KR20180099257A - Precursor of catalyst for hydrogenation reaction of co2, method for manufacturing the same, catalyst for hydrogenation reaction of co2, and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a precursor of a catalyst for the hydrogenation reaction of carbon dioxide, a production method of the precursor, a catalyst for the hydrogenation reaction of carbon dioxide, and a production method of the catalyst. One embodiment of the present invention provides a precursor of a catalyst for the hydrogenation reaction of carbon dioxide which contains CuFeO_2. According to one embodiment of the present invention, a catalyst for the hydrogenation reaction of carbon dioxide can be easily produced at a low temperature by using a delafossite precursor.

Description

TECHNICAL FIELD The present invention relates to a precursor of a catalyst for the hydrogenation of carbon dioxide, a method for producing the same, a catalyst for hydrogenation of carbon dioxide, and a method for producing the same. BACKGROUND ART SAME}

The present invention relates to a precursor of a catalyst for hydrogenation of carbon dioxide, a method for producing the precursor, a catalyst for hydrogenation of carbon dioxide, and a method for producing the same.

Recently, research has been actively conducted to convert carbon dioxide gas, one of the main causes of climate change, into chemical fuels or high value-added materials. Accordingly, the catalyst for the carbon dioxide hydrogenation reaction has been actively invested.

However, in the carbon dioxide hydrogenation reaction, a substance produced by a catalyst is limited to a hydrocarbon gas having a small molecular weight. More specifically, it is difficult to produce a hydrocarbon gas having a high molecular weight such as a liquid fuel suitable for transportation or an olefin having a higher value.

Accordingly, in one embodiment of the present invention, a catalyst capable of producing liquid hydrocarbons and olefins, such as olefins, from a carbon dioxide hydrogenation reaction, a precursor of a catalyst, and a method for producing the same will be described below.

One embodiment of the present invention provides a precursor of a catalyst for hydrogenation of carbon dioxide, a method for producing the precursor, a catalyst for hydrogenation of carbon dioxide, and a method for producing the same.

The precursor of the catalyst for hydrogenation of carbon dioxide, which is an embodiment of the present invention, may include CuFeO ₂ having a particle diameter of 800 nm or less.

The precursor may comprise a three-ring system.

In another aspect of the present invention, there is provided a process for preparing a precursor of a catalyst for hydrogenation of carbon dioxide, comprising the steps of: preparing an iron raw material and a copper raw material; Adding the iron and copper raw materials to a solvent to prepare a solution; Introducing a reducing agent into the solution; And hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor.

In this case, the iron raw material may be a FeCl _2.

The solution may be hydrothermally synthesized at a temperature ranging from 150 to 200 ° C by hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor.

The solution may be hydrothermally synthesized for 30 minutes to 5 hours.

Preparing a ferrous raw material and a copper source material; in the copper raw material can be a Cu (NO _{3) 2,} CuCl, or a combination thereof.

In the step of preparing the solution by adding the raw material to the solvent, the raw material may be added in an amount of 5 to 10 parts by weight based on 100 parts by weight of the solvent.

More specifically, sodium hydroxide (NaOH) may be further added.

More specifically, for 100 parts by weight of the solution, the sodium hydroxide may be added in an amount of 6 to 11 parts by weight.

Introducing a reducing agent into the solution; , The reducing agent may include propionaldehyde, ethylene glycol, or a combination thereof.

More specifically, with respect to 100 parts by weight of the solution, the reducing agent may be added in an amount of more than 0 and 3 parts by weight or less.

The catalyst for hydrogenation of carbon dioxide, which is another embodiment of the present invention, includes Cu and Fe, and may include a triangular system. The specific surface area of the catalyst may be 10 m ² / g or more.

The particle diameter of the catalyst may be 800 nm or less. More specifically, it may be 500 to 800 nm.

The porosity of the catalyst may be from 0.12 to 0.17 cm ³ / g.

The weight ratio of Cu to Fe (Cu / Fe) of the catalyst may be 0.594 or more.

The distance of the Fe metal (110) lattice plane of the catalyst may be 0.2 nm or more.

Spherical Cu particles may be located on the surface of the catalyst.

The amount of change (FTY) of carbon dioxide per unit time, iron oxide per unit time of the catalyst may be 1.7 x ₁₀ ^-6 molco ₂ g _fe ^-1 s ^{-1 or} more.

The olefin to paraffin ratio (O / P) value of the catalyst may be 9.0 or more.

The catalyst is used for the hydrogenation reaction of carbon dioxide, the product by the reaction includes hydrocarbon, and the hydrocarbon having C 5 or more carbon atoms relative to 100 wt% of hydrocarbons in the product may be 59 wt% or more.

With respect to 100 wt% of the hydrocarbons in the product, the hydrocarbon having carbon number C may be 6 wt% or less.

In another aspect of the present invention, there is provided a method of preparing a catalyst for hydrogenation of carbon dioxide, comprising the steps of: preparing an iron raw material and a copper raw material; Introducing the raw material into a solvent to prepare a solution; Introducing a reducing agent into the solution; Hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor; And reducing the prepared catalyst precursor; . ≪ / RTI >

In this case, the iron raw material may be a FeCl _2.

In the reducing of the prepared catalyst precursor, the catalyst precursor may be reduced in the temperature range of 200 to 500 ° C.

The catalyst precursor may be reduced for 1 to 5 hours.

More specifically, the catalyst precursor may be reduced under a hydrogen gas atmosphere, and the flow rate of the hydrogen gas may be 50 to 200 sccm.

By reducing the prepared catalyst precursor, the obtained catalyst can be provided with a catalyst containing Cu and Fe, having a trihedral form, and having a specific surface area of 10 m ² / g or more.

And hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor, the catalyst precursor may include CuFeO ₂ having a particle diameter of 800 nm or less.

The catalyst precursor may be in the form of a three-way catalyst.

According to one embodiment of the present invention, a catalyst can be easily produced at a low temperature by using a delafosite precursor. The prepared catalyst can also be used in a carbon dioxide hydrogenation reaction. In addition, the catalyst can excellently improve the production of hydrocarbons having a large molecular weight.

FIG. 1 is a SEM observation of the precursors of the catalysts according to Comparative Examples 2 to 4. FIG.
2 is a SEM observation of the precursors of the catalysts of Examples 1 to 3.
FIG. 3 is a graphical representation of the yields of Fe metals over time in Example 2, Comparative Example 1, and Comparative Example 5.
4 is a graph showing hydrocarbon selectivities of Example 2, Comparative Example 1 and Comparative Example 5. FIG.
5 shows XRD analysis results of the catalysts of Comparative Examples 1 to 3 and Examples 1 to 3.
6 is a TEM photograph showing a Fe lattice plane.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims. Like reference numerals refer to like elements throughout the specification.

Thus, in some embodiments, well-known techniques are not specifically described to avoid an undesirable interpretation of the present invention. Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

One embodiment of the present invention may provide a precursor of a carbon dioxide hydrogenation catalyst comprising CuFeO ₂ having a particle size of 800 nm or less.

More specifically, it may include CuFeO ₂ having a particle diameter of 500 to 800 nm.

By using the catalyst precursor having a small particle diameter as described above, the hydrothermal synthesis time can be reduced in the catalyst preparation step described later.

In addition, the particle size of the hydrogenation reaction catalyst thus produced may be as small as the above range. As a result, the ratio (O / P) of paraffins to olefins can be high. Therefore, the selectivity of liquid hydrocarbons can be improved.

Herein, the term "particle diameter" as used herein means an average diameter of a spherical substance present in a measurement unit. If the material is an acetal, it means the diameter of the sphere calculated by approximating the spherical material to the spherical shape.

The precursor may be a delapo site. In addition, the precursor may be in the form of a three-ring system. However, the present invention is not limited thereto.

In another aspect of the present invention, there is provided a process for preparing a precursor of a catalyst for hydrogenation of carbon dioxide, comprising the steps of: preparing an iron raw material and a copper raw material; Introducing the raw material into a solvent to prepare a solution; Introducing a reducing agent into the solution; And hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor.

First, a step of preparing an iron raw material and a copper raw material may be carried out.

The iron source material may be a FeCl _2.

The copper raw material may be Cu (NO ₃ ) ₂ , CuCl, or a combination thereof, but is not limited thereto.

Thereafter, the raw material may be added to a solvent to prepare a solution.

The raw material may be added in an amount of 5 to 10 parts by weight based on 100 parts by weight of the solvent. More specifically, 6 to 9 parts by weight, or 7 to 9 parts by weight may be added. More specifically, 8 to 9 parts by weight or 8.03 to 8.06 parts by weight may be added. The amount of the impurities can be reduced by injecting by the weight portion. At this time, the impurities may be Fe ₂ O ₃ , Cu ₂ O, or a combination thereof.

Further, 0.05 to 0.1 mol of sodium hydroxide (NaOH) may be further added to the solution.

With respect to 100 parts by weight of the solution, the sodium hydroxide may be further added in an amount of 6 to 11 parts by weight. More specifically, for 100 parts by weight of the solution, the sodium hydroxide may be further added in an amount of 8 to 11 parts by weight. More specifically, for 100 parts by weight of the solution, the sodium hydroxide may be further added in 9 to 11 parts by weight.

This is to control the basicity of the solution in the range of pH 11 to 13, and it can have a rhomboheral structure by controlling the basicity of the solution.

Thereafter, a reducing agent may be added to the solution.

More specifically, the reducing agent may include propionaldehyde, ethylene glycol, or a combination thereof. However, the present invention is not limited thereto.

The reducing agent may be added in an amount of more than 0 and 3 parts by weight based on 100 parts by weight of the solution. More specifically, for 100 parts by weight of the solution, the reducing agent may be added in an amount of 1 to 3 parts by weight. More specifically, with respect to 100 parts by weight of the solution, the reducing agent may be added in an amount of 2 to 3 parts by weight.

More specifically, the reason for introducing the reducing agent as described above is to derive the effect that copper ions are reduced one by one.

Finally, a step of hydrothermally synthesizing the solution into which the reducing agent is introduced to prepare a catalyst precursor may be performed.

At this time, the solution can be hydrothermally synthesized at a temperature range of 150 to 200 ° C.

The solution may also be hydrothermally synthesized for 30 minutes to 5 hours.

More specifically, the solution can be hydrothermally synthesized at the above temperature and time to synthesize delaposte at a low temperature.

More specifically, it may be hydrothermal synthesis using microwaves. However, the present invention is not limited thereto.

Another embodiment of the present invention is a catalyst for hydrogenation of carbon dioxide, which comprises Cu and Fe, has a trihedral form, and has a specific surface area of 10 m ² / g or more. More specifically, the specific surface area of the catalyst may be 10 m ² / g or more. More specifically, it may be 10 to 15 m ² / g.

More specifically, when the specific surface area of the catalyst is in the above range, a micropore may be generated after the hydrogen treatment. The specific surface area can be measured by the N ₂ adsorption / desorption method.

More specifically, the catalyst comprising Cu and Fe may be attributed to the above-described tri-polar precursor. Thus, the catalyst may also include a tri-zonal form, such as the precursor described above.

In addition, since the above-mentioned precursor is in a reduced form, the catalyst may have more surface pores than the precursor described above.

The porosity of the catalyst may be 0.1 to 0.2 cm ³ / g. More specifically, the porosity of the catalyst may be 0.1 to 0.18 cm ³ / g. More specifically, it may be from 0.12 to 0.17 cm ³ / g.

More specifically, when the specific surface area and the porosity of the catalyst prepared by the reduction are within the above range, the reaction rate can be improved. Further, the liquid hydrocarbon can be easily desorbed.

The weight ratio of Cu to Fe (Cu / Fe) of the catalyst may be 0.59 or more. More specifically, the weight ratio of Cu to Fe (Cu / Fe) of the catalyst may be 0.594 or more. More specifically, the weight ratio of Cu to Fe (Cu / Fe) of the catalyst may be from 0.591 to 0.595. More specifically, it may be from 0.594 to 0.5941.

When the weight ratio of Cu element to Fe element of the catalyst is in the above range, CuFeO ₂ which is a three-way system can be synthesized with high purity.

Further, spherical Cu particles may be located on the surface of the catalyst. More specifically, some or all of the total Cu particles may be spherically located on the surface of the catalyst. The proportion of Cu particles present on the surface of the catalyst may be 50 to 80 wt% of 100 wt% of the total Cu particles.

As described above, if Cu exists on the surface of the catalyst, Fe can be easily and completely reduced.

The distance of the Fe metal (110) lattice plane of the catalyst may be 0.2 nm or more. More specifically, the distance of the Fe metal (110) lattice plane of the catalyst may be between 0.2 nm and 0.21 nm. More specifically, it may be 0.2 to 0.201 nm. This can be confirmed in FIG.

When the distance between the lattice planes of the Fe metal (110) of the catalyst is in the above range, Fe carbide, which is an active site, is synthesized to have high liquefaction hydrocarbon selectivity.

The FTY (Fe time yield) value of the catalyst may be 1.7 x ₁₀ ^-6 molco ₂ g _fe ^-1 s ^{-1 or} more.

The O / P (olefin-to-paraffin ratio) value of the catalyst may be at least 9.0. More specifically, it may be 9.5 or more.

More specifically, the FTY (Fe time yield) value of the catalyst means a change amount of carbon dioxide per unit iron, per unit time. Also, the O / P (olefin-to-paraffin) value of the catalyst means the ratio of paraffins to olefins. More specifically, when the FTY value and the O / P value are in the above range, the selectivity of liquid hydrocarbons may be increased.

The catalyst may be used for the hydrogenation reaction of carbon dioxide, and the product by the reaction may include hydrocarbon.

More specifically, with respect to 100 wt% of hydrocarbons in the product, hydrocarbons having 5 or more carbon atoms can be 59 wt% or more. More specifically, it may be at least 60% by weight. More specifically, it may be at least 63 wt%. The higher the conversion ratio is, the better, but it may theoretically be 100% by weight or 99% by weight or less.

In addition, the hydrocarbon having the carbon number of C1 may be not more than 6% by weight based on 100% by weight of the hydrocarbon in the product. More specifically, it may be 5.6% by weight or less.

Finally, a method for producing a carbon dioxide hydrogenation catalyst, which is another embodiment of the present invention, comprises the steps of: preparing an iron raw material and a copper raw material; Introducing the raw material into a solvent to prepare a solution; Introducing a reducing agent into the solution; Hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor; And reducing the prepared catalyst precursor; . ≪ / RTI >

First, preparing the iron raw material and the copper raw material; Introducing the raw material into a solvent to prepare a solution; Introducing a reducing agent into the solution; And the step of hydrothermally synthesizing the solution to which the reducing agent has been added to produce a catalyst precursor are the same as the method and conditions for producing the precursor of the catalyst described above and will not be described in detail below.

Thereafter, the catalyst precursor may be further reduced.

The catalyst precursor may be reduced in the temperature range of 200 to 500 < 0 > C. More specifically, it can be reduced at 300 to 500 ° C.

The catalyst precursor may be reduced for 1 to 5 hours. More specifically, it can be reduced for 1 to 4 hours. More specifically, it can be reduced for 1 to 3 hours.

More specifically, the catalyst precursor can be completely converted to Fe metal, which is the active point, by being reduced during the temperature range and the time.

Further, in the step of reducing the prepared catalyst precursor, the catalyst precursor may be reduced in a hydrogen gas atmosphere. At this time, the flow rate of the hydrogen gas may be 50 to 200 sccm. More specifically, the flow rate of the hydrogen gas may be 50 to 150 sccm.

By limiting the flow rate of the hydrogen gas as described above, the delapositite can be completely reduced to Fe metal.

More specifically, a carbon dioxide hydrogenation catalyst can be obtained by reducing the prepared catalyst precursor.

The obtained catalyst contains Cu and Fe, has a three-way system, and may have a specific surface area of 10 m ² / g or more. More specifically, it may be at least 15 m ² / g.

Example  And Comparative Example

Catalyst Preparation Method: Example

0.99 g of FeCl ₂ .4H ₂ O and 1.2 g of Cu (NO ₃ ) ₂ .3H ₂ O were dissolved in 40 ml of distilled water to prepare a solution. Then, 4 g of 0.1 mol of NaOH was added to the solution, followed by stirring for 10 to 30 minutes. In addition, 0.5 ml of propionaldehyde was added to the solution to prepare a mixture.

The mixture was transferred to a Teflon tube (100 ml) and then hydrothermalized at 180 ° C for 1 to 3 hours. This is equivalent to hydrothermal reaction for 12 to 36 hours in a Teflon-drawn stainless steel autoclave. As a result, CuFeO ₂ -1, CuFeO ₂ -2, and CuFeO ₂ -3 catalysts synthesized by hydrothermal action of 1 hour, 2 hours, and 3 hours were prepared.

Catalyst Preparation Method: Comparative Example

The _{Fe (NO 3) 3 · 9H} 2 O 2.02g and _{Cu (NO 3) 2 · 3H} 2 O 1.2g was prepared a solution dissolved in distilled water 40ml. Thereafter, 4 g of 0.1 mol of NaOH was added to the solution, followed by stirring for 30 minutes. In addition, 0.5 ml of propionaldehyde was added to the solution to prepare a mixture.

The mixture was transferred to a 100 ml Teflon-drawn stainless steel autoclave and hydrothermalized at 180 ° C for 6 to 24 hours. As a result, CuFeO ₂ -6, CuFeO ₂ -12, and CuFeO ₂ -24 catalysts synthesized by hydrothermal action at 6 hours, 12 hours, and 24 hours were prepared as Comparative Examples 2 to 4, respectively.

In addition, a spinel structure nano powder (less than 100 nm), CuFe ₂ O ₄ The catalyst was purchased from Sigma-Aldrich and prepared as Comparative Example 1. In addition, pure Fe ₂ O ₃ was purchased from Kanto and prepared as Comparative Example 5. In addition, Cu ₂ O-Fe ₂ O ₃ Were mixed at a weight ratio of 1: 1, respectively.

Catalytic Hydrogenation of Carbon Dioxide

The catalytic hydrogenation of carbon dioxide was performed in a fixed bed of a stainless steel reactor with CO ₂ / H ₂ = 1: 3.

First, preliminary reduction was performed at 400 DEG C for 2 hours under a pure H ₂ gas atmosphere of 100 sccm. For the catalytic reaction, CO ₂ and H ₂ gases were fed into the reactor together with nitrogen gas. At this time, the reducing conditions were 300 DEG C, 10 bar, and the gas space velocity was 1800 mlg ^-1 h ^-1 .

The concentrations of CO ₂ , CO and N ₂ were measured by an on-line Agilent 7890A gas chromatograph with a thermal conductivity detector and a Carboxen 1000 packed column. C ₁ -C ₆ hydrocarbons were analyzed by GC with a flame ionization detector and an Alumina Sulfate PLOT capillary column.

As a result, high molecular weight hydrocarbon products were collected in the cooling traps. In addition, the composition of hydrocarbons having large molecular weights was calculated as weight percent of carbon atoms, using simulated distillation (SIMDIS) analysis.

Experimental Example

catalyst Carbon dioxide conversion, % Carbon monoxide selectivity,% Hydrocarbon selectivity (except for carbon monoxide), % O / P C1 C2 C3 C4 C5 + Example 1 CuFeO ₂ -1 17.5 33.8 5.6 10.0 14.1 11.0 59.3 10.3 Example 2 CuFeO ₂ -2 20.2 25.8 4.8 8.8 13 10.3 63.1 9.9 Example 3 CuFeO ₂ -3 18.9 30.7 5.2 9.6 13.9 11.0 60.3 9.7 Comparative Example 1 Fe ₂ O ₃ 14.3 33.2 60.2 22.5 11.3 3.7 2.3 0.03 Comparative Example 2 CuFeO ₂ -6 17.3 31.7 2.7 8.3 12.6 10.1 66.3 7.3 Comparative Example 3 CuFeO ₂ -12 18.1 31.9 3.9 10 14.5 11.3 60.3 7 Comparative Example 4 CuFeO ₂ -24 16.7 31.4 2.4 8.7 13.3 10.7 64.9 7.7 Comparative Example 5 CuFe ₂ O ₄ 13.3 28.4 38.3 19.7 20.1 10.5 11.4 0.02 Comparative Example 6 Cu ₂ O-Fe ₂ O ₃ 15.7 28.9 57.6 22.8 12.6 4.4 2.6 0.03

catalyst Specific surface area ,
m ² / g Particle size Existing
Crystal system Porosity Weight ratio (Cu / Fe) Example 1 CuFeO ₂ -1 Unevaluated 800 nm or less Rhomboheral , hexagonal Unevaluated 1.13 Example 2 CuFeO ₂ -2 10.2 800 nm or less Rhomboheral , hexagonal 0.166 1.13 Example 3 CuFeO ₂ -3 Unevaluated 800 nm or less Rhomboheral , hexagonal Unevaluated 1.13 Comparative Example 1 Fe ₂ O ₃ 12.4 Unevaluated Unevaluated 0.143 0 Comparative Example 2 CuFeO ₂ -6 Unevaluated 2.5 탆
level rhomboheral Unevaluated 0.593 Comparative Example 3 CuFeO ₂ -12 10.3 2.5 탆
level rhomboheral 0.12 0.593 Comparative Example 4 CuFeO ₂ -24 Unevaluated 2.5 탆
level rhomboheral Unevaluated 0.593 Comparative Example 5 CuFe ₂ O ₄ 28.1 Unevaluated spherical 0.403 Unevaluated

* Unevaluated data are those for which evaluation results were not derived at the time of filing

As shown in Table 1, the present example shows that the carbon dioxide conversion, the selectivity of hydrocarbons having a carbon number of C5 or more, and the O / P value are both superior to those of the comparative example.

More specifically, in Examples 1 to 3 of the present invention, iron precursors differ only in comparison with Comparative Examples 2 to 4. The catalyst was prepared under the same conditions.

As a result, the O / P values of Examples 1 to 3 were significantly superior to those of Comparative Examples 2 to 4, and it was confirmed that the hydrothermal synthesis time was reduced.

These results are due to the fact that the iron precursors of Examples 1 to 3 are different from the iron precursors of Comparative Examples 2 to 4. More specifically, the particle diameter of the catalyst according to the present example is smaller than the particle diameter of the catalyst according to the comparative example.

This can be confirmed also in FIGS. 1 and 2.

FIG. 1 is a SEM observation of the precursors of the catalysts according to Comparative Examples 2 to 4. FIG.

2 is a SEM observation of the precursors of the catalysts of Examples 1 to 3.

As shown in FIG. 2, it can be confirmed that the particle size of the catalyst precursor is in the range of 500 to 800 nm. On the other hand, as shown in Fig. 1, the particle diameter of the catalyst precursor of the comparative example is in the range of 1 to 2.5 mu m. Thus, the present embodiment can improve the selectivity (O / P) of liquid hydrocarbons by using a catalyst precursor having a smaller particle diameter as compared with the comparative example. In addition, the catalyst could be prepared by hydrothermal synthesis in a short time.

Also, referring to FIG. 3, it can be seen that the present example is characterized in that the amount of change in carbon dioxide is superior to that of Comparative Example.

FIG. 3 is a graphical representation of the yields of Fe metals over time in Example 2, Comparative Example 1, and Comparative Example 5.

More specifically, FIG. 3 is a graph showing the FTY (Fe time yield) value of the catalyst with respect to time, and the FTY (Fe time yield) value of the catalyst is expressed in terms of the amount of change in carbon dioxide it means.

As a result, it can be seen that the FTY value of the present embodiment is 1.7 x ₁₀ ^-6 molco ₂ g _fe ^-1 s ^-1 or more, and that the amount of change in carbon dioxide is lower in Comparative Example 1 and Comparative Example 5 than in the Examples.

4, the selectivity of hydrocarbons according to the number of carbon atoms can be confirmed by using catalysts according to Examples and Comparative Examples.

4 is a graph showing hydrocarbon selectivities of Example 2, Comparative Example 1 and Comparative Example 5. FIG.

As shown in FIG. 4, the present example shows that the selectivity of the carbon number having a large number of carbon atoms and the number of carbon atoms of C5 or more is significantly higher than those of Comparative Examples 1 and 5.

It is confirmed that, as shown in Table 1, the present Example shows that the ratio of olefin to paraffin is 9.0 or more, which corresponds to a higher effect of increasing the selectivity of liquid hydrocarbons.

5 shows XRD analysis results of the catalysts of Comparative Examples 1 to 3 and Examples 1 to 3.

More specifically, in the case of Comparative Examples 1 to 3, it can be confirmed through the XRD peak that the rhombohedral shape of delafossite CuFeO ₂ and impurities Fe ₂ O ₃ and CuO are present.

On the other hand, in Examples 1 to 3, only CuFeO ₂ mixed with a rhombohedral shape and a hexagonal shape is present.

(The three-way system and the hexagonal system can be divided into the same group.) More specifically, the three-way system is also a hexagonal system with a three-

From this, the present example can improve the selectivity of liquefied hydrocarbons and the ratio of olefin to paraffin by producing CuFeO ₂ , which is more pure than the comparative example.

That is, it has been confirmed that the catalyst according to the present invention can easily convert carbon dioxide into high-value-added materials such as diesel and gasoline because of the high selectivity of hydrocarbons having a large molecular weight.

6 is an HR-TEM and EELS mapping photograph of the Fe lattice plane of Example 2. Fig. From FIG. 6, it can be seen that iron carbide was formed during the reaction because the presence of C in Fe. As a result of checking the lattice plane in the TEM photograph, it is found that the surface is about 0.2 nm.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand.

It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (28)

A precursor of a hydrogenation catalyst of carbon dioxide, the catalyst comprising CuFeO ₂ having a particle size of 800 nm or less.
The method according to claim 1,
Wherein the precursor comprises a three-system configuration.
Preparing an iron raw material and a copper raw material;
Adding the iron and copper raw materials to a solvent to prepare a solution;
Introducing a reducing agent into the solution; And
And hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor,
Process for producing a precursor of the iron raw material is a hydrogenation catalyst for carbon dioxide would of FeCl _2.
The method of claim 3,
And hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor,
Wherein the solution is hydrothermally synthesized at a temperature in the range of 150 to 200 占 폚.
5. The method of claim 4,
And hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor,
Wherein the solution is hydrothermally synthesized for 30 minutes to 5 hours.
The method of claim 3,
Preparing an iron raw material and a copper raw material,
Process for producing a precursor of the copper source material is Cu (NO _{3) 2,} CuCl or the hydrogenation catalyst of one of a combination of carbon dioxide.
The method of claim 3,
Preparing a solution by introducing the raw material into a solvent,
Wherein the raw material is charged in an amount of 5 to 10 parts by weight based on 100 parts by weight of the solvent.
8. The method of claim 7,
Preparing a solution by introducing the raw material into a solvent,
Wherein a further addition of sodium hydroxide (NaOH) is carried out.
9. The method of claim 8,
Preparing a solution by introducing the raw material into a solvent,
Wherein the sodium hydroxide is added in an amount of 6 to 11 parts by weight based on 100 parts by weight of the solution.
The method of claim 3,
Introducing a reducing agent into the solution; in,
Wherein the reducing agent comprises propionaldehyde, ethylene glycol or a combination thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
11. The method of claim 10,
Introducing a reducing agent into the solution; in,
Wherein the reducing agent is added in an amount of more than 0 and not more than 3 parts by weight based on 100 parts by weight of the solution.
Cu and Fe,
Including a three-way system,
A catalyst for the hydrogenation of carbon dioxide having a specific surface area of 10 m ² / g or more.
13. The method of claim 12,
Wherein the catalyst has a particle diameter of 800 nm or less.
13. The method of claim 12,
Wherein the catalyst has a porosity of 0.12 to 0.17 cm < ³ > / g.
15. The method of claim 14,
Wherein the weight ratio of Cu to Fe (Cu / Fe) of the catalyst is 0.594 or more.
16. The method of claim 15,
Wherein the distance of the Fe metal (110) lattice plane of the catalyst is at least 0.2 nm.
17. The method of claim 16,
Wherein spherical Cu particles are placed on the surface of the catalyst.
18. The method of claim 17,
Wherein the amount of change (FTY) of carbon dioxide per iron per unit time of the catalyst is 1.7x10 ^-6 molco ₂ g _fe ^-1 s ^-1 or more.
19. The method of claim 18,
The catalyst is used for the hydrogenation reaction of carbon dioxide,
The product of the reaction comprises olefins and paraffins,
Wherein the ratio (O / P) of the paraffin to the olefin of the catalyst is 9.0 or more.
20. The method of claim 19,
The catalyst is used for the hydrogenation reaction of carbon dioxide,
The product of the reaction comprises hydrocarbon,
Wherein the hydrocarbon having C5 or more carbon atoms is at least 59% by weight based on 100% by weight of the hydrocarbons in the product.
21. The method of claim 20,
Wherein the hydrocarbons having a carbon number of C1 are not more than 6% by weight based on 100% by weight of hydrocarbons in the product.
Preparing an iron raw material and a copper raw material;
Introducing the raw material into a solvent to prepare a solution;
Introducing a reducing agent into the solution;
Hydrothermally synthesizing the solution to which the reducing agent is added to prepare a catalyst precursor; And
Reducing the prepared catalyst precursor; , ≪ / RTI &
The method of the iron source material is a hydrogenation catalyst for carbon dioxide would of FeCl _2.
23. The method of claim 22,
Reducing the prepared catalyst precursor,
Wherein the catalyst precursor is reduced in the temperature range of 200 to 500 < 0 > C.
24. The method of claim 23,
Reducing the prepared catalyst precursor,
Wherein the catalyst precursor is reduced for 1 to 5 hours.
25. The method of claim 24,
Reducing the prepared catalyst precursor,
The catalyst precursor is reduced in a hydrogen gas atmosphere,
Wherein the flow rate of the hydrogen gas is 50 to 200 sccm.
26. The method of claim 25,
And reducing the prepared catalyst precursor,
The obtained catalyst contains Cu and Fe,
Including a three-way system,
Wherein the specific surface area is 10 m ² / g or more.
23. The method of claim 22,
And hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor,
Wherein the prepared catalyst precursor comprises CuFeO ₂ having a particle diameter of 800 nm or less.
28. The method of claim 27,
And hydrothermally synthesizing the solution to which the reducing agent is added to produce a catalyst precursor,
Wherein the catalyst precursor comprises a three-ring system.

Images