KR101084730B1 - Method of simultaneous producing electricity and organic compound, catalyst for fuel cell electrode, and fuel cell comprising the catalyst - Google Patents

Abstract

Disclosed are a method for simultaneously producing an electric and organic compound using a fuel cell, a catalyst for a fuel cell electrode, and a fuel cell including the catalyst. Simultaneous production of electric and organic compounds using the disclosed fuel cells is a method of simultaneously producing high-value and high-value organic compounds by including a catalyst for a fuel cell electrode comprising a main catalyst and a catalyst for partial oxidation of fuel.

Description

Method of simultaneous producing electricity and organic compound, catalyst for fuel cell electrode, and fuel cell comprising the catalyst}

Disclosed are a method for simultaneously producing an electric and organic compound using a fuel cell, a catalyst for a fuel cell electrode, and a fuel cell including the catalyst. More specifically, a method and a fuel cell for simultaneously producing an electric compound with a high value and a high value by providing a catalyst for a fuel cell electrode including a main catalyst and a catalyst for partial oxidation of a fuel are disclosed.

A fuel cell is a cell that directly converts chemical energy generated by oxidation of fuel into electrical energy. The fuel cell is basically the same as a normal chemical cell in that it uses an oxidation-reduction reaction, but unlike a chemical cell that performs a cell reaction in a closed system, reactants are continuously supplied from the outside. And a battery in which the reaction product is continuously removed out of the system. Most typical are hydrogen-oxygen fuel cells. Since then, several fuel cells have been developed including gaseous fuels using fossil fuels such as methane and natural gas in addition to hydrogen, and liquid fuels such as methanol (methyl alcohol) and hydrazine. Among these fuel cells, those having an operating temperature of 300 ° C. or lower are referred to as a low temperature type and those above a high temperature type. In addition, compared to these fuel cells, the power generation efficiency was improved, but a high temperature molten carbonate fuel cell was developed without using a noble metal catalyst, which is called the second generation fuel cell and has higher efficiency. A solid electrolyte fuel cell, which generates electricity from power plants, was developed and is called the third generation fuel cell.

This conventional fuel cell mainly produces water and carbon dioxide, which are the result of complete oxidation of the fuel.

One embodiment of the present invention provides a method for simultaneously producing an electric and organic compound using a fuel cell.

Another embodiment of the present invention provides a catalyst for a fuel cell electrode including a main catalyst and a promoter for partial oxidation of a fuel.

Another embodiment of the present invention provides a fuel cell including the catalyst for the fuel cell electrode.

One aspect of the invention,

Injecting one or more first fuels into an anode of a fuel cell having an anode, an electrolyte membrane, and a cathode, and injecting an oxidant into the cathode to partially oxidize the first fuel to produce a first organic compound. It provides a method for the simultaneous production of electrical and organic compounds comprising.

Another aspect of the invention,

Injecting at least one first fuel into an anode of a fuel cell having an anode, an electrolyte membrane and a cathode, and injecting at least one second fuel together with an oxidant to the cathode to partially oxidize the second fuel at the cathode It provides a method for the simultaneous production of electricity and organic compounds comprising the step of producing two organic compounds.

The simultaneous manufacturing method of the electric and organic compounds may further include generating a third organic compound by partially oxidizing the first fuel at the anode.

Partial oxidation of the first fuel may be achieved by reacting one or more first fuels injected into the anode with ions generated at the cathode and delivered to the anode through the electrolyte membrane.

The ions reacting with the first fuel may be oxygen ions.

Partial oxidation of the first fuel may be achieved by one or more fuels injected into the anode reacting with each other at the anode.

Partial oxidation of the second fuel may be achieved by reacting one or more second fuels injected into the cathode with ions generated at the anode and delivered to the cathode through the electrolyte membrane and with the oxidant injected into the cathode.

The ions reacting with the second fuel may be hydrogen ions.

Partial oxidation of the second fuel may be achieved by one or more fuels injected into the cathode reacting with each other at the cathode.

Partial oxidation of the second fuel may be achieved by reacting one or more fuels injected into the cathode and an oxidant injected into the cathode with each other at the cathode.

Another aspect of the invention,

A catalyst for a fuel cell electrode including a main catalyst and a cocatalyst for partial oxidation of a fuel is provided.

The promoter may comprise at least one metal, metal mixture or metal alloy selected from the group consisting of Fe, Cu, Mo, V, K, Ca and Mg.

The fuel cell electrode catalyst may include 0.5 to 50 parts by weight of the promoter based on 100 parts by weight of the main catalyst.

Another aspect of the invention,

Anode;

Cathode; And

An electrolyte membrane disposed between the anode and the cathode,

At least one of the anode and the cathode provides a fuel cell comprising a catalyst for the fuel cell electrode.

According to one embodiment of the present invention, by providing a catalyst for a fuel cell electrode including a cocatalyst for partial oxidation of a fuel, a method and a fuel cell for simultaneously producing an electric compound with a high value and high added value can be provided.

Hereinafter, with reference to the accompanying drawings, a fuel cell according to an embodiment of the present invention, a fuel cell electrode catalyst included in the fuel cell and a method of simultaneously producing an electric and organic compound using the fuel cell will be described in detail.

1 is a view schematically showing a fuel cell according to an embodiment of the present invention.

Referring to FIG. 1, the fuel cell 100 includes an anode 110, a cathode 120, and an electrolyte membrane 130.

The anode 110 includes an anode catalyst (not shown) that includes a first main catalyst and a promoter for partial oxidation of fuel.

For example, at least one fuel may be injected into the anode 110, and an oxidant such as oxygen may be injected into the cathode 120, for example. Fuel injected into the anode 110 may include hydrogen, halogen gas and hydrocarbons.

The first main catalyst dissociates fuel injected into the anode 110 to generate electrons and conducts the generated electrons. This first main catalyst may comprise metals, metal alloys, metal oxides, metal precursors, nonmetallic compounds, ceramics and mixtures of two or more thereof. The metal oxide may include LSCM, Ni / YSZ, Ni / GDC, Ni / SDC, Ni / La ₂ Mo ₂ O ₉ , Cu-CeO _2, and / or LST.

The metal precursor may include at least one metal selected from Groups 3 to 15 of the periodic table. The metal precursor may include, for example, a nickel precursor. The nickel precursor may include, for example, nickel oxide, nickel chloride, nickel bromide and / or nickel hydroxide (nickel (II) hydroxide).

In addition, the first main catalyst, for example, a nickel precursor; And CeO ₂ , Pr, Nd, Sm, Gd, Dy, and Ho.

The promoter serves to generate an organic compound by partially oxidizing the fuel injected into the anode 110.

As used herein, "partial oxidation of fuel" means that oxidation of the fuel proceeds, but oxidation stops at such a degree that the fuel is not fully oxidized to water and carbon dioxide. For example, methane is completely oxidized. Carbon dioxide and water are generated, but when methane is partially oxidized, formaldehyde may be produced, etc. The organic compounds such as formaldehyde generated above are generally higher in added value than electricity generated in the fuel cell 100, and thus have high economic benefits. In the present specification, the term "organic compound" is a generic term for carbon compounds excluding carbon, carbon oxides, metal carbonates, cyanide carbides, and the like, which are single element materials.

Such promoters may comprise at least one metal, metal mixture or metal alloy selected from the group consisting of Fe, Cu, Mo, V, K, Ca and Mg. In addition, the content of the cocatalyst may be 0.5 to 50 parts by weight based on 100 parts by weight of the first main catalyst. When the content of the promoter is less than 0.5 parts by weight based on 100 parts by weight of the first main catalyst, the amount of the organic compound produced is not preferable, and when it exceeds 50 parts by weight, the electrical conductivity may fall, which is not preferable.

The anode catalyst may be an acid catalyst. An acid catalyst means a catalyst which catalyzes based on acidity of the catalyst surface. That is, H ⁺ present on the surface of the acid catalyst reacts with other substances to cause proton donation. Such acid catalysts include H ₂ PO ₄ , SiO ₂ -Al ₂ O ₃ and zeolite.

The cathode 120 includes a catalyst for a cathode (not shown) that includes a second main catalyst. The second main catalyst serves to reduce the oxidant injected into the cathode 120. Such cathode 120 may include LSM, LSCF, BSCF, LSCuF, La ₂ NiO ₄ and / or LSCM.

Fuel may be injected into the cathode 120 together with an oxidant such as oxygen. Fuel injected into the cathode 120 may include hydrogen, halogen gas, and hydrocarbons. In this case, the cathode catalyst may further include a cocatalyst for partial oxidation of the aforementioned fuel in addition to the second main catalyst. In this case, therefore, the fuel injected into the cathode 120 may be partially oxidized to generate an organic compound. That is, the aforementioned co-catalyst for partial oxidation of the fuel may be included in at least one electrode of the anode 110 and the cathode 120, and thus, at least one electrode of the anode 110 and the cathode 120. The above organic compounds can be produced.

The electrolyte membrane 130 is disposed between the anode 110 and the cathode 120 to pass only ions generated at the anode 110 and / or the cathode 120 and to block the movement of electrons. The material used for the electrolyte membrane 130 may vary depending on the operating temperature of the fuel cell 100. For example, the electrolyte membrane 130 has Nafion, phosphoric acid, [emim] HSO ₄ , [emim] C ₂ H ₅ OSO ₃ and the operating temperature of the fuel cell 100 at room temperature to 150 ° C. And / or [emim] CF ₃ SO ₃ or the like may be used; At 200-300 ° C., P ₂ O ₅ —SiO ₂ , CsHSO ₄ , Rb ₃ H (SeO ₄ ) ₂ , heteropolytungstic acid and / or heteropolymolybdic acid may be used. And; In the case of 400-900 ° C., at least one selected from the group consisting of YSZ, GDC, SDC, LSM, LSCoF, LSC, LSCuF, LSGM, La ₂ Mo ₂ O ₉ and Bicuvox may be used.

Hereinafter, a method of simultaneously producing an electric and organic compound using the fuel cell 100 will be described in detail with reference to FIG. 1.

Example 1: One fuel is injected into the anode and only oxidant is injected into the cathode

For example, a case where hydrocarbon is injected into the anode 110 and only oxygen is injected into the cathode will be described. In this case, the aforementioned co-catalyst for partial oxidation of the fuel is included only in the anode 110 and an oxygen ion conductive electrolyte is used as the electrolyte membrane 130.

Hydrocarbon injected into the anode 110 is dissociated to generate electrons (e ⁻ ), and the generated electrons are transferred to the cathode 120 through the anode 110 through the external conductor L.

The electrons transferred to the cathode 120 reduce oxygen in oxygen injected into the cathode 120 to generate oxygen ions (O ^2- ), and the generated oxygen ions are anode 110 through the electrolyte membrane 130. Is delivered.

The oxygen ions delivered to the anode 110 react with the hydrocarbon injected into the anode 110, and the hydrocarbon is partially oxidized to generate an organic compound.

Example 2: Two fuels are injected into the anode and only oxidant is injected into the cathode

For example, a case where hydrocarbon and halogen gas are injected into the anode 110 and only oxygen is injected into the cathode 120 will be described. In this case, the aforementioned co-catalyst for partial oxidation of the fuel is included only in the anode 110, and a hydrogen ion conductive electrolyte is used as the electrolyte membrane 130.

Hydrocarbon injected into the anode 110 is dissociated to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ), and the generated hydrogen ions are transferred to the cathode 120 through the electrolyte membrane 130. The electrons are transferred to the cathode 120 through the anode 110 and through the external conductor L. In addition, the anode 110 reacts hydrocarbons and halogen elements to produce methyl halides first, and the generated methyl halides react with each other to finally generate organic compounds and hydrogen halide gas. That is, the hydrocarbon is partially oxidized to produce an organic compound.

The hydrogen ions and electrons delivered to the cathode 120 react with oxygen in oxygen injected into the cathode 120 to generate water.

Example 3: A fuel is injected into the anode and a fuel is injected into the cathode together with an oxidant

For example, a case where hydrogen is injected to the anode 110 and a hydrocarbon is injected together with oxygen to the cathode 120 will be described. In this case, the aforementioned co-catalyst for partial oxidation of the fuel is included only in the cathode 120, and a hydrogen ion conductive electrolyte is used as the electrolyte membrane 130.

Hydrogen injected into the anode 110 is dissociated by the first main catalyst to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ), and the generated hydrogen ions are cathode 120 through the electrolyte membrane 130. The generated electrons are transferred to the cathode 120 through the anode 110 through the external conductor L.

The hydrogen ions and electrons delivered to the cathode 120 react with oxygen and hydrocarbons in oxygen injected into the cathode 120 to generate organic compounds and water.

Example 4: Two fuels are injected into the anode and one fuel is injected into the cathode together with the oxidant

For example, a case where hydrogen and hydrocarbon are injected into the anode 110 and methane is injected together with oxygen into the cathode 120 will be described. In this case, the co-catalyst for partial oxidation of the fuel described above is included in both the anode 110 and the cathode 120, and a hydrogen ion conductive electrolyte is used as the electrolyte membrane 130.

Hydrogen injected into the anode 110 is dissociated by the first main catalyst to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ), and the generated hydrogen ions are cathode 120 through the electrolyte membrane 130. The generated electrons are transferred to the cathode 120 through the anode 110 through the external conductor L.

In the anode 110, hydrocarbons react with each other to form alkenes, and the hydrogen ions and electrons transferred to the cathode 120 react with oxygen and methane in oxygen injected into the cathode 120 to generate methanol and water. do.

Example 5: One Fuel is Injected into the Anode and Two Fuels Are Injected with an Oxidizer in the Cathode

For example, a case in which hydrogen is injected into the anode 110 and methane and ethane are injected into the cathode 120 together with oxygen will be described. In this case, the aforementioned co-catalyst for partial oxidation of the fuel is included only in the cathode 120, and an oxygen ion conductive electrolyte is used as the electrolyte membrane 130.

Oxygen injected into the cathode 120 is reduced by the second main catalyst to generate oxygen ions (O ^2- ), and the generated oxygen ions are transferred to the anode 110 through the electrolyte membrane 130. In the anode 110, oxygen ions passing through the electrolyte 130 and hydrogen injected into the anode 110 react to generate water and electrons (e ⁻ ). The generated electrons are transferred to the cathode 120 through the external conductor L through the anode 110.

In the cathode 120, methane, ethane and oxygen react to produce propanol.

Example 6: One fuel is injected into the anode and two fuels are injected into the cathode together with the oxidant

For example, a case in which hydrogen is injected into the anode 110 and methane and ethane are injected into the cathode 120 together with oxygen will be described. In this case, the co-catalyst for partial oxidation of the fuel described above is included in the cathode 120, and a hydrogen ion conductive electrolyte is used as the electrolyte membrane 130.

Hydrogen injected into the anode 110 is dissociated by the first main catalyst to generate hydrogen ions (H ⁺ ) and electrons (e ⁻ ), and the generated hydrogen ions are cathode 120 through the electrolyte membrane 130. The generated electrons are transferred to the cathode 120 through the anode 110 through the external conductor L.

The hydrogen ions and electrons delivered to the cathode 120 react with oxygen, methane and ethane in oxygen injected into the cathode 120 to produce methanol, ethanol and water.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example

Example 1

A fuel cell of a single cell type was manufactured by the following method.

(1) Preparation of Anode Powder

NiO (Junsei Chemical Co.): 8 mol% Y ₂ O ₃ -stabilized-ZrO ₂ powder (TZ-8YS, Tosoh: hereinafter, abbreviated as YSZ): VCl ₃ (Aldrich) is mixed in a weight ratio of 48: 48: 4 The mixed powder was pulverized by ball milling for 24 hours using a zirconia ball. Thereafter, the pulverized mixed powder was dried at 90 ° C. for 6 hours on a hot plate, and then heat treated at 550 ° C. for 3 hours, and then ground again to obtain an anode powder.

(2) production of anode

75 vol% of the anode powder prepared in (1) and 25 vol% of the activated carbon were mixed, followed by ball milling for 2 weeks, followed by uniform mixing.

After mixing 100 parts by weight of the mixed powder, 25 parts by weight of distilled water, 13 parts by weight of an organic binder (poly vinyl butyral (PVB)), 8 parts by weight of a plasticizer (dibutyl phthalate) and 3 parts by weight of a lubricant (anchovy oil), The mixture was extruded using an extruder to prepare a cylindrical anode precursor having a thickness of 2 mm.

The prepared anode precursor was calcined at 1300 ° C. for 3 hours to obtain a cylindrical anode.

(3) Electrolytic membrane coating on anode

100 parts by weight of YSZ powder (TZ-8YS, Tosoh), 15 parts by weight of PVB, 15 parts by weight of dibutyl phthalate, 3 parts by weight of Triton-X and 3 parts by weight of anchovy oil, and then 170 parts by weight of toluene and 2 to the mixture. 330 parts by weight of propanol were added and ball milled at 150 rpm using a zirconia ball for 24 hours to obtain an electrolyte slurry.

The prepared electrolyte slurry was coated to a thickness of 7 μm using a dipping method on the anode prepared in (2). When dipping, both ends of the anode were blocked, soaked in the electrolyte slurry for 10 seconds, taken out, dried at 300 ° C. for 30 minutes, and co-fired at 1400 ° C. to obtain an anode-electrolyte laminate.

(4) Preparation of Cathode Powder and Cathode Slurry and Coating of the Cathode Slurry

La ₂ O ₃ powder (Yakuri Pure Chemicals Co.), SrO powder (Aldrich Chemical Company) and MnO ₂ powder (Aldrich Chemical Company) were respectively mixed in a weight ratio of 0.5: 0.5: 1, and then ball milled for 24 hours. milling) and heat-treated at 1000 ° C. for 5 hours to prepare LSM powder.

The cathode slurry was mixed by mixing 100 parts by weight of the prepared LSM powder, 25 parts by weight of PVB, 25 parts by weight of dibutyl phthalate, 6.25 parts by weight of Triton-X, 6.25 parts by weight of anchovy oil, 140 parts by weight of toluene, and 290 parts by weight of 2-propanol. Prepared.

Both ends of the cylindrical anode-electrolyte laminate prepared in (3) were blocked and dip-coated to coat the cathode slurry on the outer surface of the laminate with a thickness of 20 μm. A solid oxide fuel cell in the form of) was prepared.

(5) Preparation of high value added organic compounds using methane

The cylindrical solid oxide fuel cell prepared in (4) was fixed to the alumina tube and the cell support. Nickel felt was attached to the anode and the cathode of the fuel cell to allow current collection. Subsequently, while operating the fuel cell at a temperature of 500 ° C., methane was injected at the anode side at 300 cc / min and oxygen was injected at the cathode side at 200 cc / min. In order to confirm the type and composition of the material produced at the anode, the exhaust gas flowing out of the anode of the fuel cell was collected and liquefied, and then the liquid material was analyzed by liquid chromatography (LC). As a result of the analysis, it was confirmed that formaldehyde (HCHO) was produced at the anode. At this time, the yield of formaldehyde was 6.4%. When formaldehyde is produced using methane as described above, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: CH 4 + 2O 2- → HCHO}} + H 2 O + 4e -

The cathode ^{_{reaction: O 2 + 4e - → 2O}} 2-

Overall reaction: CH ₄ + O ₂ → HCHO + H ₂ O (E ⁰ = 0.84 V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 0.84V.

Example 2

(1) Manufacture of fuel cell

A medium-low temperature fuel cell was manufactured by the following method. Platinum was used as the main catalyst for the anode and the catalyst for the cathode. In addition, Fe ₂ O ₃ (Aldrich) and MoO ₃ (Aldrich) were used as promoters for the anode. An anode slurry was prepared by mixing 90 parts by weight of platinum, 4 parts by weight of Fe ₂ O ₃ , and 6 parts by weight of MoO ₃ : isopropyl alcohol in a weight ratio of 90:10.

In addition, the platinum: isopropyl alcohol (concentration of 99wt%, Aldrich) was mixed in a weight ratio of 90:10 to prepare a cathode slurry.

In addition, after pelletizing the GDC powder (Praxair Co.) was heat-treated at 1,300 ℃ for 6 hours to prepare a GDC electrolyte support. Thereafter, the anode slurry and the cathode slurry were screen printed on one side and the other side of the prepared GDC electrolyte support, and then co-sintered at 300 ° C. for 1 hour.

(2) Preparation of high value added organic compounds using methane

An organic compound was prepared and analyzed in the same manner as in Example (5), except that the fuel cell prepared in Example 2 (1) was used and the operating temperature of the fuel cell was changed to 400 ° C. . As a result of the analysis, it was confirmed that methanol (CH ₃ OH) was produced at the anode. At this time, the yield of methanol was 5%. When methanol is produced using methane as described above, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: CH 4 + O 2- → CH}} 3 OH + 2e -

The cathode ^{_{reaction: 1 / 2O 2 + 2e -}} → O 2-

Overall reaction: CH ₄ + 1 / 2O ₂ → CH ₃ OH (E ⁰ = 0.52V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 0.52V.

Example 3

(1) Manufacture of fuel cell

A low temperature fuel cell was manufactured by the following method. Platinum was used as the main catalyst for the anode and the catalyst for the cathode. In addition, Fe ₂ O ₃ (Aldrich) and MoO ₃ (Aldrich) were used as promoters for the anode. 90 parts by weight of the platinum, 4 parts by weight of Fe ₂ O ₃ and 6 parts by weight of MoO ₃ : isopropyl alcohol was mixed in a weight ratio of 90:10 to prepare an anode slurry, and then the anode slurry was prepared using a spray gun. An anode structure was prepared by spraying a plate having a thickness of 10 μm on a Dupont.

In addition, after mixing the platinum: isopropyl alcohol (concentration of 99wt%, Aldrich) in a weight ratio of 90:10 to prepare a cathode slurry, using a spray gun to the cathode slurry on a separate Teflon plate 10㎛ thickness Sprayed to produce a cathode structure. The anode structure and the cathode structure prepared above were disposed so that each catalyst layer faced each other, and then CsHSO ₄ (Soekawa Chemicals) was disposed therebetween, and the anode structure and the cathode structure were pressed against each other at 120 ° C. and 1000 psi for 3 minutes. Subsequently, each Teflon plate was removed from the anode structure and the cathode structure to obtain a fuel cell.

(2) Preparation of high value added organic compounds using methane and chlorine

Using the fuel cell prepared in Example 3 (1), the operating temperature of the fuel cell was changed to 50 ° C., and methane and chlorine gas were injected into the anode at the fuel cell at 20 cc / min and 20 cc / min, respectively, and toward the cathode. An organic compound was prepared in the same manner as in Example (5), except that oxygen was injected at 50 cc / min. The exhaust gas generated at the anode was then analyzed using gas chromatography (GC). As a result of the analysis, it was confirmed that ethylene (C ₂ H ₄ ) and hydrogen chloride gas were produced at the anode. At this time, the yield of ethylene was 6%. As such, when ethylene is produced using methane and chlorine gas, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode _{reaction: 2CH 4 + Cl 2 → 2CH} 3 Cl + 2H + + 2e -

2CH ₃ Cl → C ₂ H ₄ + 2HCl

The cathode _{^{reaction: 2H + + 1 / 2O 2}} + 2e - → H 2 O

Overall reaction: 2CH ₄ + Cl ₂ + 1 / 2O ₂ → C ₂ H ₄ + 2HCl + H ₂ O (E ⁰ = 1.62V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 1.62V.

Example 4

Using the fuel cell prepared in Example 2 (1) and changing the operating temperature of the fuel cell to 350 ℃, injecting 3-methyl-1-butene at 20cc / min to the anode of the fuel cell and oxygen to the cathode An organic compound was prepared and analyzed in the same manner as in Example (5), except that the compound was injected at 30 cc / min. As a result of the analysis, it was confirmed that isobutylaldehyde (CH ₃ CHCH ₃ CHO) and formaldehyde (HCHO) were produced at the anode. At this time, the yields of isobutylaldehyde and formaldehyde were 6% and 5%, respectively. When isobutylaldehyde and formaldehyde are produced using 3-methyl-1-butene as described above, the reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode _{reaction: CH 3 CHCH 3 CHCH 2 +} 2O 2- → CH 3 CHCH 3 CHO + HCHO + 4e -

The cathode ^{_{reaction: O 2 + 4e - → 2O}} 2-

Overall reaction: CH ₃ CHCH ₃ CHCH ₂ + O ₂ → CH ₃ CHCH ₃ CHO + HCHO (E ⁰ = 0.61V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 0.61V.

Example 5

(1) Manufacture of fuel cell

A fuel cell of a single cell type was manufactured by the following method.

NiO (Junsei Chemical Co.): 10 mol% Gadolinium doped Ceria powder (GDC, Praxair: hereinafter abbreviated as GDC): VCl ₃ (Aldrich) is mixed in a weight ratio of 48: 48: 4, and the mixed powder is zirconia ball An anode powder was prepared by ball milling for 24 hours using.

The anode slurry was mixed by mixing 100 parts by weight of the prepared anode powder, 25 parts by weight of PVB, 25 parts by weight of dibutyl phthalate, 6.25 parts by weight of triton-X, 6.25 parts by weight of anchovy oil, 140 parts by weight of toluene, and 290 parts by weight of 2-propanol. Prepared.

Further, La ₂ O ₃ powder (Yakuri Pure Chemicals Co.): SrO powder (Aldrich Chemical Company): MnO ₂ powder (Aldrich Chemical Company) was mixed in a weight ratio of 0.5: 0.5: 1, and then ball milling for 24 hours -milling) and heat treatment at 1,000 ℃ for 5 hours to prepare an LSM powder (cathode powder).

Subsequently, the cathode powder was mixed by mixing 100 parts by weight of PVB, 25 parts by weight of PVB, 25 parts by weight of dibutyl phthalate, 6.25 parts by weight of triton-X, 6.25 parts by weight of anchovy oil, 140 parts by weight of toluene and 290 parts by weight of 2-propanol. Slurry was prepared.

Thereafter, the GDC powder (Praxair Co.) was pelletized and heat-treated at 1,300 ° C. for 6 hours to prepare a GDC electrolyte support. Subsequently, the anode slurry and the cathode slurry were screen printed on one side and the other side of the prepared GDC electrolyte support, followed by co-sintering at 1,000 ° C. for 3 hours to complete a fuel cell.

(2) Preparation of high value added organic compounds using hydrogen and ethylene

Using the fuel cell prepared in Example 5 (1), the operating temperature of the fuel cell was changed to 500 ° C, ethylene and hydrogen were injected at 40cc / min and 40cc / min, respectively, into the anode of the fuel cell and the cathode An organic compound was prepared and analyzed in the same manner as in Example (5), except that oxygen was injected at 100 cc / min. As a result of the analysis, it was confirmed that ethanol (CH ₃ CH ₂ OH) was produced at the anode. At this time, the yield of ethanol was 6%. As such, when ethanol is produced using ethylene, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: C 2 H 4 + O 2-}} + H 2 → CH 3 CH 2 OH + 2e -

The cathode ^{_{reaction: 1 / 2O 2 + 2e -}} → O 2-

Overall Reaction: C ₂ H ₄ + H ₂ + 1 / 2O ₂ → CH ₃ CH ₂ OH (E ⁰ = 1.19V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 1.19V.

Example 6

Using the fuel cell prepared in Example 5 (1), the operating temperature of the fuel cell was changed to 400 ° C, propylene was injected at 50cc / min toward the anode of the fuel cell, and 30cc / min of oxygen toward the cathode. An organic compound was prepared and analyzed in the same manner as in Example (5), except that the compound was injected into. As a result of the analysis, it was confirmed that propylene oxide (C ₃ H ₆ O) was produced at the anode. At this time, the yield of propylene oxide was 10%. As such, when propylene oxide is used to produce propylene oxide, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: C 3 H 6 + O 2-}} → C 3 H 6 O + 2e -

The cathode ^{_{reaction: 1 / 2O 2 + 2e -}} → O 2-

Overall reaction: C ₃ H ₆ + 1 / 2O ₂ → C ₃ H ₆ O (E ⁰ = 1.33V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 1.33V.

Example 7

(1) Manufacture of fuel cell

A low temperature fuel cell was manufactured by the following method. Platinum was used as the main catalyst for the anode and the catalyst for the cathode.

First, an anode slurry is prepared by mixing the platinum: isopropyl alcohol (concentration of 99 wt%, Aldrich) in a weight ratio of 90:10, and then spraying the anode slurry on a Teflon plate with a thickness of 10 μm using a spray gun. To prepare an anode structure.

Fe ₂ O ₃ (Aldrich) and MoO ₃ (Aldrich) were used as promoters for the cathode. 90 parts by weight of platinum, 4 parts by weight of Fe ₂ O ₃ , and 6 parts by weight of MoO ₃ were mixed in a weight ratio of 90:10 to prepare a cathode slurry, and then, the spray slurry was used to separate the cathode slurry. A cathode structure was prepared by spraying a Teflon plate with a thickness of 10 μm.

Subsequently, the prepared anode structure and the cathode structure are disposed so that each catalyst layer faces each other, and then CsHSO ₄ (Soekawa Chemicals) is disposed therebetween, and the anode structure and the cathode structure are disposed at 120 ° C. and 1,000 psi for 3 minutes. Squeezed. Subsequently, each Teflon plate was removed from the anode structure and the cathode structure to obtain a fuel cell.

(2) Preparation of high value added organic compounds using hydrogen and methane

Using the fuel cell prepared in Example 7 (1), the operating temperature of the fuel cell was changed to 50 ° C., hydrogen was injected at 30cc / min toward the anode of the fuel cell, and 30cc / min each of methane and oxygen toward the cathode. And an organic compound was prepared in the same manner as in (5) of Example 1, except that it was injected at 40 cc / min. In order to confirm the type and composition of the material produced in the cathode, the exhaust gas flowing out of the cathode of the fuel cell was collected and liquefied, and then the liquid material was analyzed by liquid chromatography (LC). As a result of the analysis, it was confirmed that methanol (CH ₃ OH) was produced at the cathode. At this time, the yield of methanol was 6%. When methanol is produced using methane as described above, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: H 2 → 2H + + 2e}} -

The cathode ^{_{reaction: CH 4 + 2H + + O}} 2 + 2e - → CH 3 OH + H 2 O

Overall reaction: H ₂ + CH ₄ + O ₂ → CH ₃ OH + H ₂ O (E ⁰ = 1.63V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 1.63V.

Example 8

(1) Manufacture of fuel cell

A low temperature fuel cell was manufactured by the following method.

In other words, platinum was used as the anode main catalyst and the cathode main catalyst. In addition, VCl ₃ (Aldrich), MoO ₃ (Aldrich) and CaO (Aldrich) were used as promoters for the anode, and MoO ₃ (Aldrich) was used as the promoter for the cathode.

A mixture of 90 parts by weight of platinum, ₃ parts by weight of VCl ₃ (Aldrich), 3 parts by weight of MoO ₃ (Aldrich) and 4 parts by weight of CaO (Aldrich): 20 wt% of Nafion ionomer solution was mixed at a weight ratio of 90:10 to the anode. After the slurry was prepared, an anode structure was prepared by spraying the anode slurry on a Teflon plate with a thickness of 10 μm using a spray gun.

In addition, a mixture of 96 parts by weight of platinum and 4 parts by weight of MoO ₃ (Aldrich): isopropyl alcohol-nafion ionomer mixed solution (80 parts by weight of isopropyl alcohol: 20 parts by weight of Nafion ionomer) in a weight ratio of 90:10 After mixing to prepare a cathode slurry, the cathode slurry was sprayed onto a separate Teflon plate to a thickness of 10 μm using a spray gun to prepare a cathode structure.

The anode structure and the cathode structure prepared above were disposed so that each catalyst layer faced each other, and then Nafion was placed therebetween, and the anode structure and the cathode structure were pressed at 120 ° C. and 1,000 psi for 3 minutes. Subsequently, each Teflon plate was removed from the anode structure and the cathode structure to obtain a fuel cell.

(2) Preparation of high value added organic compounds using methane

Using the fuel cell prepared in Example 8 (1), the operating temperature of the fuel cell was changed to 50 ° C., injecting methane at 60 cc / min toward the anode of the fuel cell and 30 cc / min respectively at the cathode toward the cathode. And 45 cc / min, except that the organic compound was prepared in the same manner as in Example (5). The exhaust gas generated at the anode was then analyzed using gas chromatography (GC). In addition, in order to confirm the type and composition of the material produced in the cathode, the exhaust gas flowing out of the cathode was collected and liquefied, and then the liquid material was analyzed by liquid chromatography (LC).

As a result of the analysis, it was confirmed that ethylene (C ₂ H ₄ ) was produced at the anode and methanol (CH ₃ OH) was produced at the cathode. At this time, the yields of ethylene and methanol were 5% and 6%, respectively. As such, when methane is used to produce ethylene and methanol, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode _{reaction: 2CH 4 → C 2 H 4} + 4H + + 4e -

The cathode ^{_{reaction: CH 4 + 4H + + 3}} / 2O 2 + 4e - → CH 3 OH + 2H 2 O

Overall reaction: 3CH ₄ + 3 / 2O ₂ → C ₂ H ₄ + CH ₃ OH + 2H ₂ O (E ⁰ = 0.39V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 0.39V.

Example 9

(1) Manufacture of fuel cell

A fuel cell of a single cell type was manufactured by the following method.

NiO (Junsei Chemical Co.): 10 mol% Gadolinium doped Ceria powder (GDC, Praxair: hereinafter, abbreviated as GDC) is mixed in a weight ratio of 50:50, and the mixed powder is ball milled for 24 hours using a zirconia ball The anode powder was prepared by ball milling.

The anode slurry was mixed by mixing 100 parts by weight of the prepared anode powder, 25 parts by weight of PVB, 25 parts by weight of dibutyl phthalate, 6.25 parts by weight of triton-X, 6.25 parts by weight of anchovy oil, 140 parts by weight of toluene, and 290 parts by weight of 2-propanol. Prepared.

Further, La ₂ O ₃ powder (Yakuri Pure Chemicals Co.): SrO powder (Aldrich Chemical Company): MnO ₂ powder (Aldrich Chemical Company) was mixed in a weight ratio of 0.5: 0.5: 1, and then ball milling for 24 hours -milling) and heat-treated at 1,000 ℃ for 5 hours to prepare a LSM powder.

Subsequently, the prepared LSM powder: VCl ₃ (Aldrich chemical Company): MoO ₃ (Aldrich chemical Company) was mixed at a weight ratio of 90: 5: 5, followed by ball milling for 24 hours and heat treatment at 700 ° C. for 6 hours. Powder was prepared.

Thereafter, the prepared cathode powder 100 parts by weight, PVB 25 parts by weight, dibutyl phthalate 25 parts by weight, triton-X 6.25 parts by weight, anchovy oil 6.25 parts by weight, toluene 140 parts by weight and 2-290 parts by weight of the 2-propanol mixed cathode Slurry was prepared.

Subsequently, the GDC powder (Praxair Co.) was pelletized to prepare a GDC electrolyte support, followed by heat treatment at 1,300 ° C. for 6 hours to complete the GDC electrolyte support. Thereafter, the anode slurry and the cathode slurry were screen printed on one side and the other side of the prepared GDC electrolyte support, followed by co-sintering at 1,000 ° C. for 3 hours to complete a fuel cell.

(2) Preparation of high value added organic compounds using hydrogen, methane and ethane

Using the fuel cell prepared in Example 9 (1), the operating temperature of the fuel cell was changed to 450 ° C., hydrogen was injected at 30 cc / min toward the anode, and 30 cc / methane, ethane and oxygen were respectively fed to the cathode. injection at min, 30 cc / min and 45 cc / min. Subsequently, in order to confirm the type and composition of the material generated in the cathode, the exhaust gas flowing out of the cathode was collected and liquefied, and then the liquid material was analyzed by liquid chromatography (LC). As a result of the analysis, it was confirmed that propanol (C ₃ H ₇ OH) was produced at the cathode. At this time, the yield of propanol was 3%. As such, when propanol is produced using methane and ethane, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: H 2 + O 2- → H}} 2 O + 2e -

The cathode _{reaction: CH 4 + C 2 H 6} + 3 / 2O 2 + 2e - → C 3 H 7 OH + H 2 O + O 2-

Overall reaction: H ₂ + CH ₄ + C ₂ H ₆ + 3 / 2O ₂ → C ₃ H ₇ OH + 2H ₂ O (E ⁰ = 1.98 V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 1.98V.

Example 10

(1) Manufacture of fuel cell

A low temperature fuel cell was manufactured by the following method.

In other words, platinum was used as the catalyst for the anode and the main catalyst for the cathode. In addition, VCl ₃ (Aldrich), MoO ₃ (Aldrich) and CaO (Aldrich) were used as promoters for the cathode.

 100 parts by weight of platinum: isopropyl alcohol (Aldrich) by mixing in a weight ratio of 90:10 to prepare an anode slurry, using a spray gun to spray the anode slurry on a Teflon plate (Dupont) to a thickness of 10㎛ The anode structure was prepared.

In addition, a mixture of 90 parts by weight of platinum, ₃ parts by weight of VCl ₃ (Aldrich), 3 parts by weight of MoO ₃ (Aldrich) and 4 parts by weight of CaO (Aldrich): isopropyl alcohol was mixed at a weight ratio of 90:10 to form a cathode slurry. After the preparation, the cathode slurry was sprayed to a separate Teflon plate with a thickness of 10 μm using a spray gun to prepare a cathode structure.

The prepared anode structure and the cathode structure were disposed so that each catalyst layer faced each other, and then, CsHSO ₄ (Soekawa Chemicals) was disposed therebetween, and the anode structure and the cathode structure were pressed together at 120 ° C. and 1,000 psi for 3 minutes. . Subsequently, each Teflon plate was removed from the anode structure and the cathode structure to obtain a fuel cell.

(2) Preparation of high value added organic compounds using hydrogen, methane and ethane

Using the fuel cell prepared in Example 10 (1), the operating temperature of the fuel cell was changed to 250 ° C., hydrogen was injected at 30 cc / min toward the anode, and 30 cc / methane, ethane and oxygen were respectively fed to the cathode. injection at min, 20 cc / min and 40 cc / min. Subsequently, in order to confirm the type and composition of the material generated in the cathode, the exhaust gas flowing out of the cathode was collected and liquefied, and then the liquid material was analyzed by liquid chromatography (LC). As a result of the analysis, it was confirmed that methanol (CH ₃ OH) and ethanol (C ₂ H ₅ OH) were produced at the cathode. At this time, the yields of methanol and ethanol were 4% and 3%, respectively. As such, when methanol and ethanol are produced using methane and ethane, reactions and overall reactions occurring at the anode and the cathode are as follows.

The anode ^{_{reaction: H 2 → 2H + + 2e}} -

The cathode _{^{reaction: 2H + + CH 4 + C}} 2 H 6 + 3 / 2O 2 + 2e - → CH 3 OH + C 2 H 5 OH + H 2 O

Overall reaction: H ₂ + CH ₄ + C ₂ H ₆ + 3 / 2O ₂ → CH ₃ OH + C ₂ H ₅ OH + 2H ₂ O (E ⁰ = 2.34 V)

Therefore, it can be seen that the electromotive force E ⁰ obtained in the overall reaction is 2.34V.

Evaluation example

Yield of high value added organic compounds

The types and yields of the fuel used in Examples 1 to 10, and the high value added organic compounds produced are summarized in Table 1 below.

(Performance of fuel cell)

The performance of the fuel cell used in Examples 1 to 10 are summarized in Table 1 below.

Simultaneously producing a fuel cell of electricity and a high value-added organic compound according to an embodiment of the present invention, when comparing the price of the produced electricity and the price of the high value-added organic compound, compared with the conventional fuel cell that produces only electricity Economic effect can be obtained. In other words, the current electricity bill in Korea is 60.90 won / kWh. The kWh is 1000A x 1V x 1h, and the electrons needed to get this power are 1000 moles per hour. Therefore, if the electricity generated in the fuel cell using methane as 1 kWh, it means that 1000 mol of electrons are generated in the fuel cell for 1 hour. If methane is used as a fuel to produce electricity and methanol at the same time, in which case the amount of electricity generated is reduced to 50%, the electricity produced is 500 Wh and the amount of methanol produced is 250 moles (see Scheme below). .

_{^{CH 4 + O 2 - → CH}} 3 OH + 2e -

The price of methanol currently on sale is 500,000 won per ton, so the price per mole is 16 won. Therefore, the price of 250 moles of methanol is 4000 won. Since the reduced amount of power is 500 Wh and the price is 30.45 won, even if the amount of power is reduced, a high value-added organic compound is obtained, and the overall gain is more than 130 times. Similarly, the production of formaldehyde, ethylene and ethanol, which are more expensive than methanol, can yield much higher economic benefits. Table 2 shows the increase in economic gains compared to the production of electricity per mole of each high value-added organic compound and the production of electricity only.

Referring to Table 2, it can be seen that the economic effect of at least 130 times to 163 times as compared to the case of producing only electricity for each case.

Although the preferred embodiment according to the present invention has been described above with reference to the drawings, this is merely illustrative, and those skilled in the art can understand that various modifications and equivalent other embodiments are possible. There will be. Therefore, the protection scope of the present invention should be defined by the appended claims.

1 is a view schematically showing a fuel cell according to an embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

100: fuel cell 110: anode

120: cathode 130: electrolyte membrane

Claims (29)

delete Injecting at least one first fuel into an anode of a fuel cell having an anode, an electrolyte membrane and a cathode, and injecting at least one second fuel together with an oxidant to the cathode to partially oxidize the second fuel at the cathode Simultaneous preparation method of the electrical and organic compound comprising the step of producing an organic compound. 3. The method of claim 2, Partial oxidation of the second fuel is both electrical and organic, wherein one or more second fuels injected into the cathode are produced by the anode and reacted with ions delivered to the cathode through the electrolyte membrane and the oxidant injected into the cathode. Simultaneous preparation of compounds. The method of claim 3, Simultaneously manufacturing the electric and organic compounds ions reacting with the second fuel is hydrogen ions. 3. The method of claim 2, The partial oxidation of the second fuel is a method for producing electric and organic compounds simultaneously by at least one fuel injected into the cathode reacts with each other at the cathode. 3. The method of claim 2, The partial oxidation of the second fuel is a method for producing electrical and organic compounds simultaneously by the reaction of the at least one fuel injected into the cathode and the oxidant injected into the cathode with each other at the cathode. 3. The method of claim 2, And partially oxidizing the first fuel at the anode to produce a third organic compound. The method of claim 7, wherein Partial oxidation of the first fuel is a method of producing an electrical and organic compound at the same time by reacting with the ions generated in the cathode at least one first fuel injected into the anode and delivered to the anode through the electrolyte membrane. The method of claim 8, Simultaneously manufacturing the electrical and organic compounds ions reacting with the first fuel is oxygen ions. The method of claim 7, wherein Partial oxidation of the first fuel is a method for producing electricity and organic compounds simultaneously by the reaction of one or more fuels injected into the anode with each other at the anode. 3. The method of claim 2, And at least one of a hydrogenation reaction, a chlorination reaction, a bromination reaction, a fluorination reaction, an iodide reaction, and a sulfonation reaction at the at least one electrode of the anode and the cathode. 3. The method of claim 2, At least one of the anode and the cathode comprises an acid catalyst and at least one of the electrodes is an electrical and organic compound in which at least one of a hydration reaction, an oxymercuration-demercuration reaction, and a hydroboration-oxidation reaction further occurs Simultaneous preparation method. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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