Fractionations and separations of biochemicals and biomasses

Prof. Marjatta Louhi-Kultanen LUT Department of Chemical TechnologyTel. +358 40 7018078 marjatta.louhi@lut.fi

3 December 2012

Development thema

1. Isolation of new products2. New separation materials3. Pre-treatment of non-uniform

biomasses4. Novel ways to control separation5. New forces and external fields in

separation6. Hybrid processes7. Better modelling and simulation tools

Energy‐ and cost‐efficientselective separation process

(minimum wasteproduction)

Development of separation materials

− Novel separation materials are needed to o Reduce use of energy in separation− non-fouling materials, catalytic materials etc.− separation at extreme conditions, e.g. at extraction temperature

in biorefinerieso Improve selectivity of separation− selective separation technology (e.g. molecular recognition,

carrier facilitated membranes)− tailoring the separation material based on the product properties− modification of product propertieso Improve efficiency of separation− materials from poorer sources

Novel and sophisticated controllingmethods for separation processeso From real-time measurements to real

time control Reduced use of energy in separation

stages Efficient regeneration and washing of

separation matrixes (minimum washliquor consumption)

Longer life-time of separation materials Better possibilities to utilise and/or

combine different forces in separation Improved selectivity

o Facilitated separation e.g. by externalfields

Separation Technology Research at LUT Department of Chemical TechnologyApplications

− Energy- and material efficiency− Recycling of process waters (closed water circulations)− Cost-efficient media (adsorbents, membranes, etc.)

Separation technology− Adsorption, chromatographic separation and ion exchange

(affinities on surfaces)− Crystallization, precipitation (solubility/melting point)− Extraction (solubility)− Membrane separation (molecule size)− Solid-liquid separation (particle size)

Other: Advanced Oxidation Processes− Ozonation− Electric discharge technology− Wet oxidation

Adsorption, chromatography and ion exchange

time

concentration

wA wB

Recent projects− Removal of surfactants from water by

adsorption on polymeric adsorbents− Removal of fermentation inhibitors

from bioprocess solutions by adsorption− Recycling chromatography in acid–

sugar and glucose- galactoseseparation

− Rigorous modeling of adsorption phenomena

− Simulation and design of adsorption processes

Continuous ion exchange workstation

Crystallisation and precipitationFundamentals• Selection of: crystallisation method, 

crystallisation conditions, precipitant, etc.• Control of supersaturation• Solubility (pH, solution composition, 

temperature)Application examples• Precipitation of carbonates with CO2 (flue 

gas)• Melt crystallisation of fatty acids• Eutectic freeze concentration 

(simultaneous ice and salt crystallisation)

Research on crystallization at LUT

Solid‐liquid equilibrium 

Solubility of crystallisingcompound in different solutions at different 

temperatures

Solubility of polymorph and pseudopolymorph(hydrates/solvates) 

systems

Modeling of thermodynamics

Crystallisationprocesses 

Crystallisation kinetics (nucleation rate, crystal 

growth rate)  

Operational conditions: residence time, induction methods , temperature, chemical feeding  and 

mixing 

Solution composition: selection of reactants supersaturation control impurities and additives

Inline process monitoring and process control based on ATR FTIR and Ramanspectroscopy (PAT)

Inline particle size analysis based on laser reflection and video microscope 

(PAT) 

Characterisation of crystalline product

Crystal size and shapedistribution

Polymorphism and pseudopolymorphism(DSC, TG/DTA, Raman) 

Amorphism, crystallinity(DSC)

Down‐stream processing: filterability of crystallised

substances Filter cake washing

Fractionation of lignin and inorganic salts fromblack liquor

Inline precipitation of CaCO3 with CO2

CaCO3 precipitation in a continuous tubular reactor

CO2 (g)  Ca(OH)2 (s)+H2O

pH = 7‐8        T = 50 ºC p = 1‐3 bar pH = 7.5

pH = 5 pH > 11   PCC

CO2 (aq)          Ca2+< 1% stock 

t = t0 t = t1

pH = 11‐12

Hautaniemi et al. 2011

Precipitation of carbonates with CO2 in stirred tank

Bin et al. submitted• MgCO3 hydrates• CaCO3

MgCO3

The raw material has been treated with several chemical and enzymatic degradation methods to produce wood fluids.Waste produced by the process used in torrefaction.

BIOTULI –project

Product isolation and characterization in LUT Chemistry

BIOTULI –project

Process Steps

‐ wood fluids manufactured by hydrolysis or cultivation in pilot scale reactors

‐ solid and liquid materialsseparated

‐ liquids (permeates) filtrated with pilot‐scale instruments and membranes

‐ permeates analysed, fractionated and characterisedwith capillary electrophoresis

‐ identification with GC‐EI‐MS/MS, HPLC‐ESI‐MS and CE‐UV

Permeate

Concentrate

Feed

Isolation of antibacterial compounds.

On‐line system for manufacturing of wood based fluids.

Torrefaction from other biomasses than chips. 

Logistics of harvesting: Modelling of  logistics and material flows &trading .

BIOTULI –project

Results of the project

Estimation of costs in productivity  based on experimental data and  mathematic modelling.

MicrofiltrationMicrofiltration

UltrafiltrationUltrafiltration

Reverse osmosisReverse osmosis

0.10.1--0.2 0.2 µµm m

NanofiltrationNanofiltration 100100--150 g/mol150 g/mol

50 g/mol50 g/mol

1000 g/mol1000 g/mol

Algae

CryptosporidiumBacteria

Viruses

Giardia

Hardness

NOM and synthetic organic compounds

Pesticides

NaCl

Turbidity

Org. macromolecules

Sugars

HemicelluloseProteins

Suspended solids

Extractives

Org. acids

Peptides

H2O

Fractionation, purification and concentration

− Hemicelluloses− Oligomeric

carbohydrates− Sugars− Phenolic

compounds− Lignin− Organic acids

Membrane separation

Membrane separation

Minibatch filter CR350/5-filtration unit

Pilot device

Filtration of solid particles from liquids

Vacuum filtration (Büchner filter, drum filter) Pressure filtration (Nutsche, Larox PF)Centrifugal filtration, decanter centrifuge

Büchner Nutsche

Lignin filter cakes

Larox PF 0.1

Decanter centrifuge Centrifugal filter

Bioethanol from wastes: filtration of biomasses(non-hydrolysates)

+

Fractionations of black liquor by membraneseparation and crystallisation

Ultrafiltration

• Permeate

Acidprecipitation

• Motherliquor

Coolingcrystallization

• Motherliquor

Anti‐solventprecipitation

• Motherliquor

Nanofiltration

Retentate Lignin Inorganic Inorganic Productprecipitate crystals precipitate organic acids

Niemi et al. 2011

Hybrid separation processes

Production and recovery of monosaccharides from lignocellulose hot water extracts in a pulp mill biorefinery

Wood chips

1. Hot waterextraction

2. Ultrafiltration I

3. Ultrafiltration II 4. Acid hydrolysis

5. Chromatography XyloseMannoseGalactoseArabinoseGlucoseAcetic acidFurans

PolyphenolsHemicelluloses

Arabinose

Hydrolysis acid

Hemicelluloses

Solidsto cooking

Extract

Other research at LUT: Oxidation

Studied applications− Modification of chemicals by oxidation (lignin)− Treatment of permeates and extracts− Decomposition of fermentation inhibitors

PCD oxidation

• Pulsed Corona Discharge• Decomposition and modification of solutes

• Disinfection (cyanobacterium, bacterium coli)

• Chemical-free method

• Ultra-short gas-phase pulsed corona discharge(PCD) with a voltage pulse duration around100-200 ns generates OH-radicals in humid air:

ē + H2O = ē + ·H + ·OH

O (1D) + H2O = 2·OH

PCD reactor at LUT

PCD Oxidation

LIGNIN

− Lignin is composed of three monomers:

p‐Coumaryl alcohol  Coniferyl alcohol  Sinapyl alcohol

Modification of lignin by PCD oxidation

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Energy delivered, kWh/m3

Lignin Degradation by PCD and aldehydes formation

air lignin

oxygen lignin

alkaline lignin

oxygen aldehydes

air aldehydes

alkaline aldehydes

07/12/2012 28

Activated sludge process + nanofiltration: 10 mg/L DOC or BOD 15 PtCo units colour no UV absorbing compounds

Chemical oxidation to increase biodegradability of membrane concentrate

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Oxidation of aromatic substances in membrane concentrate

PCD oxidation improves filterability of wood extract

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VRF, -

PCD 60 minPCD 15 minPCD 0 min

Treatment  time5 kDa Psumembrane 

6‐fold fluxincrease

Summary

Biorefinary applications:− In future, it seems to be a great

need to develop energy- and cost-efficient and sustainable hybrid separation processes for new biochemical applications

− Recycling of solvents and chemicals

− In future probably multi-productfactories