세리아 첨가 제오라이트 촉매를 이용한 디메틸 에테르 합성

김보경; 고재천; 김범식; 한명완; Bo-kyung Kim; Jaecheon Koh; Beom-sik Kim; Myungwan Han

Korean Chemical Engineering Research, Vol.49, No.2, 155-160, April, 2011

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세리아 첨가 제오라이트 촉매를 이용한 디메틸 에테르 합성

Dimethyl Ether Formation Using a Zeolite Catalyst Impregnated with Ceria

김보경, 고재천, 김범식 , 한명완 ^{1, †}

한국화학연구원 그린화학연구단, 305-600 대전광역시 유성구 장동 100
¹충남대학교 화학공학과, 305-764 대전광역시 유성구 궁동 220

Bo-kyung Kim, Jaecheon Koh, Beom-sik Kim , and Myungwan Han^{1, †}

Green Chemistry Research Division, KRICT, 100 Jang-dong, Yuseong-gu, Daejeon 305-600, Korea
¹Department of Chemical Engineering, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764, Korea

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초록

디메틸 에테르(DME)는 최근 청정 연료로서 주목을 받고 있다. 본 연구에서는 메탄올 탈수반응을 통한 디메틸 에테르(DME)의 제조에 대하여 조사하였다. 이때 촉매는 제올라이트 계열인 고체산 촉매를 이용하였다. 조촉매로서 세리아가 반응전환율뿐만 아니라 DME 생성 선택도도 증가시키는 것을 발견하였다. 실리카/알루미나의 조성비와 촉매 표면의 세리아의 무게함량을 변화시켜 최적의 촉매를 선정하였다. 5 wt%의 세리아가 첨가된 ZSM5-30의 DME에 대한 반응선택성이 가장 뛰어났으며, 이 촉매는 메탄올 내에 포함되어 있는 수분의 영향을 거의 받지 않았다. 마이크로 반응기에서 얻은 데이터를 가지고 반응 속도식을 구하였다.

Dimethyl ether draws an attention as a green fuel in recent years. In this study, we investigated dehydration of methanol to produce DME using solid-acid catalysts, a series of zeolite. We found that ceria took a role of promoting the reaction conversion as well as selectivity of DME formation as a cocatalyst to the zeolite catalyst. We varied Si/Al ratio and ceria percentage on the surface of the catalyst to get high performance catalyst. ZSM5-30 with 5 wt% ceria on the surface was found to have excellent DME selectivity and to be little influenced by water content in methanol feed. We proposed a reaction model and obtained kinetic parameters for the DME formation using the catalyst based on experimental results using a microreactor.

Keywords:Dimethyl Ether;Methanol;Dehydration;Zeolite Catalyst;Ceria Cocatalyst

[References]

McCandless JC, Park GP, Mich, “Dimethyl Ether Powered Engine,” U.S. Patent 5,626,294 (1997)
Kim JW, Sim KS, Han SD, Energy Engg. J., 7(2), 157 (1998)
Choi JW, Lee SH, Sim KS, Kim JW, Kim SH, Energy Engg. J., “Direct Synthesis of Dimethyl Ether from Syngas in a Slurry Phase and Gas Phase Reactor.", 10(1), 49 (2001)
Jun KW, Roh HS, News Inf. Chem. Eng., “Status of DME Production technology in Korea,”, 20(5), 519 (2002)
Jun KW, Lee HS, Roh HS, Park SE, Bull. Korean Chem. Soc., 23, 803 (2002)
Xu MT, Lunsford JH, Goodman DW, Bhattacharyya A, Appl. Catal. A: Gen., “Synthesis of Dimethyl Ether (DME) from Methanol over Solid-acid Catalysts.", 149(2), 289 (1997)
Koo Y, Han M, Korean Chem. Eng. Res., “Dimethyl Ether Production Using a Reactive Distillation Process.", 42(1), 44 (2004)
Yaripour F, Baghaei F, Schmidt I, Perregaard J, Catal. Commun., “Catalytic Dehydration of Methanol to Dimethyl Ether(DME) over Solid-acid Catalysts.", 6, 147 (2005)
Semelsberger TA, Ott KC, Borup RL, Greene HL, Appl. Catal. B: Environ., “Role of Acidity on the Hydrolysis of Dimethyl Ether(DME) to Methanol.”, 61(3-4), 281 (2005)
Levenspiel O, Chemical Reaction Engineering, 3rd ed., John Wiley & Sons, New York (1998)

[Related Articles]

[1] McCandless JC, Park GP, Mich, “Dimethyl Ether Powered Engine,” U.S. Patent 5,626,294 (1997)

[2] Kim JW, Sim KS, Han SD, Energy Engg. J., 7(2), 157 (1998)

[3] Choi JW, Lee SH, Sim KS, Kim JW, Kim SH, Energy Engg. J., “Direct Synthesis of Dimethyl Ether from Syngas in a Slurry Phase and Gas Phase Reactor.", 10(1), 49 (2001)

[4] Jun KW, Roh HS, News Inf. Chem. Eng., “Status of DME Production technology in Korea,”, 20(5), 519 (2002)

[5] Jun KW, Lee HS, Roh HS, Park SE, Bull. Korean Chem. Soc., 23, 803 (2002)

[6] Xu MT, Lunsford JH, Goodman DW, Bhattacharyya A, Appl. Catal. A: Gen., “Synthesis of Dimethyl Ether (DME) from Methanol over Solid-acid Catalysts.", 149(2), 289 (1997)

[7] Koo Y, Han M, Korean Chem. Eng. Res., “Dimethyl Ether Production Using a Reactive Distillation Process.", 42(1), 44 (2004)

[8] Yaripour F, Baghaei F, Schmidt I, Perregaard J, Catal. Commun., “Catalytic Dehydration of Methanol to Dimethyl Ether(DME) over Solid-acid Catalysts.", 6, 147 (2005)

[9] Semelsberger TA, Ott KC, Borup RL, Greene HL, Appl. Catal. B: Environ., “Role of Acidity on the Hydrolysis of Dimethyl Ether(DME) to Methanol.”, 61(3-4), 281 (2005)

[10] Levenspiel O, Chemical Reaction Engineering, 3rd ed., John Wiley & Sons, New York (1998)