KR101654835B1 - Microalgae-derived Anodic Catalyst for Direct Alkaline Sulfide Fuel Cell and Method for Preparing the Same - Google Patents
Microalgae-derived Anodic Catalyst for Direct Alkaline Sulfide Fuel Cell and Method for Preparing the Same Download PDFInfo
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- KR101654835B1 KR101654835B1 KR1020150068673A KR20150068673A KR101654835B1 KR 101654835 B1 KR101654835 B1 KR 101654835B1 KR 1020150068673 A KR1020150068673 A KR 1020150068673A KR 20150068673 A KR20150068673 A KR 20150068673A KR 101654835 B1 KR101654835 B1 KR 101654835B1
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- microalgae
- metal catalyst
- fuel cell
- carbon support
- metal
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- H—ELECTRICITY
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- H—ELECTRICITY
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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
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Abstract
본 발명은 직접 알칼라인 황화이온 연료전지용 미세조류 유래 애노드 촉매 및 이의 제조방법에 관한 것으로, 보다 상세하게는 미세조류를 사용하여 활성 면적이 넓은 금속촉매를 합성하고, 이를 전기화학적 금속촉매로 이용하여 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시키는 방법에 관한 것이다.
본 발명에 따른 미세조류 유래 탄소 지지체에 담지된 금속촉매의 제조방법으로 합성된 금속촉매는 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시킬 수 있는 효과가 있다. 또한, 상기 금속촉매는 대량 증식하는 미세조류 잔사를 원료로 사용하여 제조될 수 있고, 값싼 금속을 포함하므로, 촉매 합성 공정 비용이 저렴하며 대량으로 생산 가능하므로 고효율·저비용 촉매의 실용화가 용이하다.The present invention relates to a microalgae-derived anode catalyst for a direct alkaline sulfide ion fuel cell and a method for producing the same. More particularly, the present invention relates to a method for preparing a metal catalyst having a large active area using microalgae, To a method for improving the electrochemical performance of alkaline sulfide ion fuel cells.
The metal catalyst synthesized by the method of preparing the metal catalyst supported on the microalgae-derived carbon support according to the present invention can improve the electrochemical performance of the direct alkaline sulfide ion fuel cell. In addition, since the metal catalyst can be produced using a microalgae residue that mass-proliferates as a raw material and includes a cheap metal, the catalyst synthesis process cost is low and it can be mass-produced, so that a high efficiency and low cost catalyst can be practically used.
Description
본 발명은 직접 알칼라인 황화이온 연료전지용 미세조류 유래 애노드 촉매 및 이의 제조방법에 관한 것으로, 보다 상세하게는 미세조류를 사용하여 활성 면적이 넓은 금속촉매를 합성하고, 이를 전기화학적 금속촉매로 이용하여 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시키는 방법에 관한 것이다.
The present invention relates to a microalgae-derived anode catalyst for a direct alkaline sulfide ion fuel cell and a method for producing the same. More particularly, the present invention relates to a method for preparing a metal catalyst having a large active area using microalgae, To a method for improving the electrochemical performance of alkaline sulfide ion fuel cells.
황화수소는 독성을 지니고 부식을 일으키는 가스로서, 자연적으로 발생하거나 산업 활동에 의해 발생된다. 황화수소는 인류의 생존에 필요한 공정 예컨대, 에너지 생산을 위한 석유 정제, 하수 처리를 위한 혐기 소화 과정 중에 다량으로 발생된다. 현재 연간 황화수소 발생량은 전 세계적으로 250만 톤으로 추산되며 계속적으로 증가할 것으로 예상되므로 황화수소를 효과적으로 제거하는 기술을 확보하는 것이 중요하다.Hydrogen sulfide is a toxic and corrosive gas that occurs naturally or by industrial activity. Hydrogen sulfide is produced in large quantities during the processes necessary for human survival, such as petroleum refining for energy production and anaerobic digestion for sewage treatment. At present, annual hydrogen sulfide production is estimated to be 2.5 million tons worldwide and it is expected to increase continuously, so it is important to secure technology to effectively remove hydrogen sulfide.
황화수소를 제거하는 방법 중 가장 상용화된 공정은 클라우스 공정(Claus process)이다. 상기 공정은 99% 이상의 황화수소 제거율로 인해 이미 널리 사용되어왔으나, 초기 설치 비용이 비쌀 뿐만 아니라 고온/고압의 운전 조건으로 인해 경제성 문제가 대두되고 있다. 또한, 공정 중 발생한 배출 가스 중 수소는 CS2, SO2, 혹은 COS 등의 부식성 부산물을 포함하고 있어 효과적으로 사용되지 못하고 있는 실정이다. 따라서, 비교적 온화한 조건에서 황화수소를 제거하면서도 에너지 손실을 최소화할 수 있는, 혹은 가능하다면 오히려 에너지를 생산할 수 있는 공정의 개발이 필요하다. The most commercially available process for removing hydrogen sulphide is the Claus process. Although the process has been widely used due to the removal rate of hydrogen sulfide of 99% or more, the initial installation cost is not only high but also economical problem is caused due to high temperature / high pressure operating condition. Also, among the exhaust gases generated during the process, hydrogen is not effectively used because it contains caustic by-products such as CS 2 , SO 2 , or COS. Therefore, it is necessary to develop a process capable of minimizing energy loss while removing hydrogen sulfide under relatively mild conditions, or, if possible, producing energy.
연료전지를 이용한 황화수소의 제거는 클라우스 공정을 대체할 수 있는 한 가지 대안으로 제시되어왔다. 특별히, 500℃ 이상 고온에서 운전되는 고체 산화물 연료전지(Solid oxide fuel cell), 혹은 100℃ 미만의 온도에서 운전되는 고분자 전해질 연료전지(Polymer electrolyte fuel cell) 형태의 플랫폼이 개발되었고, 이를 이용하여 황화수소를 연료로 산화시켜 제거함과 동시에 전기에너지를 생산하는 문헌이 보고되었다(특허문헌 1, 비특허문헌 1 및 4). 그러나, 황화수소 자체의 부식성/독성으로 인한 전극 물질(전극 소재, 촉매 등)의 피독으로 인해 연료전지의 성능이 만성적으로 감소하는 현상이 발생되었으며, 이러한 피독 현상은 운전 1시간 이내 급격한 성능 저하를 야기하기 때문에, 황화수소를 연료로 이용하여 장시간 안정적인 전기에너지 출력을 얻는 것이 비교적 어렵다고 알려져 있다. 이를 반영하여, 최근의 연구들은 황화수소로부터의 저항성을 가진 전극 촉매 개발로 진행되고 있으나, 이 역시 상용화를 고려할 때 아직은 미미한 수준이다(비특허문헌 2, 3 및 5). Removal of hydrogen sulfide using fuel cells has been suggested as an alternative to the Klaus process. Particularly, a solid oxide fuel cell operating at a temperature higher than 500 ° C. or a polymer electrolyte fuel cell operated at a temperature lower than 100 ° C. has been developed, and hydrogen sulfide (
직접 알칼라인 황화이온 연료전지(direct alkaline sulfide fuel cell)는 상기 문제점을 해결할 수 있는 대안으로 알려져 있다. 구체적으로, 황화수소 제거공정에서 황화수소를 알칼라인 용액에 흡수할 경우 100%의 제거율로 흡수가 가능하며, 생성된 황화이온을 포함하는 흡수액이 연료전지의 애노드로 유입될 경우 전기 생산이 가능하다. 또한, 알칼라인의 황화이온을 연료로 사용할 경우, 전극의 피독 없이 장시간의 성능 출력이 가능하다는 것이 알려져 있다(특허문헌 1 및 2). A direct alkaline sulfide fuel cell is known as an alternative to solve the above problems. Specifically, when hydrogen sulfide is absorbed in the alkaline solution in the hydrogen sulfide removal step, it can be absorbed at a removal rate of 100%. When the absorbing solution containing the generated sulfide ions flows into the anode of the fuel cell, electricity production is possible. Further, it is known that, when alkaline sulfide ions are used as the fuel, performance output for a long time is possible without poisoning the electrodes (
그러나, 여전히 촉매의 값비싼 문제는 연료전지 실용화를 고려할 때 심각한 문제로 제기되고 있으며, 이러한 필요에 반응하여 값싸고 높은 성능을 보유한 촉매 개발이 필요한 실정이다.However, the problem of high cost of the catalyst is still a serious problem when considering the practical use of the fuel cell, and it is necessary to develop a catalyst having low cost and high performance in response to this need.
이러한 기술적 배경 하에서, 본 발명자들은 상기 문제점을 해결하기 위하여 예의 노력한 결과, 미세조류로부터 유래한 그래파이트 탄소를 지지체로 사용할 경우 넓은 표면적의 금속촉매를 형성할 수 있고, 이를 전기화학적 금속촉매로 이용하여 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시킬 수 있음을 확인하고, 본 발명을 완성하게 되었다.
Under these technical backgrounds, the present inventors have made intensive efforts to solve the above problems. As a result, they have found that when a graphite carbon derived from microalgae is used as a support, a metal catalyst having a large surface area can be formed and used as an electrochemical metal catalyst The electrochemical performance of the alkaline sulfide ion fuel cell can be improved, and the present invention has been completed.
본 발명의 목적은 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시킬 수 있는 활성 면적이 넓은 금속촉매, 이의 제조방법, 상기 금속촉매를 포함하는 직접 알칼라인 황화이온 연료전지 시스템 및 상기 시스템을 이용한 황화수소 제거 및 전기생산방법을 제공하는 데 있다.
An object of the present invention is to provide a metal catalyst having a wide active area capable of improving the electrochemical performance of a direct alkaline sulfide ion fuel cell, a method for producing the same, a direct alkaline sulfide ion fuel cell system including the metal catalyst, Removal and electrical production methods.
상기 목적을 달성하기 위하여, 본 발명은 미세조류 유래 탄소 지지체에 금속이 담지된 것을 특징으로 하는 직접 알칼라인 황화이온 연료 전지용 금속촉매를 제공한다.In order to achieve the above object, the present invention provides a metal catalyst for a direct alkaline sulfide ion fuel cell, wherein a metal is supported on a microalgae-derived carbon support.
본 발명은 또한, (a) 미세조류를 유기용매에 분산시키는 단계; (b) 상기 미세조류 분산액에 금속촉매 또는 그 전구체를 첨가한 다음, 교반(혼합)하여 침전물을 형성시키는 단계; 및 (c) 상기 침전물을 열처리하여 미세조류 유래 탄소 지지체에 금속촉매를 담지시키는 단계를 포함하는 미세조류 유래 탄소 지지체에 담지된 금속촉매의 제조방법을 제공한다.The present invention also relates to a process for the production of microcapsules comprising: (a) dispersing microalgae in an organic solvent; (b) adding a metal catalyst or a precursor thereof to the microalgae dispersion and stirring the mixture to form a precipitate; And (c) heat treating the precipitate to deposit a metal catalyst on the microalgae-derived carbon support. The present invention also provides a method for producing a metal catalyst supported on a microalgae-derived carbon support.
본 발명은 또한, 양이온 교환막; 알칼리성 수용액을 포함하고, 황화수소를 흡수하여 황화이온을 생성시키는 H2S 흡수부; 상기 흡수부에 위치하는 애노드와 양이온 교환막에 의해 분리되고 상기 알칼리성 수용액에 위치하는 캐소드를 포함하는 직접 알칼라인 황화이온 연료전지 시스템에 있어서, 상기 애노드는 상기의 방법으로 제조된 미세조류 유래 탄소 지지체에 담지된 금속촉매를 포함하는 것을 특징으로 하는 직접 알칼라인 황화이온 연료전지 시스템을 제공한다.The present invention also relates to a cation exchange membrane; An H 2 S absorption part containing an alkaline aqueous solution and absorbing hydrogen sulfide to generate sulfide ions; A direct current alkaline sulphide ion fuel cell system comprising an anode located in the absorber and a cathode separated by a cation exchange membrane and located in the alkaline aqueous solution, wherein the anode is supported on a microalgae- The present invention provides a direct alkaline sulphide ion fuel cell system, comprising:
본 발명은 또한, 상기의 직접 알칼라인 황화이온 연료전지시스템의 H2S 흡수부에 H2S를 공급하여 알칼리성 수용액에 흡수시켜 황화이온을 생성하고, 상기 황화이온을 산화형 황 이온으로 생성시켜 전기에너지를 생산하는 황화수소 제거 및 전기생산방법을 제공한다.
The present invention also provides a method for producing sulfide ions by supplying H 2 S to an H 2 S absorption unit of the direct alkaline sulfide ion fuel cell system to absorb sulfide ions into an alkaline aqueous solution to generate sulfide ions as oxidized sulfur ions, And a method of removing hydrogen sulfide and producing electricity.
본 발명에 따른 미세조류 유래 탄소 지지체에 담지된 금속촉매의 제조방법으로 합성된 금속촉매는 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시킬 수 있는 효과가 있다. 또한, 상기 금속촉매는 대량 증식하는 미세조류 잔사를 원료로 사용하여 제조될 수 있고, 값싼 금속을 포함하므로, 촉매 합성 공정 비용이 저렴하며 대량으로 생산 가능하므로 고효율 저비용 촉매의 실용화가 용이하다.
The metal catalyst synthesized by the method of preparing the metal catalyst supported on the microalgae-derived carbon support according to the present invention can improve the electrochemical performance of the direct alkaline sulfide ion fuel cell. In addition, since the metal catalyst can be produced using a microalgae residue that mass-proliferates as a raw material and includes a cheap metal, the cost of the catalyst synthesis process is low and it can be produced in large quantities, so that a high-efficiency and low-cost catalyst can be practically used.
도 1은 본 발명의 전체 모식도이다.
도 2는 미세조류 유래 탄소 지지체 기반 촉매를 합성하는 방법으로, (a) 미세조류의 열분해로부터 생성된 그래파이트의 FE-SEM(Scanning Electron Microscopy) 사진; (b) 상기 (a)의 확대된 SEM 사진; (c) 미세조류 없이 합성된 TiO2의 FE-SEM 사진; (d) 미세조류를 지지체로 사용하여 합성된 TiO2 촉매의 FE-SEM 사진; (e) 상기 (d)의 확대된 FE-SEM 사진; 및 (f) 상기 (e)의 확대된 FE-SEM 사진을 나타낸 것이다.
도 3은 미세조류 유래 탄소 지지체 기반 촉매의 물리적 특성을 나타낸 것으로, 탄소의 양에 비한 TiO2의 양에 따른 (a) XRD(X-ray diffractometer) 스펙트럼; (b) 라만 스펙트럼; 및 (c) 질소 흡탈착 특성평가를 나타낸 그래프이다.
도 4는 미세조류 유래 탄소 지지체 기반 TiO2를 직접 알칼라인 황화이온 연료전지의 애노드(anode) 촉매로 사용한 경우, 탄소의 양에 비한 TiO2의 양에 따른 (a) 전압-전류곡선 및 전력밀도 그래프; 및 (b) 임피던스 그래프를 나타낸 것이다.1 is an overall schematic diagram of the present invention.
Figure 2 shows a method for synthesizing a microalgae-based carbon support-based catalyst, comprising: (a) FE-SEM (Scanning Electron Microscopy) photographs of graphite produced from pyrolysis of microalgae; (b) an enlarged SEM photograph of (a) above; (c) FE-SEM photograph of synthesized TiO 2 without microalgae; (d) FE-SEM photograph of TiO 2 catalyst synthesized using microalgae as support; (e) an enlarged FE-SEM photograph of (d) above; And (f) an enlarged FE-SEM photograph of (e).
FIG. 3 shows the physical properties of a microalgae-based carbon support-based catalyst, wherein (a) an X-ray diffractometer (XRD) spectrum according to the amount of TiO 2 relative to the amount of carbon; (b) Raman spectrum; And (c) nitrogen adsorption / desorption characteristics.
FIG. 4 shows (a) the voltage-current curve and the power density graph according to the amount of TiO 2 relative to the amount of carbon when the TiO 2 based on the microalgae-derived carbon support was directly used as the anode catalyst of the alkaline sulfide ion fuel cell ; And (b) an impedance graph.
달리 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법 및 이하에 기술하는 실험 방법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental methods described below are well known and commonly used in the art.
본 발명은 직접 알칼라인 황화이온 연료전지용 미세조류 유래 애노드 촉매의 제조방법에 관한 것으로, 보다 상세하게는 미세조류를 사용하여 활성 면적이 넓은 금속촉매를 합성하고, 이를 전기화학적 금속촉매로 이용하여 직접 알칼라인 황화이온 연료전지의 전기화학적 성능을 향상시키는 방법에 관한 것이다.The present invention relates to a method for preparing an anode catalyst derived from a microalgae for a direct alkaline sulfide ion fuel cell, and more particularly, to a method for producing an alkaline sulfide ion- To a method for improving the electrochemical performance of a sulfided ion fuel cell.
본 발명은 기존 황화수소 연료전지와 전혀 다른 형태의 연료전지인 직접 알칼라인 황화이온 연료전지(Direct alkaline sulfide fuel cell, DASFC)를 개발하였으며, 특히 전극소재 혹은 촉매 상 피독 없이 30시간 이상 장시간의 성능 출력이 가능하다. The present invention has developed a direct alkaline sulfide fuel cell (DASFC), which is a completely different type of fuel cell than a conventional hydrogen sulfide fuel cell. In particular, it has a long output time of more than 30 hours without poisoning of the electrode material or catalyst It is possible.
본 연료전지에서 일어나는 반응은 하기와 같다(도 1 참조).The reactions occurring in this fuel cell are as follows (see Fig. 1).
1) 애노드(anode)1) Anode
S2 - + 6OH- -> SO3 2 - + 3H2O + 6e- S 2 - + 6OH - -> SO 3 2 - + 3H 2 O + 6e -
2HS- + 8OH- -> S2O3 2 - + 5H2O + 8e- 2HS - + 8OH - -> S 2 O 3 2 - + 5H 2 O + 8e -
S2 2 - + 6OH- -> S2O3 2 - + 3H2O + 6e- S 2 2 - + 6OH - -> S 2 O 3 2 - + 3H 2 O + 6e -
2) 캐소드(cathode)2) Cathode
O2+ 2H2O + 2e- -> 4OH- O 2 + 2H 2 O + 2e - -> 4OH -
상기 DASFC는 연료전지에서 황화이온은 아황산을 거쳐 최종적으로 황산으로까지 산화되어 유해가스 제거효과와 전기에너지 생성, 그리고 부가가치물질 생산의 효과를 가지게 된다. 따라서, 직접 알칼라인 황화이온 연료전지는 유해가스 제거, 전기 생산, 다량의 부산물 생산을 동시에 가능케 하는 기능성 연료전지이다. The DASFC is oxidized to sulfuric acid finally through sulfuric acid in the fuel cell so that it has the effect of removing harmful gas, generating electrical energy, and producing value-added materials. Thus, a direct alkaline sulfide ion fuel cell is a functional fuel cell capable of simultaneously removing harmful gases, producing electricity, and producing a large amount of by-products.
본 발명의 일 실시예에서는, 미세조류 유래 탄소 지지체 기반 촉매 합성을 수행하였다. 그 결과, 도 2 및 도 3에 나타낸 바와 같이, 온도가 증가함에 따라서 첨가된 TiO2 금속 결정의 성장이 일어남과 동시에 미세조류 유래 그래파이트 탄소에 TiO2 금속 결정이 담지되는 것을 확인하였고, TiO2:그래파이트(G)의 중량 비율(wt.%)이 10:90, 30:70 또는 60:40이 되도록 그래파이트 탄소 지지체에 담지된 금속촉매를 합성하였다. In one embodiment of the present invention, microalgae-based carbon support-based catalyst synthesis was performed. As a result, as shown in Figs. 2 and 3, it was confirmed that the temperature increases, therefore adding cost is TiO 2 metal crystals supported on TiO 2 microalgae derived at the same time as this occurs the growth of the metal crystals graphite carbon, TiO 2: A metal catalyst supported on a graphite carbon support was synthesized so that the weight ratio (wt.%) Of graphite (G) was 10:90, 30:70 or 60:40.
상기 합성된 미세조류 유래 탄소 지지체 기반 촉매의 특성 분석을 수행한 결과, 도 2(d), 2(e) 및 2(f)에 나타낸 바와 같이, 미세조류를 지지체로 사용하여 합성된 TiO2 촉매는 1∼2μm 크기의 막대형 마이크로구조(microstructure)로 넓은 표면적을 형성하고 있음을 확인하였다. As shown in FIGS. 2 (d), 2 (e) and 2 (f), the synthesized microalgae-based carbon support-based catalysts were analyzed for the characteristics of the TiO 2 catalyst synthesized using microalgae as a support Was found to have a large surface area with a microstructure of 1 to 2 μm in size.
특히, 도 3(c)에 나타낸 바와 같이, 질소 흡탈착 특성평가에 따르면 미세조류를 지지체로 사용하여 합성된 TiO2 촉매인 TiO2/G의 금속촉매의 경우 BET 표면적이 158∼372.8m2g-1로 나타나 8.0m2g-1의 표면적을 가지는 TiO2에 비해 극명한 차이가 있었다.Particularly, as shown in Fig. 3 (c), according to the nitrogen adsorption / desorption property evaluation, the TiO 2 / G metal catalyst, which is a TiO 2 catalyst synthesized using microalgae as a support, has a BET surface area of 158 to 372.8 m 2 g -1 , which was significantly different from TiO 2 having a surface area of 8.0 m 2 g -1 .
또한, 도 3(a)에 나타낸 바와 같이, TiO2의 특이적인 패턴을 나타내는 XRD(X-ray diffractometer) 스펙트럼 결과에 따르면 금속촉매에 포함된 TiO2의 함유량이 증가할수록 TiO2의 anatase 형태의 피크의 강도(intensity)가 증가하였다. 이때 그래파이트 첨가로 TiO2 결정체의 특성에 미치는 영향은 없는 것으로 확인되었다.Further, FIG. 3 (a) described above, according to the XRD (X-ray diffractometer) spectra showing the specific pattern of TiO 2 increases the content of TiO 2 contained in the metal catalyst more anatase form of TiO 2 of the peak shown in Fig. The intensity of which was increased. At this time, it was confirmed that addition of graphite did not affect the properties of TiO 2 crystals.
또한, 도 3(b)에 나타낸 바와 같이, 라만 스펙트럼 결과에 따르면 TiO2의 crystalline phase를 확인하였고, TiO2/G 금속촉매에 탄소가 포함되어 있었다. 즉, anatase TiO2 phase의 전형적인 특징인 145, 196, 395, 515 및 635cm-1 파장대에서의 강한 라만 스케터링(Raman Scattering)을 확인하였고, TiO2/G 금속촉매의 경우 탄소 특이적인 D-밴드 및 G-밴드를 각각 1372 및 1592cm-1 파장대에서 확인하였다.In addition, as shown in Fig. 3 (b), Raman was confirmed that crystalline phase of TiO 2 according to the spectrum results, was a TiO 2 / G metal catalyst comprises a carbon. That is, anatase TiO 2 strong Raman scattering at the 145, 196, 395, 515 and 635 cm -1 wavelengths, typical characteristics of the TiO 2 / G metal catalyst, and carbon-specific D- and G-bands for the TiO 2 / Were confirmed at 1372 and 1592 cm -1 wavelength band, respectively.
따라서, 본 발명은 일 관점에서, 미세조류 유래 탄소 지지체에 금속이 담지된 것을 특징으로 하는 직접 알칼라인 황화이온 연료 전지용 금속촉매에 관한 것이다.Accordingly, the present invention relates to a metal catalyst for a direct alkaline sulfide ion fuel cell characterized in that a metal is supported on a microalgae-derived carbon support in one aspect.
본 발명에 있어서, 상기 미세조류 유래 탄소 지지체는 그래파이트(graphite)인 것을 특징으로 할 수 있고, 상기 금속은 귀금속, 전이금속, 귀금속의 산화물, 전이금속의 산화물 및 귀금속-전이금속의 합금으로 구성된 군에서 선택되는 것을 특징으로 할 수 있다.In the present invention, the micro-algae-derived carbon support may be graphite, and the metal may be selected from the group consisting of a noble metal, a transition metal, an oxide of a noble metal, an oxide of a transition metal, and an alloy of a noble metal and a transition metal And the like.
본 발명에 있어서, 상기 미세조류는 아크난테스(Achnanthes), 암피프로라(Amphiprora), 암포라(Amphora), 안키스트로데스무스(Ankistrodesmus), 아스테로모나스(Asteromonas), 보에켈로비아(Boekelovia), 보로디넬라(Borodinella), 보트리오코쿠스(Botryococcus), 브락테오코쿠스(Bracteococcus), 챠에토세로스(Chaetoceros), 카르테리아(Carteria), 클라미도모나스(Chlamydomonas), 클로로코쿰(Chlorococcum), 클로로고늄(Chlorogonium), 클로넬라(Chlorella), 크로모나스(Chroomonas), 크리소스파에라(Chrysosphaera), 크리코스파에라(Cricosphaera), 크립테코디늄(Crypthecodinium), 크립토모나스(Cryptomonas), 사이클로텔라(Cyclotella), 두날리엘라(Dunaliella), 엘립소이돈(Ellipsoidon), 에밀리아니아(Emiliania), 에레모스파에라(Eremosphaera), 에르노데스미우스(Ernodesmius), 유글레아(Euglena), 프란세이아(Franceia), 프라길라리아(Fragilaria), 글로에오탐니온(Gloeothamnion), 하에마토코쿠스(Haematococcus), 할로카페테리아(Halocafeteria), 히메노모나스(Hymenomonas), 아이소크리시스(Isochrysis), 레포신클리스(Lepocinclis), 마이크락티늄(Micractinium), 모노라피듐(Monoraphidium), 난노클로리스(Nannochloris), 난노클롭시스(Nannochloropsis), 바니쿨라(Navicula), 네오클로리스(Neochloris), 네프로클로리스(Nephrochloris), 네프로셀미스(Nephroselmis), 니츠치아(Nitzschia), 오크로모나스(Ochromonas), 오에도고늄(Oedogonium), 오오시스티스(Oocystis), 오스트레오코쿠스(Ostreococcus), 파블로바(Pavlova), 파라클로렐라(Parachlorella), 파스케리아(Pascheria), 파에도닥틸륨(Phaeodactylum), 파구스(Phagus), 플라티모나스(Platymonas), 플루로크리시스(Pleurochrysis), 플루로코코스(Pleurococcus), 프로토쎄카(Prototheca), 슈도클로렐라(Pseudochlorella), 피라미모나스(Pyramimonas), 피로보트리스(Pyrobotrys), 세네데스무스(Scenedesmus), 스켈레토네마(Skeletonema), 스피로기라(Spyrogyra), 스티코코쿠스(Stichococcus), 테트라셀미스(Tetraselmis), 탈라시오시라(Thalassiosira), 비리디엘라(Viridiella), 코코믹사(Coccomyxa), 시조키트리움(Schizochytrium) 및 볼복스로 구성된 군에서 선택되는 것을 특징으로 할 수 있다.In the present invention, the microalgae are arc Nantes (Achnanthes), cancer PIFF roller (Amphiprora), via a Amfora (Amphora), des mousse (Ankistrodesmus), Aspergillus Tero Pseudomonas (Asteromonas), Kel to view it should keystrokes ( Boekelovia), beam Lodi Nella (Borodinella), boat Rio nose kusu (Botryococcus), Brac Theo nose kusu (Bracteococcus), Chitose Ross (Chaetoceros) in Chatham, carte Liao (Carteria), Chlamydomonas (Chlamydomonas), chloro kokum ( Chlorococcum), claw logo uranium (Chlorogonium), Chloe Nella (Chlorella), croissants Monastir (Chroomonas), creative source file Era (Chrysosphaera), Creative COSPA Era (Cricosphaera), creep Te coordinated titanium (Crypthecodinium), crypto to Monastir (Cryptomonas ), Cyclotella , Dunaliella , Ellipsoidon , Emiliania , Eremosphaera , Ernodesmius , Euglena , Eugenia , ), Francia ( Franc eia), PRA Gila Liao (Fragilaria), under the false positives trunnion (Gloeothamnion) to glow, Mato nose kusu (Haematococcus), halo cafeteria (Halocafeteria), Hime grandma eggplant (Hymenomonas), iso-Cri sheath (Isochrysis), Lefort sinkeul Lees ( Lepocinclis , Micractinium , Monoraphidium , Nannochloris , Nannochloropsis , Navicula , Neochloris , Nephrochloris , Pro cell Miss (Nephroselmis), Chemnitz teeth (Nitzschia), oak Pseudomonas (Ochromonas), Oe Togo titanium (Oedogonium), O-City seutiseu (Oocystis), Australia Leo nose kusu (Ostreococcus), Pavlova (Pavlova), para chlorella ( Parachlorella), par Leah schedule (Pascheria), par dodak tilryum (Phaeodactylum), par Goose (Phagus), platinum Monastir (Platymonas), a flu Creative system (Pleurochrysis), fluorescein to Cocos (Pleurococcus), prototype sseka (Protothe ca), Pseudomonas Chlorella (Pseudochlorella), minnow Pseudomonas (Pyramimonas), fatigue boat-less (Pyrobotrys), three or four des mousse (Scenedesmus), skeletal retrograde nematic (Skeletonema), spiro rep (Spyrogyra), styryl Coco kusu (Stichococcus), tetra may be characterized in that the cell is selected from the miss (Tetraselmis), Tallahassee Please Shirakawa (Thalassiosira), irregularities di Ella (Viridiella), nose comic four (Coccomyxa), progenitor kit Solarium (Schizochytrium) and view the group consisting of carboxamide.
본 발명에 있어서, 상기 탄소 지지체에 담지된 금속촉매의 TiO2:그래파이트(G)의 중량 비율은 1:9∼6:4인 것을 특징으로 할 수 있고, 미세조류 유래 탄소 지지체에 담지된 금속촉매는 0.5∼3μm 크기의 막대형 마이크로구조(microstructure)인 것을 특징으로 할 수 있다.In the present invention, the weight ratio of TiO 2 : graphite (G) of the metal catalyst supported on the carbon support may be 1: 9 to 6: 4, and the metal catalyst supported on the microalgae- May be characterized by being a rod-shaped microstructure having a size of 0.5 to 3 mu m.
본 발명은 다른 관점에서, (a) 미세조류를 유기용매에 분산시키는 단계; (b) 상기 미세조류 분산액에 금속촉매 또는 그 전구체를 첨가한 다음, 혼합하여 침전물을 형성시키는 단계; 및 (c) 상기 침전물을 열처리하여 미세조류 유래 탄소 지지체에 금속촉매를 담지시키는 단계를 포함하는 미세조류 유래 탄소 지지체에 담지된 금속촉매의 제조방법에 관한 것이다.In another aspect, the present invention provides a method for producing microalgae, comprising: (a) dispersing microalgae in an organic solvent; (b) adding a metal catalyst or a precursor thereof to the microalgae dispersion and then mixing to form a precipitate; And (c) heat treating the precipitate to deposit a metal catalyst on the microalgae-derived carbon support. The present invention also relates to a method for producing a metal catalyst supported on a microalgae-derived carbon support.
본 발명에 있어서, 상기 미세조류 유래 탄소 지지체는 그래파이트(graphite)인 것을 특징으로 할 수 있으며, 상기 유기용매는 알코올인 것을 특징으로 할 수 있고, 상기 (a) 단계의 유기용매에 분산된 분산액을 추가로 30∼90초간 초음파 처리하는 것을 특징으로 할 수 있다.In the present invention, the microalgae-derived carbon support may be graphite, and the organic solvent may be an alcohol. The dispersion may be prepared by dispersing the dispersion in the organic solvent of step (a) And ultrasonication is further performed for 30 to 90 seconds.
본 발명에서, 용어 “그래파이트(graphite)”란 기계적 가공이 쉽고, 열전도율이 높으며 마찰성과 윤활성 및 높은 열적, 화학적 저항과 온도 상승에 따른 강도 증가의 특성을 지니는 물질로서, 온도나 습도의 변화에도 거의 영향을 받지 않는 장점이 있다. 카본 그래파이트라고 부르기도 한다.In the present invention, the term " graphite " refers to a material which is easy to mechanically process, has high thermal conductivity, has characteristics of friction, lubrication, high thermal and chemical resistance, There is an advantage not affected. It is also called carbon graphite.
본 발명에 있어서, 상기 금속촉매 또는 그 전구체는 귀금속, 전이금속, 귀금속의 산화물, 전이금속의 산화물 및 귀금속-전이금속의 합금으로 구성된 군에서 선택되는 것을 특징으로 할 수 있다. In the present invention, the metal catalyst or the precursor thereof may be selected from the group consisting of a noble metal, a transition metal, an oxide of a noble metal, an oxide of a transition metal, and an alloy of a noble metal and a transition metal.
본 발명에서 상기 귀금속은 금, 은, 백금 또는 팔라듐이고, 상기 전이금속은 티타늄, 니켈, 코발트, 철, 망간, 몰리브덴 또는 텅스텐일 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the noble metal may be gold, silver, platinum or palladium, and the transition metal may be titanium, nickel, cobalt, iron, manganese, molybdenum or tungsten.
본 발명에 있어서, 상기 (b) 단계의 분산액에 금속촉매 또는 그 전구체를 첨가한 다음, 증류수를 추가로 첨가함으로써 가수분해를 촉진시키는 것을 특징으로 할 수 있고, 상기 (b) 단계의 침전물은 여과하여 40∼60℃에서 건조시키는 것을 특징으로 할 수 있다.In the present invention, the metal catalyst or a precursor thereof may be added to the dispersion of step (b), and then distilled water may be further added to accelerate the hydrolysis. The precipitate of step (b) Followed by drying at 40 to 60 占 폚.
본 발명에 있어서, 상기 (c) 단계의 열처리는 350∼450℃의 아르곤 분위기(Argon atmosphere)에서 5∼7시간 동안 수행할 수 있고, 바람직하게는 400℃의 아르곤 분위기에서 6시간 동안 수행하는 것을 특징으로 할 수 있다.In the present invention, the heat treatment in step (c) may be performed in an argon atmosphere at 350 to 450 ° C for 5 to 7 hours, preferably at 400 ° C in an argon atmosphere for 6 hours .
본 발명에 있어서, 상기 미세조류는 아크난테스(Achnanthes), 암피프로라(Amphiprora), 암포라(Amphora), 안키스트로데스무스(Ankistrodesmus), 아스테로모나스(Asteromonas), 보에켈로비아(Boekelovia), 보로디넬라(Borodinella), 보트리오코쿠스(Botryococcus), 브락테오코쿠스(Bracteococcus), 챠에토세로스(Chaetoceros), 카르테리아(Carteria), 클라미도모나스(Chlamydomonas), 클로로코쿰(Chlorococcum), 클로로고늄(Chlorogonium), 클로넬라(Chlorella), 크로모나스(Chroomonas), 크리소스파에라(Chrysosphaera), 크리코스파에라(Cricosphaera), 크립테코디늄(Crypthecodinium), 크립토모나스(Cryptomonas), 사이클로텔라(Cyclotella), 두날리엘라(Dunaliella), 엘립소이돈(Ellipsoidon), 에밀리아니아(Emiliania), 에레모스파에라(Eremosphaera), 에르노데스미우스(Ernodesmius), 유글레아(Euglena), 프란세이아(Franceia), 프라길라리아(Fragilaria), 글로에오탐니온(Gloeothamnion), 하에마토코쿠스(Haematococcus), 할로카페테리아(Halocafeteria), 히메노모나스(Hymenomonas), 아이소크리시스(Isochrysis), 레포신클리스(Lepocinclis), 마이크락티늄(Micractinium), 모노라피듐(Monoraphidium), 난노클로리스(Nannochloris), 난노클롭시스(Nannochloropsis), 바니쿨라(Navicula), 네오클로리스(Neochloris), 네프로클로리스(Nephrochloris), 네프로셀미스(Nephroselmis), 니츠치아(Nitzschia), 오크로모나스(Ochromonas), 오에도고늄(Oedogonium), 오오시스티스(Oocystis), 오스트레오코쿠스(Ostreococcus), 파블로바(Pavlova), 파라클로렐라(Parachlorella), 파스케리아(Pascheria), 파에도닥틸륨(Phaeodactylum), 파구스(Phagus), 플라티모나스(Platymonas), 플루로크리시스(Pleurochrysis), 플루로코코스(Pleurococcus), 프로토쎄카(Prototheca), 슈도클로렐라(Pseudochlorella), 피라미모나스(Pyramimonas), 피로보트리스(Pyrobotrys), 세네데스무스(Scenedesmus), 스켈레토네마(Skeletonema), 스피로기라(Spyrogyra), 스티코코쿠스(Stichococcus), 테트라셀미스(Tetraselmis), 탈라시오시라(Thalassiosira), 비리디엘라(Viridiella), 코코믹사(Coccomyxa), 시조키트리움(Schizochytrium) 및 볼복스로 구성된 군에서 선택되는 것을 특징으로 할 수 있다. In the present invention, the microalgae are arc Nantes (Achnanthes), cancer PIFF roller (Amphiprora), via a Amfora (Amphora), des mousse (Ankistrodesmus), Aspergillus Tero Pseudomonas (Asteromonas), Kel to view it should keystrokes ( Boekelovia), beam Lodi Nella (Borodinella), boat Rio nose kusu (Botryococcus), Brac Theo nose kusu (Bracteococcus), Chitose Ross (Chaetoceros) in Chatham, carte Liao (Carteria), Chlamydomonas (Chlamydomonas), chloro kokum ( Chlorococcum), claw logo uranium (Chlorogonium), Chloe Nella (Chlorella), croissants Monastir (Chroomonas), creative source file Era (Chrysosphaera), Creative COSPA Era (Cricosphaera), creep Te coordinated titanium (Crypthecodinium), crypto to Monastir (Cryptomonas ), Cyclotella , Dunaliella , Ellipsoidon , Emiliania , Eremosphaera , Ernodesmius , Euglena , Eugenia , ), Francia ( Franc eia), PRA Gila Liao (Fragilaria), under the false positives trunnion (Gloeothamnion) to glow, Mato nose kusu (Haematococcus), halo cafeteria (Halocafeteria), Hime grandma eggplant (Hymenomonas), iso-Cri sheath (Isochrysis), Lefort sinkeul Lees ( Lepocinclis , Micractinium , Monoraphidium , Nannochloris , Nannochloropsis , Navicula , Neochloris , Nephrochloris , Pro cell Miss (Nephroselmis), Chemnitz teeth (Nitzschia), oak Pseudomonas (Ochromonas), Oe Togo titanium (Oedogonium), O-City seutiseu (Oocystis), Australia Leo nose kusu (Ostreococcus), Pavlova (Pavlova), para chlorella ( Parachlorella), par Leah schedule (Pascheria), par dodak tilryum (Phaeodactylum), par Goose (Phagus), platinum Monastir (Platymonas), a flu Creative system (Pleurochrysis), fluorescein to Cocos (Pleurococcus), prototype sseka (Protothe ca), Pseudomonas Chlorella (Pseudochlorella), minnow Pseudomonas (Pyramimonas), fatigue boat-less (Pyrobotrys), three or four des mousse (Scenedesmus), skeletal retrograde nematic (Skeletonema), spiro rep (Spyrogyra), styryl Coco kusu (Stichococcus), tetra may be characterized in that the cell is selected from the miss (Tetraselmis), Tallahassee Please Shirakawa (Thalassiosira), irregularities di Ella (Viridiella), nose comic four (Coccomyxa), progenitor kit Solarium (Schizochytrium) and view the group consisting of carboxamide.
본 발명에 있어서, 상기 탄소 지지체에 담지된 금속촉매의 TiO2:그래파이트(G)의 중량 비율은 1:9∼6:4인 것을 특징으로 할 수 있고, 상기 미세조류 유래 탄소 지지체에 담지된 금속촉매는 0.5∼3μm 크기의 막대형 마이크로구조(microstructure)일 수 있고, 바람직하게는 1∼2μm 크기의 막대형 마이크로구조인 것을 특징으로 할 수 있다.In the present invention, the weight ratio of TiO 2 : graphite (G) of the metal catalyst supported on the carbon support may be 1: 9 to 6: 4, and the metal supported on the carbon support of the microalgae The catalyst may be a rod-like microstructure having a size of 0.5 to 3 mu m, and preferably a rod-like microstructure having a size of 1 to 2 mu m.
본 발명의 다른 실시예에서는, 미세조류 유래 탄소 지지체 기반 촉매의 전기화학적 특성 분석을 수행하였다. 그 결과, 도 4에 나타낸 바와 같이, 10wt.% TiO2/G, 30wt.% TiO2/G 및 60wt.% TiO2/G의 최대 전력 밀도(maximum power density)는 각각 26.00mWcm-2, 33.26mWcm-2 및 38.90mWcm- 2 인 것으로 나타났다.In another embodiment of the present invention, an electrochemical characterization of the microalgae-based carbon support-based catalyst was performed. As a result, the maximum power densities of 10 wt.% TiO 2 / G, 30 wt.% TiO 2 / G and 60 wt.% TiO 2 / G were 26.00 mWcm -2 , 33.26 mWcm -2 and 38.90mWcm - was found to be 2.
결국, TiO2 담지량에 따라 연료전지의 성능이 향상됨을 확인하였으며, 미세조류 유래 그래파이트 탄소의 높은 표면적으로 인해 유의한 양의 전기에너지가 생성됨을 확인하였다. As a result, it was confirmed that the performance of the fuel cell was improved according to the TiO 2 loading amount, and it was confirmed that a significant amount of electric energy was generated due to the high surface area of the microalgae-derived graphite carbon.
따라서, 본 발명은 또 다른 관점에서, 양이온 교환막; 알칼리성 수용액을 포함하고, 황화수소를 흡수하여 황화이온을 생성시키는 H2S 흡수부; 및 상기 흡수부에 위치하는 애노드와 양이온 교환막에 의해 분리되고 상기 알칼리성 수용액에 위치하는 캐소드를 포함하는 직접 알칼라인 황화이온 연료전지 시스템에 있어서, 상기 애노드는 상기의 미세조류 유래 탄소 지지체에 담지된 금속촉매를 포함하는 직접 알칼라인 황화이온 연료전지 시스템에 관한 것이다.Accordingly, in another aspect, the present invention provides a cation exchange membrane comprising: a cation exchange membrane; An H 2 S absorption part containing an alkaline aqueous solution and absorbing hydrogen sulfide to generate sulfide ions; And a cathode disposed in the absorber and separated from the anode by a cation exchange membrane and positioned in the alkaline aqueous solution, wherein the anode comprises a metal catalyst supported on the microalgae-derived carbon support, To a direct alkaline sulfide ion fuel cell system.
상기 직접 알칼라인 황화이온 연료전지는 애노드(anode)와 캐소드(cathode) 그리고 이 둘 사이에서 이온을 운반하는 이온교환막으로 구성되어 있다. 상기 연료전지의 애노드와 캐소드의 물질은 통상적으로 사용되는 연료전지의 전극 재료에 대해 모두 가능하다. 상기 이온교환막은 상기 알칼리성 조건을 조성하기 위한 염의 양이온 종류에 따라 나트륨 혹은 칼륨으로 치환된 나피온(Nafion)이 사용될 수 있다.The direct alkaline sulfide ion fuel cell comprises an anode, a cathode, and an ion exchange membrane carrying ions between the anode and the cathode. The materials of the anode and the cathode of the fuel cell are all possible for the electrode material of the fuel cell normally used. As the ion exchange membrane, Nafion substituted with sodium or potassium may be used depending on the cation type of the salt for forming the alkaline condition.
상기 연료전지의 애노드에서는 황화수소가 알칼리성 수용액에 흡수되어 생성된 황화이온이 전극 상에서 전기화학적으로 산화되면서 황 이온을 생성하는 반응이 일어난다. 반면 캐소드에서는 애노드로부터 공급된 물, 외부 회로를 타고 온 전자, 그리고 공급되는 산소가 결합하여 수산화기로 환원되는 반응이 일어난다. 캐소드, 애노드의 반응은 황화수소의 산화로부터 전기에너지의 생산을 가능케 하는 연료전지 반응이다.In the anode of the fuel cell, hydrogen sulfide is absorbed in the alkaline aqueous solution, and the generated sulfide ions are electrochemically oxidized on the electrode to generate sulfur ions. On the other hand, in the cathode, water supplied from the anode, electrons in the external circuit, and oxygen supplied to the cathode are reduced to a hydroxyl group. The reaction of the cathode and the anode is a fuel cell reaction that enables the production of electrical energy from the oxidation of hydrogen sulphide.
상기 전기화학적으로 산화시키는 단계는 연료전지의 음극 전해액으로 사용된다. 상기 흡수액의 pH는 9~14, 바람직하게는 pH 12~14일 수 있다. pH가 9 미만일 경우에는 산화형 황 이온으로까지 산화가 이루어지지 않을 뿐만 아니라 유황 형태로 전극에 남음으로써 전극상 황의 축적을 야기한다. 흡수액의 pH를 최대한 높게 유지함으로써 황화이온의 산화반응 속도를 향상시키고 전기에너지 출력이 최대가 되도록 한다. The step of electrochemically oxidizing is used as a cathode electrolyte of a fuel cell. The pH of the absorption liquid may be 9 to 14, preferably 12 to 14. When the pH is less than 9, oxidation to sulfur oxide is not achieved, but sulfur accumulates in the form of sulfur. By maintaining the pH of the absorption liquid as high as possible, the oxidation reaction speed of sulfide ions is improved and the electric energy output is maximized.
또한, 알칼리성 조건에서는 산성 혹은 중성 조건에서의 황화이온의 산화가 유황에서 끝나는 것과는 달리 더 산화된 형태의 이온인 S2O3 2 -, SO3 2 - 또는 SO4 2 - 등과 같은 산화형 황 이온, 즉 황과 산소가 결합한 이온으로까지 산화가 이루어지며, 이러한 산화된 형태의 이온은 여러 산업적인 부가가치를 지니고 있다. 따라서 pH를 높게 유지함으로써, 이러한 부가가치물질 생산이 극대화되도록 유도한다.In addition, under alkaline conditions, oxidizing sulfur such as S 2 O 3 2 - , SO 3 2 -, or SO 4 2 - , which is an oxidized form of ions, differs from sulfide ion oxidation in acidic or neutral conditions, , That is, the oxidation of sulfur and oxygen to the combined ion, and these oxidized forms of ion have various industrial added values. Thus, by keeping the pH high, it is possible to maximize the production of such value-added materials.
본 발명은 또 다른 관점에서, 상기의 직접 알칼라인 황화이온 연료전지 시스템의 H2S 흡수부에 H2S를 공급하여 알칼리성 수용액에 흡수시켜 황화이온을 생성하고, 상기 황화이온을 산화형 황 이온으로 생성시켜 전기에너지를 생산하는 황화수소 제거 및 전기생산방법에 관한 것이다. 본 발명에서, 직접 알칼라인 황화이온 연료전지시스템을 이용하여 전기를 생산하는 것이 가능함으로써 황화수소와 같은 유해가스를 제거할 수 있고, 동시에 전기에너지를 생산할 수 있다. In another aspect of the present invention, H 2 S is supplied to the H 2 S absorption portion of the direct alkaline sulfide ion fuel cell system to absorb sulfide ions into the alkaline aqueous solution to form sulfide ions, And a method for producing hydrogen sulfide and an electric production method for producing electric energy. In the present invention, it is possible to produce electricity using a direct alkaline sulphide ion fuel cell system, thereby eliminating noxious gases such as hydrogen sulfide and simultaneously producing electric energy.
본 발명에 의한 황화수소 제거방법은 황화수소를 알칼리성 수용액에 흡수시켜 유해가스를 이온종으로 변환함과 동시에 제거하고, 생성된 흡수액을 연료전지의 애노드로 유입하여 전기에너지를 생산하고 황화이온을 산화된 형태의 이온으로 변화시킨다. The method of removing hydrogen sulfide according to the present invention is a method of removing hydrogen sulfide by absorbing hydrogen sulfide into an alkaline aqueous solution to convert harmful gas into ionic species and simultaneously removing the resulting absorbing solution to flow into the anode of the fuel cell to produce electric energy, Ions.
본 발명에 있어서, 상기 알칼리성 수용액은 수산화나트륨(NaOH), 수산화칼륨(KOH), 수산화리튬(LiOH), 수산화암모늄(NH4OH) 및 수산화칼슘(Ca(OH)2)으로 구성된 군에서 선택되는 것을 특징으로 할 수 있다. In the present invention, in that the aqueous alkaline solution is selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), ammonium hydroxide (NH 4 OH) and calcium hydroxide (Ca (OH) 2) .
본 발명에 있어서, 알칼리성 수용액의 농도는 0.1M 내지 10M일 수 있으며, 바람직하게는 1M 내지 5M인 것을 특징으로 할 수 있고, 상기 산화형 황 이온은 S2O3 2 -, SO3 2- 또는 SO4 2 -인 것을 특징으로 할 수 있고, 상기 전기에너지를 생산하는 온도는 20℃ 내지 90℃인 것을 특징으로 할 수 있다. 상기 온도가 높을수록 반응속도가 빠르므로 전기에너지 출력이 향상된다.
In the present invention, the concentration of the alkaline aqueous solution is a 0.1M to 10M, and can be, and preferably can be characterized in that the 1M to 5M, the oxidized sulfur ions S 2 O 3 2 -, SO 3 2- or SO4 < 2 & gt; - , and the electric energy And the temperature is 20 ° C to 90 ° C. The higher the temperature is, the faster the reaction rate is, and the electric energy output is improved.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예Example 1: 미세조류 유래 탄소 지지체 기반 촉매 합성 1: Microalgae-based carbon support-based catalyst synthesis
미세조류(Chlorella sp . KR-1)는 3mM KNO3; 5.44mM KH2PO4; 1.83mM Na2HPO4; 0.2mM MgSO4; 0.12mM CaCl2; 0.03mM FeNaEDTA; 0.01mM ZnSO4; 0.07mM MnCl2; 0.07mM CuSO4; 및 0.01mM Al2(SO4)3가 포함된 pH 6.5인 배지에서 세포 밀도가 1.2∼1.4g/L가 되도록 배양하였다(Hwang, T et al ., Bioresour . Technol.,139:379-282, 2013). Microalgae (Chlorella sp . KR-1) was dissolved in 3 mM KNO 3 ; 5.44mM KH 2 PO 4; 1.83mM Na 2 HPO 4; 0.2mM MgSO 4; 0.12 mM CaCl 2 ; 0.03 mM FeNaEDTA; 0.01 mM ZnSO 4 ; 0.07 mM MnCl 2 ; 0.07mM CuSO 4; And 0.01mM Al 2 (SO 4) 3 has a cell density in a pH 6.5 medium containing cultured such that 1.2~1.4g / L (Hwang, et T al . , Bioresour . Technol ., 139: 379-282, 2013).
상기 1.2g/L의 미세조류(Chlorella sp . KR-1)를 ∼4000rpm에서 원심분리하고, 증류수로 3회 세척하여 잔류 배지를 제거한 다음, 남은 미세조류 고형물을 에탄올에 분산시켰다. 적절한 양의 티타늄이소프로폭사이드(Titanium(IV) isopropoxide, Ti[OCH(CH3)2]4)를 물과 함께 미세조류 분산액에 첨가한 다음, 400℃의 아르곤 분위기(Argon atmosphere)에서 열처리를 하여 탄소 지지체에 담지된 금속촉매(TiO2:그래파이트(Graphite: G))로 수득하였다.The 1.2 g / L microalgae ( Chlorella sp . KR-1) was centrifuged at ~4000 rpm and washed three times with distilled water to remove residual medium, and the remaining microalgae solids were dispersed in ethanol. Titanium (IV) isopropoxide, Ti [OCH (CH 3 ) 2 ] 4 ) was added to the microalgae dispersion together with water and then heat treated at 400 ° C in an argon atmosphere. (TiO 2 : Graphite: G) supported on a carbon support.
일례로, TiO2:그래파이트(G)의 중량 비율이 10:90(이하 "10wt.% TiO2/G"이라 함)을 합성하는 방법은 다음과 같다. 90mg의 미세조류 고형물을 100mL의 에탄올에 분산시키고, 상기 분산액을 실온에서 약 1분간 초음파 처리하였다. 상기 초음파 처리된 분산액에 0.37mL의 티타늄이소프로폭사이드 희석용액(원액: 0.96∼1.087g/mL, Aldrich, 미국)을 한 방울씩 첨가하였다. 상기 티타늄이소프로폭사이드 용액이 첨가된 혼합물을 30분간 300rpm의 속도로 교반(혼합)하고, 티타늄이소프로폭사이드의 가수분해(hydrolysis)를 촉진하기 위해 0.1mL의 증류수를 첨가한 다음, 실온에서 4시간 교반(혼합)하여 침전물을 형성시켰다. 상기 형성된 침전물을 여과하고, 에탄올로 세척한 다음, 오븐에서 50℃로 건조시켜 합성물(composite)을 수득하였다. 상기 수득한 합성물을 6시간 동안 400℃의 아르곤 분위기(Argon atmosphere)에서 열처리하여 갈색을 띠는 10wt.% TiO2/G를 수득하였다.For example, a method of synthesizing a weight ratio of TiO 2 : graphite (G) of 10:90 (hereinafter referred to as "10 wt% TiO 2 / G") is as follows. 90 mg of microalgae solids were dispersed in 100 mL of ethanol and the dispersion was sonicated at room temperature for about 1 minute. To the ultrasonic treated dispersion was added 0.37 mL of a diluted titanium isopropoxide solution (0.96 to 1.087 g / mL of crude solution, Aldrich, USA) drop by drop. The mixture containing the titanium isopropoxide solution was stirred for 30 minutes at a rate of 300 rpm and 0.1 mL of distilled water was added to promote the hydrolysis of titanium isopropoxide, Followed by stirring (mixing) for 4 hours to form a precipitate. The precipitate formed was filtered, washed with ethanol and then dried in an oven at 50 < 0 > C to yield a composite. The resultant composite was heat-treated for 6 hours at 400 ° C in an argon atmosphere to obtain a brownish 10 wt.% TiO 2 / G.
상기 10wt.% TiO2/G 합성방법과 같은 방법으로 TiO2:그래파이트(G)의 중량 비율(wt.%)이 30:70(이하 "30wt.% TiO2/G"이라 함) 또는 60:40(이하 "60wt.% TiO2/G"이라 함)이 되도록 그래파이트 탄소 지지체에 담지된 금속촉매를 추가로 합성하였다.
The 10wt% TiO TiO 2 in the same manner as 2 / G Synthesis: graphite (G) weight ratio (. Wt%) is 30: 70 (hereinafter referred to as "30wt% TiO 2 / G. ") Or the 60: (Hereinafter referred to as "60 wt.% TiO 2 / G") was further synthesized.
실시예Example 2: 미세조류 유래 탄소 지지체 기반 촉매 특성 분석 2: Characterization of microbial-based carbon support based catalysts
실시예 1에서 합성된 촉매의 물리적 성상을 확인하기 위하여 FE-SEM(Scanning Electron Microscopy, Magellan400), FE-TEM(Transmisson Electron Microscopy, JEM-2100F), XRD(X-ray diffractometer, model RTP 300 RC, Rigaku) 및 Quantachrome Scientific adsorption analyzer(Quadrasorb-SI-MP-20)를 이용하여 분석을 수행하였다.(FE-SEM), FE-TEM (Transmission Electron Microscopy, JEM-2100F), X-ray diffractometer (XRD) and
그 결과, 도 2(d), 2(e) 및 2(f)에 나타낸 바와 같이, 미세조류를 지지체로 사용하여 합성된 TiO2 촉매는 1∼2μm 크기의 막대형 마이크로구조(microstructure)로 넓은 표면적을 형성하고 있음을 확인하였다. As a result, as shown in FIGS. 2 (d), 2 (e) and 2 (f), the TiO 2 catalyst synthesized using microalgae as a support has a microstructure of 1 to 2 μm in size It was confirmed that the surface area was formed.
특히, 도 3(c)에 나타낸 바와 같이, 질소 흡탈착 특성평가에 따르면 미세조류를 지지체로 사용하여 합성된 TiO2 촉매인 TiO2/G의 금속촉매의 경우 BET 표면적이 158∼372.8m2g-1로 나타나 8.0m2g-1의 표면적을 가지는 TiO2에 비해 극명한 차이가 있었다.Particularly, as shown in Fig. 3 (c), according to the nitrogen adsorption / desorption property evaluation, the TiO 2 / G metal catalyst, which is a TiO 2 catalyst synthesized using microalgae as a support, has a BET surface area of 158 to 372.8 m 2 g -1 , which was significantly different from TiO 2 having a surface area of 8.0 m 2 g -1 .
또한, 도 3(a)에 나타낸 바와 같이, TiO2의 특이적인 패턴을 나타내는 XRD(X-ray diffractometer) 스펙트럼 결과에 따르면 금속촉매에 포함된 TiO2의 함유량이 증가할수록 TiO2의 anatase 형태의 피크의 강도(intensity)가 증가하였다. 이때 그래파이트 첨가로 TiO2 결정체의 특성에 미치는 영향은 없는 것으로 확인되었다.Further, FIG. 3 (a) described above, according to the XRD (X-ray diffractometer) spectra showing the specific pattern of TiO 2 increases the content of TiO 2 contained in the metal catalyst more anatase form of TiO 2 of the peak shown in Fig. The intensity of which was increased. At this time, it was confirmed that addition of graphite did not affect the properties of TiO 2 crystals.
또한, 도 3(b)에 나타낸 바와 같이, 라만 스펙트럼 결과에 따르면 TiO2의 crystalline phase를 확인하였고, TiO2/G 금속촉매에 탄소가 포함되어 있었다. 즉, anatase TiO2 phase의 전형적인 특징인 145, 196, 395, 515 및 635cm-1 파장대에서의 강한 라만 스케터링(Raman Scattering)을 확인하였고, TiO2/G 금속촉매의 경우 탄소 특이적인 D-밴드 및 G-밴드를 각각 1372 및 1592cm-1 파장대에서 확인하였다.In addition, as shown in Fig. 3 (b), Raman was confirmed that crystalline phase of TiO 2 according to the spectrum results, was a TiO 2 / G metal catalyst comprises a carbon. That is, anatase TiO 2 strong Raman scattering at the 145, 196, 395, 515 and 635 cm -1 wavelengths, typical characteristics of the TiO 2 / G metal catalyst, and carbon-specific D- and G-bands for the TiO 2 / Were confirmed at 1372 and 1592 cm -1 wavelength band, respectively.
결국, 도 2 및 도 3에 나타낸 바와 같이, 온도가 증가함에 따라서 첨가된 TiO2 금속 결정의 성장이 일어남과 동시에 미세조류 유래 그래파이트 탄소에 TiO2 금속 결정이 담지되는 것을 확인하였고, 탄소 지지체에 금속 함유량이 각각 10, 30, 60wt.% 담지된 금속촉매로 10wt.% TiO2/G, 30wt.% TiO2/G, 60wt.% TiO2/G를 합성하였다.
As a result, as shown in FIG. 2 and FIG. 3, it was confirmed that as the temperature was increased, the TiO 2 metal crystal was added and the TiO 2 metal crystal was supported on the microalgae-derived graphite carbon. % TiO 2 / G, 30 wt.% TiO 2 / G, and 60 wt.% TiO 2 / G were synthesized with metal catalysts containing 10, 30 and 60 wt.
실시예Example 3: 미세조류 유래 탄소 지지체 기반 촉매의 전기화학적 특성 분석 3: Electrochemical characterization of microalgae-based carbon support-based catalysts
실시예 1에서 합성된 미세조류 유래 그래파이트 탄소 지지체에 담지된 금속 산화물 촉매의 전기화학적 성능을 평가하기 위하여, TiO2가 담지된 미세조류 유래 촉매로 도포된 70℃의 직접 알칼라인 황화이온 연료전지에서 1M Na2S+3M NaOH 용액이 연료로 사용될 경우 연료전지의 전기적 성능을 측정하였다. In order to evaluate the electrochemical performance of the metal oxide catalyst supported on the microalgae-derived graphite carbon support synthesized in Example 1, in a direct alkaline sulfide ion fuel cell coated with TiO 2 -supported microalgae-derived catalyst, When the Na 2 S + 3M NaOH solution was used as a fuel, the electrical performance of the fuel cell was measured.
그 결과, 도 4에 나타낸 바와 같이, 10wt.% TiO2/G, 30wt.% TiO2/G 및 60wt.% TiO2/G의 최대 전력 밀도(maximum power density)는 각각 26.00mWcm-2, 33.26mWcm-2 및 38.90mWcm- 2 인 것으로 나타났다.As a result, the maximum power densities of 10 wt.% TiO 2 / G, 30 wt.% TiO 2 / G and 60 wt.% TiO 2 / G were 26.00 mWcm -2 , 33.26 mWcm -2 and 38.90mWcm - was found to be 2.
결국, TiO2 담지량에 따라 연료전지의 성능이 향상됨을 확인하였으며, 미세조류 유래 그래파이트 탄소의 높은 표면적으로 인해 유의한 양의 전기에너지가 생성됨을 확인하였다.
As a result, it was confirmed that the performance of the fuel cell was improved according to the TiO 2 loading amount, and it was confirmed that a significant amount of electric energy was generated due to the high surface area of the microalgae-derived graphite carbon.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (21)
A metal catalyst for a direct alkaline sulfide ion fuel cell, wherein a metal is supported on a microalgae-derived carbon support, wherein the microalgae are selected from the group consisting of Achnanthes , Amphiprora , Amphora Ankistrodesmus , Asteromonas , Boekelovia , Borodinella , Botryococcus , Bracteococcus , Bracteococcus , Signature in Chitose Ross (Chaetoceros), carte Liao (Carteria), Chlamydomonas (Chlamydomonas), chloro kokum (Chlorococcum), claw logo titanium (Chlorogonium), claw Nella (Chlorella), chroman Pseudomonas (Chroomonas), Cri source file Era Such as Chrysosphaera , Cricosphaera , Crypthecodinium , Cryptomonas , Cyclotella , Dunaliella , Ellipsoidon , , Emiliania , Eremosphaera , Ernodesmius , Euglena , Franceia , Fragilaria , Gloeothamnion , Haocomycetes , Haematococcus , Halocafeteria , Hymenomonas , Isochrysis , Lepocinclis , Micractinium , Monoraphidium , nanno keulroriseu (Nannochloris), nanno keulrop sheath (Nannochloropsis), Barney Kula (Navicula), a neo keulroriseu (Neochloris), four Pro keulroriseu (Nephrochloris), four Pro cell Miss (Nephroselmis), Chemnitz teeth (Nitzschia), oak Pseudomonas ( Ochromonas), Oe Togo titanium (Oedogonium), O-City seutiseu (Oocystis), Australia Leo nose kusu (Ostreococcus), Pavlova (Pavlova), para chlorella (Parachlorella), Liao wave schedule (Pascheria), par dodak tilryum (Phaeodactyl um), par Goose (Phagus), platinum Monastir (Platymonas), flu into Crissy system (Pleurochrysis), fluorescein to Cocos (Pleurococcus), prototype sseka (Prototheca), pseudo Chlorella (Pseudochlorella), minnow Monastir (Pyramimonas), fatigue And are also known in the art as Pyrobotrys , Scenedesmus , Skeletonema , Spyrogyra , Stichococcus , Tetraselmis , Thalassiosira , Wherein the metal catalyst is selected from the group consisting of Viridiella , Coccomyxa , Schizochytrium , and Volkox .
The metal catalyst for a direct alkaline sulfide ion fuel cell according to claim 1, wherein the micro algae-derived carbon support is graphite.
The metal catalyst for a direct alkaline sulfide ion fuel cell according to claim 1, wherein the metal is selected from the group consisting of noble metals, transition metals, oxides of noble metals, oxides of transition metals, and noble metal-transition metal alloys.
The metal catalyst for a direct alkaline sulfide ion fuel cell according to claim 1, wherein the weight ratio of TiO 2 : graphite (G) of the metal catalyst supported on the carbon support is 1: 9 to 6: 4.
The metal catalyst for a direct alkaline sulfide ion fuel cell according to claim 1, wherein the metal catalyst supported on the microalgae-derived carbon support is a rod-shaped microstructure having a size of 0.5 to 3 m.
(a) 미세조류를 유기용매에 분산시키는 단계;
(b) 상기 미세조류 분산액에 금속촉매 또는 그 전구체를 첨가한 다음, 혼합하여 침전물을 형성시키는 단계; 및
(c) 상기 침전물을 열처리하여 미세조류 유래 탄소 지지체에 금속촉매를 담지시키는 단계,
여기서, 상기 미세조류는 아크난테스(Achnanthes), 암피프로라(Amphiprora), 암포라(Amphora), 안키스트로데스무스(Ankistrodesmus), 아스테로모나스(Asteromonas), 보에켈로비아(Boekelovia), 보로디넬라(Borodinella), 보트리오코쿠스(Botryococcus), 브락테오코쿠스(Bracteococcus), 챠에토세로스(Chaetoceros), 카르테리아(Carteria), 클라미도모나스(Chlamydomonas), 클로로코쿰(Chlorococcum), 클로로고늄(Chlorogonium), 클로넬라(Chlorella), 크로모나스(Chroomonas), 크리소스파에라(Chrysosphaera), 크리코스파에라(Cricosphaera), 크립테코디늄(Crypthecodinium), 크립토모나스(Cryptomonas), 사이클로텔라(Cyclotella), 두날리엘라(Dunaliella), 엘립소이돈(Ellipsoidon), 에밀리아니아(Emiliania), 에레모스파에라(Eremosphaera), 에르노데스미우스(Ernodesmius), 유글레아(Euglena), 프란세이아(Franceia), 프라길라리아(Fragilaria), 글로에오탐니온(Gloeothamnion), 하에마토코쿠스(Haematococcus), 할로카페테리아(Halocafeteria), 히메노모나스(Hymenomonas), 아이소크리시스(Isochrysis), 레포신클리스(Lepocinclis), 마이크락티늄(Micractinium), 모노라피듐(Monoraphidium), 난노클로리스(Nannochloris), 난노클롭시스(Nannochloropsis), 바니쿨라(Navicula), 네오클로리스(Neochloris), 네프로클로리스(Nephrochloris), 네프로셀미스(Nephroselmis), 니츠치아(Nitzschia), 오크로모나스(Ochromonas), 오에도고늄(Oedogonium), 오오시스티스(Oocystis), 오스트레오코쿠스(Ostreococcus), 파블로바(Pavlova), 파라클로렐라(Parachlorella), 파스케리아(Pascheria), 파에도닥틸륨(Phaeodactylum), 파구스(Phagus), 플라티모나스(Platymonas), 플루로크리시스(Pleurochrysis), 플루로코코스(Pleurococcus), 프로토쎄카(Prototheca), 슈도클로렐라(Pseudochlorella), 피라미모나스(Pyramimonas), 피로보트리스(Pyrobotrys), 세네데스무스(Scenedesmus), 스켈레토네마(Skeletonema), 스피로기라(Spyrogyra), 스티코코쿠스(Stichococcus), 테트라셀미스(Tetraselmis), 탈라시오시라(Thalassiosira), 비리디엘라(Viridiella), 코코믹사(Coccomyxa), 시조키트리움(Schizochytrium) 및 볼복스로 구성된 군에서 선택되는 것을 특징으로 하는 방법.
A method for preparing a metal catalyst supported on a microalgae-derived carbon support comprising the steps of:
(a) dispersing the microalgae in an organic solvent;
(b) adding a metal catalyst or a precursor thereof to the microalgae dispersion and then mixing to form a precipitate; And
(c) heat treating the precipitate to support a metal catalyst on the microalgae-derived carbon support,
Here, the microalgae arc Nantes (Achnanthes), cancer PIFF roller (Amphiprora), Amfora (Amphora), des mousse as not keystrokes (Ankistrodesmus), Aspergillus Tero Pseudomonas (Asteromonas), a Kell to the beam via (Boekelovia), beam Lodi Nella (Borodinella), boat Rio nose kusu (Botryococcus), Brac Theo nose kusu (Bracteococcus), Chitose Ross (Chaetoceros), carte Liao (Carteria), Chlamydomonas (Chlamydomonas), chloro kokum (Chlorococcum) in Chatham, Chloe logo uranium (Chlorogonium), Chloe Nella (Chlorella), croissants Monastir (Chroomonas), creative source file Era (Chrysosphaera), Creative COSPA Era (Cricosphaera), creep Te coordinated titanium (Crypthecodinium), crypto to Monastir (Cryptomonas), cycle Cyclotella , Dunaliella , Ellipsoidon , Emiliania , Eremosphaera , Ernodesmius , Euglena , Flan , Seia (Franceia), PRA La Ria (Fragilaria), false positives trunnion (Gloeothamnion), Mato nose kusu (Haematococcus), halo cafeteria (Halocafeteria), Hime grandma eggplant (Hymenomonas), iso-Cri sheath (Isochrysis), Lefort sinkeul less (Lepocinclis) under the glow, the microphone But are not limited to, micronutrients such as Micractinium , Monoraphidium , Nannochloris , Nannochloropsis , Navicula , Neochloris , Nephrochloris , Nephroselmis), Chemnitz teeth (Nitzschia), oak Monastir (Ochromonas), Oe Togo uranium (Oedogonium), oh when seutiseu (Oocystis), Australia Leo nose Syracuse (Ostreococcus), Pavlova (Pavlova), para chlorella (Parachlorella), wave schedule Ria (Pascheria), par dodak tilryum (Phaeodactylum), par Goose (Phagus), platinum Monastir (Platymonas), a flu Creative system (Pleurochrysis), fluorescein to Cocos (Pleurococcus), prototype sseka (Prototheca), pseudo Laurel La (Pseudochlorella), minnow Pseudomonas (Pyramimonas), fatigue boat-less (Pyrobotrys), three or four des mousse (Scenedesmus), skeletal retrograde nematic (Skeletonema), spiro rep (Spyrogyra), styryl Coco kusu (Stichococcus), tetra-cell miss ( Characterized in that it is selected from the group consisting of Tetraselmis , Thalassiosira , Viridiella , Coccomyxa , Schizochytrium and Volkox .
[8] The method of claim 7, wherein the microalgae-derived carbon support is graphite.
The method for producing a metal catalyst supported on a microalgae-derived carbon support according to claim 7, wherein the dispersion liquid dispersed in the organic solvent of step (a) is further subjected to ultrasonic treatment for 30 to 90 seconds.
8. The microalgae-derived carbon support according to claim 7, wherein the metal catalyst or the precursor thereof is selected from the group consisting of noble metals, transition metals, oxides of noble metals, oxides of transition metals and alloys of noble metal- Of the metal catalyst.
[8] The method according to claim 7, wherein the metal catalyst or the precursor thereof is added to the dispersion of step (b), and then the hydrolysis is promoted by further adding distilled water to the metal catalyst supported on the microalgae- Gt;
[7] The method according to claim 7, wherein the heat treatment in step (c) is performed in an argon atmosphere at 350 to 450.degree. C. for 5 to 7 hours. .
8. The method of claim 7, wherein the weight ratio of TiO 2 : graphite (G) of the metal catalyst supported on the carbon support is 1: 9 to 6: 4. Way.
8. The method according to claim 7, wherein the metal catalyst supported on the microalgae-derived carbon support is a rod-shaped microstructure having a size of 0.5 to 3 mu m.
Cation exchange membranes; An H 2 S absorption part containing an alkaline aqueous solution and absorbing hydrogen sulfide to generate sulfide ions; And an anode disposed in the absorber and a cathode separated by the cation exchange membrane and located in the alkaline aqueous solution, wherein the anode comprises the anode and the cathode, A direct alkaline sulphide ion fuel cell system comprising a metal catalyst supported on a microalgae-derived carbon support of any one of claims 6 to 10.
The H 2 S absorption unit of the direct alkaline sulfide ion fuel cell system of claim 16 is supplied with H 2 S to be absorbed into an alkaline aqueous solution to generate sulfide ions and produce sulfide ions as oxidized sulfur ions to produce electric energy Hydrogen sulphide removal and electricity production method.
18. The method of claim 17 wherein the aqueous alkaline solution is selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), ammonium hydroxide (NH 4 OH) and calcium hydroxide (Ca (OH) 2) And removing the hydrogen sulfide.
18. The method of claim 17, wherein the oxidized sulfur is S 2 O 3 2 - , SO 3 2 -, or SO 4 2 - .
18. The method of claim 17, wherein the concentration of the alkaline aqueous solution is 1M to 5M.
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