Thermochemische Verfahren zur energetischen und stofflichen

Thermochemische Verfahren zur energetischen und stofflichen

Thermochemische Verfahren zur energetischen und
stofflichen Nutzung von Biomasse
Nicolaos Boukis, Nicolaus Dahmen, Axel Funke, Andrea Kruse, Klaus
Raffelt, Jörg Sauer, Hamm, 22.07.2015
Institute of Catalysis Research and Technology - Project bioliq
KIT – Universität des Landes Baden-Württemberg und
nationales Forschungszentrum in der Helmholtz-Gemeinschaft
www.kit.edu
Outline
Motivation
Hydrothermal Processes, Hydrothermal Gasification
The bioliq Approach to BtL
Conclusion and Outlook
2
22.07.2015
Jörg Sauer
Outline
Motivation
Hydrothermal Processes: Hydrothermal Gasification
The bioliq Approach to BtL
Conclusion and Outlook
3
22.07.2015
Jörg Sauer
„Magic Triangles“ of the German Energiewende
Control /
Networks /
Storages
Energy
Efficiency
Tools of the
energy
transition
Liquid
Fuels
37%
Sustainability
Renewables
Triangle of
Energy
Policy1)
Cost
Effictiveness
Energy
Carriers2)
Security of
Supply
Electricity
21%
Naturals Gas
25%
1) Zweiter Monitoring-Bericht „Energie der Zukunft“, Bundesministerium für Wirtschaft und Energie (BMWi), Berlin, März 2014
2) AGEB, Arbeitskreis Energiebilanzen, September 2014, www.ag-energiebilanzen.de/ entnommen am 21.09.2014
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Jörg Sauer
„Energiewende in Germany“ –
Biofuels and Electricity1)
Energy Content of Energy Carriers from [PJ]
Energy Carriers from Renewables [PJ]
Electricity from
Renewables
Biofuels
1) AGEB, Arbeitskreis Energiebilanzen, September 2014, www.ag-energiebilanzen.de/ retrieved on 2014-09-21
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Jörg Sauer
Erdöl - Zahlen
Erdöl Tagesproduktion:
83 Mio bbl per day
= 13,2 Mio m³/Tag
Zum Vergleich:
Speichervolumen des Brombachsee 164 Mio m³
o Zeit bis zum Auffüllen des Brombachsees mit weltweiter
Erdölproduktion:
12 Tage 10 Stunden
Source:
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IEA, Energy Technology Perspectives 2014
http://www.landeskraftwerke.de/brombachsee.htm, entnommen am 14.07. 2014
http://www.zv-brombachsee.de/, entnommen am 14.07. 2014
Jörg Sauer
Noch mehr Zahlen
Investitionssumme für Pearl GTL
Produktionsmenge
Anteil an der Welt-Ölproduktion
Investkosten pro bbl
Mitarbeiter für Anlagenbau:
18,5 Mrd USD
0,14 Mio bbl per day
0,17%
130.000 USD/(bbl per day)
ca. 50.000
Hochrechnung auf Weltöl-Produktion:
Kosten:
10,8 Billionen USD
Investbudget der Ölkonzerne (2012): 260 Mrd USD (x 41)
ExxonMobile (2013):
42,4 Mrd USD (x 254)
Hochgerechneter Personalbedarf
ca. 30 Mio für 5 Jahre
Source:
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22.07.2015
http://www.platts.com/
http://www.shell.com/
http://ir.exxonmobil.com/
http://energypolicy.columbia.edu/
entnommen am 13.07.2014
Jörg Sauer
Contribution of the Negative Residual Load
Negative residual load:
After conversion losses:
Liquids consumption Germany 2012:
66TWh = 240 PJ
33TWh = 120 PJ
1290TWh = 4640 PJ
Potential for Liquids from residual load
Availability
2,2 Mio to (2,6%)
max. 3000h
Sources:
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22.07.2015
Deutsche Energie-Agentur GmbH (dena), Integration der erneuerbaren Energien in den
deutschen/europäischen Strommarkt, 2012
AGEB, Arbeitskreis Energiebilanzen, September 2014,
www.ag-energiebilanzen.de/ entnommen am 21.09.2014
Jörg Sauer
Feedstocks for Future Bionenergy Applications
Agriculture
Straw, hay, ….
Energy crops
Forestry
Residues (brash, tops, stumps)
Thinnings
Short rotation plantation
Marginal Farmland
Streets, railway tracks
Power transmission lines
Organic residues
Recovered waste wood
Organic waste fractions
Algae
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Jörg Sauer
Outline
Motivation
Hydrothermal Processes: Hydrothermal Gasification
The bioliq Approach to BtL
Conclusion and Outlook
10
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Jörg Sauer
Regimes for Hydrothermal Conversion
35
30
H2
CH4
Supercritical Water
Gasification
p / MPa
25
20
Hydrothermal Liquefaction /
Hydrothermal Upgrading
15
"Oil"
10
5
0
Aqeous Phase Reforming
H2
Pretreatment
200
Hydrothermal Carbonization
C
300
400
 / °C
22.07.2015
Hydrothermal conversion
to platform chemicals
Chemicals
100
11
Catalysed near-critical gasification
Critical
Point
500
600
700
Kruse et al., 2013, modified
Jörg Sauer
Gasification of Waste Biomass and Organic
Waste Fractions
Process
Conditions: T  650 °C; p  280 bar
Feed
(Sludges, not
dried)
Heat exchanger
Salt separation
Reactor
Salt concentrate
(K, P, Ca, Mg)
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H2, CH4 ,
CO2 , C2H6
Waste water,
NH4+
Jörg Sauer
Gasification Yield as Function of the
Residence Time and the Reaction Temperature
[Corn silage] = 5 wt%, p=250 bar
Working space
P. D´Jesus, N. Boukis, B. Kraushaar-Czarnetzki, E. Dinjus. Ind. Eng. Chem. Res. 2006, 45, 1622-1630
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Jörg Sauer
Properties of Water at High Temperatures and
Pressure (Tc=374 °C, pc=221 bar)
Water; isobar 300 bar
1200
Liquefaction
Gasification
-10
Regime of operation
800
-15
600
400
-20
D kg/m^3
Viscosity µPa-s
Ion Prod. 2xLog10(kW
Ion Product
Density (kg/m^3);
Viscosoty µPa.s
1000
200
0
0
300
400
T (°C)
Direct heat exchange is possible => no drying
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22.07.2015
100
200
500
600
-25
700
Salt precipitation
Jörg Sauer
LENA – Test Rig, continuous flow,
Tmax=700 °C, max. flow rate 2 l/h, VReactor=270 cm3
Salt separation
HP-Filter
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Jörg Sauer
Sewage Sludge from Oljen and Lelystad
Parameter
16
Type
wDM
Dry matter,
wt.%
Ash content by
550 °C, wt.%
Lelystad
Oijen
17,5
27,4
18,8
20,40
22.07.2015
TC
TIC
TOC ( C )
H
N
P
S
Ca
K
Mg
Na
Si
Al
As
Cd
Cu
Pb
Zn
Cr
Fe
Mo
Ni
Feed analysis
wt. [%]
wt. [%]
Oijen
Lelystad
41,6
43,5
0,1
0,1
41,5
43,4
4,22
6,37
4,22
7,28
2,4
3,16
0,78
1,11
2,25
1,4
0,36
1,14
0,31
0,72
0,088
0,105
2,65
2,63
1,22
0,56
0,02
0,02
0,01
0,01
0,56
0,018
0,011
0,02
0,086
0,032
0,0039
0,01
1,38
0,38
0,02
0,02
0,02
0,02
Jörg Sauer
Main results, steady state operation
Total sewage sludge treated 2 – 3 kg per experiment
Time
Feed
Ctotal
Type
steady
state
steady
state
steady
state
[-]
[h]
[g]
[g]
[after h]
Lelystad
Oijen
5
3,93
2115
1656,5
109,18
88,86
No
6,5
Plugging YGas
[%]
YC
[%]
67,95 80,67
71,21 81,83
TOCTOCNH4+TNbwaste
water
waste
water
waste
water
destruction
[%]
[mg/l]
[mg/l]
[mg/l]
97,8
96,7
1953
2141
11724
8821
9300
5580
Carbon balance during steady state operation is 80 % an indication of
accumulation of Carbon in the system (insoluble carbonates in the filter cakes)
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Jörg Sauer
Hydrothermal Gasification of Sewage Sludge
Sewage sludge
TReaction
Concentration
mean res. time
type
[°C]
[wt. % DM]
[min]
Lelystad
653
11,69
2,75
Oijen
649
12,71
2,76
Type Lelystad
Type Oijen
Gas composition
C3H6 0,10
vol %
C2H4 0,38
vol %
C2H6
11,27
vol %
Gas composition
C3H8 0,36
vol %
C3H6 0,17
vol %
C2H4 0,61
vol %
H2 21,81
vol %
C2H6
12,90 vol
%
C3H8 0,47
vol %
H2 17,18
vol %
CO 0,22
vol %
CO 0,04
vol %
CO2 34,25
vol %
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CH4 31,80
vol %
CO2 33,36
vol %
CH4 35,08
vol %
Jörg Sauer
The Carbon Balance
Type “Lelystad”
Type “Oijen”
Carbon distribution %
Balance; -6,58
Aq. Phase;
16,02
Carbon distribution %
Balance; -5,67
Filter aq.
Phase; 1,35
Salt
concentrate
incl. Filter;
8,30
Aq. Phase;
13,58
Filter aq.
Phase; 6,06
Salt
concentrate
incl. Filter;
6,28
Gas; 80,90
Gas; 79,75
The carbon balance for the whole experiment is much better.
About 10 % of the Carbon forms carbonates
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Jörg Sauer
Type Oijen C, N, P Detailed Analysis
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Scale-up to Pilot Scale (1)
Biomass
650°C
300 bar
Water
Preheater
Reactor
Storage
Gas tank
Phase
separation
CO2scrubber
Heat
exchanger
HP-pump
Cooler
Residual water
Colloidal
mill
VERENA pilot plant at KIT
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Jörg Sauer
Scale-up to Pilot Scale (2)
Reactor
Feeding
100 kg / h
5-20 % dmc
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35 L volume
0,11 m i.D., 3,7 m length
Inconel Ni-Alloy
External Heating
35 Mpa; 700 °C
Jörg Sauer
Conclusions for Hydrothermal Gasification
Stable operation with “difficult feedstock” sewage sludge is possible
Good carbon balance in lab scale (100 ± 10 %)
High gasification yield (80 %) and η (up to 0.9). Acceptable efficiency at
12 wt.% DM possible
Challenges
Salt separation is of utmost importance
 Fouling/ scaling e.g. in heat exchangers
 Corrosion
HTG of sewage sludge operates at the frontier of development modern
materials of construction
Suitable models for reaction kinetics and gasification reactor are
missing
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Jörg Sauer
Outline
Motivation
Hydrothermal Processes: Hydrothermal Gasification
The bioliq Approach to BtL
Conclusion and Outlook
24
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Jörg Sauer
Thermochemical BtL Value Chains
Lignocellulosic
Biomass
Torrefaction
Pyrolysis
Catalytic/hydrothermal liquefaction
Gasification
(CO+H2)
SyngasFermentation
Purification
Catalytic/Biotech.
Upgrading
Catalytic Fuel
Synthesis
Fuels and/or chemicals
25
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Jörg Sauer
Chemistry and Technology – decentralized
500 °C
Cellulose
Hemicellulose
Lignin
Biomass
Char/Ash
20 Gew.%
Biomass
Condensate
60 Gew.%
Gases
20 Gew.%
Pyrolysisgas
Sand
Heat Carrier
Flashpyrolysis
26
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Char
Ash
Condensates
Biosyncrude
Jörg Sauer
Chemistry and Technology – centralized
>1200 °C
80 bar
C O
Kat
Biosyncrude
Biosyncrude
Syngas
CO2, u.a.
Entrained Flow Gasification
22.07.2015
Hydrocarbons
Benzin
Catalysis
H2O/CO2DMESeparation Synthesis
Slag
27
Methanol
Dimethylether
O2 (Steam )
Particle - Sorption
filter
Kat
Gas Cleaning
Gasoline
Product
Synthesis separation
Diesel
Kerosine
Ethylene
Propylene
Methane
Hydrogen
…
Synthetic
biofuels
Fuel Synthesis
Jörg Sauer
bioliq®-Pilot Plant at KIT
Fast Pyrolysis
Biosyncrude-Production
Technical Validation
Mass and energy balances
Scale-up
Stability and availability
Production costs
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Gasification
Syngas-Production
&
Gas-Cleaning and
Fuel Synthesis
Platform for Research
Improved insights in processes
Optimization and development
Diagnostics, modelling, simulation
New applications of products
Jörg Sauer
Contributions to the Analysis
on the System Level
2,10 €
Photosynthesis
Water and
Carbon Dioxide
- O2
1,70 €
1,30 €
Combustion
Plants
0,90 €
Fuel-Production
+ O2
CO2 reduction potential > 80 %
0,50 €
0 MW
1000 MW
2000 MW
3000 MW
4000 MW
Production Costs
Mass Potential
of Straw
www.bioboost.eu
Potentials of sustainable supply
29
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Logistics simulation and production network
Jörg Sauer
Next steps
Improve availability of pilot plants
Process optimization and further development
Development of business models
& market implementation plans
Creation of a consortium for the development
of high performance fuel components
Units
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Chains
Networks
Systems
Investition in die Zukunft
gefördert durch die Europäische
Union Europäischer Fonds für
regionale Entwicklung und das
Land Baden-Württemberg
Jörg Sauer
Outline
Motivation
Hydrothermal Processes: Hydrothermal Gasification
The bioliq Approach to BtL
Conclusion and Outlook
31
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Jörg Sauer
The Future of Bioenergy Research at KIT (1)
„Integration into the Energy System“
bioliq®
Biomass
(eg. straw)
Flash
pyrolysis
Entrained
flow gasification
Gas
cleaning
EnergyLab
2.0
Catalytic
synthesis
Fuels, chemical
energy carriers
SyngasFermentation
Intermediates /
Biomaterials
Fischer-Tropsch
Synthesis
Methanation
Gasturbine
+ Generator
Photobioreactor
Cultivation/
harvesting
Algae Value Chain
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Elektroporation
Product
Separation
Fuels, chemical
energy carriers
Hydrothermal
liquification
Electricity
Intermediates /
biomaterials
Jörg Sauer
The Future of Bioenergy Research at KIT (2)
„Synthetic High Performance Fuel Components“
Elements
Compatible to present fuels (drop-in)
Reduced emissions
Increased performance
Reduced fuel consumption
Reduced CO2-footprint
Partikel
matter
Particulate
Conventional diesel fuel
Oxygenated diesel blend
Pure OME
1: Effect of fuel change
2: Engine modification for NOx control
1
2
Bsp.: Oxymethylenether (OME)
0
NOx
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Jörg Sauer
From Fundamentals to Applications and the
Integration into the Energy System
Processes
& Plants
Energy System
& Application
Process
Steps
Catalysts
Elementary
Steps
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Jörg Sauer
Acknowledgements
Sponsors and Funding Agencies
Partners from Industry and Academia
The teams from KIT
The audience for your kind attention
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Jörg Sauer