Tutorial8:SLEofAcetone(1)+Ethanol(2)Q1a 200

UNIFACGroups 190
Acetone Ethanol Acetone Ethanol
Subgroup (1) (2) (1) (2) 180
CH3CO 1 0 T mi /K 178.45 159.05
1
CH3 1 1 fusH (T mi )/kJmol 5.774 4.931 170
CH2 0 1 /kgm3
L
910 894 Acetone crystallisation

T/K
S 3 160
OH 0 1 /kgm 965 1002 Ethanol crystallisation
1
M /gmol 58.08 46.07 Sapgir (1929)
3 1
150
R p V /m mol 3.638E06 5.554E06
1 1 Eutectic Temperature
Jmol K kPa c p /Jmol1K1 22.73 22.53 140
8.314 101.325 0 140.32
130 1 140.32
fus H pure,i Tmi SL c p pure,i 1
1 S c p pure,i T
L
S Vpure i P Patm
L
i exp ln


R T Tmi R Tmi RT
120
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1, z1
2 Te < T Tm 2 Te < T Tm 2
x1 1 x2 L2 1 Te < T Tm1
2 L 0 x1 x1e 2 0 x1 x1e x1
1 xi 1 L x1e < x1 1
T j 1 T j 1 1
4
i i
CalculationsassumingEthanolisthesolidphase CalculationsassumingAcetoneisthesolidphase
Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 2/ 2x2 Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
K K K K
159.05 0 1 1.000 1.000 0.6339 1 0.6339 1 159.05 0
154.82 0.096 0.904 1.000 1.000 0.5683 0.904 0.5683 0.904 154.82 0 103.16 0.096 0.904 1.000 1.000 0.0960 0.1781 0.096 0.1781 103.16 0
149.64 0.205 0.795 1.000 1.000 0.4944 0.795 0.4944 0.795 149.64 0 121.74 0.205 0.795 1.000 1.000 0.2050 0.3546 0.205 0.3546 121.74 0
147.36 0.25 0.75 1.000 1.000 0.4641 0.75 0.4641 0.75 147.36 0 127.37 0.25 0.75 1.000 1.000 0.2500 0.4251 0.25 0.4251 127.37 0
140.32 0.3784 0.6216 1.000 1.000 0.3784 0.6216 0.3784 0.6216 140.32 0 Eutectic 140.32 0.3784 0.6216 1.000 1.000 0.3784 0.6216 0.3784 0.6216 140.32 3E14
136.91 0.435 0.565 1.000 1.000 0.3411 0.565 0.3411 0.565 136.91 0 145.07 0.435 0.565 1.000 1.000 0.4350 0.7065 0.435 0.7065 145.07 0
125.20 0.603 0.397 1.000 1.000 0.2320 0.397 0.2320 0.397 125.20 0 157.09 0.603 0.397 1.000 1.000 0.6030 0.9548 0.603 0.9548 157.09 0
112.64 0.742 0.258 1.000 1.000 0.1445 0.258 0.1445 0.258 112.64 0 165.42 0.742 0.258 1.000 1.000 0.7420 1.1569 0.742 1.1569 165.42 0
96.77 0.865 0.135 1.000 1.000 0.0706 0.135 0.0706 0.135 96.77 0 171.96 0.865 0.135 1.000 1.000 0.8650 1.3337 0.865 1.3337 171.96 0
178.45 1 0 1.000 1.000 1.0000 1.5260 1 1.5260 178.45 0
Setequal

140.32 0.37843 0.62157 1.000 1.000 0.378426 0.621573 0.378426 0.621573 140.32 0 Eutectic 140.32 0.37843 0.62157 1.000 1.000 0.3784 0.621575 0.378427 0.621575 140.3213
Eutectic 1 2.09E08
1 L2 T Te & x1 x1e TEtOH TAc
2
1 L 2

Estimatedphasefractionsoncoolingasolutionofx 1=0.7from200Kto155K
Tosolvefortheeutecticpoint x1 wassetasthe"bychanging"variableinExcel'ssolver Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
andwasadjusteduntilthetemperaturecalculatedfrombothliquiduslinesagreed.This
K K
wasachievebyminimisingthesquareddifferenceofliquidustemperatures.The
temperaturewasinteratedduringthesolverminimisationbyenablingiterative 155.00 0.5710 0.4290 1.000 1.000 0.5710 0.907991 0.571033 0.907991 155 0
TAc 155 7.10211E15
2
calculationswithinExcel. The155Kisothermcrossesthecalculatedacetoneliquiduslineatx1 =0.5710.The
1 2
pointwasfoundusingExcel'ssolverbyiteratingthecompositionuntilthesquare
Initialcomp 0.7 0.3 differenceofthecalcualtedactoneliquidustemperatureand155Kwasminimised.

Pureacetonesolid 30.06% acetone xacetone acetone xacetone

L 69.9% S L 1 S
zacetone xacetone 1 xacetone
Tutorial8:SLEofAcetone(1)+Ethanol(2)Q1b 200

UNIFACGroups 190
Acetone Ethanol Acetone Ethanol
Subgroup (1) (2) (1) (2) 180
CH3CO 1 0 T mi /K 178.45 159.05
170
CH3 1 1 fusH (T mi )/kJmol1 5.774 4.931 Acetone Crystallisation

T/K
CH2 0 1 L
/kgm 3
910 894 160
Ethanol Crystallisation
OH 0 1 S/kgm3 965 1002
1
150 Sapgir (1929)
M /gmol 58.08 46.07 0 153.13
3 1 Eutectic Temperature
R p V /m mol 3.638E06 5.554E06 140 1 153.13
Jmol1K1 kPa c p /Jmol1K1 22.73 22.53
130
8.314 101.325

fus H pure,i Tmi S c p pure,i 1

120
1 S c p pure,i T S Vpure i P Patm
L L L

i exp ln
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1


R T Tmi R mi
T RT
x1, z1

2 Te < T Tm2 2 Te < T Tm 2

x1 1 x2 1 xi 1 Te < T Tm1
2 L 0 x1 x1e 2 L 0 x1 x1e T j 1 T j 1 1 x1
4 i i 1 L x1e < x1 1

CalculationsassumingEthanolisthesolidphase CalculationsassumingAcetoneisthesolidphase
Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 2/ 2x2 Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
K K K K
159.05 0 1 5.163 1.000 0.6339 1 0.1228 1 159.05 0
155.51 0.0960 0.9040 3.804 1.017 0.5788 0.9193 0.1522 0.9040 155.51 0 142.42 0.096 0.904 4.195 1.019 0.4027 0.6582 0.096 0.64622 142.42 0
153.13 0.1822 0.8178 2.984 1.061 0.5435 0.8675 0.1822 0.8178 153.13 0 Eutectic 153.13 0.1822 0.8178 2.984 1.061 0.5435 0.8675 0.1822 0.81785 153.13 0
152.60 0.2050 0.7950 2.811 1.077 0.5358 0.8562 0.1906 0.7950 152.60 0 154.88 0.205 0.795 2.777 1.076 0.5693 0.9054 0.205 0.84161 154.88 0
151.65 0.2500 0.7500 2.515 1.115 0.5223 0.8363 0.2077 0.7500 151.65 0 157.62 0.25 0.75 2.445 1.111 0.6112 0.9669 0.25 0.87031 157.62 0
148.70 0.4350 0.5650 1.713 1.374 0.4818 0.7762 0.2813 0.5650 148.70 0 163.85 0.435 0.565 1.642 1.342 0.7142 1.1166 0.435 0.83220 163.85 0
146.22 0.6030 0.3970 1.325 1.834 0.4495 0.7282 0.3392 0.3970 146.22 0 167.14 0.603 0.397 1.282 1.728 0.7732 1.2018 0.603 0.69554 167.14 0
142.66 0.7420 0.2580 1.139 2.568 0.4056 0.6626 0.3562 0.2580 142.66 0 169.99 0.742 0.258 1.114 2.272 0.8267 1.2787 0.742 0.56291 169.99 0
135.06 0.8650 0.1350 1.042 3.968 0.3219 0.5357 0.3088 0.1350 135.06 0 173.30 0.865 0.135 1.031 3.054 0.8918 1.3720 0.865 0.44933 173.30 0
178.45 1 0 1.000 4.490 1.0000 1.5260 1 0.33984 178.45 0
Setequal

153.13 0.1822 0.8178 2.984 1.061 0.5435 0.8675 0.1822 0.8178 153.13 0 Eutectic 153.13 0.1822 0.8178 2.984 1.061 0.5435 0.867466 0.1822 0.8178 153.1301 0
Eutectic 1 3.98E12
1 L2 T Te & x1 x1e
1 L TEtOH TAc
2
2

Estimatedphasefractionsoncoolingasolutionofx 1=0.7from200Kto155K
Tosolvefortheeutecticpoint x1 wassetasthe"bychanging"variableinExcel'ssolver Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
andwasadjusteduntilthetemperature calculatedfrombothliquiduslinesagreed.
K K
Thiswasachievebyminimisingthesquareddifferenceofliquidustemperatures.The
temperature wasinteratedduringthesolverminimisationbyenablingiterative 155.00 0.2066 0.7934 2.763 1.077 0.5710 0.907991 0.206646 0.843061 154.9997 1.82341E06
TAc 155 7.10E15
2
calculationswithinExcel.
1 2
The155Kisothermcrossestheacetoneliquiduslineatx1 =0.2066.Thepointwas
Initialcomp 0.7 0.3 foundusingExcel'ssolverbyiteratingthecompositionuntilthesquaredifferenceof
thecalcualtedactoneliquidustemperature and155Kwasminimised.
Pureacetonesolid 62.19%
L 37.8% acetone xacetone acetone xacetone
S L 1 S
zacetone xacetone 1 xacetone
Tutorial8:SLEofAcetone(1)+Ethanol(2)Q1c 200

UNIFACGroups 190
Acetone Ethanol Acetone Ethanol
Subgroup (1) (2) (1) (2) 180
CH3CO 1 0 T mi /K 178.45 159.05
170
CH3 1 1 fusH (T mi )/kJmol1 5.774 4.931 Acetone crystallisation

T/K
CH2 0 1 L
/kgm 3
910 894 160
Ethanol crystallisation
OH 0 1 S/kgm3 965 1002
1
150 Sapgir (1929)
M /gmol 58.08 46.07
3 1 Eutectic Temperature
R p V /m mol 3.638E06 5.554E06 140 0 156.94
Jmol1K1 kPa c p /Jmol1K1 22.73 22.53 1 156.94
130
8.314 25000

fus H pure,i Tmi S c p pure,i 1

120
1 S c p pure,i T S Vpure i P Patm
L L L

i exp ln
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1


R T Tmi R mi
T RT
x1, z1

2 Te < T Tm2 2 Te < T Tm 2

x1 1 x2 1 Te < T Tm1
2 L 0 x1 x1e 2 L 0 x1 x1e x1
1 xi 1 L x1e < x1 1
T j 1 T j 1 1
4 i i
CalculationsassumingEthanolisthesolidphase CalculationsassumingAcetoneisthesolidphase
Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 2/ 2x2 Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
K K K K
163.47 0 1 4.965 1.000 0.6620 1 0.1333 1 163.47 0
159.88 0.096 0.904 3.690 1.016 0.6047 0.9189 0.1639 0.904 159.88 0 144.46 0.096 0.904 4.129 1.018 0.3963 0.6195 0.0960 0.6084 144.46 0
156.94 0.2028 0.7972 2.763 1.073 0.5603 0.8557 0.2028 0.7972 156.94 0 Eutectic 156.94 0.2028 0.7972 2.763 1.073 0.5603 0.8557 0.2028 0.7972 156.94 0
156.89 0.205 0.795 2.748 1.075 0.5596 0.8546 0.2036 0.795 156.89 0 157.10 0.205 0.795 2.745 1.075 0.5627 0.8591 0.2050 0.7993 157.10 0
155.90 0.25 0.75 2.464 1.112 0.5452 0.8341 0.2212 0.75 155.90 0 159.89 0.25 0.75 2.420 1.110 0.6049 0.9192 0.2500 0.8284 159.89 0
152.77 0.435 0.565 1.692 1.365 0.5012 0.7711 0.2962 0.565 152.77 0 166.30 0.435 0.565 1.631 1.337 0.7097 1.0673 0.4350 0.7982 166.30 0
150.09 0.603 0.397 1.317 1.813 0.4655 0.7197 0.3536 0.397 150.09 0 169.72 0.603 0.397 1.278 1.716 0.7704 1.1526 0.6030 0.6716 169.72 0
146.29 0.742 0.258 1.135 2.523 0.4180 0.6510 0.3682 0.258 146.29 0 172.66 0.742 0.258 1.112 2.247 0.8252 1.2293 0.7420 0.5470 172.66 0
138.36 0.865 0.135 1.041 3.866 0.3296 0.5219 0.3166 0.135 138.36 0 176.03 0.865 0.135 1.030 3.006 0.8913 1.3215 0.8650 0.4396 176.03 0
Setequal 181.23 1 0 1.000 4.386 1.0000 1.4722 1.0000 0.3356 181.23 0

156.94 0.2028 0.7972 2.763 1.073 0.5603 0.8557 0.2028 0.7972 156.94 0 Eutectic 156.94 0.2028 0.7972 2.763 1.073 0.5603 0.8557 0.2028 0.7972 156.94 0
Eutectic 1 2 2.14E13
1 T T & x x
1 L 2 L TEtOH TAc
e 1 1e 2

Tosolvefortheeutecticpoint thecompositionx1 wassetasthe"bychanging"

variableinExcel'ssolverandwasadjusteduntilthetemperature calculatedfromboth Estimatedphasefractionsoncoolingasolutionofx 1=0.7from200Kto155K
liquiduslinesagreed.Thiswasachievebyminimisingthesquareddifferenceof Tj x1 x2 1 2 1 2 1/ 1 2/ 2 T j+1 1/ 1x1
liquidustemperatures. Thetemperature wasinteratedduringthesolverminimisation
K K
byenablingiterativecalculationswithinExcel.
156.94 0.2028 0.7972 2.763 1.073 0.5603 0.855676 0.202768 0.797232 156.9403 0

1 2
At 25MPathe155Kisbelowtheeutectictemperature thereforethereisonlysolid
Initialcomp 0.7 0.3
present.Therewouldbe70%solidpureacetone+30%solidpureethanol.The
appearanceofthissolidwouldberegionsofpureacetonesolid(62.37%)andandsolid
Pureacetonesolid 62.37% eutectic(37.6%).
SolidEutectic 37.6%
Tutorial8:SLEofAcetone(1)+Ethanol(2)Q1d
removeall;unitstemperatureKpressurePaenthalpyJ/molentropyJ/mol/Kvolumem3/molamountsmolviscosityPasthcondW/m/KsurtenN/mdiffusionm2/s;datumenthalpycompoundentropycompound;setfractions;puredataINFODATA;
componentsoverwrite1ACETONE2ETHANOL;chardataINFOCHARTBSOEREIDE;bipsetLGSTBIP1constanteosnone;modelMUNIFACPSRKUNIFACPSRK;modelMRKSAPSRKRKSAMCVSHIFTPSRKMUNIFACPSRK;modelMSTRAPVISCSPVISCLFIT;
modelMSTRAPPSPTHCOND;modelMLGSTMRKSAPSRKLGSTMRKSAPSRKLGSTBIP;modelSOLIDACETONEFREEZEOUTACETONEMRKSAPSRK;modelSOLIDETHANOLFREEZEOUTETHANOLMRKSAPSRK;pdGASgasMRKSAPSRKMRKSAPSRKMRKSAPSRKMSTRAPVISCMSTRAPPMLGSTMRKSAPSRK;
pdLIQUID1liquidMRKSAPSRKMRKSAPSRKMRKSAPSRKMSTRAPVISCMSTRAPPMLGSTMRKSAPSRK;keyLIQUID1not007732185;pdLIQUID2liquidMRKSAPSRKMRKSAPSRKMRKSAPSRKMSTRAPVISCMSTRAPPMLGSTMRKSAPSRK;keyLIQUID2not007732185;
pdWATERliquidMRKSAPSRKMRKSAPSRKMRKSAPSRKMSTRAPVISCMSTRAPPMLGSTMRKSAPSRK;keyWATER007732185;pdSOLIDACETONEcondensedSOLIDACETONE;pdSOLIDETHANOLcondensedSOLIDETHANOL;
unitstemperatureKpressurebarenthalpyJ/molentropyJ/mol/Kvolumem3/molamountsmoleviscosityPasthcondW/m/KsurtenN/mdiffusionm2/s;setphysprops1VCS;

200
190
Components
1 ACETONE 180
2 ETHANOL 170
160
Pressure 1.01325 bar
150

T/K
140 Series1
Phasewanted SOLIDACETONE 130 Series2
Thefixedphasefractionflash wasusedto
Phasewanted SOLIDETHANOL calculatetheliquiduslines 120 Sapgir (1929)
Propertywanted TEMPERATURE 110
100
Solid Solid
Acetone Ethanol 90
x1 x2 T Ac T EtOH 80
K K 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 1 155.80 x1, z1
0.096 0.904 151.17 152.46
0.1428 0.8572 151.17 151.17 Eutectic 8.97628E10 Comment:Themelting tempeartureofpureethanolisMultiflashis3.25Ktoolow
0.205 0.795 156.40 151.17
TEtOH TAc
2
0.25 0.75 158.88 151.17
0.435 0.565 164.26 151.17
0.603 0.397 167.01 151.17
0.742 0.258 169.54 151.17
Tosolvefortheeutecticpoint x1 wassetasthe"bychanging"variableinExcel'ssolver
0.865 0.135 172.69 151.17 andwasadjusteduntilthetemperaturecalculatedfrombothliquiduslinesagreed.
1 0 177.80 Thiswasachievebyminimisingthesquareddifferenceofliquidustemperatures.

Estimatedphasefractionsoncoolingasolutionofx 1=0.7from200Kto155K
x1 x2 T Ac
K
0.1850 0.8150 155.000 The155Kisothermcrossestheacetoneliquiduslineatx1 =0.1850.Thepointwas
TAc 155
2
6.79E25 foundusingExcel'ssolverbyiteratingthecompositionuntilthesquaredifferenceof
thecalcualtedactoneliquidustemperatureand155Kwasminimised.
1 2
Initialcomp 0.7 0.3 acetone xacetone acetone xacetone
S
zacetone xacetone 1 xacetone
Pureacetonesolid 63.19%
L 36.8% L 1 S
Tutorial8:SLEofAcetone(1)+Ethanol(2)Q1eandQ1f

Datasummary DeviationsfromSagpirdata
(1a) (1b) (1c) (1d) (1a) (1b) (1c) (1d)
Sagpirdata 1atm 1atm 25MPa 1atm 1atm 1atm 25MPa
idealliq UNIFAC UNIFAC MF idealliq Unifac Unifac MF
x1 T L/K T E/K T L/K T L/K T L/K T L/K (T T Sagpir)/K (T T Sagpir)/K (T T Sagpir)/K (T T Sagpir)/K
0 159.05 159.05 159.05 163.47 155.80 0.00 0.00 4.42 3.25
0.096 156.55 154.85 154.82 155.51 159.88 152.46 1.73 1.04 3.33 4.09
0.205 154.45 154.05 149.64 154.88 157.10 156.40 4.81 0.43 2.65 1.95
0.25 154.05 154.05 147.36 157.62 159.89 158.88 6.69 3.57 5.84 4.83
0.435 164.45 154.25 145.07 163.85 166.30 164.26 19.38 0.60 1.85 0.19
0.603 168.35 157.09 167.14 169.72 167.01 11.26 1.21 1.37 1.34
0.742 171.05 165.42 169.99 172.66 169.54 5.63 1.06 1.61 1.51
0.865 173.15 171.96 173.30 176.03 172.69 1.19 0.15 2.88 0.46
1 177.55 178.45 178.45 181.23 177.80 0.90 0.90 3.68 0.25
RMSdeviations 8.21 1.41 3.36 2.56

1e Therootmeansquared(RMS)deviationofthe1atmUNIFACmodel(part1b)fromtheexperimentaldataofSagpirandthereforemodelitbest.
Method1aperformstheworstwithdeviationsfromtheexperimentaldataalmostashighas20K.Howeveritperformsbetter,aswouldbe
expected,inthedilutelimits(whenx 1>0.9ofx 1<0.1).
ThepoormeltingtemperatureofpureethanolinMultiflash'sdatabaseseemstohaveasevereimpactoftheeutecticpointcalcualtionbut
thedataiscloselymatchedatx 1>0.4.

1f Themeltingtemperatureofpureacetoneincreases2.78Kandthemeltingtemperatureofpureethanolincreasesby4.42Konapressure
increasefrom1atmto25MPa
Atx 1=0.435theliquidustemperaturehasincreasedby2.45K.
Tutorial8:WaxyCrudeinMultiflashQ2

Part a (i) 57.676 C

(ii) 42.762 C
(iii) 66.404 C

Part b N33 0.07875

Partc
WaxPrecipitationCurveOutput

P=0.1013MPa P=5MPa P=50MPa

T /C Waxmass% T /C Waxmass% T /C Waxmass%
0 5.119 0 3.611 0 3.853
4 4.521 4 3.081 4 3.368
8 3.888 8 2.539 8 2.872
12 3.234 12 2.002 12 2.372
16 2.572 16 1.508 16 1.877
20 1.937 20 1.108 20 1.420
24 1.400 24 0.816 24 1.047
28 1.005 28 0.603 28 0.773
32 0.724 32 0.447 32 0.573
36 0.525 36 0.327 36 0.426
40 0.377 40 0.239 40 0.314
44 0.271 44 0.175 44 0.230
48 0.195 48 0.121 48 0.170
52 0.131 52 0.070 52 0.121
56 0.070 56 0.023 56 0.076
60 0.017 60 0.002 60 0.033
64 0.001 63.59 0.000 64 0.005
66.40 0 68 0.000
69.09 0

Wax Precipitation Curve

6.0
Waxmass%in(liquid+wax)

5.0

4.0
3.0 P=0.1013MPa

2.0 P=5MPa

1.0 P=50MPa

0.0
0 10 20 30 40 50 60 70
Temperature/degC