COST FP0901 meeting Current needs in biorefinery analytics WG 3: Process Residues Requirements for characterization of biorefinery residues Ina Körner 1, Ron Janzon 2, Helmut Adwiraah 1, Jörn Heerenklage 1, Tim Sieker 3, Bodo Saake 2 1) Hamburg University of Technology (TUHH) Institute of Environmental Technology and Energy Economics (IUE) Bioconversion & Emission Control Group 2) Johann Heinrich von Thünen-Institut (vti) Institute of Wood Technology and Wood Biology 3) University of Kaiserslautern Department of Mechanical and Process Engineering Institute of Bioprocess Engineering
Overview 1. Biorefineries 2. Goals of characterization 3. Characterization requirements & methods 4. Summary & conclusions
Biorefineries: Principle setup thermal energy production Bioresource Pre- Incineration Pyrolysis Post- energy products treatment mechanical biological Gasification biological energy production treatment mechanical biological material products physical Biomethane physical chemical Bioethanol chemical combinations Biohydrogen combinations combinations
Substrates for biorefineries 1 st Generation Feeding beet, wheat, rye, maize (grain, whole plant, silage) 2 nd Generation Common forestry wood Fast growing wood Straw Waste Mixed Municipal waste Source separated organic waste Agricultural waste Green lignocellulosic waste
1st Generation Biorefineries: Wheat-to-Bioethanol-Biorefiniery Water corn Mashing α-amylase Liquefication straw Grain Hydrolysis Glucoamylase Energy / Lignocellulose Bioreffinery Milling/Sieving Glucose Fermentation to Ethanol CO 2 Destillation DDGS=Dried distillers grain with solubles DDGS Ethanol
2st Generation Biorefineries: Lignocellulose-to-Bioethanol-Biorefiniery Wood Lignin fraction Sieving and chipping Steam pretreatment Washing with water component separation Alkaline extraction Fibers with cellulose & lignin Extract with hemicelluloses (Furfural, 5-HMF) Hydrolysis residue (Lignin, Lignin carbohydrates, extractives) Enzymatic hydrolysis Enzymatic hydrolysis Glucose Xylose Energy generation humus products Fermentation to ethanol + fermentation residue, CO 2
Waste Biorefineries Biowaste-to-Biogas Biorefinery Emissions, Residues Heat, Electricity Biobin- Anaerobic dry Natural gas substitute Waste fermentation Biogas e.g. Bioconversion processes into a methane-rich biogas Digestate = Residue Emissions, Residues Liquide fertilizers Tailor-made composts pellets Solid mineral fertilizers
Civilisation Biorefinery Complex of biorefineries for utilization of regional bioresources Bioresource generation & collection within a region Municipal Waste Leaves Bio-bin waste Waste wood Park waste Agricultural Waste Straw Manure Renewable organic resources Grain Wood Algae Biorefinery A Biorefinery B... Biorefinery Y Biorefinery X Energetic Products Electricity Heat Fuel Material Products Materials Humus Fertilizer Product distribution & utilisation
Characterization Goals Process Design Develop process steps for transformation of solid, liquid, gaseous residues into products Design intermediate and final product storage systems and distribution systems Process and Product Control Ensure stabile and efficient run of all technological steps Ensure suitable residue qualities for further transformation, utilization or disposal
Characterization requirements Input-Output characteristics of anaerobic fermentation FM FreshMatter DM Dry Matter 100 % FM DM: 35% FM Ash: 42% DM Biowaste 100% batch-dry fermentation percolation water digestate 80% 80% FM DM: 39% FM Ash: 50% DM fluid digestate 10% FM biogas 90 m³/mg FM Air or post composting Heat drying 100% Mass Balance compost overflow 40% FM 15% FM Ash Organic H 2 O impurities 2% FM biomass fuel 50% FM are most important parameters 0% Biowaste Biowaste Digestate Digestate Biogas & Digestate Digestate
Characterization Requirements Input-Output characteristics of Bioethanol-Process 100 % DM Pulp: 59 % DM Carbohydrates: 51,7 % DM Water Addition 100 % DM Carbohydrates: 65 % DM Wood 100% Pretreatment Fermentation (SSF) CO 2 Ethanol Lignin (13 % DM) Hemicellulose Fraction (28 % DM) Residue Composition lignin, (ash), unhydrolysed, unfermented carbohydrates added water microbial biomass Ethanol: 15 % DM 25 g/l Residue Anaerobic Fermentation to Biogas Water & organic content are most important parameters SSF: Simultanious saccarification and Fermentation
Basic measurements Methods for Products: Biogas (Volume; CH 4 ; CO 2 ) Ethanol Well established Methods for Residues: Water Ash / organics Fist -method suggested in composting guidelines Material with optimal moisture content Material too dry Main Problems - Laboratory: Inhomogenity Sampling Sample Storage Sample Preparation Material too wet Main Problems - Practice: Easy Quick Cheap Various Digestates BUT: Less exact
Special Measurements: Component Analytics Carbohydrate & lignin determination used in wood science Sample is hydrolysed by a 2-step procedure with H 2 SO 4 Wood monosaccharids are detected by HPLC Hydrolysis residue (lignin) is determined gravimetrically 450 mau 300 200 Mannose Glucose [%] 50 40 30 43,2 55,0 39,7 Wood-Mix Poplar Greenwaste-Mix 32,8 37,7 100 Rhamnose Arabinose Arabinose Galaktose Xylose -50 min 0,0 10,0 20,0 30,0 40,0 4-O-Me 20 10 0 5,7 15,8 9,0 11,6 3,4 3,7 23,2 Glucose Xylose Mannose Lignin HPLC-Chromatogram of a wood-mix Components in various samples
Special Measurements: Component Analytics Van Soest analysis used in waste science Separation of the two fraction: by neutral and an acid detergents: - neutral detergent (Na-lauryl sulfate + ethylenediaminetetraacetic acid, ph =7.0) - acid detergent (cetyl trimethyl ammonium bromide in 1 N H 2 SO 4 ). solubles NFC Starch Sugar ß-glucans Sample + neutral detergent solubles insolubles NDF + acid detergent insolubles NDF: Neutral Detergent Fiber NFC: Not-Fiber-Carbohydrates ADF: Acid Detergent Fiber ADIN: Acid Detergent insoluble nitrogen AIA: Acid insoluble ash ADL: Acidic Detergent Lignin Hemicelluloses ADF Kjeldahl H 2 SO 4 /KMnO 4 Calculation of differences ADIN Ashing AIA ADL
Special Measurements: Component Analytics Raw materials Waste Van-Soest Analysis Wood Classic Wood Analysis Residues Formation of: -humic substances with immobilization of various component fractions -various microbial biomass compounds Makes analytics even more complicated! NDF: Neutral Detergent Fiber NFC: Not Fiber Carbohydrates ADF: Acid Detergent Fiber ADL: Acid Detergent Lignin Example: Humic acid from soil model
Characterization requirements Example: Digestates for direct application in agriculture Parameters to avoid harmful impacts Quality demands regarding BGK Digestates Solid Liquid MISSING: CH 4 emission potential Hygienics Impurities (>ø2 mm) Stones (>ø5 mm) Hygienization demanded 0,5 % DM (<3 % DM)* Parameters important for transport & distribution Parameter to describe value-added properties Degree of Digestion 1500 ( 4000)* mg organic acids / L FM Dry matter (% FM) ( 20)* (<12)* Organic matter (% DM) 30 (40)* 40 Odour Free of unpleasant odour MISSING: humus compounds nitrogen compounds Heavy metals Particle Size Regarding biowaste and fertilizer guidelines (compact/ spreadable)* (pumpable)* Important: short, medium, long term availability of C & N * (Last years values) Additional declarations: bulk density, mass or volume, ph, salt content, N, P 2 O 5, K 2 O, MgO, S, micronutrients, CaO
Summary & conclusions Various substrates; biorefinery types; residues; options to use residues Various characterization goals Basic characterization parameters: water, organic, ash Problems: sampling; methods for practise missing Special characterization parameters: component analytics Problems: different procedures in different science areas residue parameters more complex compared to input parameters Future demands: - Application-adapted parameter definitions (hazards, handling, value) - Standardized procedures (method book) - New methods (easily, medium, hardliy available C and N) - Easy, cheap, quick methods (organic, ash, water)
Our biorefinery projects Pilot project Lignocellulosic Bioreffinery Gefördert durch: Förderkennzeichen: 22027405 BMBF-project BERBION (2009-2013): Efficient material and energy generation from urban organic waste and waste water Soon: http://www.berbion.de/