solvent cycle, methods for solute precipitation heat and mass transfer: high pressure chemical...
TRANSCRIPT
![Page 1: Solvent Cycle, Methods for Solute Precipitation Heat and Mass Transfer: High Pressure chemical Engineering I (WS) Chapter 7](https://reader035.vdocuments.us/reader035/viewer/2022062515/56649d135503460f949e7ca8/html5/thumbnails/1.jpg)
Solvent Cycle,
Methods for Solute Precipitation
Heat and Mass Transfer:
High Pressure chemical Engineering I (WS)
Chapter 7
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Flow Scheme of a Solvent Cycle
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Solvent Cycle Steps:
separate the extract from the solvent (1),
clean the solvent for reuse (2),
remove the solvent from raffinate (3),
adjust composition of solvent mixture (if applicable) (4).
Solvent Cycle
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Single stage Multiple stage Counter- Chromato- (precipitation) current graphic
SFE Modes of Operation
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Extraction From Solids
S t S / F
Essential oils (5 %) 20 < 1 > 20
Edible oils (2 %) 40 < 1 40
Coffee decaffeination (0.01 %) 200 5 40
Black tea decaff. (0.01 %) 230 1.5 150
Total amount of solvent S, kg/kgF
Extraction time t, h
Solvent to Feed Ratio S/F, kgS /(kgF h)
Basis:
Solvent: Carbon dioxide
10 - 30 MPa, 330 K
Solvent Cycle: Solvent to feed ratio of SFE processes
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Countercurrent Separation
V/L v S / F
FAEE, FAME (5 %) 20 7.5 125
FFA (fatty acids) (2 %) 50 4.5 50
Squalene (1.5 %) 20 10 50
Tocopherol-Purif. (2.5 %) 35 20 45Solvent ratio V/L, kg/kg
Reflux ratio v, -
Solvent to feed ratio S/F, kgF /kgF
Basis:
Solvent: Carbon dioxide
10 - 30 MPa, 350 K
Solvent Cycle: Solvent to feed ratio of SFE processes
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Chromatographic Separation
Pr tr S / F
DHA / DPA 1.5 15 900 x 103 EM
Phytol-isomers 10- 30 6 900 EM 200 SMB
Productivity Pr, gP /(kgStPh h)
Retention time, min
Solvent to feed ratio S/F, kgF /kgF
Basis:
Solvent: Carbon dioxide
10 - 30 MPa, 310 K
Solvent Cycle: Solvent to feed ratio of SFE processes
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
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300 400 500 600 700 800 90010
100
1000
T = 313 K
T = 318 K
T = 333 KSol
ubili
ty [
mg/
kg C
O2]
Density [kg/m3]Birtigh, Brunner, Johannsen
Solubility of Caffeine in CO2
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Gas Circuit in the Compressor Mode
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Compressor Process, Throttling Sub-Critical
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Compressor Process, Throttling Super- Critical
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Pump Process
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Pump Process, Throttling, Sub-Critical
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Pump Process, Throttling Super- Critical
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Extraction temperature: 313 K
Energy Consumption by Various Solvent Cycles
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Mechanical EnergyThermal energy inThermal energy out
Pump with heat recovery
Pump without heat recovery
Compressor with heat recovery
Compressor without heat recovery
Ex
tra
cti
on
pre
ss
ure
[M
Pa
]
Energy [kJ/kg]
Energy needed for the gas cycle
70 kJ/kgCO2
95 kJ/kgCO2
for S/F 125 kg/kg:
8750 kJ/kgFeed
11875 kJ/kgFeed
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Reduction of pressure or density (temperature)
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
Modes For Product Recovery
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Brunner 1983
Solubility in a Gas With a Modifier (Entrainer)
Influence of temperature
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Data by:Gährs 1984Ebeling, Franck 1984Johannsen, Brunner 1994
Solubility of Caffeine in CO2
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
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Gährs 1984
Anti-Solvent: Solubility of Caffeine in CO2
Influence of nitrogen
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
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PC
WT2
1
PC
P1
B1
RV3
PC
WT1 K1
RV1
RV2
M1
18 MPa323 K
P = 2 MPa
Coupling with a Membrane Unit
Solvent Cycle With Membrane Separation
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GKSS-membrane (organic, active dense layer)
CO2
OC
Permeate
Retentate
1.86 wt.-%
< 0.06 wt.-%
p = 2.0 MPa
active dense layer
1.5 mole CO2
kg/(m2 h)
P = 18 MPa, T = 323 K
Separation by Membranes
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Solvent Cycle in a T,s - Diagram
Extraction/separation
Precipitation athigh p
Precipitation atlow p
Compressor mode
Entropy
Te
mp
era
ture
CO 2
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53 kJ/ kgCO2
21 kJ/ kgCO2
7.6 kJ/ kgCO2
1
2
3
Wie in 2Like in 2
Energy For Different Solvent Cycles
Pump-Cycle
Compressor-Cycle
Membrane-Cycle
Sartorelli 2001
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
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0 100 200 300 400 500 600 700 800
Y [mg/kg CO 2]
0
0.1
0.2
0.3
0.4
0.5X
[k
g/kg
AC
]
T=318 KP=13 MPaP=20 MPaP=30 MPaP=13 MPa LangmuirP=20 MPa LangmuirP=30 MPa Langmuir
Adsorption of Caffeine on Activated Carbon
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Silica with 52% loading,loaded by high pressure
adsorption
Silica with 50% loading, loaded by mixing,
conventional process
Recovery of Tocopherolacetate by Adsorption
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200 250 300 350 400 450 500 550 600
40
45
50
55
60
autoclave: 333K, 20MPafixed bed adsorber: 353Kflow: 20g
solvent/min
feed in autoclave: TA ca. 97 wt.-% TA ca. 73 wt.-%
Load
ing
of a
dsor
bate
[wt.-
%]
Density CO
2
[kg/m3]
Recovery of Tocopherolacetate by Adsorption
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
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100 1000 10000
10
100
1000
P = 19 MPa
T = 343,1 K
T = 323,1 K
P = 28 MPa
T = 343,1 K
Caf
fein
e Lo
adin
g in
SC
F P
hase
[mg/
kg]
Caffeine Loading in Water Phase [mg/kg]
Phase Equilibrium Caffeine - Water - CO2
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Reduction of pressure or density
Anti solvent
Membrane separation
Adsorption
Absorption
De-Entrainment
......
Modes For Product Recovery
![Page 35: Solvent Cycle, Methods for Solute Precipitation Heat and Mass Transfer: High Pressure chemical Engineering I (WS) Chapter 7](https://reader035.vdocuments.us/reader035/viewer/2022062515/56649d135503460f949e7ca8/html5/thumbnails/35.jpg)
Brunner 1983
Solubility in a Gas With a Modifier (Entrainer)
Influence of temperature
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0 0.05 0.1 0.15 0.2 0.25 0.3
mwater / mtotal
00.10.20.30.40.50.60.70.8
toco
chro
man
ol fr
actio
n
in fl
uid
phas
e [m
ass%
]
solubility tocochromanol in CO2
Figure 4:Tocochromanol fraction in SCF phase as function of the total water fraction
Birtigh
De-Entrainment
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Generalization of Precipitation: Membership - Functions
Temperature at the Swimming Pool
T [oC] x25 35 450
1
(x)
„Hot“Not yet hot Too hot
(x): relative number of statements from people at the pool
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0 1 2
0.1 0.5 0.9 0.2 0.9 1.6
1 4 7
Molar weight solute [kg/mol]
Loading
Reduced Pressure
Residence time [min]
fluid phase [wt%]
0.0
0.5
1.0
0.0
0.5
1.0
0 1 20.0
0.5
1.0
0.0
0.5
1.0
0.0
0.5
1.0
1 4 70.0
0.5
1.0
0.0 0.5 1.00.0
0.5
1.0
Inlet loading
Solubility in separator1 10 100
0.0
0.5
1.0
2
0 3 60.0
0.5
1.0
Inlet loading
Solubility in extractor
Birtigh
Membership Functions P Adsorption Membrane
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Solubility of solute
Residence time
Solvent ratio
0.0 0.1 0.2
Absorbent
0.0 0.05 0.100.0
0.5
1.0
0.0 0.05 0.10.0
0.5
1.0
0.0
0.5
1.0
0.0 0.05 0.1
in water [g/g]
0.0
0.5
1.0
0.0 0.5 1.0
Inlet loadingSolubility in Separator
1 10 1000.0
0.5
1.0
21 10 1000.0
0.5
1.0
2 1 10 1000.0
0.5
1.0
2
TSeparator
TDecomposition
0.0
0.5
1.0
0.0 0.2 0.4
0 3 60.0
0.5
1.0
0 3 60.0
0.5
1.0
0 3 60.0
0.5
1.0
0 3 60.0
0.5
1.0
0.0
0.5
1.0
0.0 0.1 0.20.0
0.5
1.0
Reduced pressure
1 3 50.0
0.5
1.0 if only 1 phase in Extractor
0.0
0.5
1.0
0.0 0.2 0.4
[min]
if 2 phases in Extractor
Absorption De-Entrain T T
Birtigh
Membership Functions