Methanol-DMC 이성분계의기액상평형실험및 …...Methanol-DMC...
Transcript of Methanol-DMC 이성분계의기액상평형실험및 …...Methanol-DMC...
Methanol-DMC 이성분계의 기액 상평형 실험 및
압력변환 증류공정에 대한 공정 최적화 연구압력변환 증류공정에 대한 공정 최적화 연구
2013년 9월 27일(금)2013년 9월 27일(금)
조재숙, 김동선, 조정호, 고재천†, 백준현†
공주대학교, †포항산업과학연구원(RIST)
서론 : Pressure-Swing Distillation의 원리
1.0 BC
< 압력변환 증류공정의 원리 >
0.8
0.9 LP ColumnHP ColumnDiagonal line
C
D
F2
hano
l)
0 5
0.6
0.7D
C 근처D 근처
F1
F2
y (m
eth
0.3
0.4
0.5
B A
0.1
0.2
FA : 고순도 DMCB : 고순도 Methanol
각 Point의 정의
x (methanol)0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.0A
F1B : 고순도 MethanolC : 고압에서의 공비 조성D : 저압에서의 공비 조성F1 : LP Column의 Feed 조성F2 : HP Column의 Feed 조성
2
F2 : HP Column의 Feed 조성
서론 : 기액 상평형 실험의 필요성
MeOH-DMC 계의 Txy 선도 at P=30 kPa ChemCAD v6.3.1
PRO/II with PROVISION 9.1 Aspen Plus v7.3
기액 상평형 실험을 통한MeOH-DMC 이성분계 매개변수 도출 필요MeOH DMC 이성분계 매개변수 도출 필요
3
기액 상평형 실험 - 방법
< 기-액 상평형 실험 방법 >
기-액 상평형 실험 전 표준시료 제조를 통한검량선 작성검량선 작성
순수 성분의 끓는점 측정을 이용한순수 성분의 끓는점 측정을 이용한기-액 상평형 실험 장치 검증
상압(1013 mbar) 및 저압(300 mbar) 조건에서상압(1013 mbar) 및 저압(300 mbar) 조건에서기-액 상평형 실험 수행
기 액 상평형 실험 결과를 정리하여
Fischer사의 기-액 상평형 실험 장비
기-액 상평형 실험 결과를 정리하여TXY 및 XY Plot 작성
4
기액 상평형 실험 - 표준시료 제조
표준시료 제조 (MeOH-DMC)
wt% MeOH 질량 (g) DMC 질량 (g) 총 질량 (g) MeOH 실제질량 (g) MeOH 실제농도 (wt%)
0 0.00 20.00 20.00 0.000 0.000
※ MeOH 순도 : 99.9 wt%, DMC 순도 : 99.5 wt%
10 2.01 17.99 20.00 2.008 10.040
20 4.00 15.99 19.99 3.996 19.990
30 6.00 14.00 20.00 5.994 29.970
40 8 00 12 00 20 00 7 992 39 96040 8.00 12.00 20.00 7.992 39.960
50 10.00 10.00 20.00 9.990 49.950
60 12.01 7.99 20.00 11.998 59.990
70 14 00 6 01 20 01 13 986 69 89570 14.00 6.01 20.01 13.986 69.895
80 16.00 4.00 20.00 15.984 79.920
90 18.00 2.00 20.00 17.982 89.910
100 20 00 0 00 20 00 19 960 99 800100 20.00 0.00 20.00 19.960 99.800
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기액 상평형 실험 - 검량선 작성
x1 x2 x3 y SDx1 x2 x3 y SD
16.42 16.37 16.23 10.04 0.08
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기액 상평형 실험 - MeOH-DMC 이성분계
평형 도달 체크사항
메탄올 이용하여기-액 상평형 장치 세척
메탄올에 DMC를 조금씩가하면서 Sampling 수행
채취한 Sample의GC 정량분석 및 농도 확인
평형 도달 체크사항
액상과 응축된 기상이일정하게 떨어짐
기상과 액상의 온도의시간에 따른 일정함
Control valve와 Control box를이용하여 설정한 압력
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기액 상평형 실험 데이터 (상압 : 1 atm)
상압(1 atm)에서의 실험 수행
질소 가스를 이용하여 1 atm 압력을 구현한 후 실험을 수행Pressure Throttle valve를 이용하여 좀 더 세밀하게 압력을 조절함
ol
0.9
1.0
899193
Liquid mole fraction of methanolVapor mole fraction of methanol
tion
of m
etha
n
0 5
0.6
0.7
0.8
atur
e(℃
)
777981838587
Vapor mole fraction of methanol
Vapo
r mol
e fr
ac
0.2
0.3
0.4
0.5
Tem
pera
676971737577
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0V
0.0
0.1
Mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
636567
8
기액 상평형 실험 데이터 (저압 : 30 kPa)
저압(30 kPa)에서의 실험 수행
진공 펌프를 이용하여 30 kPa 압력을 구현한 후 실험을 수행진공 펌프에 별도의 Valve를 설치하여 좀 더 세밀하게 압력을 조절함
ol
0.9
1.0
55
57
59
Liquid mole fraction of methanolVapor mole fraction of methanol
tion
of m
etha
n
0 5
0.6
0.7
0.8
atur
e(℃
)
47
49
51
53p
Vapo
r mol
e fr
ac
0.2
0.3
0.4
0.5
Tem
pera
37
39
41
43
45
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0V
0.0
0.1
Mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.033
35
37
9
기액 상평형 실험 데이터 (고압 : 10 atm)
고압(10 atm)에서의 실험 데이터
RIST로부터 제공받은 논문(S.-J. Wang et al. 2010)에서고압 조건에서의 기액 상평형 실험 데이터 이용
ol
0.9
1.0
183
ctio
n of
met
han
0 5
0.6
0.7
0.8
atur
e(℃
)
163
173
Vapo
r mol
e fra
c
0.2
0.3
0.4
0.5
Tem
per
143
153
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0V
0.0
0.1
Mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
133
10
NRTL Parameters regression (상압 : 1 atm)
1.0
hano
l
0.8
0.9실험값 Regression값
공비조성 0.85 0.8599
on o
f met
h
0.6
0.7
i : methanol, j : DMC
공비온도 63.62℃ 63.45℃
mol
e fr
acti
0 3
0.4
0.5 Thermodynamic Model
Binaryparameter
aij -7.6996
Vapo
r m
0.1
0.2
0.3
Calc. Data at 1 atmEXP Data at 1 atm (KNU 2013)
NRTL-RK
aji 4.4904
bij 3026.1
bji -1464.2
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
EXP. Data at 1 atm (KNU. 2013)αij 0.3
q
11
NRTL Parameters regression (저압 : 30 kPa)
1.0 실험값 Regression값
hano
l
0.8
0.9 공비조성 0.81 0.7969
공비온도 35.11℃ 34.71℃
on o
f met
h
0.6
0.7
Thermodynamic Model
Binaryparameter
i : methanol, j : DMC
mol
e fr
acti
0 3
0.4
0.5 Model parameter
aij -11.844
aji 4.9493
Vapo
r m
0.1
0.2
0.3
Calc. Data at 30 kPaEXP. Data at 30 kPa (KNU. 2013)
NRTL-RKbij 4155.7
bji -1502.7
αij 0.3
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
( )βij -0.000229
q
12
NRTL Parameters regression (고압 : 10 atm)
1.0
hano
l
0.8
0.9실험값 Regression값
공비조성 0.9621 0.9206
on o
f met
h
0.6
0.7
i : methanol, j : DMC
공비온도 137.09℃ 136.85℃
mol
e fr
acti
0 3
0.4
0.5 Thermodynamic Model
Binaryparameter
aij 2.0
Vapo
r m
0.1
0.2
0.3
Calc. Data at 10 atmEXP. Data at 10 atm (S.-J. Wang et al. 2010)
NRTL-RK
aji -1.9085
bij -372.89
bji 784.54
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
( g )αij 0.3
q
13
NRTL Parameters regression (고압 : 10 atm)
1.0
hano
l
0.8
0.9실험값 Regression값
공비조성 0.9621 0.9610
on o
f met
h
0.6
0.7
i : methanol, j : DMC
공비온도 137.09℃ 137.18℃
mol
e fr
acti
0 3
0.4
0.5 Thermodynamic Model
Binaryparameter
aij 1.9009
Vapo
r m
0.1
0.2
0.3
Calc. Data at 10 atmEXP. Data at 10 atm (S.-J. Wang et al. 2010)
NRTL-RK
aji -1.9085
bij -392.89
bji 784.54
Liquid mole fraction of methanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
( g )αij 0.3
q
14
Design of PSD: (Paper) using Aspen Plus
Feed
#7#10
P=1.2 MPa
Feed
378 kg/hrMeOH 89.01 wt%DMC 10.89 wt%NH3 0 099 %
P=0.1 MPa#32 #26
0.6949 MW=0.5979 Mkcal/hr
0.5266 MW=0.4531 Mkcal/hr
NH3 0.099 wt%
(99.5 wt%) (99.5 wt%)
300 TPA DMC
0.5979 Mkcal/hr 0.4531 Mkcal/hr
Design and Control of Dimethyl Carbonate-Methanol Separationvia Pressure-Swing Distillation
H M i W i F W J Li Zh B Li
15
Hong-Mei Wei, Feng Wang, Jun-Liang Zhang, Bo Liao, Ning Zhao, Fu-kui Xiao, Wei Wei, and Yu-Han Sun
압력에 따른 Regression 결과
1.0
hano
l
0.8
0.9 97.00 mole%
on o
f met
h
0.6
0.7
mol
e fr
actio
0.4
0.5
84.83 mole%
Vapo
r m
0 1
0.2
0.3
Calc. Data at 1 barCalc. Data at 12 barC l D t t 0 3 b
79.69 mole%
Li id l f ti f th l
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.1 Calc. Data at 0.3 bar
Liquid mole fraction of methanol
16
PSD 모델링 : High(12 bar)-Low(1 bar) 배열
NH3 제거NH3 제거
High P=12 bar Low P=1 bar
Feed
378 kg/hr378 kg/hrMeOH 95.64 mole%DMC 4.16 mole%NH3 0.002 mole%
DMC 99 5 %DMC 99.5 wt% MeOH 99.5 wt%
17
공정 최적화 (Column spec. MeOH 조성)
)
3.0
)0.315
0.320
T01 Reboiler dutyT02 Reboiler duty
High pressure column optimization
High pressure column optimization
boile
r dut
y(10
6 kca
l/hr)
1.5
2.0
2.5
boile
r dut
y(10
6 kca
l/hr)
0 300
0.305
0.310
0.315
2.4
2.6
2.8
20
22
24
Reboiler dutyReflux ratio
High pressure column optimization
Mole percent of methanol
93.6 93.7 93.8 93.9 94.0 94.1 94.2 94.3 94.4
T01
Reb
0.5
1.0 T02
Reb
0.290
0.295
0.300
106 k
cal/h
r)
1.8
2.0
2.2
ratio16
18
20
Mole percent of methanol
hr) 3.0
3.5
High pressure column optimization
eboi
ler d
uty(
1
1.2
1.4
1.6
Reflu
x r
10
12
14
oile
r dut
y(10
6 kca
l/h
2.0
2.5
Re
0 4
0.6
0.8
1.0
4
6
8
93.6 93.7 93.8 93.9 94.0 94.1 94.2 94.3 94.4
Tota
l reb
o
0.5
1.0
1.5
(93.6, 0.9698)Mole percent of methanol
93.6 93.7 93.8 93.9 94.0 94.1 94.2 94.3 94.40.4
18
Mole percent of methanol
공정 최적화 (Column spec. MeOH 조성)
) 0.70
0.72
)0.38
0.40
T01 Reboiler dutyT02 Reboiler duty
Low pressure column optimization
Low pressure column optimization
boile
r dut
y(10
6 kca
l/hr)
0 64
0.66
0.68
0.70
boile
r dut
y(10
6 kca
l/hr)
0 32
0.34
0.36
0.38
0 8
0.918
20
Reboiler dutyReflux ratio
Low pressure column optimization
Mole percent of methanol
85.0 85.2 85.4 85.6 85.8 86.0 86.2 86.4 86.6 86.8 87.0
T01
Re
0.60
0.62
0.64
T02
Re
0.28
0.30
0.32
106 k
cal/h
r)
0.6
0.7
0.8
ratio
12
14
16
/hr) 1.01
1.02
Low pressure column optimization
p
eboi
ler d
uty(
1
0.4
0.5
Reflu
x r
8
10
boile
r dut
y(10
6 kca
l/
0.99
1.00
Re
0.2
0.3
2
4
6
85.0 85.5 86.0 86.5 87.0
Tota
l reb
0.96
0.97
0.98
(86.0, 0.9698)Mole percent of methanol
84.5 85.0 85.5 86.0 86.5 87.02
19
Mole percent of methanol
85.0 85.5 86.0 86.5 87.0
공정 최적화 (이론단수)
55
60High pressure column optimization
50
55
Low pressure column optimization
etic
al s
tage
s
45
50
55
etic
al s
tage
s
40
45
50
초기 투자비용 증가
mbe
r of t
heor
e
30
35
40
mbe
r of t
heor
e
25
30
35
32단 26단운전비용 증가
3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4
Nu
20
25
30
3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0Nu
15
20
25운전비용 증가
Reflux ratio Reflux ratio
20
공정 최적화 (Feed 유입단)
High pressure column optimization Low pressure column optimization
0.85
High pressure column optimization
0.9
Low pressure column optimization
06 kca
l/hr)
0.75
0.80
06 kca
l/hr)
0.7
0.8
boile
r dut
y(1
0.70
boile
r dut
y(1
0.5
0.6
Reb
0.60
0.65
(16, 0.5941)
Reb
0.3
0.4(9, 0.3050)
Feed tray location
4 6 8 10 12 14 16 18 20 22 24 26
Feed tray location
0 2 4 6 8 10 12 14 16 18 20 22
21
High-Low 배열 PSD 공정 최적화 결과
NH3 제거
Feed
378 kg/hr
NH3 제거0.5509 Mkcal/hr 0.3384 Mkcal/hr
MeOH 95.64 mole%DMC 4.16 mole%NH3 0.002 mole%
MeOH 93.6 mole% MeOH 86 mole%
#9
Hi h P 12 b L P 1 b
#16
High P=12 bar
#32
Low P=1 bar
#26MeOH 91.59 mole%
0 3050 Mkcal/hr
DMC 99 5 t% MeOH 99 5 wt%
0.5941 Mkcal/hr0.3050 Mkcal/hr
22
DMC 99.5 wt% MeOH 99.5 wt%
공정모사 결과 비교
Reference by H.M. Wei et al. High-Low configuration
High P (12 bar) Low P (1 bar) Hi h P (12 b ) L P (1 b )High P (12 bar) Low P (1 bar)
Nstage 32 26
Feed tray location 10 7
High P (12 bar) Low P (1 bar)
Nstage 32 26
Feed tray location 16 9
Product at Bottom 99.5 wt% DMC 99.5 wt% MeOH
Reboiler duty (Mkcal/hr)
0.5979 0.4531
y
Product at Bottom 99.5 wt% DMC 99.5 wt% MeOH
Reboiler duty (Mkcal/hr)
0.5941 0.3050(Mkcal/hr)
Total duty(Mkcal/hr)
1.0510
(Mkcal/hr)
Total duty(Mkcal/hr)
0.8991
Reference 보다 PRO/II를 이용한 High-Low 배열 최적화 시 14 4% 총 duty 감소 효과
23
Reference 보다 PRO/II를 이용한 High Low 배열 최적화 시 14.4% 총 duty 감소 효과
PSD 모델링 : Low(1 bar)-High(12 bar) 배열
NH3 제거
Low P=1 bar High P=12 bar
Feed
378 kg/hrM OH 95 64 l %
M OH 99 5 %
MeOH 95.64 mole%DMC 4.16 mole%NH3 0.002 mole%
DMC 99.5 wt%MeOH 99.5 wt%
24
공정 최적화 (Column spec. MeOH 조성)
Low pressure column optimization ) 0.50
0.55
)
0.62
T01 Reboiler dutyT02 Reboiler duty
Low pressure column optimization
0.50
0.55
22
24
Reboiler dutyReflux ratio
Low pressure column optimization
boile
r dut
y(10
6 kca
l/hr)
0.35
0.40
0.45
boile
r dut
y(10
6 kca
l/hr)
0.56
0.58
0.60y
06 kca
l/hr)
0.40
0.45
atio16
18
20
Mole percent of methanol
84.0 84.5 85.0 85.5 86.0 86.5 87.0
T01
Reb
0.20
0.25
0.30
T02
Reb
0.52
0.54
boile
r dut
y(1
0 30
0.35
0. 0
Reflu
x ra
10
12
14Mole percent of methanol
hr) 0.92
0.94
Low pressure column optimization
Reb
0.25
0.30
4
6
8
boile
r dut
y(10
6 kca
l/
0.88
0.90
Mole percent of methanol
84.0 84.5 85.0 85.5 86.0 86.5 87.00.20
84.5 85.0 85.5 86.0 86.5
Tota
l reb
0.82
0.84
0.86
(85.6, 0.8330)
25
Mole percent of methanol
공정 최적화 (Column spec. MeOH 조성)
0.34 0.22
T01 Reboiler dutyT02 R b il d t
High pressure column optimization
0 20
0.22
6Reboiler dutyReflux ratio
High pressure column optimization
oile
r dut
y(10
6 kca
l/hr)
0.31
0.32
0.33
oile
r dut
y(10
6 kca
l/hr)
0.16
0.18
0.20T02 Reboiler duty
06 kca
l/hr)
0.18
0.20
tio4
5
Reflux ratio
90.0 90.5 91.0 91.5 92.0 92.5 93.0
T01
Rebo
0.28
0.29
0.30
T02
Rebo
0.10
0.12
0.14
oile
r dut
y(10
0.14
0.16
Reflu
x ra
t
3
4 Mole percent of methanol
r) 0 47
0.48
High pressure column optimization
Rebo
0.12
1
2
oile
r dut
y(10
6 kca
l/hr
0.45
0.46
0.47
Mole percent of methanol
90.0 90.5 91.0 91.5 92.0 92.5 93.00.10
90 0 90 5 91 0 91 5 92 0 92 5 93 0
Tota
l reb
o
0.43
0.44
0.45
(91.4, 0.4373)
26
Mole percent of methanol
90.0 90.5 91.0 91.5 92.0 92.5 93.0
공정 최적화 (이론단수)
50
55Low pressure column optimization
45
High pressure column optimization
etic
al s
tage
s
40
45
50
etic
al s
tage
s
35
40
초기 투자비용 증가
mbe
r of t
heor
e
25
30
35
mbe
r of t
heor
e
25
30
28단 25단
운전비용 증가
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Nu
15
20
25
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8Nu
15
20운전비용 증가
Reflux ratio Reflux ratio
27
공정 최적화 (Feed 유입단)
High pressure column optimizationLow pressure column optimization
0.19
0.20
High pressure column optimization
1 0
1.2
Low pressure column optimization
06 kca
l/hr)
0.17
0.18
06 kca
l/hr)
0.8
1.0
boile
r dut
y(1
0 15
0.16
boile
r dut
y(1
0.6
Re
0.14
0.15
(15, 0.1355)
Re
0.4(10, 0.2924)
Feed tray location
4 6 8 10 12 14 16 18 20 22 240.13
Feed tray location
0 2 4 6 8 10 12 14 16 18 20 220.2
28
Low-High 배열 PSD 공정 최적화 결과
0 1217 Mk l/h
NH3 제거
0.2963 Mkcal/hr 0.1217 Mkcal/hr
MeOH 91.4 mole%
MeOH 85.6 mole%#10
MeOH 94 14 mole%
#15
Low P=1 bar
#28
High P=12 bar
#25
MeOH 94.14 mole%
0 1355 Mkcal/hr
Feed
378 kg/hrMeOH 95.64 mole%
C 6 %
DMC 99 5 wt%MeOH 99 5 wt%
0.2924 Mkcal/hr0.1355 Mkcal/hrDMC 4.16 mole%
NH3 0.002 mole%
29
DMC 99.5 wt%MeOH 99.5 wt%
Heat integration 적용 (Low-High 배열)
NH3 제거NH3 제거
MeOH 94.14 mole%
Feed
378 kg/hr378 kg/hrMeOH 95.64 mole%DMC 4.16 mole%NH3 0.002 mole%
Low P=1 bar High P=12 bar
DMC 99.5 wt%MeOH 99.5 wt%
T02의 Condenser duty만큼T01의 R b il 와 열통합
MeOH 99.5 wt%
30
T01의 Reboiler와 열통합
공정모사 결과 비교
High-Low configuration Low-High configuration
High P (12 bar) Low P (1 bar) L P (1 b ) Hi h P (12 b )High P (12 bar) Low P (1 bar)
MeOH at Top 93.6 mole% 86.0 mole%
Product at Bottom 99.5 wt% DMC 99.5 wt% MeOH
Low P (1 bar) High P (12 bar)
MeOH at Top 85.6 mole% 91.4 mole%
Product at Bottom 99.5 wt% DMC 99.5 wt% MeOH
Reboiler duty (Mkcal/hr)
0.5941 0.3050
Total duty(Mkcal/hr)
0.8991
Reboiler duty (Mkcal/hr)
0.2924 0.1355
Total duty(Mkcal/hr)
0.4279(Mkcal/hr) (Mkcal/hr)
0 3062 Mkcal/hr
High-Low 배열보다 Low-High 배열이 52.4% 총 duty 감소 효과
Heat integration 적용 시 65 9% 총 duty 감소 효과
31
0.3062 Mkcal/hrHeat integration 적용 시, 65.9% 총 duty 감소 효과
감사합니다감사합니다.
32