2016-04-06 Print Scriptum Gamse

Solid Liquid Extraction
Thomas GAMSE
Ao.Univ.Prof.Dipl.-Ing.Dr.techn.
Institute of Chemical Engineering and Environmental Technology

Graz University of Technology
Inffeldgasse 25/C, A-8010 Graz, Austria
CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb
Thomas Gamse, Graz University of Technology

CEEPUS Teaching Staff Mobility 2016 1
Solid Liquid Extraction (Leaching)
removal of extractable compounds

from solid matrix
by a liquid solvent


Applications
food industry: environmental technology:
production of instant coffee decontamination of soils
decaffeination of coffee and tea recycling of resources
production of flavour and fragrances

mining, metallurgy:
sugar production metal production of ores
edible oil production
....
pharmaceutical and cosmetic industry
active ingredients from natural materials ....
high quality fats from animal cadaver utilisation


Basics
underflow = wet solids
solution = B + C
A = inert material
B = resource
overflow = extract solution

C = solvent = miscella


Basics
requirements for solid-extraction
1.) preparation of extraction material:

milling, grinding, rolling, pelletising
2.) choice of solvent
3.) high concentration in overflow counter-current extraction
4.) solvent separation from overflow and underflow


Basics
requirements for high extraction velocity
1.) high temperature

lower viscosity of solvent and extract
higher solubility of extract in solvent
2.) short capillary paths
3.) high percolation velocity
4.) for multistep extractions

dripping zones for separation underflow - overflow
good efficiencies of single steps


Conventional Extraction Process
Flue Gas Solvent
Condensation
Solvent
Condensation and
Purification
of Solvent
thermal mechanical
separation separation of
underflow underflow (filter,
(drying) centrifuge, )
thermal separation overflow
(evaporation, distillation,
crystallisation, )
Purification
Solid Residue overflow
Extract


Basics
solvent requirements
1.) high solubility and high selectivity
2.) low specific heat capacity, low evaporation enthalpy

3.) non inflammable, no explosive mixtures with air
4.) non toxic
5.) non corrosive
6.) good penetration in solid matrix,

easy and complete removal from underflow
for food industry: no influence on taste and smell
7.) chemical and thermal stability

constant and not too high boiling temperature


Basics
important solvents
hydrocarbons (benzines, hexane, )

benzene
sulphur hydrocarbons
ethyl ether
acetone
chlorinated hydrocarbons
alcohols (ethanol, isopropanol, .)
water
solvent mixtures


Discontinuous Extraction
single step extraction process
only one extraction step separation overflow - underflow



displacement process
extraction separation overflow - underflow next extraction of underflow
Step 1 Step 2 Step 3
disadvantage
overflow concentration becomes lower step by step



displacement process
enrichment process
solvent in counter-current flow

high enrichment of extractable compounds in overflow
cascade operation
Step 1 Step 2 Step m Step n


Cascade Operation
separator
1 2 3


Cascade Operation
1 2 3
123
231
312
123
.




Continuous Extraction
percolation process
solvent passes through stationary solid bed

requirement: good percolation properties of solid material
advantages:
no mechanical treatment of solid material
self filtration effect
immersion process
total mixing of solvent and solid material
advantages:
no requirements for percolation properties
disadvantages:
no self filtration effect


Continuous Horizontal Extractor


Hildebrandt Extractor, Screw Extractor


Bonotto - Extractor


Bollmann - Extractor


Kennedy - Extractor


Rotocell Extractor, Carousel - Extractor


Rotocell Extractor, Carousel - Extractor


Lurgi - Extractor


Diagrams
C
Right Angle Triangular Diagram 1
a ... constant underflow
b ... variable underflow
Y = C / (A + B + C)
DE .. tie line D
O
ve
r
F
fl o
w
(e
xt
ra
ct)
E c
a
b
0 1
A X = B / (A + B + C) B


Diagrams
Ponchon - Savarit -Diagram
a ... constant underflow
b ... variable underflow E a

F
DE .. tie line
b
L = solution = B + C
N = A / (B + C)
N*L = amount of A
L*X, L*Y = amount of B
c
D 1
0 X,Y = B / (B + C)

Supercritical Fluid Extraction
Thomas GAMSE
Institute of Chemical Engineering and Environmental Technology

Inffeldgasse 25/C, A-8010 Graz, Austria

Fundamentals

Fundamentals
= oldest and industrial applied application of supercritical fluids
Design Criteria
many advantages
Extraction especially for natural plant materials
Plants
Applications
Combined
Processes
Impregnation
Dyeing
TUG CEEPUS Teaching Staff Mobility, 25.5. 29.5.2015, University of Zagreb

Critical Point, Supercritical Fluid

P
Supercritical
Fluid
Fundamentals
PC
Design Criteria
Extraction
solid liquid
Plants
Applications
PTR
Combined
Processes
vapour
Impregnation
Dyeing
TTR TC T

Critical Point, Supercritical Fluid
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Critical Parameters of Different Solvents

TC PC Explosive Limit
Gas [C] [bar] [%vol]
Ethene 9.21 50.32 0.085 2.7 - 34
Xenon 16.59 58.40 0.008 ---
Fundamentals Fluoroform (R23) 25.74 48.36 0.260 ---
Chlorotrifluoromethane (R13) 28.81 39.46 0.180 ---
Design Criteria
Carbon Dioxide 31.04 73.81 0.225 ---
Extraction Ethane 32.27 48.80 0.099 3 - 12.5
Plants
Nitrous Oxide 36.42 72.45 0.165 ---
Applications Propene 92.42 46.65 0.144 2 - 11.7
Combined Chlorodifluoromethane (R22) 96.15 49.71 0.221 ---

Processes
Propane 96.67 42.49 0.153 2.1 - 9.5
Impregnation Dichlorodifluoromethane (R12) 111.80 41.25 0.204 ---
Dyeing
Chloromethane 143.10 66.79 0.153 7.1 - 18.5
1-Butene 146.44 40.20 0.191 1.6 - 10
n-Butane 152.03 37.97 0.199 1.5 - 8.5

Physical Properties at different aggregation
Fundamentals Gas Supercritical Liquid

Fluid
Design Criteria
Density [kg/dm3] 10-3 0.3 0.9 1
Extraction
Plants Diffusion coefficient [cm2/s] 10-1 10-3 10-4 10-5
Applications
Viscosity [g/cm s] 10-4 10-4 10-3 10-2
Combined
Processes
Impregnation
Dyeing

Density Behaviour of CO2
80 bar 400 bar

1200
0C 1082,10 bei 0C
1000 962,63 bei 0C
Fundamentals 20C 1020,70 bei 20C
828,80 bei 20C
31C
800 989,01 bei 31C
Dichte [kg/m3]
Design Criteria
40C
699,90 bei 31C
60C 956,73 bei 40C
Extraction 600 80C
Plants Zwei- 100
890,55 bei 60C
phasen- KP
400 gebiet
Applications 281,33 bei 40C 823,15 bei 80C
Combined 191,48 bei 60C

Processes 200
160,04 bei 80C
Impregnation
Dyeing 0
0 50 100 150 200 250 300 350 400
Druck [bar]

Viscosity Behaviour of CO2
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Typical Trend of Extraction Lines
100
90
diffusion
80
Fundamentals extraction yield [%]
70
Design Criteria 60 p3
p2
50
Extraction T3 T2 p1
solubility
Plants 40
T1
Applications 30
20 T1 < T2 < T3
Combined
Processes 10 p1 < p2 < p3
Impregnation 0
Dyeing
0 1 2 3 4 5 6
extraction time [h]
CO2 amount [kg]

Extraction Yield
E = ks * as * Vt * cm
ks = mass transfer coefficient [m/s]
Fundamentals
Design Criteria as = specific interfacial area [m2/m3]

Extraction
Plants
Vt = total bed volume [m3]
Applications
cm = mean concentration gradient
Combined
Processes
Impregnation
Dyeing

Extraction Yield
Fundamentals
ks = mass transfer coefficient [m/s]
Design Criteria
Extraction Correlation of Sherwood number

Plants
Applications
Sh = ks * d / D12 = 2 + 1,1 * Sc1/3 * Re0,6 for 3 < Re < 3.000
Combined
Processes
Impregnation
Dyeing Sc = / D12 Re = (v * D) /

Extraction Yield
Fundamentals
ks can be influenced by diffusion coefficient D12
Design Criteria
shorter diffusion length d smaller particle size

Extraction
Plants
Applications higher specific interfacial area as

Combined
Processes
Impregnation
Dyeing

Extraction Yield
Fundamentals
ks can be influenced by diffusion coefficient D12
Design Criteria
shorter diffusion length d

Extraction
Plants
higher flow rates larger cm
Applications
Combined
Processes higher velocity v higher Re-number
Impregnation
Dyeing
better mixing effect, up to fluidised bed

SFE Conventional Extraction Process

Conventional Extraction Process
Flue Gas Solvent
Fundamentals Condensation
Solvent
Condensation and
Purification
Design Criteria
of Solvent
Thermal Mechanical
Extraction
Separation Separation of
Plants
Solid - Solid - Solution
Solvent (Filter,
Applications (Drying) Centrifuge, ) Thermal Separation
(Evaporation, Distillation,
Crystallisation, )
Combined
Processes
Impregnation Purification
Solid Residue Solution
Dyeing
Extract

SFE Conventional Extraction Process

SFE Process
Solvent
Recompression
Fundamentals
Recompression
Flue Gas Condensation
Design Criteria Solvent
Extraction
Plants Expansion of
Condensation and
Solid Residue
Purification
Applications of Solvent
Combined
Processes
Expansion
of Solution
Impregnation Solid Residue
Dyeing
Extract Purification

Pump Process
4 5 = 6, 7
100
90
80
.
Fundamentals n st 8
70
co
=
Design Criteria
60 4 P
Temperatur [C]
50 4
EXTRACT
40 8
Extraction
3
H=
Plants 30
con
8
3
s t.
20 6
Applications
10 1 5 7
2
Combined 0
Processes
-10
Impregnation -20
Dyeing 2 1
-30
0.7 0.8 0.9 1
1
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2
Entropie [kJ/kg*K]

Compressor Process
2
100
90 2
80
70
Fundamentals Temperature [C]
60
3 3
50 3
Design Criteria
40
st .
Extraction 30
con
Plants
20
1 1
P=
Applications 10 6 4 5 H
=
co
Combined
0
1 ns
t.
Processes -10
Impregnation
-20
4 = 5,6 1
Dyeing -30
0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2
Entropy S [kJ/kg*K] EXTRACT

Extraction Plants
INDIA Spices and Herbs

Multipurpose plant 2 x 600 litres, 550 bar
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing
separators
extractors (600 L, 550 bar)


Extraction Plants
Fundamentals
Design Criteria
CO2 condenser
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing
CO2 storage tank

Extraction Plants
GERMANY Decaffeination of Tea
1988 turn-key, 3,000 t/a
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
ITALY Decaffeination of Coffee
1992 Turn-key, 10,000 t/a
Fundamentals
Extractors:
3 x 21,5 m3
Design Criteria
325 bar
Extraction Washing Column:
Plants
p = 285 bar
Applications Di = 1,4 m
H = 22 m
Combined Weight = 122 tons
Processes
Impregnation
Dyeing

Extraction Plants
TAIWAN Rice Treatment Plant
3 x 5,2 m3, 325 bar, Capacity 90 t per day
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
3 x 2.500 litres
South Korea 2003 Sesame Oil
550 bar
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
San Vicente / Spain Cork Extraction
2005
Fundamentals
3 x 8.300 Litres
Design Criteria 150 bar
Extraction 15.000 kg/h CO2
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
2005
Fundamentals
3 x 8.300 Litres
Extraction 15.000 kg/h CO2
Plants
Applications
Combined
Processes 2010
Impregnation 3 x 10.500 Litres
Dyeing
150 bar

Extraction Plants
Ceret / France Cork Extraction
2015
Fundamentals
3 x 20.000 Litres
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Extraction Plants
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Applications
decaffeination of coffee and tea 100.000 t/a
Fundamentals hop extraction 60.000 t/a
Design Criteria
pesticides from rice 30.000 t/a
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Applications
Removal of solvents
mainly for pharmaceutical products

Fundamentals
including thermal sensitive substances
Design Criteria
Extraction
Plants
Attention
Applications
solvents may act as modifier
Combined
Processes
possible extraction of active compounds
Impregnation
Dyeing

Applications
Dry Cleaning Systems
washing systems for

Fundamentals
electronic industry (wavers, ...)
mechanical parts
Design Criteria clothes
Extraction
Plants
operation in most cases with liquid CO2
Applications
Combined
Processes
Impregnation
Dyeing

Applications

CarbonetR (LCO2) - SEPAREX(FR)
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Applications

SCCO2 degreasing unit - Chematur Eng. (SW)
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Applications

LCO2 Dry Cleaning Alliance Laundry System(US)
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Impregnation, Dyeing
Usage of good transport properties of supercritical fluids

< viscosity, < surface tension
Fundamentals > diffusion coefficients
Design Criteria
Extraction
Advantage:
Plants
homogeneous distribution in solid matrices
Applications
no residual solvent after treatment
Combined
Processes
faster process
Impregnation
Dyeing

long term pharmaceuticals

Impregnation of biodegradable polymer with drug
Fundamentals
Design Criteria
Extraction
Plants
polymer
Applications
Combined drug
Processes
Impregnation
Dyeing SC-CO2


Impregnation of biodegradable polymer with drug
uniform concentration of drug over cross section
Fundamentals constant drug concentration over time
dose rate
Design Criteria
toxical dose
Extraction
Plants
Applications
Combined
Processes
dose without effect
Impregnation
Dyeing
time


treatment of old books
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
1st Step: CO2 Extraction of degradation substances
Impregnation
Dyeing
2nd Step: Impregnation of paper


wood impregnation
Fundamentals
Design Criteria Denmark, Start Up 2002

Extraction
Plants
Applications
Volume: 3 x 8.000 l,
Combined
Processes Pressure: 170 bar
Impregnation
Dyeing
Capacity: 40.000 - 60.000 m3 / a


wood impregnation
Fundamentals
dyeing
Design Criteria
Disadvantages of Conventional Dyeing Process with Water

Extraction
Plants
agents for treatment of hydrophobic materials
Applications drying process energy intensive
Combined large amount of waste water (100-150 liters/kg textile)
Processes
Impregnation Advantages of CO2-Dyeing

Dyeing
good penetration of dyestuff into the material
excess dyestuff can be reused


wood impregnation
Fundamentals
dyeing
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing


wood impregnation
Fundamentals
dyeing Taipei, Taiwan, Startup 2014
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing


wood impregnation
Fundamentals
dyeing
impregnation of hip and knee endoprosthesis
Design Criteria
Extraction
Plants
UHMW-PE
Applications
Combined
Processes
Impregnation
Dyeing

Impregnation of Hip and Knee

Endoprosthesis
Impregnation of finished hip cups
170C, 300 bar, 12 h impregnation time
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Impregnation of Hip and Knee

Endoprosthesis
Impregnation of finished hip cups
170C, 300 bar, 12 h impregnation time
Fundamentals
Design Criteria
Extraction
Plants
Applications
Combined
Processes
Impregnation
Dyeing

Conclusion
Fundamentals
industrial applied application
Design Criteria
marketing essential for new products and extraction plants
Extraction
Plants
competition with existing processes and plants
Applications
high pressure not common in most companies

Combined
Processes
convincing management
training of personal

ESS-HPT 2016
The European Summer School in High Pressure Technology
14 Days Intensive Course
3rd 10th July 2016 University Maribor/SI
11thJuly 2016 Visit of NATEX Company, Transfer to Graz
12th 17th July 2016 Graz University of Technology/A
All participants have to present their research topic (10 min + 5 min discussion) and have to send
in advance an abstract (max. 4 pages) for the book of abstracts.
Costs (including accommodation and full board):

Universities: 1.400
Companies: 1 week: 2.000
2 weeks: 3.000
Deadline Registration: 29th April 2016

Further Information:
Email: Thomas.Gamse@TUGraz.at

NATEX Prozesstechnologie GesmbH

Werkstrasse 7, A 2630 Ternitz, AUSTRIA
Tel: +43 2630 32120 Fax: +43 2630 38163
E-mail: office@natex.at Web: www.natex.at

Thomas Gamse
Department of Chemical Engineering and

Environmental Technology
Inffeldgasse 25/C, A-8010 Graz
Tel: ++43 316 873 7477
Email: Thomas.Gamse@TUGraz.at


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Solid Liquid Extraction

Solid Liquid Extraction

Institute of Chemical Engineering and Environmental Technology

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction (Leaching)

removal of extractable compounds

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

food industry: environmental technology:

production of instant coffee decontamination of soils

decaffeination of coffee and tea recycling of resources

production of flavour and fragrances

high quality fats from animal cadaver utilisation

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

overflow = extract solution

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

requirements for solid-extraction

1.) preparation of extraction material:

2.) choice of solvent

3.) high concentration in overflow counter-current extraction

4.) solvent separation from overflow and underflow

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

requirements for high extraction velocity

1.) high temperature

2.) short capillary paths

3.) high percolation velocity

4.) for multistep extractions

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

Flue Gas Solvent

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

1.) high solubility and high selectivity

2.) low specific heat capacity, low evaporation enthalpy

6.) good penetration in solid matrix,

7.) chemical and thermal stability

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

hydrocarbons (benzines, hexane, )

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

single step extraction process

only one extraction step separation overflow - underflow

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

single step extraction process

Step 1 Step 2 Step 3

CEEPUS Teaching Staff Mobility, 4.4. 8.4.2016, University of Zagreb

Thomas Gamse, Graz University of Technology

Solid Liquid Extraction

single step extraction process

solvent in counter-current flow