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)

Our biorefinery projects

Soon: http://www.berbion.de/

BMBF-project BERBION (2009-2013): Efficient material and energy generation from

urban organic waste and waste water

Gefördert durch:

Förderkennzeichen: 22027405

Pilot project „Lignocellulosic Bioreffinery“