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    ๊ฑด๊ฐ•๋ณดํ—˜์ •์ฑ…์‹ฌ์˜์œ„์›ํšŒ์˜ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์™€ ์˜์‚ฌ๊ฒฐ์ • ๊ณผ์ •์— ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์š”์ธ

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    ํ•™์œ„๋…ผ๋ฌธ (์„์‚ฌ)-- ์„œ์šธ๋Œ€ํ•™๊ต ๋ณด๊ฑด๋Œ€ํ•™์› : ๋ณด๊ฑดํ•™๊ณผ(๋ณด๊ฑด์ •์ฑ…๊ด€๋ฆฌํ•™ ์ „๊ณต), 2015. 8. ๊น€์ฐฝ์—ฝ.๋ณด๊ฑด์˜๋ฃŒ ์ •์ฑ…์˜ ์˜์‚ฌ๊ฒฐ์ •๊ณผ์ •์—์„œ ๊ณต๊ณต ์ฐธ์—ฌ์˜ ์ค‘์š”์„ฑ์€ ์˜ค๋ž˜ ์ „๋ถ€ํ„ฐ ๊ฐ•์กฐ๋˜์—ˆ์ง€๋งŒ ์ž๋ฌธ์ด๋‚˜ ์˜๊ฒฌ ์ฒญ์ทจ ์ˆ˜์ค€์— ํ•œ์ •๋˜๋Š” ๊ฒฝ์šฐ๊ฐ€ ๋งŽ์•˜๋‹ค. ๊ฑด๊ฐ•๋ณดํ—˜์ •์ฑ…์‹ฌ์˜์œ„์›ํšŒ(์ดํ•˜, ๊ฑด์ •์‹ฌ)๋Š” ๊ฑด๊ฐ•๋ณดํ—˜์ •์ฑ… ๊ฒฐ์ •์˜ ๊ฐ€์žฅ ๋†’์€ ์ˆ˜์ค€์˜ ๊ถŒํ•œ์„ ๊ฐ€์ง„ ๊ฐ€์ž…์ž ์ฐธ์—ฌ ์ œ๋„์ด์ง€๋งŒ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์ž๋“ค์ด ์ถฉ๋ถ„ํ•œ ์˜ํ–ฅ๋ ฅ์„ ๋‚˜ํƒ€๋‚ด์ง€ ๋ชปํ•œ๋‹ค๊ณ  ํ‰๊ฐ€๋˜๊ณ  ์žˆ๋‹ค. ๊ทธ๋Ÿฌ๋‚˜ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์ž๋“ค์ด ์–ด๋–ป๊ฒŒ ์ฐธ์—ฌํ•˜๊ณ  ์˜์‚ฌ๊ฒฐ์ •์„ ํ•˜๊ณ  ์žˆ๋Š”์ง€์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋Š” ์—†๋‹ค. ๋”ฐ๋ผ์„œ ๋ณธ ์—ฐ๊ตฌ๋Š” ๊ฑด์ •์‹ฌ์˜ ๊ฐ€์ž…์ž ๋‹จ์ฒด ์ฐธ์—ฌ๊ณผ์ •์˜ ์‹คํƒœ๋ฅผ ๊ธฐ์ˆ ํ•˜๊ณ  ์˜์‚ฌ๊ฒฐ์ • ๊ณผ์ •์— ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์š”์ธ์ด ๋ฌด์—‡์ธ์ง€๋ฅผ ๋ฐํžˆ๊ธฐ ์œ„ํ•ด ์ˆ˜ํ–‰๋˜์—ˆ๋‹ค. ๋ณธ ์—ฐ๊ตฌ๋Š” ๊ฑด์ •์‹ฌ์˜ ๊ฐ€์ž…์ž ๋Œ€ํ‘œ ๋‹จ์ฒด์ธ 8๊ฐœ ๋‹จ์ฒด์˜ ์ฐธ์—ฌ์ž๋“ค์„ ๋Œ€์ƒ์œผ๋กœ ํ•˜๋Š” ์‹ฌ์ธต๋ฉด๋‹ด๊ณผ ํšŒ์˜์ž๋ฃŒ์™€ ๋ณด๋„์ž๋ฃŒ๋ฅผ ์ž๋ฃŒ์›์œผ๋กœ ํ•œ ์งˆ์  ๋‚ด์šฉ ๋ถ„์„ ๋ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์˜€๋‹ค. ์‹ฌ์ธต๋ฉด๋‹ด์—๋Š” ๋ชฉ์  ํ‘œ์ง‘๋ฐฉ๋ฒ•์œผ๋กœ ์ˆ˜์ง‘๋œ 7๋ช…์ด ์ฐธ์—ฌํ•˜์˜€์œผ๋ฉฐ, ํšŒ์˜์ž๋ฃŒ๋Š” 2014๋…„, 2015๋…„ ๊ฑด์ •์‹ฌ ํšŒ์˜์ž๋ฃŒ๋ฅผ ์ด์šฉํ•˜์˜€๋‹ค. ๋ฉด๋‹ด์ž๋ฃŒ๋ฅผ ๊ฐœ๋ฐฉ ์ฝ”๋”ฉ์œผ๋กœ ๋ฒ”์ฃผํ™”ํ•˜๊ณ  ์ฐธ์—ฌ์  ์˜์‚ฌ๊ฒฐ์ •์ด๋ก ๊ณผ ๋น„๊ตํ•˜์˜€๋‹ค. ์—ฐ๊ตฌ ๊ฒฐ๊ณผ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์ž๋“ค์˜ ์˜์‚ฌ๊ฒฐ์ •๊ณผ์ •์— ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์š”์ธ์€ ํ™˜๊ฒฝ์  ์š”์ธ, ์ œ๋„์  ์š”์ธ, ํ–‰์œ„์ž ์š”์ธ์œผ๋กœ ์„ค๋ช…ํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ํ™˜๊ฒฝ์  ์š”์ธ๊ณผ ๊ด€๋ จํ•˜์—ฌ ์ฐธ์—ฌ์ž๋“ค์€ ์กฐ์ง ๊ฐ„ ์ด๊ฒฌ์ด ํ†ตํ•ฉ๋˜์ง€ ์•Š์•„ ์ œํ•œ์ ์ธ ํ˜‘๋ ฅ๊ด€๊ณ„๋ฅผ ์œ ์ง€ํ•˜๊ณ  ์žˆ์—ˆ์œผ๋ฉฐ, ๋‹ค๋ฅธ ์กฐ์ง์— ๋Œ€ํ•œ ์‹ ๋ขฐ๊ฐ€ ๋‚ฎ์•˜๋‹ค. ์ œ๋„์  ์š”์ธ๊ณผ ๊ด€๋ จํ•˜์—ฌ ์ฐธ์—ฌ์ž๋“ค์€ ํ˜‘์˜๊ธฐ๊ตฌ ๊ตฌ์„ฑ ๊ณผ์ •์ด ๋ถˆ๊ณต์ •ํ•˜๊ณ  ๊ฐ€์ž…์ž๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ๊ณต๊ธ‰์ž๋‚˜ ์ •๋ถ€์— ๋น„ํ•ด ๋ถˆ๋ฆฌํ•˜๋‹ค๊ณ  ๋Š๋ผ๊ณ  ์žˆ์—ˆ๋‹ค. ๋˜ํ•œ ์ž๋ฃŒ๊ฐ€ ๋Šฆ๊ฒŒ ์ œ๊ณต๋˜๊ณ  ๋ถˆ์ถฉ๋ถ„ํ•˜๊ฒŒ ์ œ๊ณต๋˜๋Š” ๊ฒƒ์— ํฐ ๋ถˆ๋งŒ์„ ์ œ๊ธฐํ•˜์˜€๋‹ค. ํ† ๋ก ์€ ์†Œ์ˆ˜์˜ ๋ฐ˜๋Œ€์ž์™€ ๋‹ค์ˆ˜์˜ ์นจ๋ฌต์œผ๋กœ ์ง„ํ–‰๋˜์–ด ์ถฉ๋ถ„ํ•˜๊ฒŒ ์ด๋ฃจ์–ด์ง€์ง€ ์•Š์•˜๋‹ค. ์ฐธ์—ฌ์ž๋“ค์€ ๊ฑด์ •์‹ฌ์˜ ์‚ฌ์•ˆ์ด ์–ด๋ ต๊ณ  ์ดํ•ด๊ด€๊ณ„๊ฐ€ ๋ณต์žกํ•˜๋‹ค๊ณ  ์ƒ๊ฐํ•˜์˜€๋‹ค. ์ฐธ์—ฌ ์œ„์›๋งˆ๋‹ค ์—ญ๋Ÿ‰๊ณผ ์ž๋ฐœ์„ฑ ์ˆ˜์ค€์ด ๋‹ค๋ฅด๊ฒŒ ๋‚˜ํƒ€๋‚ฌ์œผ๋‚˜, ๋Œ€๋ถ€๋ถ„ ์ถฉ๋ถ„ํžˆ ํ•™์Šตํ•˜์ง€ ๋ชปํ•˜์˜€์œผ๋ฉฐ ์กฐ์ง ๋‚ด ์˜๊ฒฌ์ˆ˜๋ ด์ด๋‚˜ ์™ธ๋ถ€ ์ฐธ์—ฌ์ž์™€์˜ ์†Œํ†ต๊ธฐ์ œ๋„ ๋ถ€์กฑํ–ˆ๋‹ค. ์ฐธ์—ฌ์ž๋“ค์€ ์†Œ์† ์กฐ์ง์— ๋”ฐ๋ฅธ ์ž…์žฅ์„ ์œ ์ง€ํ•˜๊ธฐ ๋•Œ๋ฌธ์— ์ด๊ฒฌํ•ด์†Œ๊ฐ€ ๋ถˆ๊ฐ€๋Šฅํ•˜๋‹ค๊ณ  ์ƒ๊ฐํ•˜์˜€๋‹ค. ์ฐธ์—ฌ์  ์˜์‚ฌ๊ฒฐ์ •์ด๋ผ๋Š” ๊ด€์ ์—์„œ ๋ณด์•˜์„ ๋•Œ, ๊ฑด์ •์‹ฌ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์ž๋“ค์€ ์ถฉ๋ถ„ํ•œ ํ•™์Šต๊ณผ ์ˆ™์˜, ํ•ฉ์˜์— ์˜ํ•ด ์˜์‚ฌ๊ฒฐ์ •์„ ํ•˜์ง€ ์•Š๋Š” ๋ชจ์Šต์„ ๋ณด์˜€๋‹ค. ๊ทธ๋ ‡์ง€๋งŒ ์กฐ์ง์˜ ์˜๊ฒฌ์ˆ˜๋ ด๊ณผ ์กฐ์ง์˜ ์ดํ•ด๋ฅผ ๋Œ€๋ณ€ํ•˜๊ณ  ํ˜‘์ƒํ•˜๋Š” ๊ณผ์ •์ธ ์กฐํ•ฉ์ฃผ์˜์  ์˜์‚ฌ๊ฒฐ์ •๋„ ์ผ์–ด๋‚˜์ง€ ์•Š๋Š” ํŠน์ง•์„ ๊ฐ–๋Š”๋‹ค. ๋”ฐ๋ผ์„œ ์œ„์› ๊ฐœ์ธ์˜ ์ „๋ฌธ์„ฑ์— ์˜์กดํ•œ ์ž๋ฌธ(consultation) ์ˆ˜์ค€์˜ ์˜์‚ฌ๊ฒฐ์ •์— ๊ฐ€๊น๋‹ค. ๊ฑด์ •์‹ฌ์—์„œ ๊ฐ€์ž…์ž ์ฐธ์—ฌ์˜ ์˜ํ–ฅ๋ ฅ์„ ๋†’์ด๊ธฐ ์œ„ํ•ด์„œ๋Š” ๊ทผ๋ณธ์ ์œผ๋กœ ๊ฑด์ •์‹ฌ์˜ ๋ชฉ์ ๊ณผ ์—ญํ• ์„ ์ œ๊ณ ํ•˜์—ฌ ๋” ๋งŽ์€ ์‹œ๋ฏผ์ด ์ฐธ์—ฌํ•˜๊ณ  ์˜๊ฒฌ์„ ๋ฐ˜์˜ํ•  ์ˆ˜ ์žˆ๋Š” ์ƒˆ๋กœ์šด ๊ตฌ์กฐ๊ฐ€ ํ•„์š”ํ•˜๋‹ค. ์–ด๋–ค ๊ตฌ์กฐ์—์„œ๋“ ์ง€ ์ฐธ์—ฌ์ž์— ๋Œ€ํ•œ ๊ณต์ •ํ•œ ๊ธฐ์ค€๊ณผ, ์ฐธ์—ฌ์ž์˜ ์˜๊ฒฌ์ด ๋ฐ˜์˜๋  ์ˆ˜ ์žˆ๋Š” ํˆฌ๋ช…ํ•œ ์ ˆ์ฐจ์— ์˜ํ•ด ๊ฒฐ์ •๋˜์–ด์•ผ ํ•œ๋‹ค. ์ง€๊ธˆ์˜ ๊ตฌ์กฐ์—์„œ๋Š” ์ฐธ์—ฌ์ž๋“ค์˜ ์—ญ๋Ÿ‰์„ ํ–ฅ์ƒ์‹œํ‚ค๊ธฐ ์œ„ํ•œ ๊ฐœ์„  ๋ฐฉ์•ˆ์ด ํ•„์š”ํ•˜๋‹ค.๋ชฉ ์ฐจ โ… . ์„œ๋ก  1 1. ์—ฐ๊ตฌ๋ฐฐ๊ฒฝ 1 2. ์—ฐ๊ตฌ์˜ ํ•„์š”์„ฑ 3 3. ์—ฐ๊ตฌ๋ชฉ์ ๊ณผ ์—ฐ๊ตฌ์งˆ๋ฌธ 5 โ…ก. ์ด๋ก ์  ๋ฐฐ๊ฒฝ 6 1. ๋ณด๊ฑด์˜๋ฃŒ ์ •์ฑ…์˜ ์‹œ๋ฏผ์ฐธ์—ฌ 6 2. ์œ„์›ํšŒ ์กฐ์ง๊ณผ ์ฐธ์—ฌ์  ์˜์‚ฌ๊ฒฐ์ • 14 3. ๊ฑด๊ฐ•๋ณดํ—˜์ •์ฑ…์‹ฌ์˜์œ„์›ํšŒ 19 โ…ข. ์—ฐ๊ตฌ ๋ฐฉ๋ฒ• 26 1. ์—ฐ๊ตฌ์„ค๊ณ„ 26 2. ์ž๋ฃŒ ์ˆ˜์ง‘ 29 3. ์ž๋ฃŒ ๋ถ„์„ 34 4. ํƒ€๋‹น๋„์™€ ์‹ ๋ขฐ๋„ ํ™•๋ณด 36 โ…ฃ. ์—ฐ๊ตฌ ๊ฒฐ๊ณผ 37 1. ๊ฐ€์ž…์ž ์ฐธ์—ฌ ์˜์‚ฌ๊ฒฐ์ •๊ตฌ์กฐ 37 2. ํ™˜๊ฒฝ์  ์š”์ธ 44 3. ์ œ๋„์  ์š”์ธ 56 4. ํ–‰์œ„์ž ์š”์ธ 74 โ…ค. ๋…ผ์˜ 92 1. ๊ฐ€์ž…์ž ์ฐธ์—ฌ ์˜์‚ฌ๊ฒฐ์ •๊ณผ์ •์˜ ํŠน์ง• 92 2. ๊ฐ€์ž…์ž ์ฐธ์—ฌ ๊ฐœ์„ ์„ ์œ„ํ•œ ์ œ์–ธ 101 โ…ฅ. ๊ฒฐ๋ก  104 1. ์š”์•ฝ ๋ฐ ๊ฒฐ๋ก  104 2. ์—ฐ๊ตฌ์˜ ํ•œ๊ณ„ ๋ฐ ์ œ์–ธ 106 ์ฐธ๊ณ ๋ฌธํ—Œ 108 Abstract 114Maste

    5-ํ•˜์ด๋“œ๋ก์‹œ๋ฉ”ํ‹ธ-2-ํ“จ๋ž„๋ฐํ•˜์ด๋“œ์˜ ์„ ํƒ์  ์ˆ˜์†Œ์ฒจ๊ฐ€ ์ด‰๋งค ๋ฐ˜์‘๊ณผ ์ดํ„ฐํ™” ๋ฐ˜์‘์„ ํ†ตํ•œ ๊ณ ๋ถ€๊ฐ€๊ฐ€์น˜ ํ™”ํ•™๋ฌผ์งˆ ์ƒ์‚ฐ

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    ํ•™์œ„๋…ผ๋ฌธ (์„์‚ฌ)-- ์„œ์šธ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› : ํ™”ํ•™์ƒ๋ฌผ๊ณตํ•™๋ถ€, 2016. 2. ์ด์œค์‹.The transformation of lignocellulosic biomass-derived 5-hydroxymethyl-2-furaldehyde (HMF) to fuels and additives is of considerable interest for reducing the dependence on fossil fuels. This study presents an efficient process to produce 2,5-bis(alkoxymethyl)furan (BAMF) as a potential biodiesel. We have synthesized Ru(OH)x/ZrO2 catalyst for selective hydrogenation of HMF to 2,5-bis(hydroxylmethyl)furan (BHMF). Ru(OH)x/ZrO2 catalyst showed excellent performance of selective hydrogenation of HMFs aldehyde group to alcohol group under optimized condition. This reaction proceeded well in various n-alcohol solvents in more than 98 % yield. Moreover, the catalyst can be reused 5 times without significant loss of catalytic activity. The resulting solution of BHMF in various alcohol solvents was sequentially etherified to BAMF by Amberlyst-15 catalyst. From this two-step sequential reaction process, the valuable potential biodiesel chemical, BAMF, which has diverse alkoxy groups, can be obtained efficiently. The yields of BAMF were more than 70 % except for 2,5-bis(methoxymethyl)furan (BMMF) which gave 50 % yield.I. Introduction 2 I. Carbohydrate from Lignocellulosic Biomass 3 I. 1 5-Hydroxymethyl-2-furaldehyde as Platform Chemical 5 I. 2 2,5-Bis(hydroxymethyl)furan as Polymer Building Block 7 I. 3 2,5-Bis(alkoxymethyl)furan as Potential Biodiesel 8 II. Catalytic Conversion of HMF to Valuable Chemicals 9 II. 1 Catalytic Hydrogenation of HMF to BHMF using Metal Catalyst 9 II. 2 Catalytic Reaction of HMF to BAMF using Metal and Acid Catalyst 10 III. Research Objectives 12 II. Experimental Section 14 I. General 15 I. 1 Materials 15 I. 2 Characterization 16 II. Hydrogenation of HMF to BHMF Catalyzed by Ru(OH)x/ZrO2 17 II. 1 Preparation of Ru(OH)x/ZrO2 17 II. 2 Hydrogenation of HMF to BHMF Catalyzed by Ru(OH)x/ZrO2 18 III. Etherification of BHMF to BAMF Catalyzed by Amberlyst-15 19 IV. Two-step Sequential Reaction of HMF to BAMF in Various n-Alcohol Solvents 20 III. Results and Discussion 21 I. Characterization of Ru(OH)x/ZrO2 Catalyst 22 II. Hydrogenation of HMF to BHMF Catalyzed by Ru(OH)x/ZrO2 26 II. 1 Optimization of Hydrogenation of HMF to BHMF 26 II. 2 Active site of Ru catalyst for hydrogenation of HMF to BHMF 36 II. 3 Recycling test of Ru(OH)x/ZrO2 in HMF hydrogenation reaction 39 III. Etherification of BHMF to BAMF Catalyzed by Amberlyst-15 41 IV. Two-step Sequential Reaction of HMF to BAMF in various n-alcohol solvents 50 IV. Conclusion 53 References 55 Abstract in Korean 61 Appendix 63Maste
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