Solid Liquid Extraction

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Thomas Gamse, Graz University of Technology

CEEPUS Teaching Staff Mobility 2016 1

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

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

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Thomas Gamse, Graz University of Technology

from solid matrix

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Thomas Gamse, Graz University of Technology

food industry:

production of instant coffee

decaffeination of coffee and tea

production of flavour and fragrances

sugar production

pharmaceutical and cosmetic industry

edible oil production

active ingredients from natural materials

high quality fats from animal cadaver utilisation

environmental technology:

decontamination of soils

recycling of resources

....

mining, metallurgy:

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Thomas Gamse, Graz University of Technology

A = inert material

B = resource

C = solvent

solution = B + C

overflow = extract solution

= miscella

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Thomas Gamse, Graz University of Technology

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

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Thomas Gamse, Graz University of Technology

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

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Thomas Gamse, Graz University of Technology

thermal separation overflow (evaporation, distillation, crystallisation, …) mechanical separation of underflow (filter, centrifuge, …) thermal separation underflow (drying) Extract Condensation and Purification of Solvent Purification overflow Solid Residue Condensation Solvent

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Thomas Gamse, Graz University of Technology

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

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

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Thomas Gamse, Graz University of Technology

hydrocarbons (benzines, hexane, …)

benzene

sulphur hydrocarbons

ethyl ether

acetone

chlorinated hydrocarbons

alcohols (ethanol, isopropanol, ….)

water

solvent mixtures

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Thomas Gamse, Graz University of Technology

single step extraction process

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Thomas Gamse, Graz University of Technology

displacement process

extraction



separation overflow - underflow



next extraction of underflow

disadvantage

overflow concentration becomes lower step by step

Step 1 Step 2 Step 3

single step extraction process

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Thomas Gamse, Graz University of Technology

enrichment process

solvent in counter-current flow



high enrichment of extractable compounds in overflow



cascade operation

Step 1 Step 2 Step m Step n

displacement process

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Thomas Gamse, Graz University of Technology

separator

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Thomas Gamse, Graz University of Technology

1

2

3

1



2



3

2



3



1

3



1



2

1



2



3

….

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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:

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Thomas Gamse, Graz University of Technology

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

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

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CEEPUS Teaching Staff Mobility, 4.4. – 8.4.2016, University of Zagreb C A 0 1 1 B F D E O ve rflo_w (e xtr_ac t) X = B / (A + B + C) Y = C / (A + B + C) c a b

a ... constant underflow

b ... variable underflow

Right Angle Triangular Diagram

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Thomas Gamse, Graz University of Technology

0 X,Y = B / (B + C) 1 N = A / (B + C) F E D c b a

Ponchon - Savarit

-

Diagram

L = solution = B + C

N*L = amount of A

L*X, L*Y = amount of B

a ... constant underflow

b ... variable underflow

DE ….. tie line

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Thomas Gamse, Graz University of Technology

Thomas GAMSE

Ao.Univ.Prof.Dipl.-Ing.Dr.techn.

Institute of Chemical Engineering and Environmental Technology

Inffeldgasse 25/C, A-8010 Graz, Austria

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Thomas Gamse, Graz University of Technology

TUG

_{CEEPUS Teaching Staff Mobility, 25.5. – 29.5.2015, University of Zagreb}

Supercritical Fluid Extraction

many advantages

especially for natural plant materials

= oldest and industrial applied application of supercritical fluids

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

P T solid vapour liquid PTR T_TR PC TC

Supercritical

Fluid

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

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TUG

Gas T_C [°C] P_C [bar]  Explosive Limit [%vol] Ethene 9.21 50.32 0.085 2.7 - 34 Xenon 16.59 58.40 0.008 ---Fluoroform (R23) 25.74 48.36 0.260 ---Chlorotrifluoromethane (R13) 28.81 39.46 0.180

---Carbon Dioxide

31.04 73.81 0.225

---Ethane 32.27 48.80 0.099 3 - 12.5 Nitrous Oxide 36.42 72.45 0.165 ---Propene 92.42 46.65 0.144 2 - 11.7 Chlorodifluoromethane (R22) 96.15 49.71 0.221 ---Propane 96.67 42.49 0.153 2.1 - 9.5 Dichlorodifluoromethane (R12) 111.80 41.25 0.204 ---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 Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

Gas

Supercritical

Fluid

Liquid

Density [kg/dm

3

]

10

-3

0.3 – 0.9

1

Diffusion coefficient [cm

2

/s]

10

-1

10

-3

– 10

-4

10

-5

Viscosity [g/cm s]

10

-4

10

-4

– 10

-3

10

-2 Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

0 200 400 600 800 1000 1200 0 50 100 150 200 250 300 350 400 D ic h te [k g /m 3 ] Druck [bar] 0°C 40°C 60°C 80°C 100° KP Zwei- phasen-gebiet 31°C 20°C 80 bar 962,63 bei 0°C 828,80 bei 20°C 699,90 bei 31°C 281,33 bei 40°C 191,48 bei 60°C 160,04 bei 80°C 400 bar 1082,10 bei 0°C 1020,70 bei 20°C 989,01 bei 31°C 956,73 bei 40°C 890,55 bei 60°C 823,15 bei 80°C Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

0 10 20 30 40 50 60 70 80 90 100 0 1 2 3 4 5 6 extraction yield [% ] extraction time [h] CO₂amount [kg]

solubilit

y

diff

usion

p₁< p₂ < p₃ p₁ p₂ p₃ T₁< T₂ < T₃ T₁ T₂ T₃ Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

k

_s

= mass transfer coefficient [m/s]

a

_s

= specific interfacial area [m

2

/m

3

]

V

_t

= total bed volume [m

3

]



c

_m

= mean concentration gradient

E = k

_s

* a

_s

* V

_t

* c

_m Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

k

_s

= mass transfer coefficient [m/s]

Correlation of Sherwood – number

Sh = k

_s

* d / D

₁₂

= 2 + 1,1 * Sc

1/3

* Re

0,6

for 3 < Re < 3.000

Sc =



/ D

₁₂

Re = (v * D) /



E = k

_s

* a

_s

* V

_t

* c

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Thomas Gamse, Graz University of Technology

TUG

k

_s

can be influenced by diffusion coefficient D

₁₂

shorter diffusion length d

smaller particle size

higher specific interfacial area a

_s

E = k

_s

* a

_s

* V

_t

* c

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Thomas Gamse, Graz University of Technology

TUG

higher flow rates

higher velocity v

higher Re-number

larger c

_m

better mixing effect, up to fluidised bed

k

_s

can be influenced by diffusion coefficient D

₁₂

shorter diffusion length d

E = k

_s

* a

_s

* V

_t

* c

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Thomas Gamse, Graz University of Technology

TUG

Conventional Extraction Process

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

Flue Gas _Solvent

Impregnation Dyeing

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TUG

SFE Process

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

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Thomas Gamse, Graz University of Technology

TUG

_{CEEPUS Teaching Staff Mobility, 25.5. – 29.5.2015, University of Zagreb} -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 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 Entropie [kJ/kg*K] T e m p er at u r [ °C ] 1 2 3 4 5 6 7 8 P = con st. H = c_o n st_. -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 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 Entropie [kJ/kg*K] T e m p er at u r [ °C ] 1 2 3 4 5 6 7 8 P = con st. H = c_o n st_. EXTRACT

1

2

3

4

5 = 6, 7

8

1

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TUG

-30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 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] Tem p er at ur e [ °C ] 1 2 3 4 5 P = co nst . H =_co nst . EXTRACT 6

1

3

4 = 5,6

1

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TUG

extractors (600 L, 550 bar)

separators

INDIA

Spices and Herbs

Multipurpose plant 2 x 600 litres, 550 bar

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

CO

₂

condenser

CO

₂

storage tank

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Thomas Gamse, Graz University of Technology

TUG

GERMANY

Decaffeination of Tea

1988 turn-key, 3,000 t/a

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Thomas Gamse, Graz University of Technology

TUG

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TUG

1992 Turn-key, 10,000 t/a

ITALY

Decaffeination of Coffee

Applications Extraction Plants Fundamentals Design Criteria Combined Processes

Extractors:

3 x 21,5 m

3

325 bar

Washing Column:

p = 285 bar

D

_i

= 1,4 m

H = 22 m

Weight = 122 tons

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Thomas Gamse, Graz University of Technology

TUG

TAIWAN

Rice Treatment Plant

3 x 5,2 m

3

, 325 bar, Capacity 90 t per day

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Sesame Oil

South Korea 2003

3 x 2.500 litres

550 bar

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Thomas Gamse, Graz University of Technology

TUG

Cork Extraction

3 x 8.300 Litres

150 bar

15.000 kg/h CO

₂

San Vicente / Spain

Applications Extraction Plants Fundamentals Design Criteria Combined Processes

2005

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TUG

San Vicente / Spain

2010

3 x 10.500 Litres

150 bar

3 x 8.300 Litres

150 bar

15.000 kg/h CO

₂

2005

Cork Extraction

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Thomas Gamse, Graz University of Technology

TUG

Cork Extraction

Ceret / France

3 x 20.000 Litres

150 bar

2015

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Thomas Gamse, Graz University of Technology

TUG

Cork Extraction

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Thomas Gamse, Graz University of Technology

TUG

decaffeination of coffee and tea

100.000 t/a

hop extraction

60.000 t/a

pesticides from rice

30.000 t/a

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Removal of solvents

mainly for pharmaceutical products

including thermal sensitive substances

Attention

solvents may act as modifier



possible extraction of active compounds

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Dry Cleaning Systems

washing systems for

electronic industry (wavers, ...)

mechanical parts

clothes

operation in most cases with liquid CO

₂

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Carbonet

R

(LCO

2

) -

SEPAREX(FR)

Dry Cleaning Systems

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

SCCO

₂

degreasing unit

-

Chematur Eng. (SW)

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

LCO

₂

Dry Cleaning –

Alliance Laundry System(US)

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Usage of good transport properties of supercritical fluids

< viscosity, < surface tension

> diffusion coefficients

Advantage:

•

homogeneous distribution in solid matrices

•

no residual solvent after treatment

•

faster process

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Thomas Gamse, Graz University of Technology

TUG

•

long term pharmaceuticals

Impregnation of biodegradable polymer with drug

polymer

drug

SC-CO

₂ Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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Thomas Gamse, Graz University of Technology

TUG

dose without effect

toxical dose

time

dose rate

uniform concentration of drug over cross section



constant drug concentration over time

•

long term pharmaceuticals

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

•

treatment of old books

1

st

Step:

CO

2

– Extraction of degradation substances

2

nd

Step:

Impregnation of paper

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Denmark,

Start Up 2002

•

wood impregnation

•

treatment of old books

Volume: 3 x 8.000 l,

Capacity: 40.000 - 60.000 m

3

/ a

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Thomas Gamse, Graz University of Technology

TUG

Disadvantages of Conventional Dyeing Process with Water

agents for treatment of hydrophobic materials

drying process



energy intensive

large amount of waste water (100-150 liters/kg textile)

Advantages of CO

₂

-Dyeing

good penetration of dyestuff into the material

excess dyestuff can be reused

•

dyeing

•

wood impregnation

•

treatment of old books

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Thomas Gamse, Graz University of Technology

TUG

•

long term pharmaceuticals

•

dyeing

•

wood impregnation

•

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Thomas Gamse, Graz University of Technology

TUG

•

long term pharmaceuticals

•

dyeing

•

wood impregnation

•

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Thomas Gamse, Graz University of Technology

TUG

UHMW-PE

•

dyeing

•

wood impregnation

•

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Thomas Gamse, Graz University of Technology

TUG

170°C, 300 bar, 12 h impregnation time

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

170°C, 300 bar, 12 h impregnation time

Applications Extraction Plants Fundamentals Design Criteria Combined Processes Impregnation Dyeing

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TUG

Supercritical Fluid Extraction

industrial applied application

marketing essential for new products and extraction plants

competition with existing processes and plants

high pressure not common in most companies



convincing management



training of personal

Applications Extraction Plants Fundamentals Design Criteria Combined Processes

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Thomas Gamse, Graz University of Technology

ESS-HPT 2016

The European Summer School in High Pressure Technology

14 Days Intensive Course

3

rd

– 10

th

July 2016 University Maribor/SI

11

th

July 2016 Visit of NATEX Company, Transfer to Graz

12

th

– 17

th

July 2016 Graz University of Technology/A

Further Information:

Email: [email protected]

Deadline Registration: 29

th

April 2016

Costs (including accommodation and full board):

Universities: 1.400

€

Companies: 1 week:

2.000 €

2 weeks:

3.000 €

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.

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Thomas Gamse, Graz University of Technology

TUG

NATEX Prozesstechnologie GesmbH Werkstrasse 7, A – 2630 Ternitz, AUSTRIA Tel: +43 2630 32120 Fax: +43 2630 38163 E-mail: [email protected] Web: www.natex.at

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TUG

Thomas Gamse

Ao.Univ.Prof.Dipl.-Ing.Dr.techn.

Department of Chemical Engineering and

Environmental Technology

Inffeldgasse 25/C, A-8010 Graz

Tel: ++43 316 873 7477