined shape is printed, and then the printed structure is dried and fired to prepare a catalyst structure.

The 3D printer is a 3D printer of a material extruding method, which continuously extrudes a 3D printing ink composition through a tip and moves the position of the tip to print a 3D catalyst structure in a desired shape. The 3D printer of the material extruding method controls the 3D shape by stacking the ink composition extruded through the tip of the 3D printer, so the precision of the catalyst structure is determined by the thickness of the layer extruded through the tip. , As the pore structure of the structure is controlled by the interval between the layers, it is easy to manufacture a catalyst structure of various shapes, and the surface area and pore volume of the catalyst structure can be easily controlled.

At this time, the tip size of the 3D printer of the material extrusion method may have a diameter of 100 µm to 1,000 µm, and a discharge pressure may be 0.1 to 10 bar.

Thus, the structure of a predetermined shape printed by the 3D printer is dried to evaporate the solvent, and sintering is performed to increase the inherent strength and hardness of the catalyst carrier powder.

The sintering temperature can be variously changed in consideration of the inherent glass transition temperature according to the type of catalyst carrier powder, but it is preferable to improve the strength and hardness of the catalyst structure while maintaining the extruded shape without cracking the structure in the firing step. It can be calcined for 1 hour to 24 hours at 400 ℃ ~ 2,000 ℃ in an oxygen-containing atmosphere. At this time, since the rapid temperature change cannot maintain the shape of the extruded structure due to rapid evaporation and oxidation of the solvent, cracks and voids are generated and the strength is significantly reduced. Therefore, it is recommended to gradually increase the temperature to a temperature of 10 ℃ or less per minute. desirable.

On the other hand, the catalyst structure according to the present invention may be prepared by mixing the catalytically active ingredient with a 3D printing ink composition, or may be used by containing the catalytically active ingredient by a known method such as an impregnation method or a dip coating method. .

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.

< Example With 1 to 12 Comparative example 1>

Boehmite, an inorganic binder, was mixed with ZSM-5 (Si/Al=15, average particle size of 10 μm) in the contents shown in Table 1, respectively, and nitric acid was added to 30 g of distilled water in the contents of Table 1 The resulting mixture and a mixture containing 56.57 g of cobalt nitrate (CO(NO ₃ ) ₂ ˙6H ₂ O), which is a catalytic active material of the FT synthesis reaction, were added to 30 g of distilled water, and then uniformly stirred at room temperature for 20 minutes. Thus, an ink composition for 3D printing was prepared. The prepared ink composition for 3D printing was put into a 3D printer (MEB-1 model of Illuminated Corporation) of a material extrusion method, and printed to obtain a structure.

At this time, the tip diameter size of the 3D printer was 400 μm, and the discharge pressure was set to 5 bar. The obtained structure was dried at room temperature for 10 hours and then calcined in an oven at 550° C. in an air atmosphere at 1° C./min. for 5 hours to prepare a catalyst structure.

division Catalyst carrier powder
Content(g) Inorganic binder
Content (g) Acid additive content
(g) Solvent content
(g) Example 1 10 1.11 3.09 6.0 Example 2 10 2.00 3.09 6.0 Example 3 10 5.00 3.09 6.0 Example 4 10 8.00 3.09 6.0 Example 5 10 9.00 3.09 6.0 Example 6 10 1.11 0.1 6.0 Example 7 10 1.11 0.3 6.0 Example 8 10 1.11 0.5 6.0 Example 9 10 1.11 1.0 6.0 Example 10 10 1.11 2.0 6.0 Example 11 10 1.11 3.0 6.0 Example 12 10 1.11 6.0 6.0 Comparative Example 1 10 1.11 - 6.0

< Experimental example 1: Measurement of the strength of the catalyst structure>

In accordance with the UTM 4482 standard, the compressive strength of the catalyst structures prepared in Examples 1 to 4 was pressed at a constant speed of 1 mm/min using a Universal Testing Machine, and the impact strength was measured, and the result Is shown in Figure 1.

As shown in FIG. 1, it was found that as the content of the inorganic binder relative to the content of the catalyst carrier powder increased, the compressive strength also increased.

In addition, the compressive strength of the catalyst structures prepared in Examples 6 to 12 was measured in the same manner as described above, and the impact strength was measured, and the results are shown in FIG. 2.

As shown in FIG. 2, as the content of the acid additive relative to the content of the catalyst carrier powder increases, the strength of the catalyst structure increases, and the increase rate of the strength relative to the content of the acid additive is found to be insignificant. In particular, in the case of Comparative Example 1, it was confirmed that cracks occurred visually in the catalyst structure after firing and the strength was decreased.

< Experimental example 2: Evaluation of catalytic activity of the catalyst structure>

In order to measure the activity of the FT synthesis reaction of the catalyst structures prepared in Examples 1 to 5, the FT synthesis reaction was performed. Before the FT synthesis reaction, 5% H ₂ /Ar gas was flowed to the catalyst structures prepared in Examples 1 to 5 at 100 cc/min, and activated at 400° C. for 5 hours. 0.5 g of the catalyst structures of Examples 1 to 5 activated as described above were charged into a fixed bed reactor, and alumina balls, which are diluents, were charged at the top and bottom of each reactor in order to control catalyst heat generation in the reactor. The reaction conditions of the reactor were carried out at T = 250 °C, P = 20 bar, SV = 4,000 ml/g.cat/h for 72 hours, and the reaction was carried out using H ₂ /CO = 2.0 volume fraction of syngas. Became. The reaction measurement was shown in FIG. 3 by measuring the CO conversion rate through On-line GC (TCD, FID).

Meanwhile, in order to measure the activity of the FT synthesis reaction of the catalyst structures prepared in Examples 7, 8 and 10 to 12, the FT synthesis reaction was performed by the above-described method, and the results are shown in FIG. 4.

3 and 4, it was found that the CO conversion rate was different depending on the inorganic binder and the acid additive, and as in Examples 1 to 3, the inorganic binder was 10 parts by weight to 50 parts by weight based on 100 parts by weight of the catalyst carrier powder. It was found to be preferable in terms of CO conversion, and it was found that it was preferable in terms of CO conversion that the acid additive contained 3 parts by weight to 20 parts by weight based on 100 parts by weight of the catalyst carrier powder, as in Examples 7 to 10. .

< Example 13>

A 3D printing ink composition was prepared after mixing with 0.39 g of nitric acid and 7.3 g of distilled water using 1.11 g of commercial boehmite as a binder in 10 g of commercial zeolite ZSM-5 (Si/Al=15). The resulting ink composition was printed by material extrusion through a 3D printer of the same manufacturer used above, dried at room temperature, and fired in an oven at 550° C. at 2° C./min. for 5 hours to obtain a catalyst structure. The obtained catalyst structure was prepared by applying an impregnation method to cobalt nitrate (CO(NO ₃ ) ₂ ˙6H ₂ O) to prepare a catalyst structure carrying cobalt as a catalytic active material, dried at room temperature, and then at 550°C. The catalyst structure was prepared by firing in an oven at 2° C./min. for 5 hours. The thus prepared catalyst structure was photographed to compare with the catalyst structure of Example 1 and shown in FIG. 5.

As shown in FIG. 5, the 3D printing ink composition according to the present invention contains a catalytic active material during the manufacturing process of the catalyst structure as in Example 1 to prepare a catalyst structure, or after preparing a catalyst structure as in Example 13. , It was confirmed that the catalytically active material can be contained in the prepared catalyst structure.

As the specific parts of the present invention have been described in detail above, it will be apparent to those of ordinary skill in the art that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (11)

3D printing ink composition for producing a catalyst structure, comprising a catalyst carrier powder, an inorganic binder, an acid additive, and a solvent.
The method of claim 1,
The 3D printing ink composition comprises 10 parts by weight to 90 parts by weight of an inorganic binder, 0.5 parts by weight to 70 parts by weight of an acid additive, and 50 parts by weight to 100 parts by weight of a solvent based on 100 parts by weight of the catalyst carrier powder. 3D printing ink composition for manufacturing structures.
The method of claim 1,
The catalyst carrier powder is a carbide, oxide, nitride of a metal selected from alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium diboride, yttria, silicon nitride, titanium nitride, tungsten carbide and boron carbide, 3D printing ink composition for producing a catalyst structure comprising a sulfide or a mixture thereof.
The method of claim 3,
The catalyst carrier powder is a 3D printing ink composition for producing a catalyst structure, characterized in that the zeolite.
The method of claim 1,
The catalyst carrier powder is a 3D printing ink composition for producing a catalyst structure, characterized in that the average particle diameter of 0.1 ㎛ to 50 ㎛.
The method of claim 1,
The inorganic binder is at least one selected from the group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite. 3D printing ink composition for producing a catalyst structure, characterized in that.
The method of claim 1,
The acid additive is at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid and perchloric acid. 3D printing ink composition for manufacturing a catalyst structure, characterized in that.
The method of claim 1,
The solvent is a 3D printing ink composition for producing a catalyst structure, characterized in that selected from the group consisting of water, C1 to C4 alcohol and a mixture thereof.
(a) Injecting the 3D printing ink composition of any one of claims 1 to 8 into a 3D printer, and printing a structure having a predetermined shape; And
(b) A method for producing a catalyst structure using a 3D printing ink composition comprising drying and firing the printed structure.
The method of claim 9,
The method of manufacturing a catalyst structure, characterized in that the 3D printer of step (a) is an extrusion 3D printer.
The method of claim 9,
The method for producing a catalyst structure, characterized in that the sintering of step (b) is performed at 400° C. to 2000° C. for 1 hour to 24 hours.

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