KR101458410B1 - Method for making oxide and synthetic gas by carbon dioxide plasma torch and the oxide thereof - Google Patents

Method for making oxide and synthetic gas by carbon dioxide plasma torch and the oxide thereof Download PDF

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KR101458410B1
KR101458410B1 KR1020120107773A KR20120107773A KR101458410B1 KR 101458410 B1 KR101458410 B1 KR 101458410B1 KR 1020120107773 A KR1020120107773 A KR 1020120107773A KR 20120107773 A KR20120107773 A KR 20120107773A KR 101458410 B1 KR101458410 B1 KR 101458410B1
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carbon dioxide
oxide
plasma
plasma torch
dioxide plasma
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KR1020120107773A
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KR20140041003A (en
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홍용철
천세민
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한국기초과학지원연구원
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Carbon And Carbon Compounds (AREA)
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Abstract

The present invention relates to a method for providing an oxide and a syngas using a carbon dioxide plasma, the method comprising: generating an electromagnetic wave to transfer the electromagnetic wave into a plasma generator; supplying a carbon dioxide gas to the plasma generator to generate a carbon dioxide plasma torch; To a process for providing an oxide and a syngas using a carbon dioxide plasma, wherein the carbon dioxide decomposes and reacts with the reaction material to produce a synthesis gas and an oxide.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for providing oxides and syngas using a carbon dioxide plasma torch,

The present invention relates to a method for reusing carbon dioxide using a carbon dioxide plasma torch to produce compounds and synthesis gas necessary for industrial processes and real life.

Carbon dioxide is the most important cause of global warming. Decomposing and extinguishing such carbon dioxide is very important from an environmental point of view. Furthermore, if carbon dioxide can be used as a new renewable raw material while decomposing carbon dioxide, utilization value will be high.

Carbon dioxide technology can be divided into abatement technology and treatment technology. Carbon dioxide capture and storage (CCS) technology is currently being developed, but it can be used as a renewable source of energy and energy for CO2 capture. Recycling technology is needed.

Carbon dioxide resource technology is one of the technologies that solve global warming problem and resource depletion problem at the same time, and its importance as a basic chemical raw material as well as energy has increased, and efforts to convert it into a useful harmful substance have become a big concern.

Carbon dioxide can be chemically, biologically, optically, or electrochemically synthesized and recycled into a variety of chemicals. Therefore, the technology of reusing carbon dioxide, that is, the technology of generating new compounds by conversion, would be a very useful technique.

The present invention seeks to utilize carbon dioxide plasma torch technology using electromagnetic waves to reuse such carbon dioxide and generate new compounds.

Korean Patent No. 10-1166444 discloses a technology for reusing carbon dioxide with a plasma torch using electromagnetic waves. The present invention relates to a carbon dioxide torch produced by an electromagnetic wave and its application, and its object is to generate a pure carbon dioxide plasma torch by heating a carbon dioxide gas with an electromagnetic wave and to generate a gas, liquid or solid hydrocarbon compound in the generated carbon dioxide plasma To produce synthesis gas raw materials.

As a soot removal technique using microwave plasma, Korean Patent Registration No. 10-0375423 is available.

An object of the present invention is to achieve a carbon dioxide reuse technology, which has become necessary as described above, by utilizing plasma torch technology using electromagnetic waves.

Further, it is an object of the present invention to provide a high-temperature and high-density microwave plasma stabilized by using carbon dioxide (CO 2 ) which can cause global warming and to inject a reaction material such as a transition metal into the high- And a device and a method for producing a compound and a syngas necessary for the process and the real life.

The present invention provides a method for providing an oxide and a syngas using a carbon dioxide plasma.

The method includes generating an electromagnetic wave to transfer the electromagnetic wave into a plasma generator, supplying a carbon dioxide gas to the plasma generator to produce a carbon dioxide plasma torch, and supplying the reaction material to the carbon dioxide plasma torch, Decomposed and reacted with the reaction material to produce synthesis gas and oxide.

In another aspect of the present invention, the present invention provides an oxide produced using a carbon dioxide plasma.

The oxide generates an electromagnetic wave to transfer the electromagnetic wave into the plasma generator, generates a carbon dioxide plasma torch by supplying carbon dioxide gas to the plasma generator, supplies the reaction material to the carbon dioxide plasma torch, and the carbon dioxide is decomposed , And an oxide produced by reacting with the reaction material.

The reaction material is a transition metal. Preferably, Zn (zinc), Ti, magnesium, vanadium, Fe, cadmium, Cu, tin, tellurium and Si 0.0 > (silicon). < / RTI >

For example, in the case of Zn, Ti or Mg, the oxide are each ZnO, TiO 2, or MgO.

The reaction formula is as follows.

xCO 2 + yZn → aZnO + bCO

xCO 2 + yTi → aTiO 2 + bCO

xCO 2 + yMg → aMgO + bCO

ZnO, TiO 2 , or MgO have mainly photocatalytic properties. It decomposes volatile organic compounds (VOCs) and removes germs and the like, and is used in air purifiers, air conditioners, etc., and is used by being coated on inner walls of buildings, water tanks and glass. It is also used as anti-fogging agent on the principle of hydrophilicity. As semiconductor, it has wavelength (380nm) corresponding to wide band gap (3.37eV, 3.2eV), and it is advantageous that bonding energy is large at room temperature.

The transition metal oxide such as ZnO, TiO 2 , or MgO obtained through the method of the present invention is doped with C 2 (impurity) and has a reduced band gap energy, so that the photocatalytic reaction can be more efficiently enhanced.

The reaction material may further comprise H 2 O, a hydrocarbon compound or H 2 O and a hydrocarbon compound. This can control the molar ratio of the product.

In particular, by injecting a hydrocarbon compound, the band gap energy of the synthesized metal oxide can be further narrowed.

When H 2 O is added as a reaction material, the following reaction is performed.

1.aCO 2 + bH 2 O + cZn → xZnO + yCO + zH 2

2.aCO 2 + bH 2 O + cTi → xTiO + yCO + zH 2

3.aCO 2 + bH 2 O + cMg → xMgO + yCO + zH 2

As an example of a hydrocarbon compound, when further adding CH 4 as a reaction material, the following reaction is performed.

2 + 4 + 1.aCO bCH cZn → xZnO + yCO + zH 2

2 + 4 + 2.aCO bCH cTi → xTiO + yCO + zH 2

2 + 4 + 3.aCO bCH cMg → xMgO + yCO + zH 2

Preferably, the electromagnetic wave is 2.45 GHz, 902 to 928 MHz, or 886 to 896 MHz.

And the reaction material is injected into the brightest region of the carbon dioxide plasma torch.

And the oxide is a C 2 -doped oxide.

The absorption wavelength of the oxide is red-shifted.

The present invention provides carbon dioxide as a raw material utilization technique and a reduction method by converting carbon dioxide which is a global warming material into a useful material by reacting with a synthetic material and injecting a synthesis material such as a transition metal into a carbon dioxide microwave plasma, And provides carbon monoxide production technology from carbon dioxide plasma material synthesis.

Transition metal oxides produced according to the present invention, especially ZnO, TiO 2 and MgO, are red-shifted by the doping of C 2 radicals (impurities) as photocatalysts. That is, it is possible to cause a catalytic reaction in a visible light region, which is energy smaller than the ultraviolet region, and to increase the photocatalytic reaction more efficiently.

Particularly, the transition metal oxide obtained under a plasma torch by carbon dioxide and hydrocarbon compounds is red-shifted by doping with more C 2 radicals (impurities), and the band gap is reduced.

1 is a block diagram conceptually illustrating an apparatus for producing a syngas using a carbon dioxide plasma according to a preferred embodiment of the present invention.
FIG. 2 illustrates the syngas production apparatus using the carbon dioxide plasma of the present invention more specifically.
3 is a more detailed view of the plasma generator 150 and the reactor 170. As shown in FIG.
4A is a photograph showing a carbon dioxide plasma torch flame generated from the carbon dioxide plasma torch generator of the present invention using 2.45 GHz electromagnetic waves.
4B is a photograph showing a carbon dioxide plasma torch flame generated from the carbon dioxide plasma torch generator of the present invention using 915 MHz electromagnetic waves.
5 is an emission spectrum of the plasma torch flame of the carbon dioxide (black graph) and the mixed gas of carbon dioxide and methane (blue graph) according to the 2.45 GHz electromagnetic wave by the OES spectrometer.
Figure 6a shows the results of EDX analysis of conventional commercially available ZnO powders. FIG. 6B shows the EDX analysis results of the ZnO powder obtained through the above-described embodiment.
Figure 7 shows the UV-Visible spectra of samples (a), (b), (c) and commercial ZnO of the embodiments of the present invention.
8 is a TEM photograph showing the reaction material and the oxide of Example 2. Fig.

1. CO2 plasma torch generator using electromagnetic wave

1 is a block diagram conceptually showing an apparatus for generating a carbon dioxide plasma torch using electromagnetic waves according to a preferred embodiment of the present invention.

As for the carbon dioxide plasma torch generator, reference is made to Korean Patent Publication No. 10-0394994, which is a previously registered patent of the present inventor. This patent is incorporated herein by reference in its entirety.

1, the apparatus of the present invention includes a power supply unit 110, a microwave oscillator 120, a microwave transmission line 130, a material supply unit 140, a plasma generation unit 150, a carbon dioxide injection unit 160 ), And a reactor (170).

The power supply unit 110 is configured to include a propagation voltage multiplier and a pulse and direct current (DC) device to supply power to the microwave oscillator 120.

The microwave oscillator 120 uses a magnetron that oscillates electromagnetic waves in the 10 MHz to 10 GHz band. Preferably, the microwave oscillator 120 oscillates 2.45 GHz electromagnetic waves.

The microwave transmission line 130 is a waveguide, and is configured to transmit the microwave to the plasma generator 150.

The plasma generating unit 150 is provided at a terminating end of the microwave transmission line 130 to provide a space in which plasma is generated by electromagnetic waves input through the microwave transmission line 130.

The carbon dioxide injector 160 is configured to be injected into the plasma generator 150 such that a carbon dioxide plasma torch is generated. 3 is referred to.

The reactor 170 is a space in which a generated carbon dioxide plasma torch is disposed on the opposite side of the plasma generating part in the direction of injection of the carbon dioxide injecting part.

The material supply part 140 is configured to supply the reaction material to the reactor. In particular, the material supply part 140 is configured to supply the reaction material with the carbon dioxide plasma torch.

FIG. 2 illustrates the syngas production apparatus using the carbon dioxide plasma of the present invention more specifically.

The power supply unit 110 supplies power to the microwave oscillator 120. The microwave oscillator generates electromagnetic waves. The generated electromagnetic waves are sequentially transmitted to the plasma generator 150 through the circulator 210, the directional coupler 220, the matching device 230, and the microwave transmission line 130.

A more detailed description of the plasma generator 150 and the reactor 170 is given in FIG.

The carbon dioxide gas is injected through one side of the plasma generator 150.

The carbon dioxide plasma torch is supplied to the plasma generating unit 150 and carbon dioxide is generated in the reactor 170 while the electromagnetic wave is transmitted to the plasma generating unit 150 through the microwave transmission line 130.

The reaction material 320 is supplied through the material supply 140 to any selected position of the carbon dioxide plasma torch 310.

2. Example 1

A carbon dioxide plasma torch generator using the electromagnetic waves described above was used. The microwave oscillator 120 oscillated 2.45 GHz and 915 MHz microwaves. Carbon dioxide was injected from the carbon dioxide injection unit 160 into the plasma generation unit 150 at a predetermined injection rate. As a result, a CO2 plasma torch using 2.45 GHz and 915 MHz electromagnetic waves was generated.

4A is a photograph showing a carbon dioxide plasma torch flame generated from a carbon dioxide plasma torch generator of the present invention using 2.45 GHz electromagnetic waves.

4B is a photograph showing a carbon dioxide plasma torch flame generated from the carbon dioxide plasma torch generator of the present invention using 915 MHz electromagnetic waves.

Referring to FIG. 4A, the carbon dioxide plasma torch flame is divided into a bright region in the blue region as the temperature increases.

5 is an emission spectrum of the plasma torch flame of the carbon dioxide (black graph) and the mixed gas of carbon dioxide and methane (blue graph) according to the 2.45 GHz electromagnetic wave by the OES spectrometer.

Zn powder was injected through the material supply unit 140 into the carbon dioxide plasma torch flame according to 2.45 GHz electromagnetic wave. The injection position was varied according to the position of the carbon dioxide plasma flame.

Zn powder reacts with carbon dioxide and generates ZnO and CO as shown in the following reaction formula.

xCO 2 + yZn → aZnO + bCO

ZnO according to the present invention is doped with C 2 .

The reactant obtained by injecting the Zn powder into the brightest region 410 of the carbon dioxide plasma flame was defined as sample (a), and the reactant obtained by injecting into the slightly white region 420 of the carbon dioxide plasma flame was defined as sample (b) , And the reaction product obtained by injecting the gas into the blue region 430 of the carbon dioxide plasma flame was defined as a sample (c).

In order to confirm whether or not the sample (c) obtained through the example as described above was doped with C 2, the following analysis was made.

6A shows the results of EDX analysis of commercially available commercial ZnO powders. FIG. 6B shows the EDX analysis results of the ZnO powder obtained through the above-described embodiment.

As shown in FIG. 6B, it can be seen that the weight percentage of C element is higher than that of commercial ZnO. It is confirmed that the intensity of C-specie is increased by doping C 2 radical (impurity) of CO 2 plasma.

In order to confirm the red-shift phenomenon of ZnO obtained through the above-described embodiment, the following analysis was made.

Figure 7 shows the UV-Visible spectra of samples (a), (b), (c) and commercial ZnO of the embodiments of the present invention.

The samples of the present invention can be confirmed that the red-shifting phenomenon of ZnO occurs due to the doping of C 2 radicals (impurities) in the plasma. It can be confirmed that the catalytic reaction can be caused in the visible light region which is smaller than the ultraviolet region. In particular, it can be confirmed that the sample (a) is red-shifted a lot.

Further, more C 2 doping and band gap reduction by the plasma torch of the mixed gas of carbon dioxide and hydrocarbon gas can be confirmed as follows.

As can be seen in FIG. 5, in the case of a plasma torch of a mixed gas of carbon dioxide and methane, the intensity of C 2 was stronger than that of carbon dioxide only. This means that there are more C 2 species, and if the transition metal is reacted in this atmosphere, the transition metal oxide can be doped with C 2 more. Therefore, the transition metal oxide obtained by reacting the transition metal with a plasma torch of a mixed gas of carbon dioxide and methane gas is a catalyst having a narrow band gap.

3. Example 2

The same experiment as in Example 1 described above was carried out except that a mixed metal powder of Cd and Zn was used as a reaction material in the carbon dioxide plasma torch.

8 is a TEM photograph showing the reaction material and the oxide of Example 2. Fig.

As shown in Fig. 8, it is confirmed that when the transition metal mixed powder is used as the reaction material in the carbon dioxide plasma torch of the present invention, nanoparticles of oxides of various structures can be produced.

Claims (16)

delete delete delete delete delete delete delete delete delete As an oxide of a reaction material produced using a carbon dioxide plasma torch,
Preferably,
A plasma processing method comprising: transferring an electromagnetic wave into a plasma generator, generating a carbon dioxide plasma torch by supplying carbon dioxide gas to the plasma generator, supplying a reaction material to the carbon dioxide plasma torch,
Wherein the carbon dioxide is decomposed, reacted with the reaction material,
Wherein the oxide is a C 2 doped oxide.
Oxides of reaction materials produced using carbon dioxide plasma torches.
11. The method of claim 10,
Characterized in that the reaction material is a transition metal.
Oxides of reaction materials produced using carbon dioxide plasma torches.
12. The method of claim 11,
The transition metal may be at least one selected from the group consisting of Zinc, Ti, Ti, Mg, V, Fe, Cd, Si (silicon). ≪ RTI ID = 0.0 >
Oxides of reaction materials produced using carbon dioxide plasma torches.
The method according to claim 10 or 11,
Wherein the electromagnetic wave is 2.45 GHz, 902 to 928 MHz, or 886 to 896 MHz.
Oxides of reaction materials produced using carbon dioxide plasma torches.
The method according to claim 10 or 11,
Characterized in that the reaction material is injected into the brightest region of the carbon dioxide plasma torch.
Oxides of reaction materials produced using carbon dioxide plasma torches.
delete The method according to claim 10 or 11,
Characterized in that the absorption wavelength of the oxide is red-shifted.
Oxides of reaction materials produced using carbon dioxide plasma torches.
KR1020120107773A 2012-09-27 2012-09-27 Method for making oxide and synthetic gas by carbon dioxide plasma torch and the oxide thereof KR101458410B1 (en)

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KR102326833B1 (en) * 2019-10-23 2021-11-17 강원대학교산학협력단 Method for producing metal oxide nanostructures doped with a heterogeneous element using microwave plasma device, the metal oxide nanostructures doped with the heterogeneous element manufactured using the same, and photocatalysts including the metal oxide nanostructures doped with a heterogeneous element
KR102291144B1 (en) 2019-11-14 2021-08-17 동의대학교 산학협력단 Method for producing a transition metal oxide using a gas torch and a composition for treating inflammatory diseases comprising the transition metal oxide prepared by the method
KR102675592B1 (en) * 2022-11-29 2024-06-17 주식회사 엔비유 Dual structure plasma generator for efficient reforming of landfill gas and biogas

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KR20110094748A (en) * 2010-02-17 2011-08-24 인하대학교 산학협력단 Preparation method of nano-sized zno powder during the decomposition of co2 by thermal plasma
KR20110138461A (en) * 2010-06-21 2011-12-28 엄환섭 A carbon dioxide torch powered by microwaves and its applications

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110094748A (en) * 2010-02-17 2011-08-24 인하대학교 산학협력단 Preparation method of nano-sized zno powder during the decomposition of co2 by thermal plasma
KR20110138461A (en) * 2010-06-21 2011-12-28 엄환섭 A carbon dioxide torch powered by microwaves and its applications
KR101166444B1 (en) * 2010-06-21 2012-07-19 엄환섭 A carbon dioxide torch powered by microwaves and its applications

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