Experiences from the PDU Mats Galbe Department of Chemical Engineering Lund University Process Development Unit (PDU) PDU: lab and process equipment o Research in bench-scale, i.e., max size 100 litre fermentor vessel National facility placed at Lund University, mainly financed by the Swedish Energy Agency o Commissioned work for companies and universities o Internal research Purpose of a Process Development Unit Research Increased know-how Tests of new ideas Create models… • Lab scale Development Test of process configs. Optimisation Products & By-products • PDU • Pilot scale Verification Evaluation Test of methodology Final optimisation Data for scale-up • Industrial scale Process Development Unit (PDU) Steam pretreatment unit 10 litre reactor 160 - 230 °C Impregnation with H2SO4 or SO2 or other catalysts Main purposes Hydrolysis of hemicellulose Improve the enzymatic hydrolysis of cellulose Success: A number of units constructed & sold Pretreatment unit (small) •4-litre capacity •Jacket for less heat losses •Improved control of temperature •Surface-coated flash-off vessel Implemented in large reactor Steam pretreatment or acid hydrolysis? What do we actually mean? o Steam pretreatment renders a material suitable for further processing (e.g, by enzymatic hydrolysis) With or without catalyst (acid or base) o Acid hydrolysis (strong or dilute) ideally produces monomers that can be used without further treatment Dilute-acid hydrolysis • Dilute-acid hydrolysis: – Concentrations typically less than 2% – Temperatures 180-220°C – Residence time usually < 15 min – One- or two-step hydrolysis – Advantage: rather fast and simple – Drawback: results in degradation products -> may be difficult to ferment • Pentose sugars -> furfural • Hexose sugars -> HMF, formic and levulinic acid Acid hydrolysis of spruce One-step at two temperatures 30 Glucose [g/100g] Mannose [g/100g] Xylose [g/100g] 25 Total C6 Sugars Glucose [g/100g]2 20 Mannose [g/100g]2 Xylose [g/100g] Total C6 Sugars [g/100g DM] 15 10 5 0 2.6 2.8 3 3.2Combined Severity3.4 3.6 3.8 4 By-products in one-step acid hydrolysis using a temperature profile 8 HMF [g/100g] 7 Furf ural [g/100g] R² = 0.9756 Acetic acid [g/100g] 6 Levulinic acid [g/100g] Formic Acid [g/100g] Expon. (Levulinic acid [g/100g]) 5 Expon. (Formic Acid [g/100g]) R² = 0.9413 4 3 2 1 0 2.6 2.8 3 3.2 3.4 3.6 3.8 4 Steam pretreatment • Addition of a catalyst during pretreatment • Milder conditions than in acid hydrolysis – Acid results in hydrolysis of the hemicellulose • H2SO4, H3PO4, SO2 – Alkali mainly oligo- and polymers • NaOH, NH3 – Enzymatic hydrolysis (SHF) or simultaneous saccharification and fermentation (SSF) Different materials behave… …differently Agricultural materials – Wheat straw – Corn stover – Sugar cane bagasse – Sorghum (sweet/fibre) – Arundo donax – Rice straw – Hemp – Barley straw – Paja Brava Forest materials o Spruce o Pine o Poplar o Cypress o Salix PDU – International partner •Borregaard, Norway: Steam pretratment •Chemtex, Italy: SSF, steam pretreatment •Cargill, Germany: Steam pretreatment •Mitsui Engineering & Shipbuilding, Japan: SSF •Nagurjana Hills, India: SSF •NBE Sweden: Hydrolysis, analysis, fermentation •SGCC (State grid of China): Project and cooperation Currently •SEKAB: SSF, analysis building full- •Taurus: Pretreatment and fermentation scale plant in •… Italy •CTH •KTH •Brazil-EU: Partner in Cane Biofuel •NILE (EU): SSF, pretreatment (Partner) •University of Florida •University of Georgia •National Renewable Energy Labs (NREL), USA •… High-WIS applications (WIS: Water-Insoluble Solids) • High WIS is good… – Potentially higher sugar concentrations -> Higher ethanol concentrations -> Less energy requirements • …(or is it?) – Increased viscosity • Higher inhibitor concentrations • Less available liquid -> unfriendly environment • Heat transport affected! • pH control initially difficult • OPTIMISATION! Higher dry-matter concentrations o Terrafors (originally for solid-state fermentations) o Difficult to control pH o Mixing less efficient with increased liquefaction High-WIS hydrolysis quick tests Rotating with steel balls for mixing High-WIS (SHF or SSF) Test of equipment First test of enzymatic hydrolysis of spruce 100 Concentrations (g/L) 90 80 70 60 50 40 30 Cellobiose Glucose Xylose Galactose Arabinose Mannose 20 10 0 0 24 48 Hydrolysis time (hours) 72 96