Designed polymers for purification of flavor oils

Designed polymers for purification of flavor oils IFEAT Conference 2014 Rome, September 23, 2014 Ecevit Yilmaz, PhD Global Product Manager Industrial Resins MIP Technologies AB a subsidiary of Biotage AB Ecevit.Yilmaz@biotage.com 2014 Biotage 1

Overview of the presentation» The company» Separation techniques» Chromatography, adsorbents and selective separations» Case study: selective pesticide removal from lemon oil» Summary 2014 Biotage 2

About Biotage and MIP Technologies 2014 Biotage 3

Where we are Charlotte Uppsala Corporate headquarter Lund Cardiff Tokyo Shanghai Legend Sales office Production and R&D Nearly 300 employees ca 500 M SEK turnover 2014 Biotage 4

MIP Technologies Experts in polymeric adsorbents» Founded in 2000, Lund Sweden» Acquired by Biotage AB in 2010» Total of 12 chemists (9 PhD)» R&D team to develop novel adsorbents» Full analytical lab to test and QC» Pilot plant to scale-up and manufacture» Activities:» Polymeric adsorbents» Development of new adsorbents and applications» Problem solving service for customers:» High success rate (~ 75 %) in conducted projects» Worked with many of top 100 companies» ~ 15 years in the business 2014 Biotage 5

Overview of the presentation» The company» Separation techniques» Chromatography, Adsorbents and Selective separations» Case study: Selective pesticide removal from lemon oil» Summary 2014 Biotage 6

Separations and purifications» Separations/Purifications basically have 2 goals:» 1) to remove unwanted substances» Example: remove toxic or allergenic from complex mixtures» 2) to recover a desired substance» Example: extract a valuable compound from a mixture» Selectivity is the ability to distinguish one molecule from other molecules» Target compound» Other compounds etc» Adsorbent = Polymer = Resin 2014 Biotage 7

Separation techniques A few generic examples» Distillation» By volatility» Membranes /Filtration» By permeability 2014 Biotage 8

Separation techniques» Liquid/Liquid Extraction» By solubility» Precipitation / Re-crystallisation» By solubility 2014 Biotage 9

Column Chromatography By reversible surface interactions 10 mm Adsorbent 1 2 Typical adsorbent properties Particle size ~ 100 µm Pore size ~ 100 Å Pore volume ~ 0.5 ml/g Surface area ~ 500 m 2 /g Cross-linking ~ 50 % Ligand density ~ 0.5 mmol/g 2014 Biotage 11

Adsorbent surface landscape + + + + + + - O Reversed Phase Ionic/Polar Designed Imprinted Affinity Selectivity Non-selective materials (hydrophobic, ionic/polar): wide-spread general use. For difficult separations, selective materials are needed: Affinity, imprinted adsorbents, designed adsorbents... In general: non-selective materials are cheap, selective materials cost more Most affinity materials are fragile (biological molecules as ligands) 2014 Biotage 12

Potential of selective adsorbents» Resolution of difficult-to-separate compounds» Selective removal of unwanted contaminants» Targeted recovery or enrichment of valuable compounds» Cumbersome purifications with many or large columns» Replacing distillation or liquid-liquid extraction» Energy consumption, purity, contaminants» Avoiding undesired chemicals e.g. salts, flammable organic solvents or toxic chemicals» Green chemistry 2014 Biotage 13

Citrus flavor oils Extracted from the peel Important ingredient in» Food industry» Drinks industry» Fragrances» Etc Flavor oils may be contaminated with agricultural residues 2014 Biotage 15

Pesticides in lemon oil Toxic: similar to nerve agents (e.g. sarin) Many pesticides have a thiophosphoester moiety Present at ppm levels 2014 Biotage 16

Selective pesticide removal» Distillation and other standard unit operations cannot always remove the pesticides well» Pesticides and lemon oil constituents are chemically similar (e.g. vapor pressure)» Heat may influence aroma / taste profile» Standard adsorbents do not exhibit sufficient selectivity Development of a selective adsorbent to remove pesticides without affecting key aroma molecules 2014 Biotage 17

How to find the best adsorbent? Screen Material opt. Application Note ------ ------ Method opt. Adsorbent library 2500 candidates Hit Adsorbent Extraction Method 2014 Biotage 18

Adsorbent surface chemistries O Acidic/ Anionic OH O B OH OH O S O OH N O S O OH Basic/ Cationic H N N N + Cl- NH 2 N N Neutral/ hydrophilic N O O NH R NH O NH 2 OH Neutral/ hydrophobic N Adsorbents have combinations of chemistries 2014 Biotage 19

EA001 EA002 EA003 EA004 EA005 EA006 EA007 EA008 EA009 EA010 EA011 EA012 EA013 EA014 EA015 EA016 EA017 EA018 EA019 EA020 EA021 EA022 EA023 EA024 EA025 EA026 EA027 EA028 EA029 EA030 EA031 EA032 % Bound Outcome of a screening example Using the MIP Tech adsorbent library 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 Phase 2014 Biotage 20

Adsorbent design & optimisation» Material morphology» Pore size» Surface area» Pore volume» Bead size» Rigidity Surface chemistry Interaction design Ligand density Binding site design + - O 2014 Biotage 21

Optimised designed adsorbent Pesticide clean-up in one step Citrus oil containing pesticides RENSA 101 column 2014 Biotage 22

Selective pesticide removal GC-MS scan Selective extraction of pesticides without extracting vital matrix components 2014 Biotage 23

Unaffected color, flavor and aroma The cleaned-up lemon oil passed all sensory tests with no impact on the oil quality 2014 Biotage 24

Summary» Pressure from regulation will force raw material producers and users to evaluate new technologies» New agricultural residues or other contaminants» New knowledge about problematic natural constituents» Separation techniques have pros and cons» Distillation is versatile & established but energy demanding» Old techniques may be expensive and less efficient» Many techniques do not deliver sufficient selectivity» Choosing the right adsorbent + method may be a challenge» Novel adsorbents could improve or lead to new quality of essential oils and economics of processing 2014 Biotage 26

Thank you! www.biotage.com Email: ecevit.yilmaz@biotage.com 2014 Biotage 27