Research on Dry HTHP Syngas Cleaning in the Environment of

Microsoft PowerPoint - IFC 2014 Radebeul.pptxKARLSRUHE INSTITUTE OF TECHNOLOGY Institute for Technical Chemistry
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Research on Dry HTHP Syngas Cleaning in the Environment of the bioliq Process
Hans Leibold, Robert Mai, Alfred Linek, Urs Rhyner1, Serge Biollaz1
1Paul Scherrer Institut, Villigen, Switzerland
6th International Freiberg Conference on IGCC & XTL Technologies
19-22 May 2014 Dresden/Radebeul, Germany
Institute for Technical Chemistry Pretreatment / Gas cleaning
2 19.05.2014 IFC 2014 Hans Leibold
Outline
Approach and test rigs for research
R&D on HT/HP filtration
R&D on dry sorption of sour gases
Summary/Outlook
BtL process 2nd generation fuels
Biogenic residues with high ash content
Decentralized / centralized concept
Centralized: Continuous HTHP process
The bioliq® process scheme
separation
Catalyst
High pressure entrained flow gasification
Slag
Syngas composition – commissioning gasifier
2013-V10 2013-V11 2013-V14 Gasifier pressure 40 bar 40 bar 80 bar Fuel input MW 4.46 4.94 5.17 Fuel Model slurry 22 Model slurry 22 Model slurry 23 Liquid phase glycol Solid phase beechwood char / straw ash Solids content %w/w 30 30 30 λ 0.56 0.54 0.48 VSG m³/h STP 1519 1635 1537
H2 Vol% 24.28 25.11 32.38 CO Vol% 29.05 30.06 32.26 CO2 Vol% 20.10 18.47 16.46 H2O Vol% 4.99 5.44 1.35 CH4 Vol% n.d. n.d. n.d. H2S Vol% 0.00 0.00 0.00 N2 Vol% 21.27 18.89 18.94
Design of the bioliq high hemperature high pressure (HTHP) syngas cleaning
Syngas 700 m³/h STP; 800 °C / 80 bar
Particulate filter system with CPP recleaning
Sorption units: Entrained flow and fixed bed (HCl, H2S, alkali)
Catalytic conversion (organics, NH3)

Dry HT/HP syngas cleaning
Sorption HTHP Syngas cleaning
Hydrocarbons, tar NH3, HCN
p, T, process design
Dry HTHP Syngas cleaning
Synthesis gas
100 200 300 400 500 600 700 800 900 1000 0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Temper atur e
Filtration design and grade efficiency
97.5%
98.0%
98.5%
99.0%
99.5%
100.0%
overall efficiency E > 99,9 %
Filter specification 4 sections à 5 filter elements Type DIA-SCHUMALITH® N 10-20 Material SiC grain ceramic / mullite Dimensions 60/40 x 250 mm
Filter candle structure
Coupled Pressure Pulse recleaning Raw gas
Clean gas Flow element
R ec
le an
in g
pr es
su re
in k
Recleaning intensity adjustable to the dust properties Filter permeability controlls the recleaning
pressure not the system pressure No feedback of dust load on the recleaning
efficiency
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Pr es
su re
dr op
in k
Time in min
3 Filter candles / 500 °C Tank overpressure 0.1 MPa Cycle time 10 min Trona/Na2S 1 g/min
Modelling CPP recleaning of rigid filter candles
T= 450 °C DS 10-20 Sector 1
Generic model of CPP recleaning for variable filter configurations and filter scale-up
Monitoring of filter performance based on operating data
Rhyner, U. et al. 2013
Sorption of sour gas components
Low-cost minerals Trona and chalk
Solid reaction products
Stability of sorbents and reaction products
NaHCO3, Na2CO3 · 2 H2O + HCl + H2S 2 CO2 + 4 H2O + NaCl + Na2S
2 CaCO3 + 2 HCl + H2S 2 CO2 + 2 H2O + CaCl2 + CaS
Temperature Syngas pressure Syngas components Clean gas level Sorption capacity Calcination / Hydrolysis Sintering effects Fixed bed sorption versus entrained
flow sorption
Bulk density and specific surface of sorbents
Species °C g/cm³ Species °C g/cm³
Trona (65) 2.1-2.2
Na2CO3 851 2.53 CaCO3 825 2.71
Na2O 1132 2.27 CaO 2572 3.34
NaCl 801 2.17 CaCl2 772 2.15
Na2S 1180 1.86 CaS 845 2.59
Trona, original Trona, pretreatment 150 °C Trona, aged 750 °C, 0.5 h
0
1
2
3
4
5
6
Sp ec
ifi c
su rf
ac e
ar ea
in m
Original 100 °C, 500 °C, 750 °C,
18 h 1 0.5 h 2 0.5 h 3
Sorbens A 98 150 159 109 NaHCO3 0.39 5.3 0.27 0.14 Trona 0.39 3.7 0.27 0.14 1 Pretreated; ² Quantachrome; ³ Micromeritics
Melting points and density of sorbents and reaction products
Supported sorbents in fixed bed
Dispersed sorbents in entrained flow
Gas C in Vol.%
Single sorption of HCl and H2S
Na2CO3: 7 – 10 % Al2O3 supported Fixed bed 50 – 100 mm Size 3 – 5 mm Shape Spheres tRes 1 - 2 s
Temperature 500 – 800 °C
0.01
0.1
1
H C
Sorption experiments in flow reactor
Gas α Vol.%
Simultaneous sorption of HCl and H2S
Sorbents Na2CO3 - Al2O3 supported CaCO3/CaO/NaOH
tRes 0,85 - 1 s
Temperature 500 – 630 °C
HClRaw in mg/m³
Na2CO3 α Na2CO3 ß CaCO3, 500 °C, 1 s CaCO3, 630 °C, 0,85 s Na2CO3, 500 °C
0.1
1
10
Summary and outlook
bioliq demonstration plant: 2 MWtherm BtL process for production of
2nd generation fuels from residual biomass; Initial startup 2 June 2014
Innovative dry HTHP syngas cleaning (700 m³/h STP, 80 bar/800°C)
combines hot gas filtration with mineral sorption of trace contaminants
and a final catalyst converter
Accompanying research involves gas cleaning and conditioning topics
from lab-scale to pilot scale
Research from single process step to process chain ( interferences)
Provides research platform on the dry cleaning and conditioning of
synthesis gas, gas analysis, process control
BMELV / Fachagentur nachwachsende Rohstoffe Förderkennzeichen: 22017809
Synthesekraftstofferzeugung aus Biomasse Bauabschnitt III und IV
Gasreinigung und Kraftstoffsynthese

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Research on Dry HTHP Syngas Cleaning in the Environment of