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Systematic Downstream Development, Optimization and Equipment Design for Biobased Products and Processes

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Systematic Downstream

Development, Optimization, and

Equipment Design for Biobased

Products and Processes

Andreas Bednarz, Bettina Rüngeler, Peter Scherübel, Markus Schmidt, Andreas Pfennig

[email protected]

Products, Environment, and Processes (PEPs) Department of Chemical Engineering

Université de Liège www.chimapp.ulg.ac.be

ProcessNet-Jahrestagung und 32. DECHEMA-Jahrestagung der Biotechnologen 12.-15.09.2016, Aachen, Germany

outline

challenges for biomass as feedstock

cascaded option trees

problems in downstream processing

example

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exergy as measure sorting the options

0 10 20 30 40 50 60 80 100 120 140 PA 6 .6 poly styr ene PET PVC poly prop ylen e poly carb onat e H2O, CO2 methanol glucose amylose ethanol glycerol lactic acid CO poly lact ic a cid poly ethy lene ethene plant oil coal crude oil

methane, natural gas

c h e m ic a l e x e rg y i n M J /k g hydrogen

fossil biomass intermediates products feedstock glucose fermentation net reaction conventional process

COH composition

+H2-H2O PE PLA H O

fossil raw materials bio-based feedstock conventional polymers bio-based polymers

lignin

starch, cellulosehemicellulose

glucose oleic acid natural gas crude oil coal C PET PHB water CO2 -CO2 -H2O

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challenges for biomass as feedstock

new processes, new chemistry

higher oxygen content

lower vapor pressure

higher viscosity

solids content

new thermodynamics

biotechnological steps

separate hydrophilic components from water

microbes act as solids

option 1 overall performance criterion 1 criterion 2 criterion 3 ... option 2 ... -0 + evaluation: not tested not feasible acceptable good

characterizing options

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general process flow sheet

-distillation -biocompatibility thermal stability product concentration 0 + + solvent extraction 0 + + + reactive extraction + + 0 0 crystallization 0 0 0 + extractant 1 0 equilibrium coalescence toxicity of auxiliaries + + + extractant 2 + -+ extractant 3

-cascading the tree

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evaluation of criteria

expert knowledge

literature information

modelling, simulation

experiment

... you name it

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basics of reactive extraction

0 1 2 3 4 5 6 7 8 9 0 20 40 60 80 100 d e g re e o f e x tr a c ti o n pH model experimental data , , organic phase: kerosene + X.X wt% D2EHPA 2.5 5.0 10.0 20.0 100.0 aqueous phase: 1.0 g/l 1,6-diamino hexane phase ratio: 1/1 temperature: 30°C

crud basics

crud

Crud:

Chalk River Undefined Deposit

corrosion residual unidentified deposit

S. Ruckes, A. Pfennig, 2010: Untersuchungen zum Einfluss von Mulm auf das Abscheideverhalten organisch-wässriger Stoffsysteme. AiF-Abschlussbericht zu Projekt 14997 N

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13 valve valve glas cylinders DN 80 x 300 internals tube DN 20 counter-rotating stirrers

top vessel

bottom

vessel

standardized lab experiment for settling

h

e

ig

h

t

sedimentation

zone

coalesced

disperse phase

principles of settling

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influence of solids in settling experiment

S. Ruckes, A. Pfennig, 2010: Untersuchungen zum Einfluss von Mulm auf das Abscheideverhalten organisch- wässriger Stoffsysteme. AiF-Abschlussbericht zu Projekt 14997 N

phase separation

6.0 6.2 6.4 6.6 6.8 7.0 7.2 0 100 200 300 400 500 600 700 s e p a ra ti o n t im e i n s pH organic phase:

kerosene + 20 wt% isostearic acid aqueous phase:

70 mM ammonium phosphate buffer 0.1 g/L 1,6-diamino hexane, 30°C phase ratio organic/aqueous:

4/1 2/1 1/2

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phase separation with cells

6.6 6.7 6.8 6.9 7.0 7.1 0 100 200 300 400 500 s e tt lin g t im e i n s pH organic phase:

kerosene + 20 wt% isostearic acid aqueous phase:

70 mM ammonium phosphate buffer 0.1 g/L 1,6-diamino hexane, 30°C phase ratio organic/aqueous:

4/1 2/1 without cells with cells

option trees

liquid-liquid extraction physical extraction reactive extraction

criterion 3: phase separation

kerosene criterion 2: extraction criterion 1: toxicity bis(2-ethylhexyl)-phtalate kerosene benzyl benzoate methyl laurate cis-9-octadecene-1-ol bis(2-ethylhexyl)-phtalate extractant DEHPA possible diluents:

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optimization criteria

bio-compatible pH

extractant concentration

capacity

p

H-shift between extraction and reextraction

phase separation

examples for different levels

overall process options

principal downstream options

unit operations

solvent selection

direction of dispersion

operating conditions like pH, phase ratio, etc.

type of equipment

...

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cascaded option trees

clear book-keeping of options

cascading through levels

allows very different character of evaluations

documentation

clear view of status also for communication

clear view of second-best alternatives

creates prototypes of procedures

intuitive to use

A. Bednarz, B. Rüngeler, A. Pfennig:

Use of Cascaded Option Trees in Chemical-Engineering Process Development Chem. Ing. Tech. 2014, 86(5), 611–620

Systematic Downstream

Development, Optimization, and

Equipment Design for Biobased

Products and Processes

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option tree method

choose starting level of detail - note all feasible options - note all relevant critical criteria - sort criteria by relevance

evaluate otpions and criteria, preferably most critical criteria first

at least one feasible option left? rank available options refinement required? step to next level of detail solution found no solution possible no no yes yes

some criteria for bio-downstream design

• extractant selection

• biocompatible physical-extraction system?

• partition coefficient in physical extraction

• biocompatible reactive extraction system.

reactive extractant, diluent/solvent, modifyer

• equilibrium without cells

• equilibrium with cells

• extraction kinetics

• ease of phase separation (column or mixer-settler or none)

• phase separation with cells

• ease of re-extraction (T or pH shift?)

• fate of reactants, minor components, impurities

• ...crud, choice of nutrient system, buffer system,...

• equipment design

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