cost fp0901 meeting „current needs in biorefinery
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COST FP0901 meeting „Current needs in biorefinery analytics“WG 3: Process Residues
Requirements for characterization of biorefinery residues
Ina Körner1, Ron Janzon2, Helmut Adwiraah1, Jörn Heerenklage1, Tim Sieker3, Bodo Saake2
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 KaiserslauternDepartment of Mechanical and Process Engineering
Institute of Bioprocess Engineering
1.1. BiorefineriesBiorefineries
2.2. Goals of Goals of characterizationcharacterization
3.3. CharacterizationCharacterization requirementsrequirements & & methodsmethods
4.4. SummarySummary & & conclusionsconclusions
Overview
Biorefineries: Principle setup
Bioresource
biological energy production
thermalenergy production
Biomethane
Biohydrogen
Bioethanol
Post-treatment
Pre-treatment
mechanical
biological
physical
chemical
combinations
combinations
combinations
material products
energy products
mechanical
biological
physical
chemical
Incineration
Pyrolysis
Gasification
Substrates for biorefineries
1st GenerationFeeding beet, wheat, rye, maize (grain, whole plant, silage)
2nd GenerationCommon forestry wood
Fast growing woodStraw
WasteMixed Municipal waste
Source separated organic wasteAgricultural waste
Green lignocellulosic waste
1st Generation Biorefineries: Wheat-to-Bioethanol-Biorefiniery
Grain
Milling/Sieving
Mashing
Liquefication
Hydrolysis
Fermentation to Ethanol
Destillation
DDGS
α-Amylase
Water
Glucoamylase
CO2
Ethanol
corn
straw
Energy /Lignocellulose
Bioreffinery
DDGS=Drieddistillers grainwith solubles
Glucose
Sieving andchipping
Lignin
Washing with water component separation
Glucose Xylose
Fermentation to ethanol + fermentation residue, CO2
Steam pretreatment
Enzymatichydrolysis
Enzymatichydrolysis
Wood
Extract with hemi-celluloses
(Furfural, 5-HMF)
Fibers withcellulose & lignin
Hydrolysis residue(Lignin, carbohydrates,
extractives)
Energy generation
Alkalineextraction
Ligninfraction
2st Generation Biorefineries: Lignocellulose-to-Bioethanol-Biorefiniery
humus products
Anaerobic dry fermentation
Biobin-Waste
Biogas
Digestate =
Residue
Waste BiorefineriesBiowaste-to-Biogas Biorefinery
Bioconversion processes
into a methane-rich biogas
e.g.
Liquide fertilizers
Tailor-made composts
pellets
Solid mineral fertilizers
Heat, Electricity
Natural gas substitute
Emissions, Residues
Emissions, Residues
Civilisation BiorefineryComplex of biorefineries for utilization of regional bioresources
Biorefinery A
Municipal WasteLeaves
Waste woodPark waste
…
ElectricityHeatFuel
Product distribution & utilisation
MaterialsHumus Fertilizer
Biorefinery B
Biorefinery X
. . .
Biorefinery YMaterialProducts
Agricultural Waste
Manure…
Renewable organic resources
GrainWoodAlgae
…
EnergeticProducts
Bio-resource
generation & collection
withina region
Bio-bin waste
Straw
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
• Ensure stabile and efficient run of all technological steps
• Ensure suitable residue qualities for further transformation, utilization ordisposal
Process and Product Control
Biowaste
100%
biogas
90 m³/Mg FM
100 % FMDM: 35% FMAsh: 42% DM
80% FMDM: 39% FMAsh: 50% DM
digestate
80%
percolation water
fluid digestate
10% FM
post composting
compost
40% FM
overflow
15% FM
impurities
2% FM
or
drying
biomass fuel
50% FM
Air Heat
0%
100%
Biowaste Digestate Digestate
Characterization requirementsInput-Output characteristics of anaerobic fermentation
AshAsh
HH22OO
OrganicOrganic
FM – Fresh MatterDM – Dry Matter
Biogas &Digestate
Biowaste Digestate
batch-dry fermentation
Mas
sB
alan
ce
are most importantparameters
Characterization Requirements Input-Output characteristics of Bioethanol-Process
Wood
100%
100 % DMCarbohydrates: 65 % DM
Water Addition
Pretreatment
Residue Composition• lignin, (ash), • unhydrolysed, unfermented carbohydrates • added water • microbial biomass
Fermentation(SSF)
Ethanol: 15 % DM25 g/L
Ethanol
Residue
CO2
Water & organic content are most importantparameters
AnaerobicFermentation
to Biogas
100 % DMPulp: 59 % DM
Carbohydrates: 51,7 % DM
HemicelluloseFraction (28 % DM)Lignin (13 % DM)
SSF: Simultanioussaccarification and
Fermentation
Methods for Products:
• Biogas (Volume; CH4; CO2)• Ethanol
Methods for Residues:
• Water• Ash / organics
Basic measurements
Well established
Main Problems - Laboratory:
Inhomogenity SamplingSample Storage Sample Preparation
Various Digestates
Main Problems - Practice:
Easy Quick Cheap
BUT: Less exact
„Fist“-method suggestedin composting guidelines
Material with optimalmoisture content
Material too dry
Material too wet
Carbohydrate & lignin determination used in wood science
Sample is hydrolysed by a 2-step procedure withH2SO4
Hydrolysis residue (lignin) isdetermined gravimetrically
Wood monosaccharids aredetected by HPLC
0,0 10,0 20,0 30,0 40,0-50
100
200
300
450 mAU
Rha
mno
se
Man
nose
Ara
bino
se G
alak
tose
Xyl
ose
Glu
cose
4-O
-Me
Ara
bino
seG
alak
tose
min
HPLC-Chromatogram of a wood-mix
Glucose Xylose Mannose Lignin
[%]
0
10
20
30
40
50
43,2
55,0
5,7
15,811,6
3,4
32,8
23,2
39,7
9,0
3,7
37,7
Wood-MixPoplarGreenwaste-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 H2SO4).
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
Ashing
H2SO4/KMnO4
Sample +
neutral detergent
solubles insolubles
NFC NDF+
aciddetergent
StarchSugar
ß-glucans solubles insolubles
ADFKjeldahl
Hemicelluloses
ADIN
AIA
ADL
Special Measurements: Component Analytics
Calculation of differences
Special Measurements: Component AnalyticsRaw materials Residues
Formation of:-humic substances with immobilization of various component fractions
-various microbial biomass compounds
Makes analyticseven more complicated !
Example: Humic acid from soil model
WoodWaste
Van-SoestAnalysis
ClassicWood Analysis
NDF: Neutral Detergent FiberNFC: Not Fiber CarbohydratesADF: Acid Detergent Fiber ADL: Acid Detergent Lignin
Characterization requirementsExample: Digestates for direct application in agriculture
DigestatesSolid Liquid
Hygienics Hygienization demanded
Impurities (>ø2 mm) ≤0,5 % DM
Stones (>ø5 mm) (<3 % DM)*
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
Heavy metals Regarding biowaste and fertilizer guidelines
Particle Size (compact/spreadable)*
(pumpable)*
Parameters to avoid harmful impacts
MISSING:CH4 emission potential
Parameters important for transport & distribution
Parameter to describe value-added properties
MISSING:humus compounds
nitrogen compounds
Important: short, medium, longterm availability of C & N
Quality demands regarding BGK
* (Last years values)Additional declarations: bulk density, mass or volume, pH, salt content, N, P2O5, K2O, MgO, S, micronutrients, CaO
Summary & conclusions
Various substrates; biorefinery types; residues; options to use residues
Various characterization goals
Basic characterization parameters: water, organic, ashProblems: sampling; methods for practise missing
Special characterization parameters: component analyticsProblems:
different procedures in different science areasresidue 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)
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