Fractionation Technologies

1
Fractionation Technologies

• Forest Cluster Biorefinery Program
• Kick-Off Meeting, 25-09-08

2
Agenda

• Introduction (Sx)
• Scope of project application
• Objectives
• Tasks within subprojects elements to be
  considered
• Project plan
• Individual Presentations
• Discussion
• Pre-structuring of project elements presented
• To-do-list Homework for next meeting
• Summary, scheduling next meeting
• Closing

3
Scope of Project Application

• Ionic Liquid Aided Fractionation (ILAF)
• High Temperature Water Treatment (HITWAT)
• SeparationPurification of Hydroxyacids from
  Kraft Liquor (HOXY)

4
Objectives

• Drafting a high-level research application on
  Fractionation Technologies with emphasis on
  creating new knowledge embedded in a complete
  engineering concept.
• At the best, the necessary informations to
  develop commercial application in subsequent
  industrial research work should be provided.

5
Objectives

• For both ILAF and HITWAT two different targets
  should be pursued
• Preservation of polymeric structure of cellulose
  and other wood polymers POLY.
• Destruction of polymeric structure of wood
  components MONO.

6
Tasks within Process Chain

• An appropriate toolbox has to be established to
  comprise all necessary steps necessary for a
  complete process design as for example for the
  development of an IL suitable for selective
  dissolution of hemicelluloses

Solubility Parameters
Synthesis of IL
solute-solvent Interaction par
Kneader, Reactor System
design of stable selective solvent
Dissolution Parameters
shear forces, retent. time, heat transfer,..
Phase Separation
Analytical Methods
Recycling of Solvent
educt/productpurification
Functionalization
Others
Properties of Residue
Engineering Concept
Environmental Impact
Induced side reactions
Separation Technology
Dissolution Kinetics
7
Projectplan

• Project name
• Background, A5
• Product, process, business
• Connections to Forestcluster research strategy
• Results and connection to previous research
• Targets, 2A4
• Main target of the project
• Economical, technical targets
• Targets related to research content and
  competences
• Targets related to environment and to sustainable
  development
• Tasks and collaboration, 2A4
• Tasks to be accomplished that targets are
  obtained (?)
• Timetable, 1A4
• Main timetable when the planned targets are to be
  achieved (?)
• Project timetable for planned tasks (?)
• Ressources and organization, 1A5
• Steering group, coordinator, manager
  organization, parties (?)
• Cost and funding plan, 1A4
• Costs and funding plan (?)

Detailed Description/ Concepts??
8
Research Focus

• Herbert Sixta

9
Dissolution of Wood

• Certain ILs are able to dissolve wood
• bmimCl, amimCl blended with bnMIMCl
  transparent solution of milled wood is obtained
  80-130ºC, 4-10h1.
• DBU hydrogensulfate or bmimMeSO4 selectively
  dissolve lignin 100-120ºC, 2-24h2,3.
• DBUCl, OAc, others completely dissolve wood with
  only moderate mechanical pretreatment2.

1Kilpeläinen, I. et al. J. Agric.Food Chem, 2007,
55/22), 9142 2 DAndola G. et al. WO 2008/043837
A1, 2008, 3Pu, Y et al. J. Wood Chem And
Technol., 2007, 27, 23
10
Fractionation Concepts
A) Complete Dissolution of Wood (no focus) W
Sequential Polymer Fraction-ation with
Non-Solvent(s)
IL
wood
Mechanical pretreatment
Dissolution
Fractionation according to MW (hydrodynamic
volume) ? SEC
Homogeneous Functionalization of Wood Components
H
Monomers
Partially interested in cellulose fractionation
11
Fractionation Concepts
12
Depolymerization and Catalytic Conversions
Depolymerization to monosugars in aqueous
conditions is accompanied with severe side
reactions which can be largely avoided in
appropriate ionic liquids
13
High Temperature Water Treatment- HTW
14
HTW Properties

• At temperatures beyond 200ºC water changes its
  physical parameters significantly.
• Supercritical properties are attained at Tgt 374ºC
  and P gt 218 atm.
• HTW behaves more like a polar organic solvent. At
  the same the acidity of water expressed as the
  ion product (Kw) increases significantly

15
Lignin Pre-activation

• Short subcritical water treatment favors
  homolytic cleavage of b-O-4 linkages over
  recondensation reaction in a consecutive-type of
  reaction.
• Thus lignin solubility in organic solvents
  increases substantially while preserving
  carbohydrate yield.

16
Concepts of HTW Fractionation
A) Preservation of Carbohydrate Polymer
Structure (e.g. Pulp)

• Delignification
• alkaline extraction
• EtOH extraction
• ILs
• others

Wood
HTW 180 - 280ºC

• Membrane filtration
• Chromatographic
• Separation
• scrCO2extraction
• others

Pulp
Lignin
Fractionation

• Dissolution
• ILs
• others

Sugars extractives
17
Concepts of HTW Fractionation
B) Fragmentation to high-value added Lignin and
Carbohydrate products
Sugars M, Oligo
carbohydrates
Water soluble
Wood
HTW supercritical
HTW subcritical
Dehydrated LG, HMF, F
Fragmented C4,C3,C2
Water insoluble
R-OH soluble Lignin
lignin
R-OH insoluble Lignin

• Separation technologies
• membrane separation
• Filtration
• Extraction
• others

18
Annex
19
Aspen Wood Meal 1. Autohydrolysis at a LS
11 2. Intermediate Washing 3. Extraction for 4 h
with Dioxane Water 9010

• Steam/Water Treatment
• With increasing temperature at decreasing
  reaction times, the lignin solubility in organic
  solvents increases substantially while preserving
  carbohydrate yield.
• Lignin undergoes homolytic degradation reactions.
  
• The fragmentation reaction is highly favoured
  over the re-condensation reaction with increasing
  temperature.

J.H. Lora, M. Wayman, Tappi 1978, 61, 47-50.
20
HTW ? W Tunable Solvent

• Water is a tunable solvent by itself polymers,
  polymer degradation products are dissolved at HTW
  conditions and precipitate during cooling

aqueous solution
cooling
WOOD WATER
precipitate
homogeneous Dissolution reaction
separation
21
Contact adresses

• Herbert Sixta Herbert.sixta_at_tkk.fi      
• Klaus Niemela Klaus.niemela_at_kcl.fi
• Kleen Marjatta Marjatta.kleen_at_kcl.fi
• Raimo Alen ralen_at_cc.jyu.fi
• Jyri-Pekka Mikkola jpmikko_at_abo.fi
• Päivi Mäki-Arvela pmakiarv_at_abo.fi
• Ilkka Kilpelainen Ilkka.kilpelainen_at_helsinki.fi
• Adriaan Van Heiningen adriaan.vanheiningen_at_tkk.fi
• Ilkka Kruus Ilkka.kruus_at_danisco.com
• Matti Siika-aho Matti.siika-aho_at_vtt.fi
• Riitta Keiski Riitta.keiski_at_oulu.fi
• Outi Krause outi.krause_at_tkk.fi
• Kati Vilonen kati.vilonen_at_tkk.fi
• Vesa Karvonen Vesa.karvonen_at_lut.fi
• Mikka Mänttäri mika.manttari_at_lut.fi
• Hannu Ilvesniemi Hannu.ilvesniemi_at_metla.fi
• Ari Karki Finex ari.karki_at_finex.fi
• Ulf Hotanen Ulf.hotanen_at_upm-kymmene.com
• Jari Rasanen Jari.rasanen_at_storaenso.com