Sulfolane A Study on the Simulation of Toluene Recovery ...

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Transcript of Sulfolane A Study on the Simulation of Toluene Recovery ...

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129

Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006, pp. 129-135

Sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๊ณต์ •์˜ ๋ชจ์‚ฌ์— ๊ด€ํ•œ ์—ฐ๊ตฌ

์กฐ ์ • ํ˜ธ

๋™์–‘๋Œ€ํ•™๊ต ์ƒ๋ช…ํ™”ํ•™๊ณตํ•™๊ณผ

750-711 ๊ฒฝ๋ถ ์˜์ฃผ์‹œ ํ’๊ธฐ์ ๊ต์ดŒ๋™ 1

(2005๋…„ 10์›” 22์ผ ์ ‘์ˆ˜, 2006๋…„ 1์›” 30์ผ ์ฑ„ํƒ)

A Study on the Simulation of Toluene Recovery Process using

Sulfolane as a Solvent

Jungho Cho

Department of Chemical Engineering, Dong Yang University, 1, Kyochon-dong, Poongki-eup, Youngju, Kyungbook 750-711, Korea

(Received 22 October 2005; accepted 30 January 2006)

์š” ์•ฝ

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์šฉ๋งค๋กœ์จ sulfolane์„ ์‚ฌ์šฉํ•˜๊ณ  2๊ธฐ์˜ ์ฆ๋ฅ˜ํƒ‘์„ ์ด์šฉํ•˜์—ฌ ํ†จ๋ฃจ์—”์ด ๊ณผ๋Ÿ‰ ํ•จ์œ ๋œ ๋น„ ๋ฐฉํ–ฅ์กฑ ํ˜ผํ•ฉ๋ฌผ๋กœ

๋ถ€ํ„ฐ ๊ณ  ์ˆœ๋„์˜ ํ†จ๋ฃจ์—”์„ ์ƒ์‚ฐํ•ด ๋‚ด๋Š” ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์— ๋Œ€ํ•œ ์ „์‚ฐ๋ชจ์‚ฌ ์ž‘์—…์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. Sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ์ถ”

์ถœ์ฆ๋ฅ˜๊ณต์ •์˜ ๋ชจ์‚ฌ๋ฅผ ์œ„ํ•œ ์—ด์—ญํ•™ ๋ชจ๋ธ์‹์œผ๋กœ๋Š” NRTL ์•ก์ฒด ํ™œ๋™๋„๊ณ„์ˆ˜ ๋ชจ๋ธ์‹์„ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ ๋ฒ”์šฉ์„ฑ ํ™”ํ•™๊ณต์ • ๋ชจ

์‚ฌ๊ธฐ์ธ Aspen Plus 12.1์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๋ชจ์‚ฌ ๊ฒฐ๊ณผ ์ตœ์ข…์ œํ’ˆ์œผ๋กœ ์–ป์–ด์ง„ ํ†จ๋ฃจ์—”์˜ ์ˆœ๋„๋Š” 99.8 wt๏ผ…์˜€์œผ๋ฉฐ, ์›๋ฃŒ์— ๋Œ€

ํ•œ ํšŒ์ˆ˜์œจ์€ 99.65๏ผ…๋กœ ๋‚˜ํƒ€๋‚จ์„ ์•Œ ์ˆ˜ ์žˆ์—ˆ๋‹ค.

Abstract โˆ’ In this study, computer modeling and simulation works were performed to obtain nearly pure toluene prod-

uct from toluene containing non-aromatic compounds using sulfolane as a solvent through an extractive distillation pro-

cess. NRTL liquid activity coefficient model was adopted for phase equilibrium calculations and Aspen Plus release

12.1, a commercial process simulator, was used to simulate the extractive distillation process. In this study, it was con-

cluded that the toluene product with a purity of 99.8 percent by weight and a recovery of 99.65 percent was obtained

through an extractive distillation process.

Key words: Extractive Distillation, Solvent, NRTL Liquid Activity Coefficient Model, Simulation, Modeling

โ€ To whom correspondence should be addressed.E-mail: [email protected]

1. ์„œ ๋ก 

ํ†จ๋ฃจ์—”์€ ๋›ฐ์–ด๋‚œ ์šฉํ•ด๋ ฅ๊ณผ ์ฆ๋ฐœ์†๋„๋ฅผ ์ง€๋‹Œ ๋Œ€ํ‘œ์ ์ธ ๋ฐฉํ–ฅ์กฑ ์šฉ

์ œ๋กœ์„œ ํŽ˜์ธํŠธ, ์ž‰ํฌ, ์ ‘์ฐฉ์ œ ๋“ฑ ์ฝ”ํŒ… ์ „ ๋ถ„์•ผ์™€ ๋†์•ฝ์šฉ์ œ ๋ฐ ํด๋ฆฌ์šฐ

๋ ˆํƒ„์˜ ์›๋ฃŒ์™€ ํœ˜๋ฐœ์œ ์— ๋ฐฐํ•ฉํ•˜์—ฌ ์˜ฅํƒ„๊ฐ€ ํ–ฅ์ƒ์šฉ ์›๋ฃŒ ๋“ฑ์œผ๋กœ ๊ด‘๋ฒ”

์œ„ํ•˜๊ฒŒ ์‚ฌ์šฉ[1]๋˜๋Š” ๊ฒƒ์œผ๋กœ ์ด์— ๋Œ€ํ•œ ๊ธฐ๋ณธ์ ์ธ ๋ฌผ์„ฑ์น˜๋“ค์„ Table 1

์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

ํ†จ๋ฃจ์—”๊ณผ ๊ฐ™์€ ๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„์€ ๋ฒค์  ์ด๋‚˜ ์—ํ‹ธ๋ฒค์   ๋“ฑ๊ณผ ๊ฐ™์€ ๋‹ค๋ฅธ

๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„์ด๋‚˜ ๋ฉ”ํ‹ธ ์‚ฌ์ดํด๋กœํ—ฅ์‚ฐ์ด๋‚˜ ์—ํ‹ธ ์‚ฌ์ดํด๋กœํ—ฅ์‚ฐ ๋˜๋Š”

์˜ฅํƒ„ ์„ฑ๋ถ„๋“ค๊ณผ ๊ฐ™์€ ๋“๋Š”์ ์ด ๋น„์Šทํ•œ ๋‹ค๋ฅธ ํƒ„ํ™”์ˆ˜์†Œ ์„ฑ๋ถ„๋“ค๊ณผ ํ˜ผํ•ฉ

๋˜์–ด ์žˆ๋Š” ๊ฒฝ์šฐ์—๋Š” ๋ถ„๋ฆฌํ•˜๊ธฐ ์–ด๋ ค์›Œ์ง„๋‹ค. ๋”ฐ๋ผ์„œ ์ฆ๋ฅ˜ํƒ‘์˜ ๋‹จ์ˆ˜๋ฅผ

๋งค์šฐ ๋†’์ด๊ฑฐ๋‚˜ ํ™˜๋ฅ˜๋น„๋ฅผ ์ฆ๊ฐ€ํ•˜์—ฌ ๋ถ„๋ฆฌํ•˜๊ฑฐ๋‚˜ ๋˜๋Š” ์—ฌ๋Ÿฌ ๊ธฐ์˜ ์ฆ๋ฅ˜

ํƒ‘์„ ์‚ฌ์šฉํ•ด์„œ ๋ถ„๋ฆฌํ•˜์—ฌ์•ผ ํ•˜๊ธฐ ๋•Œ๋ฌธ์— ์ดˆ๊ธฐ ํˆฌ์ž๋น„์šฉ์ด ๋งŽ์ด ์†Œ์š”

๋œ๋‹ค. ๋”ฐ๋ผ์„œ ํ†จ๋ฃจ์—”๊ณผ ์„ ํƒ์ ์œผ๋กœ ์นœํ™”์„ฑ์ด ๊ฐ•ํ•œ ์šฉ๋งค์ธ sulfolane

์ด๋‚˜ normal formyl morpholine์„ ์‚ฌ์šฉํ•ด์„œ ์ถ”์ถœ์ฆ๋ฅ˜[2, 3]ํ•˜๋Š” ๋ฐฉ

๋ฒ•์„ ์‚ฌ์šฉํ•˜๊ฑฐ๋‚˜ sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ์ถ”์ถœ๊ณต์ •[4]์„ ์ด์šฉํ•˜๋ฉด

ํšจ๊ณผ์ ์œผ๋กœ ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๋“ค๋กœ๋ถ€ํ„ฐ ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์„ ๋ถ„๋ฆฌ ํšŒ์ˆ˜ํ•  ์ˆ˜

์žˆ๋‹ค.

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์šฉ๋งค๋กœ์จ sulfolane์„ ์‚ฌ์šฉํ•˜๋Š” ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์„ ํ†ต

Table 1. The basic properties of toluene

Property Value

Normal boiling point (K) 351.470

Molecular weight 92.142

Standard liquid density (Kg/m3) 870.980

Critical temperature (K) 591.720

Critical pressure (kPa) 4,108.700

Critical volume (m3/k-mole) 0.316

Critical compressibility factor 0.26391

Acentric factor 0.2635

Heat of formation (kJ/k-mole) 50,032

Free energy of formation (kJ/k-mole) 122,240

Page 2: Sulfolane A Study on the Simulation of Toluene Recovery ...

130 ์กฐ ์ • ํ˜ธ

ํ™”ํ•™๊ณตํ•™ ์ œ44๊ถŒ ์ œ2ํ˜ธ 2006๋…„ 4์›”

ํ•ด์„œ ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๋“ค๋กœ๋ถ€ํ„ฐ ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์„ ํšŒ์ˆ˜ํ•ด ๋‚ด๋Š” ๊ณต์ •์— ๋Œ€

ํ•œ ์ „์‚ฐ๋ชจ์‚ฌ ์ž‘์—…์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ ์‚ฌ์šฉํ•œ ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •

์€ ํ†ต์ƒ์ ์œผ๋กœ 2๊ธฐ์˜ ์ฆ๋ฅ˜ํƒ‘์œผ๋กœ ๊ตฌ์„ฑ๋˜๋Š”๋ฐ ๊ณต์ • ๊ฐœ๋…๋„๋Š” Fig. 1์—

๋‚˜ํƒ€๋‚ธ ๋ฐ”์™€ ๊ฐ™๋‹ค. ์ฒซ ๋ฒˆ์งธ ์ฆ๋ฅ˜ํƒ‘์ธ T-101์€ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์œผ๋กœ์จ ๊ทธ

์—ญํ• ์€ ์›๋ฃŒ ์•ก์ธ ๋ฐฉํ–ฅ์กฑ๊ณผ ๋น„๋ฐฉํ–ฅ์กฑ ํ˜ผํ•ฉ๋ฌผ๋กœ๋ถ€ํ„ฐ ํ†จ๋ฃจ์—”๊ณผ ๊ฐ™์€

๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๊ณผ ์„ ํƒ์ ์œผ๋กœ ์นœํ™”์„ฑ์ด ๊ฐ•ํ•œ ์šฉ๋งค์ธ sulfolane์„ ์‚ฌ์šฉ

ํ•ด์„œ ํ†จ๋ฃจ์—” ์„ฑ๋ถ„๋งŒ์„ ์„ ํƒ์ ์œผ๋กœ ์ถ”์ถœํ•ด ๋‚ด๋Š” ๊ฒƒ์ด๋‹ค. ์ฒซ ๋ฒˆ์งธ ์ฆ

๋ฅ˜ํƒ‘์„ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์ด๋ผ๊ณ  ํ•˜๋Š” ๊ฒƒ์€ ์›๋ฆฌ์ƒ ์›๋ฃŒ ์•ก๋„ ์•ก์ƒ์ด๊ณ  ์šฉ

๋งค๋ฅผ ์‚ฌ์šฉํ•˜๊ธฐ ๋•Œ๋ฌธ์— ์ถ”์ถœ์— ํ•ด๋‹นํ•˜์ง€๋งŒ ํƒ‘์ƒ์— ์‘์ถ•๊ธฐ๊ฐ€ ์žˆ๊ณ , ํƒ‘

์ €์— ์žฌ๋น„๊ธฐ๊ฐ€ ์žˆ์œผ๋ฉฐ ํƒ‘๋‚ด์—์„œ๋Š” ์ฆ๊ธฐ์™€ ์•ก์ด ํ‰ํ˜•๋‹จ์œผ๋กœ ์ ‘์ด‰ํ•˜

๊ธฐ ๋•Œ๋ฌธ์— ์ฆ๋ฅ˜์— ํ•ด๋‹นํ•˜๋ฏ€๋กœ ์ถ”์ถœ๊ณผ ์ฆ๋ฅ˜๊ฐ€ ๋™์‹œ์— ํ•˜๋‚˜์˜ column

์—์„œ ์ด๋ฃจ์–ด์ง€๊ธฐ ๋•Œ๋ฌธ์— ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์ด๋ผ๊ณ  ํ•˜์˜€๋‹ค. ์šฉ๋งค๋ฅผ ์‚ฌ์šฉํ•œ

์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์˜ ์›๋ฆฌ๋Š” Fig. 2์— ๊ฐœ๋…์ ์œผ๋กœ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. Fig. 2์—

๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ๋“๋Š”์ ์ด ๋น„์Šทํ•˜์—ฌ ์ƒ๋Œ€ํœ˜๋ฐœ๋„ ์ฐจ์ด๊ฐ€ ๋ณ„๋กœ ๋‚˜์ง€

์•Š๋Š” ๋ฐฉํ–ฅ์กฑ๊ณผ ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๋“ค ์‚ฌ์ด์— ๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๊ณผ ์„ ํƒ์ ์œผ๋กœ

์นœํ™”์„ฑ์ด ๊ฐ•ํ•œ ๋“๋Š”์ ์ด ๋†’์€ ์šฉ๋งค๊ฐ€ ์ถ”๊ฐ€๋จ์œผ๋กœ ์ธํ•˜์—ฌ ๋ฐฉํ–ฅ์กฑ ์„ฑ

๋ถ„์˜ ์ƒ๋Œ€ํœ˜๋ฐœ๋„๋ฅผ ํฌ๊ฒŒ ๋‚ฎ์ถ”์–ด ์ฃผ๊ธฐ ๋•Œ๋ฌธ์— ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์„ ์ถ”์ถœ์ฆ

๋ฅ˜ํƒ‘ ํ•˜๋ถ€๋กœ ์–ป์–ด๋‚ด๊ณ  ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๋“ค์€ raffinate๋กœ์จ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘

์ƒ๋ถ€๋กœ ์–ป์–ด๋‚ด๊ฒŒ ๋œ๋‹ค.

ํ•œํŽธ, extract๋กœ์จ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘ ํ•˜๋ถ€์—์„œ ์–ป์–ด์ง€๋Š” ์šฉ๋งค์™€ ์šฉ๋งค์—

์„ ํƒ์ ์œผ๋กœ ๋…น์•„ ์žˆ๋Š” ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์€ ๋‘ ๋ฒˆ์งธ ์ฆ๋ฅ˜ํƒ‘์ธ ์šฉ๋งค ํšŒ์ˆ˜

ํƒ‘(T-102)์˜ ํƒ‘์ € ์ œํ’ˆ๊ณผ ์—ด๊ตํ™˜๋œ ํ›„ ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์˜ ์ค‘๊ฐ„ ์ง€์ ์œผ

๋กœ ์ฃผ์ž…๋œ๋‹ค. ์—ฌ๊ธฐ์—์„œ๋Š” ์šฉ๋งค์™€ ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์˜ ๋ถ„๋ฆฌ๊ฐ€ ์ด๋ฃจ์–ด์ง€๋Š”

๋ฐ, ํ†จ๋ฃจ์—” ์„ฑ๋ถ„์ด ํƒ‘์ƒ์ œํ’ˆ์œผ๋กœ ์–ป์–ด์ง€๊ณ  ์šฉ๋งค์ธ sulfolane์€ ํƒ‘์ €

์—์„œ ์–ป์–ด์ ธ์„œ ์—ด๊ตํ™˜๋œ ํ›„ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์œผ๋กœ ํ™˜๋ฅ˜๋œ๋‹ค. ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘

์€ ์ƒ์••๋ณด๋‹ค ์•ฝ๊ฐ„ ๋‚ฎ์€ ๊ฐ์••ํ•˜์—์„œ ์šด์ „ํ•˜์—ฌ์•ผ ํ•˜๊ธฐ ๋•Œ๋ฌธ์— ์ง„๊ณต

์‹œ์Šคํ…œ(V-101)์ด ํ•„์š”ํ•œ๋ฐ ๊ทธ ์ด์œ ๋Š” ์ฒซ์งธ ๋ณธ ์—ฐ๊ตฌ์— ์ ์šฉํ•œ ๋Œ€์ƒ

๊ณต์ •์—์„œ ๊ณต๊ธ‰ ๊ฐ€๋Šฅํ•œ ์ŠคํŒ€์˜ ๊ณต๊ธ‰์˜จ๋„์— ๋งž์ถ”๊ธฐ ์œ„ํ•จ๊ณผ ๋‘ ๋ฒˆ์งธ๋กœ

๋Š” ์šฉ๋งค์ธ sulfolane์ด ์—ด์— ์˜ํ•œ ๋ณ€์„ฑ์„ ๋ง‰๊ธฐ ์œ„ํ•ด์„œ ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘

์˜ ์šด์ „์˜จ๋„๋ฅผ ์ผ์ • ์˜จ๋„ ์ดํ•˜๋กœ ๋‚ฎ๊ฒŒ ์œ ์ง€ํ•˜๊ธฐ ์œ„ํ•ด์„œ์ด๋‹ค.

์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์˜ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๋ฅผ ์œ„ํ•œ ์šฉ๋งค๋กœ์จ sulfolane์„ ์„ ์ •ํ•œ

๊ธฐ์ค€์€ Fig. 3[5]๊ณผ ๊ฐ™์ด ์šฉ๋งค์ธ sulfolane๊ณผ ๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„์ธ ๋ฒค์   ์„ฑ

๋ถ„ ๋ฐ ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„์ธ ๋…ธ๋ง ํ—ตํƒ„ ์‚ฌ์ด์˜ ์‚ผ์„ฑ๋ถ„๊ณ„ ์•ก์•ก ์ƒํ‰ํ˜• ์‹ค

ํ—˜ ๋ฐ์ดํ„ฐ์™€ ์ด๋ฅผ ์ž˜ ์„ค๋ช…ํ•  ์ˆ˜ ์žˆ๋Š” ์—ด์—ญํ•™ ๋ชจ๋ธ์‹์˜ ์ด์„ฑ๋ถ„๊ณ„ ์ƒ

ํ˜ธ์ž‘์šฉ ๋งค๊ฐœ๋ณ€์ˆ˜๋ฅผ ๋ฌธํ—Œ์„ ํ†ตํ•ด์„œ ์ถฉ๋ถ„ํžˆ ์–ป์„ ์ˆ˜ ์žˆ๊ธฐ ๋•Œ๋ฌธ์ด๋‹ค.

์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์˜ ์ „์‚ฐ๋ชจ์‚ฌ๋ฅผ ์œ„ํ•œ ์กฐ์ž‘๋ณ€์ˆ˜๋Š” ์—ฌ๋Ÿฌ ๊ฐ€์ง€๊ฐ€ ๊ฐ€๋Šฅ

Fig. 1. A schematic diagram of an extractive distillation process for toluene recovery from non aromatic components using sulfolane as a solvent.

Fig. 2. Principles of extractive distillation process using sulfolane as a

solvent.

Page 3: Sulfolane A Study on the Simulation of Toluene Recovery ...

Sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๊ณต์ •์˜ ๋ชจ์‚ฌ์— ๊ด€ํ•œ ์—ฐ๊ตฌ 131

Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

ํ•˜์ง€๋งŒ ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์›ํ•˜๋Š” ์ˆœ๋„ ๋ฐ ์ˆ˜์œจ์„ ์–ป๊ธฐ ์œ„ํ•œ ์šฉ๋งค์˜

์ˆœํ™˜์œ ๋Ÿ‰๊ณผ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘๊ณผ ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์˜ ์„ค๊ณ„ ๋ฐ ์šด์ „์กฐ๊ฑด์„ ๊ฒฐ

์ •ํ•˜์˜€๋‹ค.

2. ์ด ๋ก 

์šฉ๋งค๋กœ์จ sulfoane์„ ์‚ฌ์šฉํ•˜์—ฌ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๋ฅผ ์œ„ํ•œ ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •

์˜ ๋ชจ๋ธ๋ง์„ ์œ„ํ•œ ๊ธฐ์•ก ๋ฐ ์•ก์•ก ์ƒํ‰ํ˜• ์ถ”์‚ฐ์„ ์œ„ํ•œ ์—ด์—ญํ•™ ๋ชจ๋ธ ์‹

์œผ๋กœ Renon๊ณผ Prausnitz๊ฐ€ ์ œ์•ˆํ•œ NRTL(non random two liquid

mixture) ์•ก์ฒด ํ™œ๋™๋„๊ณ„์ˆ˜ ๋ชจ๋ธ ์‹[6]์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ํ˜ผํ•ฉ๋ฌผ ์ค‘์˜ โ€˜iโ€™

์„ฑ๋ถ„์— ๋Œ€ํ•œ ์•ก์ฒด ํ™œ๋™๋„๊ณ„์ˆ˜ ํ‘œํ˜„์‹์€ ๋‹ค์Œ์˜ (1)์‹๊ณผ ๊ฐ™์ด ํ‘œํ˜„

๋œ๋‹ค.

(1)

์œ„์˜ (1)์‹์—์„œ ฯ„ij์™€ Gij๋Š” ๊ฐ๊ฐ ์‹คํ—˜๋ฐ์ดํ„ฐ์™€์˜ ํŽธ์ฐจ๋ฅผ ์ตœ์†Œํ™”ํ•˜

๊ธฐ ์œ„ํ•œ ์ตœ์ ์˜ ์ด์„ฑ๋ถ„๊ณ„ ์ƒํ˜ธ์ž‘์šฉ ๋งค๊ฐœ๋ณ€์ˆ˜๋กœ์จ ๋‹ค์Œ์˜ (2)์‹,

(3)์‹๊ณผ ๊ฐ™์ด ๋‚˜ํƒ€๋‚ผ ์ˆ˜ ์žˆ๋‹ค.

(2)

(3)

์œ„์˜ (2)์‹์—์„œ ์˜จ๋„ T๋Š” ์ ˆ๋Œ€์˜จ๋„์ด๋ฉฐ, ๊ฐ๊ฐ์˜ ์ด์„ฑ๋ถ„๊ณ„์— ๋Œ€ํ•˜์—ฌ

์˜จ๋„ ์˜์กด ํ•ญ๊นŒ์ง€ ํฌํ•จํ•˜์—ฌ, aij, aji, bij, bji ๋ฐ aij์˜ ๋‹ค์„ฏ ๊ฐœ์˜ ์ƒํ˜ธ

์ž‘์šฉ ๋งค๊ฐœ๋ณ€์ˆ˜๋ฅผ ๊ฐ€์ง„๋‹ค. Table 2์—๋Š” ๊ฐ๊ฐ์˜ ๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๊ณผ ๋น„๋ฐฉ

ํ–ฅ์กฑ ์„ฑ๋ถ„ ๋ฐ ์šฉ๋งค ์‚ฌ์ด์˜ ์ด์„ฑ๋ถ„๊ณ„์˜ ๊ธฐ์•ก ๋ฐ ์•ก์•ก ์ƒํ‰ํ˜• ์‹คํ—˜

๋ฐ์ดํ„ฐ๋ฅผ ์ž˜ ์ถ”์‚ฐํ•  ์ˆ˜ ์žˆ๋Š” NRTL ๊ธฐ์•ก ๋ฐ ์•ก์•ก ์ƒํ‰ํ˜• ๋งค๊ฐœ๋ณ€์ˆ˜

๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๋˜ํ•œ Aspen Plus ํ™”ํ•™๊ณต์ • ๋ชจ์‚ฌ๊ธฐ์— ๋‚ด์žฅ๋˜์–ด ์žˆ

์ง€ ์•Š์€ ์ด์„ฑ๋ถ„๊ณ„ ์ƒํ˜ธ์ž‘์šฉ ๋งค๊ฐœ๋ณ€์ˆ˜์— ๋Œ€ํ•ด์„œ๋Š” ๋ฌธํ—Œ์„ ํ†ตํ•ด์„œ ๊ตฌ

ํ•œ ์ด์„ฑ๋ถ„๊ณ„ ์ƒํ˜ธ์ž‘์šฉ ๋งค๊ฐœ๋ณ€์ˆ˜ ๊ฐ’์„ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ ๋ฌธํ—Œ์„ ํ†ตํ•ด์„œ

๋„ ๊ตฌํ•  ์ˆ˜ ์—†๋Š” ์ด์„ฑ๋ถ„๊ณ„ ์Œ์— ๋Œ€ํ•œ ์—ด์—ญํ•™์ ์ธ ๋น„์ด์ƒ์„ฑ์„ ์„ค๋ช…

ํ•˜๊ธฐ ์œ„ํ•ด์„œ UNIFAC[7] Option์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

3. ํ†จ๋ฃจ์—” ํšŒ์ˆ˜ ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ • ๋ชจ๋ธ๋ง ๋ฐ ๋ชจ์‚ฌ

ํ†จ๋ฃจ์—” ํšŒ์ˆ˜ ์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์˜ ๋ชจ๋ธ๋ง์„ ์œ„ํ•˜์—ฌ ์ƒ์šฉ์˜ ํ™”ํ•™๊ณต์ •

๋ชจ์‚ฌ๊ธฐ์ธ Aspen Technology์‚ฌ์˜ Aspen Plus release 12.1์„ ์‚ฌ์šฉํ•˜

์˜€๋‹ค. ์ •์ƒ์ƒํƒœ์˜ ์ฆ๋ฅ˜ํƒ‘ ๊ฑฐ๋™์„ ํ•ด์„ํ•˜๊ธฐ ์œ„ํ•œ ์•Œ๊ณ ๋ฆฌ์ฆ˜์œผ๋กœ๋Š”

Aspen Plus ๋‚ด์— ๋‚ด์žฅ๋˜์–ด ์žˆ๋Š” SUM-RATES ์•Œ๊ณ ๋ฆฌ์ฆ˜[8]์„ ์‚ฌ์šฉ

ํ•˜์˜€๋‹ค. ๋‹ค์Œ์˜ Fig. 4๋Š” SUM-RATES ์•Œ๊ณ ๋ฆฌ์ฆ˜์„ ์ด์šฉํ•ด์„œ ์ฆ๋ฅ˜ํƒ‘

์˜ ๊ฑฐ๋™์„ ํ•ด์„ํ•˜๊ธฐ ์œ„ํ•œ ์ž„์˜์˜ ๋‹จ์„ ๋„์‹์ ์œผ๋กœ ๋‚˜ํƒ€๋‚ธ ๊ฒƒ์ด๋‹ค.

Fig. 4์— ๋‚˜ํƒ€๋‚ธ ์ž„์˜์˜ ์ฆ๋ฅ˜๋‹จ์— ๋Œ€ํ•œ ์„ฑ๋ถ„ ๋ฌผ์งˆ์ˆ˜์ง€, ์—๋„ˆ์ง€ ์ˆ˜์ง€,

๊ธฐ์•ก ํ‰ํ˜• ๊ด€๊ณ„์‹ ๋ฐ ์กฐ์„ฑ์˜ ํ•ฉ์— ๋Œ€ํ•œ ์ œํ•œ์กฐ๊ฑด์€ ๋‹ค์Œ์˜ (4)์‹๊ณผ

(8)์‹ ์‚ฌ์ด์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

(4)

ฮณiln

ฯ„j iGj ixj

jโˆ‘

Gk ixk

k

โˆ‘

------------------------=xjGi j

Gk jxk

k

โˆ‘

------------------- ฯ„i j

xkฯ„k jGk j

k

โˆ‘

Gk jxk

k

โˆ‘

--------------------------โ€“

โŽ โŽ โŽœ โŽŸโŽœ โŽŸโŽœ โŽŸโŽ› โŽž

jโˆ‘+

ฯ„i j ai j

bi j

T-----+=

G i j ฮฑi jฯ„i jโ€“( )exp=

Mi j, Xi j,( )Liexp Yi j,( )Viexp Xi 1 j,โ€“( ) Li 1โ€“

Li 1โ€“

Dโ€“( )expโ€“+=

Yi+1 j,

( ) Vi 1+V i 1+

Dโ€“( )expโ€“ fi j,

Lfi 1 j,โ€“

Vโ€“โ€“

i 1 NT j 1 NC,=, ,=

Fig. 3. Ternary liquid-liquid equilibria data and its prediction with

NRTL model for sulfolane/benzene/normal heptane component.

Table 2. NRTL binary interaction parameters for each binary set

Component I Component JA(I, J)

A(J, I)

B(I, J)/K

B(J, I)/KAlpha

Toluene Benzene 2.1911

โˆ’2.8852

โˆ’863.7308

1,123.9501

0.3000

Toluene MCH 0.0000

0.0000

4.0625

โˆ’43.2404

0.3000

Toluene Octane 0.0000

0.0000

265.2227

โˆ’142.116313

0.3000

Toluene Ethyl benzene 0.0000

0.0000

โˆ’369.4598

549.2948

0.3000

Benzene MCH 0.0000

0.0000

377.8787

โˆ’197.2841

0.3000

Benzene Octane โˆ’7.2344

2.8325

3,004.3057

โˆ’1,247.0682

0.3000

Benzene Ethyl benzene โˆ’1.4701

1.1017

642.1115

โˆ’515.4272

0.3000

MCH Ethyl benzene 1.6942

โˆ’1.8888

โˆ’370.6175

539.4158

0.3000

Octane Ethyl benzene โˆ’1.5859

โˆ’2.3937

โˆ’650.2850

1,050.9279

0.3000

Toluene Sulfolane 1.3984

โˆ’0.3310

71.4079

223.1410

0.3000

Benzene Sulfolane 0.0000

0.0000

498.8326

-50.4476

0.3000

MCH Sulfolane โˆ’15.9860

56.1830

2,379.0299

โˆ’1,524.4739

0.3000

Octane Sulfolane โˆ’134.5789

โˆ’43.2772

1,000.0000

2,792.4300

0.1215

Ethyl benzene Sulfolane 0.0000

0.0000

649.1000

353.1500

0.5810

DMCH Sulfolane 0.9709

โˆ’2.1132

1,192.1132

1,401.0628

0.2000

Page 4: Sulfolane A Study on the Simulation of Toluene Recovery ...

132 ์กฐ ์ • ํ˜ธ

ํ™”ํ•™๊ณตํ•™ ์ œ44๊ถŒ ์ œ2ํ˜ธ 2006๋…„ 4์›”

(5)

(6)

(7)

(8)

์—ฌ๊ธฐ์—์„œ Fi๋Š” ์ž„์˜์˜ โ€˜iโ€™๋‹จ์œผ๋กœ ์ฃผ์ž…๋˜๋Š” ์ด ๋ชฐ์œ ๋Ÿ‰์„, Li๋Š”

์ž„์˜์˜ โ€˜iโ€™๋‹จ์œผ๋กœ๋ถ€ํ„ฐ ๋‚˜์˜ค๋Š” ์ด ์•ก์ƒ ๋ชฐ์œ ๋Ÿ‰์„, Vi๋Š” ์ž„์˜์˜ โ€˜iโ€™๋‹จ

์œผ๋กœ๋ถ€ํ„ฐ ๋‚˜์˜ค๋Š” ์ด ๊ธฐ์ƒ ๋ชฐ์œ ๋Ÿ‰์„, Qi๋Š” ์ž„์˜์˜ โ€˜iโ€™๋‹จ์œผ๋กœ ์ฃผ์ž…๋˜

๋Š” ์‹œ๊ฐ„๋‹น ์—ด๋Ÿ‰์„, Ti๋Š” ์ž„์˜์˜ โ€˜iโ€™๋‹จ์˜ ์˜จ๋„๋ฅผ, Xi,j๋Š” ์•ก์ƒ์˜ ๋ชฐ๋ถ„

๋ฅ ์— ์ž์—ฐ๋กœ๊ทธ๋ฅผ ์ทจํ•œ ๊ฐ’์„, Yi, j๋Š” ๊ธฐ์ƒ์˜ ๋ชฐ๋ถ„๋ฅ ์— ์ž์—ฐ๋กœ๊ทธ๋ฅผ ์ทจ

ํ•œ ๊ฐ’์„, NC๋Š” ์„ฑ๋ถ„์˜ ์ˆ˜๋ฅผ, NT๋Š” ์ด๋ก ๋‹จ์ˆ˜๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค.

์›๋ฃŒ์˜ ์กฐ์„ฑ๊ณผ ์˜จ๋„, ์••๋ ฅ ๋ฐ ์œ ๋Ÿ‰ ์กฐ๊ฑด์€ ์•„๋ž˜์˜ Table 3์— ๋‚˜ํƒ€

๋‚ธ ๋ฐ”์™€ ๊ฐ™๋‹ค. Aspen Plus ํ™”ํ•™๊ณต์ • ๋ชจ์‚ฌ๊ธฐ๋ฅผ ์ด์šฉํ•ด์„œ ๊ตฌํ˜„ํ•œ ์ถ”

์ถœ์ฆ๋ฅ˜๊ณต์ •์€ Fig. 5์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

3-1. ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์˜ ๋ชจ์‚ฌ

Sulfolane์„ ์šฉ๋งค๋กœ ์ด์šฉํ•˜์—ฌ ๋น„๋ฐฉํ–ฅ์กฑ ํ˜ผํ•ฉ๋ฌผ๋กœ๋ถ€ํ„ฐ ํ†จ๋ฃจ์—” ์„ฑ๋ถ„

์„ ์„ ํƒ์ ์œผ๋กœ ํšŒ์ˆ˜ํ•˜๋Š” ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์„ Fig. 6์— ๋„์‹์ ์œผ๋กœ ๋‚˜ํƒ€๋‚ด์—ˆ

๋‹ค. Fig. 6์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ์ด๋ก ๋‹จ์ˆ˜๋Š” ์‘์ถ•๊ธฐ์™€ ์žฌ๋น„๊ธฐ๋ฅผ ํฌํ•จํ•˜

์—ฌ 35๋‹จ์œผ๋กœ ์ •ํ•˜์˜€๋‹ค. ๊ทธ ์ด์œ ๋Š” ํ˜„์žฌ ๊ตญ๋‚ด์—์„œ ๊ฐ€๋™๋˜๊ณ  ์žˆ๋Š” ์šฉ๋งค

๋ฅผ ์ด์šฉํ•œ ๋ฐฉํ–ฅ์กฑ ํšŒ์ˆ˜ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์˜ ์‹ค์ œ๋‹จ์ˆ˜๊ฐ€ 75๋‹จ[9]์ธ๋ฐ ๋น„ํ•˜์—ฌ

์ฆ๋ฅ˜ํƒ‘์˜ ํšจ์œจ์€ 45๏ผ… ์ •๋„๋กœ ์ถ”์‚ฐ๋˜๊ธฐ ๋•Œ๋ฌธ์ด๋‹ค. ์ฆ๋ฅ˜ํƒ‘์˜ ๋‹จ ํšจ์œจ

๊ณ„์‚ฐ์— ๋Œ€ํ•œ ๊ทผ๊ฑฐ๋Š” Gerald[10]๊ฐ€ ์ œ์•ˆํ•œ ์ฆ๋ฅ˜ํƒ‘์˜ ํšจ์œจ์€ ์ฆ๋ฅ˜ํƒ‘์˜

ํƒ‘์ƒ๊ณผ ํƒ‘์ €์˜ ํ‰๊ท  ์˜จ๋„ ์กฐ๊ฑดํ•˜์—์„œ ์›๋ฃŒ ์•ก์ƒ์˜ ์ ๋„ ํ•จ์ˆ˜๋กœ ํ‘œํ˜„

ํ•œ ๊ฒƒ์œผ๋กœ์จ ์ด๋Š” Fig. 7์— ๋„์‹์ ์œผ๋กœ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. Fig. 7์— ๋‚˜ํƒ€๋‚ธ

๊ฒƒ๊ณผ ๊ฐ™์ด ์›๋ฃŒ ์•ก์˜ ํ‰๊ท  ์ ๋„๊ฐ€ 0.34 cP ์ด๋ฏ€๋กœ ์ ๋„์— ๋Œ€ํ•œ ์ฆ๋ฅ˜ํƒ‘

์˜ ํšจ์œจ ์ƒ๊ด€๊ด€๊ณ„์‹์— ์˜ํ•˜์—ฌ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์˜ ํšจ์œจ์ด 45๏ผ… ๊ฐ€๋Ÿ‰ ๋˜๋ฏ€๋กœ

์ด๋ฅผ ์ ์šฉํ•˜์—ฌ ์ด๋ก ๋‹จ์ˆ˜๋ฅผ 35๋‹จ์œผ๋กœ ์ •ํ•˜์˜€๋‹ค. ์›๋ฃŒ ์œ ๋Ÿ‰์— ๋Œ€ํ•œ ์šฉ

๋งค์˜ ์ฃผ์ž… ์œ ๋Ÿ‰์€ ๋ฌด๊ฒŒ ๋น„๋กœ 3.61:1๋กœ ์ •ํ•˜์˜€๋‹ค. ์ด๋Š” ์ฃผ์–ด์ง„ ์ถ”์ถœ์ฆ

๋ฅ˜ํƒ‘์˜ ์ด๋ก ๋‹จ์ˆ˜ ์กฐ๊ฑดํ•˜์—์„œ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜์œจ์„ ๋งŒ์กฑ์‹œํ‚ค๋Š” ์ตœ์ ์˜ ์šฉ

๋งค ์ˆœํ™˜์œ ๋Ÿ‰์œผ๋กœ ์ •ํ•œ ๊ฒƒ์ด๋‹ค. ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์— ๋Œ€ํ•œ ์žฅ์น˜ ๋ฐ ์šด์ „ ์กฐ

๊ฑด์€ Table 4์— ์ •๋ฆฌํ•˜์˜€๋‹ค. Table 4์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘

์˜ ๋ชจ์‚ฌ๋ฅผ ์œ„ํ•ด์„œ ์›๋ฃŒ๋Š” 21๋‹จ์— ์ฃผ์ž…ํ•˜์˜€์œผ๋ฉฐ, ์šฉ๋งค๋Š” 7๋‹จ์œผ๋กœ ์ฃผ

์ž…ํ•˜์˜€๋‹ค. ๊ทธ ๊ฒฐ๊ณผ ํ™˜๋ฅ˜๋น„๋Š” 40.51์ด๋ฉฐ ํ™˜๋ฅ˜ ์œ ๋Ÿ‰์œผ๋กœ๋Š” 500 Kg/hr

Ei LiHi

LViHi

VLi 1โ€“

Li 1โ€“

Dโ€“( )Hi

LVi 1+

Vi 1+

Dโ€“( )Hi 1+

Vโ€“โ€“+=

) ) ) )

i 1 NT,= Qiโ€“ Fi

LHi

FLโ€“ Fi 1+

VHi 1+

FVโ€“

) )

Q i j,

Yi j,

Xi j,

โ€“ Ki j,

( )ln i 1 NT j 1 NC,=, ,=,โ€“=

S i 1 X i j,

( )exp

j 1=

NC

โˆ‘ i 1 NT,=,โ€“=

S i โ€ฒ 1 Yi j,

( )exp

j 1=

NC

โˆ‘ i 1 NT,=,โ€“=

Table 3. Feed stream information

Component Flow rate (Kg/hr) Weight Percent

Toluene 660.5811 98.32

Benzene 11.411 10.21

Methyl cylcohexane 12.217 10.33

Dimethyl cyclohexane 14.470 10.67

Octane 11.747 10.26

Ethyl benzene 11.075 10.16

Temperature (oC) 35.00

Pressure (bar) 12.50

Flow rate (Kg/hr) 671.901

Fig. 4. Schematic of a simple stage for the sum-rates algorithm.

Fig. 5. Process flow sheet for the extractive distillation process of Aspen Plus 12.1.

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Sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๊ณต์ •์˜ ๋ชจ์‚ฌ์— ๊ด€ํ•œ ์—ฐ๊ตฌ 133

Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

๊ฐ€ ๊ณ„์‚ฐ๋˜์—ˆ์œผ๋ฉฐ ํ†จ๋ฃจ์—”์˜ ์ˆœ๋„๋Š” 99.65๏ผ…๋ฅผ ์–ป์—ˆ์œผ๋ฉฐ raffinate์—์„œ

ํ†จ๋ฃจ์—”์˜ ํ•จ๋Ÿ‰์€ ๋ฌด๊ฒŒ๋น„๋กœ 18.90๏ผ…๊ฐ€ ์–ป์–ด์กŒ๋‹ค.

3-2. ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์˜ ๋ชจ์‚ฌ

์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘ ํ•˜๋ถ€์—์„œ ์šฉ๋งค์— ์šฉํ•ด๋œ ํ†จ๋ฃจ์—”์ด ์–ป์–ด์ง„๋‹ค. ์ด

extract ์„ฑ๋ถ„์€ ์—ด๊ตํ™˜๋˜์–ด์„œ ๋”์šฑ ๊ฐ€์—ด๋˜์–ด์ง„ ํ›„์— ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์œผ

๋กœ ์ฃผ์ž…๋˜์–ด์„œ ์šฉ๋งค์™€ ํ†จ๋ฃจ์—” ์‚ฌ์ด์˜ ๋ถ„๋ฆฌ๊ฐ€ ์ด๋ฃจ์–ด์ง„๋‹ค. ์šฉ๋งค ํšŒ

์ˆ˜ํƒ‘์€ ์ „ํ˜•์ ์ธ ์ฆ๋ฅ˜ํƒ‘์˜ ๋ฐฐ์—ด์„ ๊ฐ€์ง€๋Š”๋ฐ Fig. 8์— ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘

์„ ๋„์‹์ ์œผ๋กœ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. Fig. 8์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ์ด๋ก ๋‹จ์ˆ˜๋Š”

์‘์ถ•๊ธฐ์™€ ์žฌ๋น„๊ธฐ๋ฅผ ํฌํ•จํ•˜์—ฌ 10๋‹จ์œผ๋กœ ์ •ํ•˜์˜€๋‹ค. ๊ทธ ์ด์œ ๋Š” ํ˜„์žฌ ๊ตญ

๋‚ด์—์„œ ๊ฐ€๋™๋˜๊ณ  ์žˆ๋Š” ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ๋ฐฉํ–ฅ์กฑ ํšŒ์ˆ˜ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์˜ ์‹ค

์ œ๋‹จ์ˆ˜๊ฐ€ 40๋‹จ์ธ๋ฐ ๋น„ํ•˜์—ฌ ์ฆ๋ฅ˜ํƒ‘์˜ ํšจ์œจ์€ 25๏ผ… ์ •๋„๋กœ ์ถ”์‚ฐ๋˜๊ธฐ

๋•Œ๋ฌธ์ด๋‹ค. ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์— ๋Œ€ํ•œ ์žฅ์น˜ ๋ฐ ์šด์ „ ์กฐ๊ฑด์€ Table 5์— ์ •๋ฆฌ

ํ•˜์˜€๋‹ค. Table 5์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์˜ ๋ชจ์‚ฌ๋ฅผ ์œ„ํ•ด์„œ

์›๋ฃŒ๋Š” ์ค‘๊ฐ„ ๋‹จ์ธ ์ œ 5๋‹จ์— ์ฃผ์ž…ํ•˜์˜€๋‹ค. ๊ทธ ๊ฒฐ๊ณผ ํ™˜๋ฅ˜๋น„๋Š” 0.5์ด๋ฉฐ

ํ™˜๋ฅ˜ ์œ ๋Ÿ‰์œผ๋กœ๋Š” 329.75 Kg/hr๊ฐ€ ๊ณ„์‚ฐ๋˜์—ˆ์œผ๋ฉฐ ํƒ‘์ƒ ์ œํ’ˆ์—์„œ ํ†จ๋ฃจ

์—”์˜ ์ˆœ๋„๋Š” 99.81 wt๏ผ… ์ด์ƒ์„ ์–ป์„ ์ˆ˜ ์žˆ์—ˆ๋‹ค.

Fig. 6. A schematic diagram of the extractive distillation column.

Fig. 7. Overall tray efficiencies as a function of average feedstock liquid

viscosity (Viscosity is average of feed as liquid at top and bottom

temperatures of the column).

Table 4. Input data, specified parameters and output data for the

simulation of extractive distillation column

Input/output data and specified parameters Value

Input data

Feed flow rate (Kg/hr) 671.90

Solvent flow rate (Kg/hr) 2,418.50

Feed toluene composition (weight ๏ผ…) 98.32

Specified design and operating parameters

Theoretical number of stage 35

Operating pressure at column top (bar) 1.20

Feedstock feed tray location 21

Solvent feed tray location 7

Reflux ratio 40.51

Reflux rate (Kg/hr) 500.00

Output data

Condenser duty (Kcal/hr) โˆ’57,279.50

Reboiler duty (Kcal/hr) 124,459.73

Toluene recovery (๏ผ…) 99.65

Toluene weight percent at raffinate 18.90

Fig. 8. A schematic diagram of the solvent recovery column.

Page 6: Sulfolane A Study on the Simulation of Toluene Recovery ...

134 ์กฐ ์ • ํ˜ธ

ํ™”ํ•™๊ณตํ•™ ์ œ44๊ถŒ ์ œ2ํ˜ธ 2006๋…„ 4์›”

4. ๊ฒฐ๊ณผ ๋ฐ ๊ณ ์ฐฐ

์›๋ฃŒ๋Š” Table 3๊ณผ ๊ฐ™์€ ์˜จ๋„, ์••๋ ฅ, ์œ ๋Ÿ‰ ๋ฐ ์กฐ์„ฑ์„ ๊ฐ–๊ณ  ์ƒ์‚ฐ๋˜

๋Š” ํ†จ๋ฃจ์—”์˜ ์ˆœ๋„๋Š” 99.8 wt๏ผ… ์ด์ƒ์˜ ์ œํ’ˆ์„ ์ƒ์‚ฐํ•˜๋Š” ๊ฒƒ์„ ๋ชฉํ‘œ

๋กœ ์ „์‚ฐ๋ชจ์‚ฌ๋ฅผ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ํ•œํŽธ, ์ถ”์ถœ ์ฆ๋ฅ˜ํƒ‘์—์„œ ๊ฐ ์„ฑ๋ถ„์˜ ์•ก์ƒ

์˜ ๋ฌด๊ฒŒ ๋ถ„๋ฅ ์„ ๊ฐ ๋‹จ์˜ ํ•จ์ˆ˜๋กœ Fig. 9์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. Fig. 9์— ๋‚˜ํƒ€

๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ํ†จ๋ฃจ์—”์˜ ๋†๋„๋Š” ๊ฐ ๋‹จ์— ๋Œ€ํ•˜์—ฌ ๊ฑฐ์˜ ์ผ์ •ํ•œ ๊ฐ’์„ ๋ณด

์ธ ๋ฐ˜๋ฉด์— ๋‚˜๋จธ์ง€ ์„ฑ๋ถ„๋“ค์€ ์›๋ฃŒ ์ฃผ์ž…๋‹จ์ธ 21๋‹จ ์ดํ•˜์—์„œ ๊ธ‰๊ฒฉํžˆ

๊ฐ์†Œํ•˜์˜€์œผ๋ฉฐ ํŠนํžˆ ์ถ”์ถœ ์ฆ๋ฅ˜ํƒ‘ ํƒ‘์ €์—์„œ 0.01 wt๏ผ… ์ดํ•˜๋กœ ๊ฐ์†Œํ•จ

์„ ์•Œ ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์ด๋Š” ์šฉ๋งค์ธ sulfolane์ด ์ถ”๊ฐ€๋จ์œผ๋กœ์จ ์šฉ๋งค์™€ ์นœ

ํ™”๋ ฅ์ด ์ ์€ ๋น„๋ฐฉํ–ฅ์กฑ ์„ฑ๋ถ„๋“ค์€ ๋ชจ๋‘ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘ ์ƒ๋ถ€๋กœ ๋†์ถ•๋˜๊ธฐ

๋•Œ๋ฌธ์ž„์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ํ•œํŽธ, Fig. 10์€ light key component์ธ methyl

cylcohexane๊ณผ heavy key component์ธ ํ†จ๋ฃจ์—” ์‚ฌ์ด์˜ Separating

factor๋ฅผ tray number์˜ ํ•จ์ˆ˜๋กœ ๋„์‹œํ•œ ๊ฒƒ์ด๋‹ค. Fig. 10์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ

๊ณผ ๊ฐ™์ด ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘ ์ „ ๋‹จ์— ๊ฑธ์ณ์„œ separating facot ๊ฐ’์ด ์ฆ๊ฐ€ํ•˜๋‹ค

๊ฐ€ ๊ฐ์†Œํ•œ ํ›„์— ๋‹ค์‹œ ์ฆ๊ฐ€ํ•˜๋Š” ํ˜„์ƒ์ด ์—†์ด ์—ฐ์†์ ์œผ๋กœ ๋ณ€ํ™”ํ•จ์„

์•Œ ์ˆ˜ ์žˆ๋‹ค. ์ด๊ฒƒ์€ ๊ฐ ๋‹จ์—์„œ key component๋“ค์˜ ์กฐ์„ฑ์ด ์—ฐ์†์ ์œผ

๋กœ ๋ณ€ํ™”ํ•จ์„ ์˜๋ฏธํ•œ๋‹ค. ๊ฐ ๋‹จ์ด ๋ถ„๋ฆฌ๋‹จ์˜ ์—ญํ• ์„ ์ž˜ ์ˆ˜ํ–‰ํ•˜๊ณ  ์žˆ์Œ

์„ ์˜๋ฏธํ•˜๊ณ  ๋”์šฑ์ด ์›๋ฃŒ ์ฃผ์ž…๋‹จ์ธ 21๋‹จ์„ ์ค‘์‹ฌ์œผ๋กœ separating

factor ๊ฐ’์˜ fluctuation ํ˜„์ƒ์ด ์ผ์–ด๋‚˜์ง€ ์•Š์Œ์œผ๋กœ ์›๋ฃŒ ์ฃผ์ž…๋‹จ์˜ ์œ„

์น˜๊ฐ€ ์ œ๋Œ€๋กœ ๊ฒฐ์ •๋˜์–ด์กŒ์Œ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค.

์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์—์„œ ๊ฐ ์„ฑ๋ถ„์˜ ์•ก์ƒ์˜ ๋ฌด๊ฒŒ ๋ถ„๋ฅ ์„ ๊ฐ ๋‹จ์˜ ํ•จ์ˆ˜๋กœ

Fig. 11์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. Fig. 11์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด ํ†จ๋ฃจ์—”์˜ ๋†๋„๋Š”

ํƒ‘์ƒ ์ œํ’ˆ์—์„œ ๊ฑฐ์˜ 100๏ผ…์˜ ์ˆœ๋„๋ฅผ ๋ณด์˜€์œผ๋ฉฐ ๋ฐ˜๋ฉด์— ํƒ‘์ €์—์„œ๋Š”

๊ฑฐ์˜ ๋‚˜ํƒ€๋‚˜์ง€ ์•Š์•˜๋‹ค. ์ด๊ฒƒ์€ ์šฉ๋งค ํšŒ์ˆ˜ํƒ‘์—์„œ ์šฉ๋งค์™€ ํ†จ๋ฃจ์—” ์‚ฌ

์ด์˜ ๋ถ„๋ฆฌ๊ฐ€ ์ž˜ ์ด๋ฃจ์–ด์กŒ์„ ๋ฟ๋งŒ ์•„๋‹ˆ๋ผ ํ†จ๋ฃจ์—”์˜ ํšŒ์ˆ˜์œจ๋„ ๋†’์Œ์„

Table 5. Input data, specified parameters and output data for the

simulation of solvent recovery column

Input/output data and specified parameters Value

Input data

Feed flow rate (Kg/hr) 3,078.00

Feed toluene composition (weight ๏ผ…) 21.38

Specified design and operating parameters

Theoretical number of stages 10

Operating pressure at column top (bar) 0.42

Feedstock feed tray location 5

Reflux ratio 0.5

Reflux rate (Kg/hr) 329.75

Output data

Condenser duty (Kcal/hr) โˆ’106,441.79

Reboiler duty (Kcal/hr) 166,432.84

Toluene weight percent at top product > 99.81

Fig. 9. Composition profile along the extractive distillation column.

Fig. 10. Plot of separating factor between toluene (heavy key component)

and methyl cyclohexane (light key component) as a function of

tray number.

Fig. 11. Composition profile along the solvent recovery distillation column.

Page 7: Sulfolane A Study on the Simulation of Toluene Recovery ...

Sulfolane ์šฉ๋งค๋ฅผ ์ด์šฉํ•œ ํ†จ๋ฃจ์—” ํšŒ์ˆ˜๊ณต์ •์˜ ๋ชจ์‚ฌ์— ๊ด€ํ•œ ์—ฐ๊ตฌ 135

Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

๋‚˜ํƒ€๋‚ด๋Š” ๊ฒƒ์ด๋‹ค. ๋‹ค๋ฅธ ์„ฑ๋ถ„๋“ค์€ ์›๋ฃŒ ์ฃผ์ž…๋‹จ ์•„๋ž˜์—์„œ ๊ฑฐ์˜ ๊ฒ€์ถœ๋˜

์ง€ ์•Š์Œ์„ ์•Œ ์ˆ˜ ์žˆ์—ˆ๋‹ค. ํ•œํŽธ, ์ „์ฒด ๊ณต์ •์— ๋Œ€ํ•œ ๋ฌผ์งˆ์ˆ˜์ง€๋Š” Table 6

์— ์ •๋ฆฌํ•˜์˜€๋‹ค.

5. ๊ฒฐ ๋ก 

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์—ฐ๋ฃŒ ์ฒจ๊ฐ€์ œ ๋ฐ ๊ฐ์ข… ๊ณต์—…์šฉ ์šฉ์ œ ๋“ฑ์œผ๋กœ ์ฃผ๋กœ ์‚ฌ

์šฉ๋˜๊ณ  ์žˆ๋Š” 99.8 wt๏ผ… ์ด์ƒ์˜ ํ†จ๋ฃจ์—”์„ ์šฉ๋งค์ธ sulfoale์„ ์‚ฌ์šฉํ•˜์—ฌ

์ถ”์ถœ์ฆ๋ฅ˜๊ณต์ •์„ ํ†ตํ•ด์„œ ๋ถ„๋ฆฌํ•ด ๋‚ด๊ธฐ ์œ„ํ•œ ์ „์‚ฐ๋ชจ์‚ฌ ์ž‘์—…์„ ์ˆ˜ํ–‰ํ•˜

์˜€๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ ์‹คํ–‰ํ•œ ์ „์‚ฐ๋ชจ์‚ฌ ์ž‘์—…์„ ํ†ตํ•˜์—ฌ ์ถ”์ถœ์ฆ๋ฅ˜ํƒ‘์œผ๋กœ

์ฃผ์ž…๋˜๋Š” ์šฉ๋งค์˜ ์ค‘๋Ÿ‰๋น„๋Š” ์›๋ฃŒ ๋Œ€๋น„ 3.61๋ฐฐ์ผ ๋•Œ ํ†จ๋ฃจ์—”์˜ ํšŒ์ˆ˜์œจ

์„ 99.56๏ผ… ์ด์ƒ์„ ์–ป์„ ์ˆ˜ ์žˆ์—ˆ์œผ๋ฉฐ ํ†จ๋ฃจ์—”์˜ ์ˆœ๋„๋Š” 99.81 wt๏ผ… ์ด

์ƒ์„ ์–ป์„ ์ˆ˜ ์žˆ์—ˆ๋‹ค.

์‚ฌ์šฉ๊ธฐํ˜ธ

T : absolute temperature [K]

Fi : total feed flow rate to tray i [Kmole/hr]

Li : total liquid flow rate from tray i [Kmole/hr]

Vi : total vapor flow rate from tray i [Kmole/hr]

Qi : heat added to tray I [MM Kcal/hr]

Ti : temperature of tray I [K]

NC : number of components

NT : number of trays

N : number of experimental data points

ฮณi : activity coefficient of component i

xj, xk : liquid mole fraction of component j and k

aij, aji, bij, aji, ฮฑij : binary interaction parameter in van der Waals

mixing rule

Fp : total molar flow rate feeding to the plate p

Vp : total vapor molar flow rate coming out of the plate p

Lp : total liquid molar flow rate coming out of the

plate p

Sv,p : total vapor side draw flow rate coming of the

plate p

Sl,p : total liquid side draw flow rate coming of the

plate p

xp, yp, zF,p : mole fraction contained in Lp, Vp and Fp, respectively

Kj,p : K-value of component โ€˜jโ€™ at the plate p

fj,p : molar flow rate of component โ€˜jโ€™ feeding to the

plate p

lj,p : liquid molar flow rate of component โ€˜jโ€™ coming

out of the plate p

vj,p : vapor molar flow rate of component โ€˜jโ€™ coming

out of the plate p

sj,p : side stream molar flow rate of component โ€˜jโ€™ coming

out of the plate p

hF,p : total molar enthalpy feeding to the plate p

hp : total liquid molar enthalpy coming out of the plate p

Hp : total vapor molar enthalpy coming out of the plate p

qc,1 : overhead condenser heat duty

h0' : saturated liquid molar enthalpy of overhead product

์ฐธ๊ณ ๋ฌธํ—Œ

1. http://www.hyundaicorp.co.kr/global/prd_main.asp?sOffice_id=14

2. http://www.gtchouston.com/articles/operational๏ผ…20Experience๏ผ…

20with๏ผ…20gt-btx.pdf

3. http://www.etis.net/balpyo/work19/23.pdf

4. http://www.uop.com/objects/55๏ผ…20Sulfolane.pdf

5. Sungjin, L. and Hwayong, K., โ€œLiquid-liquid Equilibria for the

Ternary Systems Sulfolane+Octane+Toluene, and Sulfolane+Octane

+p-xylene at Elevated Temperatures,โ€ J. Chem. Eng. Data, 43,

358-361(1998).

6. Renon, H. and Prausnitz, J. M., โ€œLocal Composition in Thermo-

dynamic Excess Functions for Liquid Mixtures,โ€ AIChE J., 14, 135-

144 (1968).

7. Larsen, B. L., Rasmussen, P. and Fredenslund. Aa., โ€œA Modified

UNIFAC Group Contribution Model for Prediction of Phase

Equilibria and Heats of Mixing,โ€ Ind. Eng. Chem. Res., 26, 2274-

2286(1987).

8. Russel, R. A., โ€œA Flexible and Reliable Method Solves Sing-

tower and Crude-distillation-column Problems,โ€ Chem. Eng., 90,

53-59 (1983).

9. http://www.gtchouston.com/articles/Aromatics๏ผ… 20Design๏ผ… 20-

๏ผ… 20The๏ผ… 20Future๏ผ… 20is๏ผ… 20Now.pdf

10. Gerald, L. K., Refinery Process Modeling: A Practical Guide to

Steady State Modeling of Petroleum Processes, 1st ed., Kaes

Enterprises, Inc.(2000).

Table 6. Material balance for the extractive distillation process

1 2 3 4 5 6 7

Crude feed Raffinate Rich solvent Feed to T-102 Toluene product T-102 bottom product Lean solvent recycled to T-101

Flow, Kg/hr 671.800 12.300 3,078.000 3,078.000 659.500 2,418.500 2,418.500

Toluene 660.581 2.321 658.261 658.261 658.260 0.001 0.001

Benzene 1.411 1.263 0.147 0.147 0.147 โˆ’ โˆ’

MCH 2.217 2.217 < 0.001 < 0.001 < 0.001 โˆ’ โˆ’

DMCH 4.470 4.763 0.007 0.007 0.007 โˆ’ โˆ’

Octane 1.747 1.736 0.010 0.010 0.010 โˆ’ โˆ’

Ethyl benzene 1.705 โˆ’00 1.075 1.075 1.075 < 0.001 < 0.001

Solfolane 0.00 < 0.001 2,418.500 2,418.500 < 0.001 2,418.499 2,418.499

Temp. (oC) 35.00 50.00 148.400 157.000 45.000 264.900 105.000