KR20240003777A - Catalytic Materials for Direct Methane Conversion, Methods for Production of Carbon-Containing Compounds, and Continuous Reaction Apparatus - Google Patents

Abstract

The present invention relates to a methane direct conversion reaction technology that can produce useful carbon compounds by directly reacting methane and carbon dioxide. More specifically, the direct reaction of carbon dioxide in the air with methane is different from what is possible in an environment where very high energy is input. Unlike other catalyst-type reactants for methane direct conversion reaction that can produce various carbon compounds by directly reacting with methane under low-temperature, low-energy input conditions, method of producing carbon compounds through methane direct conversion reaction using the same, and continuous reaction device for methane direct conversion reaction It is about technology that provides.

Description

Catalytic reaction materials for direct methane conversion reaction, method for producing carbon compounds through direct methane conversion reaction using the same, and continuous reaction device for direct methane conversion reaction {Catalytic Materials for Direct Methane Conversion, Methods for Production of Carbon-Containing Compounds, and Continuous Reaction Apparatus}

The present invention relates to a methane direct conversion reaction technology that can produce useful carbon compounds by directly reacting methane and carbon dioxide. More specifically, the direct reaction of carbon dioxide in the air with methane is different from what is possible in an environment where very high energy is input. Unlike other catalyst-type reactants for methane direct conversion reaction that can produce various carbon compounds by directly reacting with methane under low-temperature, low-energy input conditions, method of producing carbon compounds through methane direct conversion reaction using the same, and continuous reaction device for methane direct conversion reaction It is about technology that provides.

Around the world, cheap fossil energy is used as an energy source, but the carbon dioxide generated in this process is captured and decomposed into methane to convert it into synthesis gas consisting of a mixture of carbon monoxide and hydrogen, and this synthesis gas is reused as an energy source. Technology is being developed to manufacture and recycle chemical products such as methanol and DME (Dimethyl ether) using this synthetic gas as a raw material.

For example, conventionally, acetic acid was mainly synthesized through the oxidation reaction process of acetaldehyde, but currently, it is synthesized through the carbonylation reaction process of methanol using carbon monoxide. For the carbonylation reaction of methanol, the Rh catalyst-based Monsanto process and the Ir catalyst-based Cativa process are commercialized. The two commercialized processes synthesize acetic acid through almost the same process under conditions of 30-60 bar and 150-200 ℃, but the Monsanto process Compared to the Cativa process, it has economic and environmental advantages in that it uses less water and produces fewer by-products, so the Monsanto process, which was commercialized first, is being replaced by the Cativa process. However, both processes have the problem of not being highly efficient in terms of energy and cost, not only because they operate in a high temperature and pressure environment, but also because they utilize expensive noble metal-based homogeneous catalysts.

In addition, the process of synthesizing methanol by reacting CO ₂ and H ₂ is currently commercialized. Cu/ZnO/Al ₂ is produced at a molar ratio of CO ₂ :H ₂ = 1:3 under conditions of 70 bar and 250 ℃. A technology to synthesize methanol in high yield using O ₃ catalyst has been developed. However, it has the disadvantage of being less economical in terms of utilizing expensive hydrogen gas and requiring very high pressure and high temperature reaction conditions in terms of generating a liquid product through a gas phase reaction.

Carbon monoxide is synthesized through a process of reacting coal or coke with carbon dioxide, oxygen, or water vapor and then purifying it. Carbon monoxide synthesis using carbon dioxide requires high temperature conditions of over 800°C, so processes using oxygen or water vapor are mainly used. In this way, a carbon dioxide reduction effect can be expected in that carbon dioxide is consumed to produce carbon monoxide, but in terms of reacting carbon dioxide, which has little reactivity, a very high temperature environment is created and high energy is input for this, resulting in energy efficiency. This is a very low process.

Acetaldehyde was previously synthesized using ethanol or acetylene as a reactant, but is now synthesized through an oxidation reaction of ethylene called the Wacker or Hoechst-Wacker process. The Wacker process utilizes a homogeneous palladium/copper catalyst under conditions of 130°C and 4 bar. This synthesizes acetaldehyde. Therefore, from the perspective of producing acetaldehyde using ethylene with high added value, it is inevitably an inefficient process because a product with low added value is manufactured through a process with low economic efficiency.

Domestic registered patent number 10-1730799

As a result of research efforts to solve the above-mentioned problems, the present inventors completed the present invention by developing a technology that can produce various carbon compounds by directly reacting methane and carbon dioxide through low energy input.

Therefore, the purpose of the present invention is to selectively produce carbon compounds with higher added value compared to carbon dioxide and methane, such as acetic acid, methanol, carbon monoxide, and acetaldehyde, through a direct methane conversion reaction in which carbon dioxide and methane react directly in a low-temperature, low-energy input environment. The aim is to provide a catalytic reaction material for methane direct conversion reaction, a method for producing carbon compounds through methane direct conversion reaction using the same, and a continuous reaction device for methane direct conversion reaction.

Another object of the present invention is to collect carbon dioxide with various metal oxides in order to semi-permanently reduce carbon dioxide, and the resulting metal carbonate is buried in the ground or seafloor. Catalytic reactant for methane direct conversion reaction that can produce high value-added carbon compounds by using metal carbonate produced by capturing carbon dioxide as a raw material without the need to bury it in the ground or seabed, and methane using this The aim is to provide a method for producing carbon compounds through direct conversion reaction and a continuous reaction device for methane direct conversion reaction.

The objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the description below.

In order to achieve the object of the present invention described above, the present invention provides a metal carbonate; It provides a catalytic reaction material for methane direct conversion reaction comprising; and metal nanoparticles supported on the metal carbonate.

In a preferred embodiment, the metal carbonate is at least one selected from the group consisting of zinc carbonate, calcium carbonate, cerium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, copper carbonate, and cobalt carbonate.

In a preferred embodiment, the metal nanoparticle is one or more selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). .

In a preferred embodiment, the metal nanoparticles are contained in an amount of 0.1 to 5% by weight based on the metal carbonate.

In a preferred embodiment, the diameter of the metal nanoparticles is 1 to 10 nm.

In a preferred embodiment, carbon dioxide, which is reactive with methane gas, is discharged at a temperature of 25°C - 600°C and a pressure of 5 bar to 50 bar.

In addition, the present invention includes a charging step of charging any one metal carbonate of cobalt carbonate, zinc carbonate, and cerium carbonate into the reactor; Supplying methane gas to the reactor filled with the metal carbonate; Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 300°C and a pressure of 5 bar to 50 bar; and obtaining acetic acid produced through performing the methane direct conversion reaction.

In a preferred embodiment, when the metal carbonate charged in the reactor is cobalt carbonate, the temperature of the reactor is adjusted to 50°C to 150°C.

In a preferred embodiment, when the metal carbonate charged in the reactor is zinc carbonate, the temperature of the reactor is adjusted to 100°C to 200°C.

In a preferred embodiment, when the metal carbonate charged in the reactor is cerium carbonate, the temperature of the reactor is adjusted to 50°C to 250°C.

In a preferred embodiment, the methane gas composition does not contain carbon dioxide.

In a preferred embodiment, when a metal oxide salt of cobalt oxide, zinc oxide, or cerium oxide is produced through the methane direct conversion reaction, the metal oxide salt is reacted with carbon dioxide to collect carbon dioxide in the metal oxide salt; and reusing any one of cobalt carbonate, zinc carbonate, and cerium carbonate generated in the carbon dioxide collecting step in the charging step.

In addition, the present invention includes the steps of charging any one of the above-described reactants into a reactor; Supplying a methane gas composition to a reactor filled with the reactant; Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 600°C and a pressure of 5 bar to 50 bar; and obtaining a carbon compound obtained by the methane direct conversion reaction.

In a preferred embodiment, the carbon compound includes one or more selected from the group consisting of acetic acid, acetaldehyde, methanol, and carbon monoxide.

In a preferred embodiment, if the reactant charged in the reactor is one in which platinum nanoparticles are supported on calcium carbonate, the temperature of the reactor is adjusted to 300°C to 600°C.

In a preferred embodiment, the methane gas composition does not contain carbon dioxide.

In a preferred embodiment, when carbon dioxide is discharged from the reactant through the methane direct conversion reaction to produce a metal oxide salt carrying metal nanoparticles, the metal oxide salt carrying the metal nanoparticles is reacted with carbon dioxide to produce the metal oxide salt. A step in which carbon dioxide is captured; and reusing the reactant produced in the carbon dioxide capturing step in the charging step.

In addition, the present invention provides a reaction space filled with metal carbonate or any of the above-described reactants; a reaction gas supply unit providing methane gas to the reaction space; a product storage unit where carbon compounds generated in the reaction space are discharged and stored; And a carbon dioxide supply unit that provides carbon dioxide to the reaction space where the carbon compound is discharged. It provides a reaction device for a methane direct conversion process including a.

In a preferred embodiment, it further includes a separation unit connected to the product storage unit to extract and separate the carbon compound.

According to the present invention described above, carbon compounds with higher added value than carbon dioxide and methane, such as acetic acid, methanol, carbon monoxide, and acetaldehyde, can be selectively produced through a direct methane conversion reaction in which carbon dioxide and methane react directly in a low-temperature, low-energy input environment. there is.

In addition, according to the present invention, in order to semi-permanently reduce carbon dioxide, carbon dioxide is captured with various metal oxides and the resulting metal carbonate is buried in the ground or seafloor. Carbon dioxide is contained in the metal oxide. The collected and produced metal carbonate can be used as a raw material to produce high value-added carbon compounds without the need to bury it in the ground or seabed.

Therefore, in the present invention, the metal oxide obtained from metal carbonate reacted with methane can be recycled to capture and remove carbon dioxide in the air, and the metal carbonate thus obtained can be used again as a catalytic reaction material for methane direct conversion reaction to provide high added value. It has the advantage of being a highly economical and environmentally friendly process technology in that it can implement a continuous process to produce carbon compounds.

These technical effects of the present invention are not limited to the scope mentioned above, and even if not explicitly mentioned, the effects of the invention that can be recognized by a person of ordinary skill in the art from the description of the specific contents for implementing the invention described later. Of course it is included.

Figure 1 is a schematic diagram of the entire process of producing acetic acid by directly reacting with methane using zinc carbonate (ZnCO ₃ ).
Figure 2 is a schematic diagram of the entire process of producing acetic acid by directly reacting with methane using platinum-supported calcium carbonate.
Figure 3 is a schematic diagram of a gas phase batch reaction device that directly reacts with methane using a reaction catalyst material.
Figure 4 shows the results of monitoring the process of carbon dioxide being released from the metal carbonate skeleton according to temperature through thermogravimetric analysis for zinc carbonate and calcium carbonate.
Figures 5a and 5b are X-ray diffraction pattern results observing the structural changes of zinc carbonate and platinum-supported calcium carbonate before and after the methane direct conversion reaction, respectively.
Figure 6 is a transmission electron microscope photograph of platinum-supported calcium carbonate.
Figure 7 shows a gas chromatography chromatogram (left: full area, right: enlarged area) of a product obtained by directly reacting zinc carbonate with methane as a reaction catalyst.
Figure 8 shows a gas chromatography chromatogram of the gas contained in the batch reactor after direct reaction with methane using zinc carbonate as a reaction catalyst material.
Figure 9 shows a gas chromatography chromatogram (left: entire area, right: enlarged area) of a product obtained by directly reacting methane with platinum-supported calcium carbonate (Pt/CaCO ₃ ) as a reaction catalyst.
Figure 10 shows a gas chromatography chromatogram of the gas contained in the batch reactor after direct reaction with methane using platinum-supported calcium carbonate (Pt/CaCO ₃ ) as a reaction catalyst material.
Figure 11 shows the results of X-ray photoelectron spectroscopy of the reaction catalyst material before and after direct reaction with methane using platinum-supported calcium carbonate (Pt/CaCO ₃ ) as the reaction catalyst material.
Figure 12 is a graph showing methane conversion rate, product selectivity, and productivity according to the type of reaction catalyst material in the methane direct conversion reaction.
Figure 13 is a schematic diagram of a fixed bed continuous reaction device that directly reacts with methane using a reaction catalyst material.
Figure 14 shows the results of monitoring the process of carbon dioxide being released from the cobalt carbonate skeleton according to temperature through thermogravimetric analysis of cobalt carbonate.
Figure 15 shows the results of an X-ray diffraction pattern observing the structural change before and after the direct conversion reaction of cobalt carbonate to methane.
Figure 16 shows a gas chromatography chromatogram (left: entire area, right: enlarged area) of a product obtained by directly reacting methane with cobalt carbonate as a reaction catalyst material.
Figure 17 shows a gas chromatography chromatogram of the gas discharged from the fixed bed continuous reaction device after direct reaction with methane using cobalt carbonate as a reaction catalyst material.
Figure 18 shows the results of X-ray photoelectron spectroscopy of the reaction catalyst material before and after direct reaction with methane using cobalt carbonate as the reaction catalyst material in the fixed bed continuous reaction device of Figure 13.
Figure 19 is a schematic diagram of the entire process of adsorption of carbon dioxide using cobalt oxide, direct reaction with methane, and production of acetic acid by applying the fixed bed continuous reaction device shown in Figure 13 as a pulse-mode reaction.
Figure 20 shows experimental conditions for operating the entire process of adsorption of carbon dioxide using cobalt oxide, direct reaction with methane, and production of acetic acid by applying the fixed bed continuous reaction device shown in Figure 13 as a pulse-mode reaction. It's a graph.
Figure 21 shows the IR absorption spectrum over time during CO ₂ Activation during the process shown in Figure 20 using cobalt oxide.

The terms used in the present invention are general terms that are currently widely used as much as possible. However, in certain cases, there are terms arbitrarily selected by the applicant, and in this case, the meaning described or used in the detailed description of the invention rather than the simple name of the term is considered. Therefore, its meaning must be understood.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the present invention, should not be interpreted in an idealized or excessively formal sense. No.

The terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the description of the invention, but are intended to indicate the presence of one or more other It should be understood that this does not exclude in advance the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof.

Terms such as first, second, etc. may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component without departing from the scope of the present invention.

The term "catalytic reactant for methane direct conversion reaction" used in the present invention provides raw materials for methane direct conversion reaction and is used as a catalyst at the same time, and is capable of regenerating and recycling the structure of the initial material by adsorbing carbon dioxide after the reaction is completed. means substance.

When interpreting a component, it is interpreted to include the margin of error even if there is no separate explicit description. In particular, when terms of degree such as "about", "substantially", etc. are used, they may be interpreted as being used at or close to that value when manufacturing and material tolerances inherent in the stated meaning are presented. .

In the case of a description of a temporal relationship, for example, if a temporal relationship is described as ‘~after’, ‘after~’, ‘~next’, ‘before’, etc., ‘immediately’ or ‘directly’ This also includes non-consecutive cases unless used.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to the attached drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numerals used to describe the invention throughout the specification represent like elements.

The technical feature of the present invention is to use metal carbonate, which is produced by capturing carbon dioxide in metal oxide, as a raw material without the need to bury it in the ground or seabed, and to produce metal carbonate from metal carbonate in a low-temperature, low-energy input environment. A catalytic reaction material for methane direct conversion reaction that can selectively produce carbon compounds with higher added value compared to carbon dioxide and methane, such as acetic acid, methanol, carbon monoxide, and acetaldehyde, through the methane direct conversion reaction in which desorbed carbon dioxide and methane directly react. The aim is to provide a method for producing carbon compounds through methane direct conversion reaction and a continuous reaction device for methane direct conversion reaction using this method.

Metal oxides are readily available materials, and each metal oxide can reversibly adsorb and desorb carbon dioxide at a specific temperature depending on the metal element. When carbon dioxide is adsorbed, metal oxides are converted into metal carbonate, and using this principle, metal oxides are used as materials that can adsorb and remove carbon dioxide in many industrial processes that emit carbon dioxide. However, since metal carbonates that adsorb carbon dioxide are usually disposed of by burying in the ground or the seabed, it is difficult to determine that carbon dioxide has been permanently removed.

Therefore, the catalytic reactant for methane direct conversion reaction of the present invention includes metal carbonate; and metal nanoparticles supported on the metal carbonate.

Metal carbonate is not limited as long as it is suitable for being effectively used as a catalytic reactant for methane direct conversion reaction in a low energy input environment, but examples include zinc carbonate (ZnCO ₃ ), calcium carbonate (CaCO ₃ ), and cerium carbonate (Ce). ₂ (CO ₃ ) ₂ ), magnesium carbonate, strontium carbonate, barium carbonate, copper carbonate, and cobalt carbonate (CoCO ₃ ).

Metal nanoparticles are components that perform the function of activating carbon dioxide to be easily desorbed from metal carbonate even in a low-energy input environment. Metal nanoparticles are not limited as long as they are metal elements that have high activity and are used as catalysts, but one embodiment includes ruthenium (Ru), It may be one or more selected from the group consisting of rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).

In other words, metal oxides or metal carbonates of transition metal materials contain transition metals as active sites for methane molecules, so they can activate methane on their own and produce various compounds through simultaneous activation and direct reaction of methane and carbon dioxide. Since alkaline earth metal-based metal oxides or metal carbonates do not have catalytic sites for methane activation, they cannot activate methane on their own, making it impossible to react directly with carbon dioxide. However, as will be described later, it has been confirmed that methane can be activated by carrying on the surface a precious metal catalyst that shows high activity against methane molecules, such as nanoparticles of platinum group elements, and through this, various compounds can be produced.

Metal nanoparticles are contained in an amount of 0.1 to 5% by weight relative to the metal carbonate. If the amount is less than 0.1% by weight, they cannot contribute to the activation reaction in which carbon dioxide contained in the metal carbonate is desorbed, and if it exceeds 5% by weight, it is not only uneconomical. This is because it may actually inhibit the carbon dioxide desorption reaction. The diameter of metal nanoparticles may be 1 to 10 nm, but if the diameter exceeds 10 nm, there may be a problem of catalytic activity not appearing.

As an example, looking at the activation effect of metal nanoparticles on the carbon dioxide desorption reaction, calcium carbonate (CaCO ₃ ), one of the metal carbonates with a very high reversible adsorption/desorption temperature of carbon dioxide, is mainly used industrially in the cement manufacturing process. In order to be used as a component of cement, it must be converted into calcium oxide, and for this purpose, it is heat treated at a high temperature of about 800 ℃, and it is known that a large amount of carbon dioxide is emitted during this process. However, according to the present invention, when platinum nanoparticles supported on calcium carbonate become a catalyst-type reactant for methane direct conversion reaction, various compounds can be produced by directly reacting with methane at a low temperature of 300 - 500 ° C. As a result, according to the present invention, when calcium carbonate among metal carbonates reacts with methane, the reaction proceeds under relatively low temperature conditions compared to the cement process, and carbon dioxide is consumed to produce a high value-added compound, and calcium carbonate is produced in this process. It is meaningful in that it can be converted into calcium oxide.

As such, the catalytic reaction material for direct methane conversion reaction of the present invention may have different temperatures and pressures at which carbon dioxide is desorbed and directly reacts with methane depending on the type of metal carbonate and the type of supported metal nanoparticles, but is generally maintained at 25°C. - Carbon dioxide, which is reactive with methane gas, can be discharged at a temperature of 600°C and a pressure of 5 bar to 50 bar.

Next, the method for producing acetic acid through the direct methane conversion reaction of the present invention includes a charging step of charging any one metal carbonate of cobalt carbonate, zinc carbonate, and cerium carbonate into the reactor; Supplying a methane gas composition to the reactor filled with the metal carbonate; Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 300°C and a pressure of 5 bar to 50 bar; and obtaining acetic acid produced through performing the methane direct conversion reaction. At this time, the methane gas composition does not contain carbon dioxide, but in one embodiment, it may contain an inert gas containing methane and nitrogen. The content of methane in the methane gas composition may be at least 60% by volume.

In addition, it was confirmed through numerous experiments that cobalt carbonate, zinc carbonate, and cerium carbonate charged into the reactor in the charging stage have a reversible carbon dioxide adsorption/desorption phenomenon in the low temperature range of 300°C or lower even if metal nanoparticles are not contained. In addition, it was confirmed that only acetic acid was produced through a direct methane conversion reaction.

In particular, the temperature of the reactor for generating a direct methane conversion reaction is different depending on the type of metal carbonate charged in the reactor. In one embodiment, if the metal carbonate is cobalt carbonate, the temperature of the reactor is adjusted to 50°C to 150°C. Methane and carbon dioxide desorbed from metal carbonate react to produce only acetic acid. As another embodiment, if the metal carbonate is zinc carbonate, when the temperature of the reactor is adjusted to 100°C to 200°C, methane and carbon dioxide desorbed from the metal carbonate may react to produce only acetic acid. As another embodiment, if the metal carbonate is cerium carbonate, when the temperature of the reactor is adjusted to 50°C to 250°C, methane and carbon dioxide desorbed from the metal carbonate may react to produce only acetic acid. However, when metal nanoparticles are supported on cobalt carbonate, zinc carbonate, and cerium carbonate and prepared as a catalytic reaction material for the methane direct conversion reaction of the present invention, various types of useful carbon compounds, including acetic acid, are converted into methane directly, as will be described later. It was created through a conversion reaction.

Meanwhile, when the methane direct conversion reaction is performed in the step of performing the methane direct conversion reaction, a desorption reaction of carbon dioxide occurs from the metal carbonate, and cobalt carbonate, zinc carbonate, and cerium carbonate are converted into cobalt oxide, zinc oxide, and cerium oxide through the methane direct conversion reaction. Any one of the metal oxides may be generated. In this case, the acetic acid production method of the present invention includes the steps of reacting the produced metal oxide with carbon dioxide instead of landfilling and disposing of it, so that carbon dioxide is captured in the metal oxide; and reusing any one of cobalt carbonate, zinc carbonate, and cerium carbonate generated in the carbon dioxide collecting step in the charging step. As such, the acetic acid production method of the present invention directly reacts carbon dioxide desorbed from metal carbonate with methane to produce acetic acid with higher added value than methane and carbon dioxide while consuming carbon dioxide, and adsorbs carbon dioxide to the metal oxide obtained in this process to produce metal carbonate. It is possible to implement a circulation process that produces and reacts with methane again.

More specifically, in the method of producing acetic acid through direct methane conversion reaction of the present invention, acetic acid can be produced by reacting the methane gas composition injected using the device shown in Figure 3 or Figure 13 with carbon dioxide desorbed from metal carbonate. , a direct methane conversion reaction as shown in Figure 1 may occur.

Next, the method for producing carbon compounds through the direct methane conversion reaction of the present invention includes the steps of charging any one reactant having the above-described structure into the reactor; Supplying a methane gas composition to a reactor filled with the reactant; Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 600°C and a pressure of 5 bar to 50 bar; and obtaining a carbon compound obtained through the methane direct conversion reaction. At this time, the methane gas composition does not contain carbon dioxide, but in one embodiment, it may contain an inert gas containing methane and nitrogen. The content of methane in the methane gas composition may be at least 60% by volume.

In addition, the carbon compound obtained from the methane direct conversion reaction includes one or more selected from the group consisting of acetic acid, acetaldehyde, methanol, and carbon monoxide. The type and content of the carbon compound produced are determined by the catalytic reaction material for the methane direct conversion reaction. It may vary depending on the type and content of metal carbonate and metal nanoparticles included.

Meanwhile, the temperature of the reactor for generating the methane direct conversion reaction is different depending on the type of metal carbonate contained in the catalyst-type reaction material for the methane direct conversion reaction charged in the reactor. In one embodiment, the reaction material charged in the reactor is If platinum nanoparticles are supported on calcium carbonate, the temperature of the reactor can be adjusted to 300°C to 600°C.

In addition, when carbon dioxide is released from the reactant through the methane direct conversion reaction and a metal oxide carrying metal nanoparticles is produced, the metal oxide carrying the metal nanoparticles is reacted with carbon dioxide to collect carbon dioxide in the metal oxide; And it may further include a step of reusing the reactant produced in the carbon dioxide capturing step in the charging step. As such, the carbon compound production method of the present invention directly reacts carbon dioxide desorbed from the reactant with methane to produce various carbon compounds with higher added value than methane and carbon dioxide while consuming carbon dioxide, and the carbon dioxide obtained in this process is converted into the desorbed reactant. In other words, a circulation process can be implemented in which carbon dioxide is adsorbed on the metal oxide carrying metal nanoparticles to generate a reactant and then reacted with methane again.

More specifically, in the method of producing carbon compounds through direct methane conversion reaction of the present invention, the methane gas composition injected using the device shown in FIG. 3 or FIG. 13 reacts with carbon dioxide desorbed from the reactant to produce various carbon compounds. In this case, a direct methane conversion reaction as shown in FIG. 2 may occur.

Next, the reaction apparatus for direct methane conversion reaction of the present invention includes a reaction space filled with metal carbonate or any of the above-mentioned reactants; a reaction gas supply unit providing methane gas to the reaction space; a product storage unit where carbon compounds and unreacted methane gas generated in the reaction space are discharged and stored; and a carbon dioxide supply unit that provides carbon dioxide to the reaction space where the generated carbon compound is discharged. If necessary, it may further include a separation unit connected to the product storage unit to extract and separate the carbon compound.

Here, the form or type of the reaction space is not particularly limited as long as the reaction temperature can be adjusted so that the carbon compound produced by reacting the metal carbonate or the reactant with methane gas is obtained in a gaseous state, and is used as a starting material. A batch reactor that can inject metal carbonate or a reactant and a methane gas composition as a reactant gas, or carbon dioxide and form a closed system, or a circulating fluidized bed such as a fluidized bed reactor or riser that can continuously introduce starting materials or transfer the product to another place. It may be a reactor. Additionally, the use of other types of reactors such as fixed bed reactors is not limited.

The product storage unit may be implemented so that the gaseous carbon compounds and unreacted methane gas generated in the reaction space can be transferred and stored. As an embodiment, it can be implemented as a condenser that can separate the liquid carbon compound, methane gas composition, and carbon monoxide by condensing and liquefying the gaseous carbon compound and the unreacted methane gas composition, and a gaseous storage unit that stores the gaseous methane gas and carbon monoxide. there is.

In the separation unit, any known technology can be used as long as it can separate the liquid and/or gaseous carbon compounds stored in the product storage unit into individual carbon compounds, but a distillation tower capable of performing a distillation method for the liquid carbon compounds is used. It can be implemented with a configuration that includes: Among the carbon compounds produced through the direct methane conversion process, liquid products such as acetic acid, methanol, and acetaldehyde can be easily vaporized, so each compound can be easily separated if a distillation method is performed to separate each component according to the difference in boiling point. Because. In particular, the boiling points of acetic acid, methanol, and acetaldehyde are 118 ℃, 65 ℃, and 20 ℃, respectively, making it easy to separate components. Since they can exist in a liquid phase in the low temperature range of 0 to 20 ℃, they can be separated from unreacted methane in the gas phase. There is an advantage to being able to do it.

In addition, outside and/or inside the reaction space, there is an inlet pipe through which gas supplied from the reaction gas supply section and the carbon dioxide supply section can flow into the reaction space, and an outlet pipe through which the carbon compound generated in the product storage section is discharged, as well as direct methane conversion. A configuration that can provide the temperature and pressure conditions necessary for the reaction, that is, a temperature control device (heater and/or cooling device) and a pressurizing device, may be provided.

Example 1

Add 10 g of CaCO ₃ to 500 mL of distilled water and stir at room temperature for 2 hours, then add 0.1745 g of Platinum (IV) chloride hydrate, stir for 2 hours, and recover the platinum-supported calcium carbonate using a rotary evaporator. The recovered platinum-supported calcium carbonate was dried in an oven at 100°C for 6 hours to prepare 1 wt% platinum-supported calcium carbonate.

Example 2

1 wt% palladium-supported calcium carbonate was prepared in the same manner as in Example 1, except that 0.2529 g of Palladium (II) nitrate dihydrate was used instead of 0.1745 g of Platinum (IV) chloride hydrate.

Example 3

The following steps were performed in the device shown in FIG. 3 to produce acetic acid through the methane direct conversion reaction as shown in FIG. 1.

1. Charging stage

A batch reactor was charged with 2g of zinc carbonate.

2. Step of supplying methane gas composition

A mixed gas of methane and nitrogen (CH ₄ 77%) was supplied to a batch reactor filled with zinc carbonate until the pressure reached 8 bar.

3. Step of performing direct methane conversion reaction

A direct methane conversion reaction was performed in which carbon dioxide was desorbed from zinc carbonate and reacted with methane gas for 120 minutes at 200°C and 8 bar pressure.

4. Obtaining acetic acid

The temperature inside the reactor was lowered to 10°C, and only liquid acetic acid among the acetic acid, zinc oxide, and unreacted methane gas present inside the reactor was discharged to the product storage unit to obtain acetic acid.

5. Step of capturing carbon dioxide in zinc oxide

After removing the unreacted methane gas remaining inside the reactor, carbon dioxide is injected into the reactor and treated under conditions of 50 ℃ and 20 bar to capture carbon dioxide in zinc oxide, and carbon dioxide is bound to zinc carbonate in monodentate and bidentate form on the surface of zinc oxide. The charging step was performed by forming.

Example 4

The following steps were performed in the device shown in FIG. 13 to produce carbon monoxide, acetic acid, acetaldehyde, and methanol through the methane direct conversion reaction as shown in FIG. 2.

1. Charging stage

The fixed bed column of the fixed bed continuous reactor was charged with 0.5 g of 1 wt% platinum-supported calcium carbonate prepared in Example 1.

2. Step of supplying methane gas composition

A mixed gas of methane and nitrogen (CH ₄ 77%) was supplied to a fixed bed column filled with 1 wt% platinum-supported calcium carbonate until the pressure reached 8 bar.

3. Step of performing direct methane conversion reaction

A direct methane conversion reaction was performed in which carbon dioxide was desorbed from 1 wt% platinum-supported calcium carbonate and reacted with methane gas for 120 minutes at 350°C and 8 bar pressure.

4. Obtaining carbon compounds

The carbon compounds, that is, acetic acid, acetaldehyde, methanol, and carbon monoxide, and the unreacted methane gas composition generated while passing through the fixed bed column were transferred to the first product storage unit and the temperature was lowered to 10°C, and acetic acid, acetaldehyde, and methanol were obtained in liquid form. , gaseous carbon monoxide and unreacted methane composition were discharged to the second product storage unit to obtain a liquid carbon compound.

5. Step of separating carbon products

The liquid acetic acid, acetaldehyde, and methanol obtained in the first product storage section were transferred to the separation section and then distilled to separate acetic acid, acetaldehyde, and methanol at each boiling point. The carbon monoxide and methane gas compositions stored in the second product storage unit were separated using a gas separation membrane using the difference in permeability of each gas to obtain carbon monoxide.

6. Step of capturing carbon dioxide in 1wt% platinum-supported calcium oxide

Carbon dioxide is injected into the reactor and treated under conditions of 500°C and 20 bar to capture carbon dioxide in 1wt% platinum-supported calcium oxide. Carbon dioxide is bonded to the surface of 1wt% platinum-supported calcium oxide in monodentate and bidentate form. The charging step was performed by forming

Experimental Example 1

In the batch reactor shown in FIG. 3, zinc carbonate and calcium carbonate are each added and then heated to 25-800°C at a rate of 5°C/min under nitrogen conditions. The mass change that occurs as the metal carbonate decomposes into metal oxide and carbon dioxide is measured. Observation was made through thermogravimetric analysis, and the results are shown in Figure 4.

As shown in Figure 4, in the case of zinc carbonate, it is observed that the mass decreases from 100% to about 70%, and in particular, it is confirmed that the mass decreases significantly around 200°C. The peak due to heat absorption during this process can be confirmed in the Heat Flow graph. In the case of calcium carbonate, it can be seen that the mass decreases from 100% to 60% around 700°C.

Experimental Example 2

2 g of zinc carbonate was added as a reactant to the batch reactor shown in FIG. 3, and a mixed gas of methane and nitrogen (CH ₄ 77%) was supplied until the pressure reached 8 bar, and then reacted with the zinc carbonate at 200° C. for 120 minutes. After performing the methane direct conversion reaction, the structural changes of the reactants before and after the methane direct conversion reaction were observed through X-ray diffraction patterns through XRD crystal structure analysis, and the results are shown in Figure 5a.

As shown in Figure 5a, when the reactant is zinc carbonate, it has the structure of zinc carbonate before the methane direct conversion reaction, but due to the desorption of carbon dioxide and conversion to zinc oxide during the methane direct conversion reaction, it has the structure of zinc oxide after the reaction. You can see that it has changed.

Experimental Example 3

As a reactant, 0.5 g of 1 wt% platinum-supported calcium carbonate obtained in Example 1 was reduced in a fixed bed reactor under the conditions of 50 cc/min of hydrogen and nitrogen by raising the temperature to 300°C for 4 hours and maintaining the temperature at 300°C for 4 hours. Methane and nitrogen mixed gas (CH ₄ 77%) was supplied to the batch reactor filled with the reduced 1 wt% platinum-supported calcium carbonate until the pressure reached 8 bar, and then reacted with the 1 wt% platinum-supported calcium carbonate at 350°C. The methane direct conversion reaction was carried out for 120 minutes. Afterwards, the structural change of the reactant before and after the methane direct conversion reaction was observed using an X-ray diffraction pattern through XRD crystal structure analysis, and the results are shown in Figure 5b.

As shown in Figure 5b, even when the reactant is 1 wt% platinum-supported calcium carbonate, it has a 1 wt% platinum-supported calcium carbonate structure before the methane direct conversion reaction, but due to the desorption of carbon dioxide and conversion to calcium oxide during the methane direct conversion reaction. After the reaction, it can be confirmed that the structure has changed to a 1wt% platinum-supported calcium oxide structure.

As shown in FIG. 4, the separation reaction of carbon dioxide occurs only when the temperature of calcium carbonate is above 600°C to 700°C. However, when platinum-supported calcium carbonate obtained by supporting platinum as in the present invention is used as a reactant, the reaction temperature is 350°C. It shows that a direct methane conversion reaction in which carbon dioxide is separated from the surface and reacts with methane gas is possible even at ℃.

Experimental Example 4

The 1 wt% platinum-supported calcium carbonate obtained in Example 1 was observed with a transmission electron microscope, and the resulting photograph is shown in FIG. 6.

As shown in Figure 6, it can be seen that platinum nanoparticles of about 5 nm in size are evenly dispersed on the surface of the calcium carbonate particles.

Experimental Example 5

In Experimental Example 2, after the methane direct conversion reaction was completed, the reaction catalyst material was recovered from the reactor and the product adsorbed on the surface of the reaction catalyst material was extracted using ethanol as a solvent. Based on 2 g of reaction catalyst material, 3 mL of ethanol was used and stirred for 1 hour, and then the reaction catalyst material and extract were separated through centrifugation. Butanol was added as an internal standard to the separated extract, and the results of analysis using a gas chromatography flame ionization detector are shown in Figure 7.

As shown in Figure 7, it can be confirmed that the product obtained by directly reacting zinc carbonate with methane as a reaction catalyst is acetic acid (left: entire area, right: enlarged area). In other words, it can be seen that ethanol used as an extraction solvent, butanol as an internal standard, and acetic acid as a product are separated through gas chromatography.

From these results, it can be confirmed that when a direct methane conversion reaction is performed using zinc carbonate (ZnCO ₃ ) as a reaction catalyst material, only acetic acid is obtained as a product.

Experimental Example 6

In Experimental Example 2, after the methane direct conversion reaction was completed, the gas contained in the reactor was detected through a thermal conductivity detector of gas chromatography, and the resulting chromatogram is shown in FIG. 8.

As shown in Figure 8, it can be confirmed that carbon dioxide separated from nitrogen, which is an internal standard gas, and methane, which is a reactant, and zinc carbonate are detected.

Experimental Example 7

In Experimental Example 3, after the methane direct conversion reaction was completed, the reaction catalyst material was recovered from the reactor and the product adsorbed on the surface of the reaction catalyst material was extracted using ethanol as a solvent. Based on 2 g of reaction catalyst material, 3 mL of ethanol was used and stirred for 1 hour, and then the reaction catalyst material and extract were separated through centrifugation. Butanol was added as an internal standard to the separated extract, and the results of analysis using a gas chromatography flame ionization detector are shown in Figure 9.

As shown in Figure 9, it can be confirmed that the products obtained by directly reacting with methane using 1w% gold-supported calcium carbonate (Pt/CaCO ₃ ) as a reaction catalyst are methanol, acetaldehyde, and acetic acid (left: entire area) , right: enlarged area). In other words, it can be seen that ethanol used as an extraction solvent, butanol as an internal standard, and methanol, acetaldehyde, and acetic acid as products are separated through gas chromatography.

Experimental Example 8

In Experimental Example 3, after the methane direct conversion reaction was completed, the gas contained in the reactor was detected through a thermal conductivity detector of gas chromatography, and the resulting chromatogram is shown in FIG. 10.

As shown in Figure 10, it can be confirmed that nitrogen, which is an internal standard gas, carbon monoxide, which is a product, methane, which is a reactant, and carbon dioxide separated from calcium carbonate are detected.

Experimental Example 9

In Experimental Example 3, the reaction catalyst materials before and after the methane direct conversion reaction were analyzed using X-ray photoelectron spectroscopy, and the obtained results are shown in FIG. 11.

As shown in Figure 11, the reaction catalyst material before the methane direct conversion reaction (1Pt/CaCO ₃ Fresh) and the reaction catalyst material after the reaction (1Pt/CaCO ₃ CH ₄ rxn.) are in the C, O, Ca, and Pt regions. As a result of the analysis, an increase in the C 1s peak in the carbon region was observed, which was a change that occurred as methane was activated on the surface of the reaction catalyst material.

Experimental Example 10

If the reaction catalyst materials are cobalt carbonate, zinc carbonate, cerium carbonate, and calcium carbonate, use the method of Experimental Example 2, and if the reaction catalyst materials are 1w% platinum-supported calcium carbonate and 1w% palladium-supported calcium carbonate, methane will be produced by the method of Experimental Example 3, respectively. The product obtained by performing the direct conversion reaction was analyzed for methane conversion rate, product selectivity, and productivity, and the results are shown in Figure 12 and Table 1.

From Figure 12 and Table 1, if the reaction catalyst materials are cobalt carbonate, zinc carbonate, and cerium carbonate, only acetic acid can be obtained as a product through methane direct conversion reaction, and the reaction catalyst materials are 1w% platinum-supported calcium carbonate and 1w% palladium-supported carbonate. It can be seen that when a noble metal, such as calcium, is supported on a metal carbonate, carbon compounds including acetic acid, acetaldehyde, methanol, and carbon monoxide can be obtained as products through a methane direct conversion reaction.

In addition, it can be seen that the conversion rate of methane during the methane direct conversion reaction is better for the noble metal-supported metal carbonate than for the metal carbonate.

Experimental Example 11

After adding cobalt carbonate to the fixed bed continuous reaction device shown in FIG. 13 and heating it to 25-800°C at a rate of 5°C/min under nitrogen conditions, the mass change that occurs as the metal carbonate decomposes into metal oxide and carbon dioxide is measured as thermogravimetric weight. Observation was made through the analysis method, and the results are shown in Figure 14.

As shown in Figure 14, in the case of cobalt carbonate, it is observed that the mass decreases from 100% to about 60%, and in particular, two reduction sections are confirmed around 220°C. The entire range of 220 ℃ is a change that occurs as water adsorbed on the surface falls, and the decrease after 220 ℃ is a change that occurs as carbon dioxide falls.

Experimental Example 12

2 g of cobalt carbonate was added as a reaction catalyst to the fixed bed continuous reaction device shown in FIG. 13, moisture was removed at 150°C and nitrogen was 25 cc/min, and methane and nitrogen mixed gas (CH ₄ 77%) was added at 100°C and 30%. The reaction was carried out for 4 hours while flowing at 25 cc/min under bar conditions, and then the structural changes of the reactants before and after the methane direct conversion reaction were observed using X-ray diffraction patterns through XRD crystal structure analysis, and the results are shown in Figure 15. It was.

As shown in Figure 15, a cobalt carbonate structure appears before the methane direct conversion reaction, but it can be confirmed that the structure is a cobalt oxide structure after the reaction due to the desorption of carbon dioxide and conversion to cobalt oxide during the reaction process.

Experimental Example 13

2 g of cobalt carbonate was added as a reaction catalyst to the fixed bed continuous reaction device shown in FIG. 13, moisture was removed at 150°C and nitrogen was 25 cc/min, and methane and nitrogen mixed gas (CH ₄ 77%) was added at 100°C and 30%. The reaction was carried out for 4 hours while flowing at 25 cc/min under bar conditions, and then the reaction catalyst material was recovered and the product adsorbed on the surface of the reaction catalyst material was extracted using ethanol as a solvent. Based on 2 g of reaction catalyst material, 3 mL of ethanol was used and stirred for 1 hour, and then the reaction catalyst material and extract were separated through centrifugation. Butanol was added as an internal standard to the separated extract, and the results of analysis using a gas chromatography flame ionization detector are shown in Figure 16.

As shown in Figure 16, it can be confirmed that the product obtained by directly reacting methane with cobalt carbonate as a reaction catalyst material is acetic acid (left: entire area, right: enlarged area). In other words, it can be seen that ethanol used as an extraction solvent, butanol as an internal standard, and acetic acid as a product are separated through gas chromatography.

From these results, it can be confirmed that when a direct methane conversion reaction is performed using cobalt carbonate (CoCO ₃ ) as a reaction catalyst material, only acetic acid is obtained as a product.

Experimental Example 14

In Experimental Example 13, the gas discharged from the fixed bed continuous reaction device during the methane direct conversion reaction was detected in real time through a thermal conductivity detector of gas chromatography, and the resulting chromatogram is shown in FIG. 17.

As shown in Figure 17, it can be confirmed that carbon dioxide separated from nitrogen, which is an internal standard gas, and methane, which is a reactant, and cobalt carbonate are detected.

Experimental Example 15

In Experimental Example 13, the reaction catalyst materials before and after the methane direct conversion reaction were analyzed using X-ray photoelectron spectroscopy, and the obtained results are shown in FIG. 18. As a comparison group, the results of heat treatment without methane gas under the same conditions as the reaction temperature and the results after extraction are included. Analysis was conducted on the C, O, and Co regions.

As shown in Figure 18, a decrease in peak intensity in the C region is confirmed due to carbon dioxide desorption due to heat treatment, but in the case of the reaction catalyst material after the methane direct conversion reaction, an increase in the peak of C 1s in the carbon region can be observed, This is a change that appears as methane is activated on the catalyst surface. In the case of a reactant catalyst after extraction, the peak of C 1s decreases as the product is separated from the reaction catalyst material.

Experimental Example 16

The reaction was carried out in a pulse mode in which reaction gases were sequentially and alternately injected in the fixed bed continuous reaction apparatus shown in Figure 13. Add 2 g of cobalt oxide and remove surface moisture in an N ₂ atmosphere at 150°C. After that, CO ₂ gas flows at 25 cc/min under conditions of 100°C and 20 bar. After that, CH ₄ gas flows at 25 cc/min under conditions of 150°C and 20 bar. Acetic acid adsorbed on the catalyst surface is extracted by flowing vaporized water or an alcohol-based organic solvent such as ethanol. The schematic diagram, experimental conditions, and process of Experimental Example 16 are shown in Figures 19, 20, and 21.

Figures 19 and 20 show the entire process of adsorption of carbon dioxide using cobalt oxide, direct reaction with methane, and production of acetic acid by applying the fixed bed continuous reaction device shown in Figure 13 as a pulse-mode reaction, and the overall process of producing acetic acid. It shows the experimental conditions for operation.

Referring to Figure 21, which shows the IR absorption spectrum over time during CO ₂ Activation during the process shown in Figure 20 using cobalt oxide, Fresh, which is the state before CO ₂ Activation (adsorption), and corresponding to 1 to 30 min. You can check the graph, and in the 30 min graph, you can see the peak increase in the region of about 1300~1700 cm ^-1 due to carbon dioxide adsorption.

Experimental Example 17

The methane conversion rate, selectivity, and productivity of the products obtained by performing a direct methane conversion reaction using the method of Experimental Example 16 using cobalt carbonate and 1w% platinum-supported calcium carbonate as reaction catalyst materials were analyzed, and the results were reported. It is shown in Table 2.

When the reaction catalyst material was cobalt carbonate, comparing the results in Table 1 to Table 2, there was no difference in selectivity even when a fixed bed continuous reaction device was used. However, it was confirmed that the methane conversion rate improved by 3% and productivity improved by about 20 times from 0.005 to 0.09.

On the other hand, when the reaction catalyst material was 1w% platinum-supported calcium carbonate, when a fixed bed continuous reaction device was used, not only did the product show 97.0% selectivity for acetaldehyde, but the productivity was also improved by more than 35 times to 14.95 mmol.

Therefore, it can be seen that by varying the type of reaction catalyst material as well as the type of reactor and reaction conditions for the methane direct conversion reaction, the desired carbon compound can be obtained with higher selectivity and production volume.

Although the present invention has been illustrated and described by way of preferred embodiments as described above, it is not limited to the above-described embodiments and is intended to be used by those skilled in the art without departing from the spirit of the invention. Various changes and modifications will be possible.

Claims (19)

metal carbonate; and
A catalytic reaction material for methane direct conversion reaction comprising metal nanoparticles supported on the metal carbonate.
According to claim 1,
A catalytic reactant for methane direct conversion reaction, wherein the metal carbonate is at least one selected from the group consisting of zinc carbonate, calcium carbonate, cerium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, copper carbonate and cobalt carbonate.
According to claim 1,
The metal nanoparticles are methane direct conversion, characterized in that at least one selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). Catalytic reactant for reaction.
According to claim 1,
A catalytic reaction material for methane direct conversion reaction, characterized in that the metal nanoparticles are contained in an amount of 0.1 to 5% by weight based on the metal carbonate.
According to claim 4,
A catalytic reaction material for methane direct conversion reaction, characterized in that the diameter of the metal nanoparticles is 1 to 10 nm.
The method according to any one of claims 1 to 5,
A catalytic reaction material for methane direct conversion reaction, characterized in that carbon dioxide reactive with methane gas is emitted at a temperature of 25 ℃ - 600 ℃ and a pressure of 5 bar to 50 bar.
A charging step of charging any one metal carbonate of cobalt carbonate, zinc carbonate, and cerium carbonate into the reactor;
Supplying methane gas to the reactor filled with the metal carbonate;
Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 300°C and a pressure of 5 bar to 50 bar; and
A method for producing acetic acid through a methane direct conversion reaction, comprising: obtaining acetic acid produced through performing the methane direct conversion reaction.
According to claim 7,
If the metal carbonate charged in the reactor is cobalt carbonate, the temperature of the reactor is adjusted to 50°C to 150°C.
According to claim 7,
If the metal carbonate charged in the reactor is zinc carbonate, the temperature of the reactor is adjusted to 100°C to 200°C. A method of producing acetic acid through methane direct conversion reaction.
According to claim 7,
If the metal carbonate charged in the reactor is cerium carbonate, the temperature of the reactor is adjusted to 50°C to 250°C. The method according to any one of claims 7 to 10,
A method of producing acetic acid through a direct methane conversion reaction, characterized in that the methane gas composition does not contain carbon dioxide.
The method according to any one of claims 7 to 10,
When a metal oxide salt of any one of cobalt oxide, zinc oxide, and cerium oxide is produced through the methane direct conversion reaction, reacting the metal oxide salt with carbon dioxide to collect carbon dioxide in the metal oxide salt; and reusing any one of cobalt carbonate, zinc carbonate, and cerium carbonate generated in the carbon dioxide capture step in the charging step.
Charging the reactant of any one of claims 1 to 5 into a reactor;
Supplying a methane gas composition to a reactor filled with the reactant;
Performing a direct methane conversion reaction by setting the reactor to a temperature of 25°C - 600°C and a pressure of 5 bar to 50 bar; and
A method for producing a carbon compound through a methane direct conversion reaction, comprising: obtaining a carbon compound obtained by the methane direct conversion reaction.
According to claim 13,
A method of producing a carbon compound through a methane direct conversion reaction, wherein the carbon compound includes one or more selected from the group consisting of acetic acid, acetaldehyde, methanol, and carbon monoxide.
According to claim 13,
If the reactant charged in the reactor is one in which platinum nanoparticles are supported on calcium carbonate, the temperature of the reactor is adjusted to 300°C to 600°C.
According to claim 13,
A method of producing a carbon compound through a methane direct conversion reaction, characterized in that the methane gas composition does not contain carbon dioxide.
According to claim 13,
When carbon dioxide is released from the reactant through the methane direct conversion reaction and a metal oxide salt carrying metal nanoparticles is produced, the metal oxide salt carrying the metal nanoparticles is reacted with carbon dioxide to collect carbon dioxide in the metal oxide salt. ; and reusing the reactant produced in the carbon dioxide capturing step in the charging step.
A reaction space filled with metal carbonate or the reactant of any one of claims 1 to 5;
a reaction gas supply unit providing methane gas to the reaction space;
a product storage unit where carbon compounds generated in the reaction space are discharged and stored; and
A reaction device for a methane direct conversion process comprising a carbon dioxide supply unit that provides carbon dioxide to the reaction space where the carbon compound is discharged.
According to claim 18,
A reaction device for a methane direct conversion process further comprising a separation unit connected to the product storage unit to extract and separate the carbon compound.