Materials and processes for treatment of biogas - Dr. Burkhardt Faßauer, Marc Lincke 19.03.2019, Paris
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Materials and processes for treatment of biogas
Dr. Burkhardt Faßauer, Marc Lincke
19.03.2019, Paris
Facilitator
Agenda
• Bio-Methane – Situation in Germany and Europe - Overview
• Desulphurization
• state of the art technologies in brief
• Chemical-adsorptive removal of hydrogen sulfide with iron oxide and recovery of sulfur
• Separation of CO2
• state of the art technologies in brief
• using ceramic membranes
Facilitator
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Biomethan | 19.03.2019 | Seite 2
Biomethane – Situation in Germany
Number of
installations Capacity in Nm³/h
• 2017: 208 installations with
128.000 m³ biomethane/h
• 11 TWh electricity and heat for appr.
780.000 households (3 persons)
• 500.000 gas powered cars with 20.000
km per year
• appr. 100.000 cars in Germany with gas
• Biomethane => Gas grid
• => heat market 75 %
• => car market 25 % Number of
Capacity in Nm³/h
installations
Source:
Deutsche Energie-Agentur GmbH (dena) Erneuerbare Energien und energieeffiziente Mobilität; biogaspartner – gemeinsam
einspeisen. Biogaseinspeisung in Deutschland und Europa – Markt, Technik und Akteure. 11/2015
Facilitator Bundesnetzagentur für Elektrizität, Gas, Telekommunikation, Post und Eisenbahnen (Hg.) (2017): Bericht - Monitoringbericht
2017. Bonn.
Bioenergie mit Fokus auf Gewinnung von
Biomethan | 19.03.2019 | Seite 3
Biogas-Upgrading in Europe
Source: European Biogas Association
• The Netherlands, Sweden and Switzerland with long
lasting experience; Germany with most installations
Source: Deutsche Energie-Agentur GmbH (dena) Erneuerbare Energien und • Many countries use municipal organic waste as
energieeffiziente Mobilität; biogaspartner – gemeinsam einspeisen. Biogaseinspeisung
in Deutschland und Europa – Markt, Technik und Akteure. 11/2015 substrate, Germany mainly uses agricultural waste
Facilitator
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Treatment of biogas - overview
desulphu-
rization CHP
Advanced
CO2
desulphu- Drying Odorisation Compression
separation
rization
• Pre-Treatment of biogas (before CHP or feeding into Natural Gas Grid)
• Desulphurization
• Removal of siloxane
• Separation/removal of CO2
• After-Treatment of biogas (exhaust gas CHP)
• Selective Catalytical Reaction (SCR): NO, NO2 => N2,H2O
• Biogas Oxidation Catalysts (BOC): formaldehyde CH2O => CO2 + H2O; CO => CO2
Facilitator
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Desulphurization of Biogas
Facilitator
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Need for desulphurization
• Biogas is a mixture of methane (40-70 %), carbon
dioxide (20-60 %), water vapor (100 %), hydrogen https://pm-lubri-tec.com/wp-content/uploads/2014/09/bts-biogas-bhkw.jpg
sulphide (0-3 %) and other trace gases
• CHP on site
• with BOC: < 5 ppm H2S https://pm-lubri-tec.com/wp-content/uploads/2014/09/bts-biogas-bhkw.jpg
• ignition jet units without BOC: < 40 ppm H2S http://etw-energie.de/fileadmin/_migrated/pics/BMA-Seelow-
02_670x240.jpg
• Gas Otto engine without BOC: < 15 ppm H2S
• Feeding to the natural gas grid
• advanced desulfurization (3-7 ppm H2S),
• CO2 separation and drying
http://etw-energie.de/fileadmin/_migrated/pics/BMA-Seelow-02_670x240.jpg
Facilitator
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Biomethan | 19.03.2019 | Seite 7
Methods of desulphurization
Processes for the desulphurization of biogas
very common,
internal only for rough
external
treatment
physical chemical/ common for
chemical biological physical / chemical
/ biological biological advanced
treatment
Adsorption Adsorption Absorption
Sulphide H2S oxidizing H2S oxidizing Scrubbing with
Adsorption with chemical with catalytical With biological
precipitation microorganisms microorganisms chem. reaction reaction oxidation oxidation
Air injection Pressure Modif. activ. Modif. activ.
into the gas Percolating Activated
Iron salt water carbon carbon Iron bioprocess
space filter carbon scrubbing (MnO4, NaOH) (Kl, K2CO3)
Gas scrubbing
Iron hydroxide Bio filter with Zinc oxide
amines
Alkaline
Bio scrubber Scrubbing Iron hydroxide
(NaOH)
iron chelate
Iron oxide
aerobic
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Methods of desulphurization - examples
Biological Desulphurization Adsorption with active Adsorption with iron- Scrubbing
by injection of air into gas carbon oxide or -hydroxid
space
https://www.ugn-
umwelttechnik.de/gasentschwefelung/filtermate
encrypted-tbn0.gstatic.com/ www.biobg.de/bilder/2015/10/aktivkohle.jpg https://sulphtec.com/biogasentschwefelung/sh-sulphpur/
rial.html#c422
Facilitator
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Biomethan | 19.03.2019 | Seite 9
Sulfur removal with iron oxid on metal foam
a new approach
• energy- and resource - efficient desulphurization system with metal
foam as carrier (nickel)
• suitable for advanced desulphurization with no waste materials
• compliance with the H2S limit of < 4 ppm according to DVGW regulation
• continuous regeneration with air and occasionally thermal reactivation
under recovery of elemental sulfur, completely recyclable material
• partner:
Source: Fraunhofer IKTS, Fraunhofer IFAM-DD, Emission Partner
Facilitator
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Biomethan | 19.03.2019 | Seite 10Sulfur removal with iron oxid on metal foam
Basic principle of loading and continuous regeneration
gas with low concentration
• Continuous regeneration of hydrogen sulphide (< 5 ppm) inert gas N2
• Injection of oxygen or air
• Conversion of iron sulphide to iron-oxide, -
hydroxide and elemental sulphur
in-situ reactivation with air-oxygen
• Aimed capacity 0,4 – 0,6 kg S/kg adsorber
desulphurisation of gas
reactivation medium
material „air“ or „oxygen“ inert ga
(loading cycle)
> 300 °C
• Sulphur deposits on the surface
reaktor 1 reaktor 2
• Sorbent is ready for further loading
• 10 x regeneration without significant loss of
performance => thermal reactivation
Loading:
Fe2O3 + 3 H2S → 2 FeS + 1/8 S8 + 3 H2O Regeneration:
2 Fe(OH)3 + 3 H2S → 2 FeS + S + 6 H2O 2 FeS + 3/2 O2 → Fe2O3 + S2
Facilitator 4 FeS + 3 O2 + 6 H2O → 4 Fe(OH)3 + 4S
inert gas N2
Source: Fraunhofer IKTS gas with hydrogen sulphide < 300 °C
Veranstaltung | Datum | Seite 11Sulfur removal with iron oxid on metal foam
Principle of occasional thermal reactivation
gas with low concentration
of hydrogen sulphide (< 5 ppm) inert gas N2
• Reactivation
• elemental sulphur reduces the active surface → thermal
regeneration to remove the sulphur is required inert gas
in-situ reactivation with air-oxygen
• Sulphur is converted into the gas phase
desulphurisation of gas
reactivation medium
inert gas heater
• Carrier gas transports sulphur
(loading cycle) „air“ or „oxygen“
from adsorber foam
> 300 °C
reaktor 1 reaktor 2
• sulphur recovery reaktor 3
sulfur loaded
• Condensation of gaseous sulphur N2 + S
• Sulphur is available as a raw material > 300 °C
ex-situ thermal regeneration
condensation
• 4 x thermal reactivation without significant loss
of performance
inert gas N2
gas with hydrogen sulphide < 300 °C sulfur (liquid or solid)
Facilitator > 150 °C
Source: Fraunhofer IKTS
Veranstaltung | Datum | Seite 12Sulfur removal with iron oxid on metal foam
Performance adsorbe foam after regeneration
550
input concentration H2S: 511 ppm
concentration H2S [ppm]
500
• Hydrogen sulfide breakthrough
450
curves for thermally
400
regenerated foam for different 350
space velocities 300
250
200
150
1st regeneration 7th regeneration
100
new
50 2nd regeneration
0
0:00 0:50 1:40 2:30 3:24 4:14 5:04 5:54 6:44 7:34 8:24 9:14 10:04 10:54 11:44
time [hh:mm]
V19.4_2 L/min V19.5_2 L/min V19.6_2 L/min V19.1_1 l/min
V19.2_1 L/min V19.3_1 L/min V19.7_1 L/min
Source: Fraunhofer IKTS
Facilitator
Veranstaltung | Datum | Seite 13Sulfur removal with iron oxid on metal
foam - Pilot plant
• Construction and commission of pilot
plant completed in the technical center
of partner GICON
• Adsorber foam produced for filling and
installed in two modules
• Long-term operational tests with real
biogas
Source: GICON, Emission Partner
Facilitator
Bioenergie mit Fokus auf Gewinnung von
Biomethan | 19.03.2019 | Seite 14Sulfur removal with iron oxid on metal foam
Economical example for biogas plant 500 kWel.
• Analysis of costs for adsorber material, investment, biogas production (raw gas) 300 m³/h
operation, regeneration, recycling, disposal methane content 53 %
• Depending on number of reactivations the metal – methan production 159 m³/h
foam based advanced desulphurization system biogas production 2.580.000 Nm³/a
achieves 10 – 40 % lower total costs compared to 250 ppm
active carbon H2S 385 mgH2S/m³
0,116 kgH2S/h
S 0,109 kgS/h
Source: Fraunhofer IKTS
Facilitator
Bioenergie mit Fokus auf Gewinnung von
Biomethan | 19.03.2019 | Seite 15Separation/Removal of CO2
Facilitator
Veranstaltung | Datum | Seite 16Need for CO2-separation
• High-Gas („H-Gas“ 11 kWh/m3) in South-, East- and North-Germany, Low-Gas
(„L-Gas“ 8,9 kWh/m3) in Northwest-Germany (30 %)
• until 2030 complete switch to „H-Gas“ is planed
Water scrubbing
Chemical scrubbing
Membrane Technology
Chem./phys. scrubbing
Kryotechnology
Source:
Facilitator Deutsche Energie-Agentur GmbH (dena) Erneuerbare Energien und energieeffiziente Mobilität; biogaspartner –
gemeinsam einspeisen. Biogaseinspeisung in Deutschland und Europa – Markt, Technik und Akteure. 11/2015
Bioenergie mit Fokus auf Gewinnung von
Biomethan | 19.03.2019 | Seite 17Need for CO2-separation
North Natural Gas-H GUS Natural Gas - H Natural Gas - L
Methane CH4 Vol. % 90 97,3 81,8
Ethane C2H6 Vol. % 5 1,3 2,8
Propane C3H8 Vol. % 0,7 0,5 0,4
Buthan C4H10 Vol. % 0,2 0,1 0,2
CO2 Vol. % 1 0 0,8
Nitrogen N2 Vol. % 3,1 0,8 14
calorific value kWh/m3 11,21 11,18 10,3
Density compared to air 0,61 0,57 0,64
Source: www.unternehmensberatung-babel.de/industriegase-lexikon/industriegase-lexikon-a-bis-m/erdgas/index.html
http://etw-enere.de/fileadmin/_migrated/pics/BMA-Seelow-02_670x240.jpg
Facilitator
Bioenergie mit Fokus auf Gewinnung von
Biomethan | 19.03.2019 | Seite 18Methods of CO2-Separation
Criteria Water Amin Hybrid processes
PSA Polyglykol Membrane
scrubbing scrubbing Membrane/ Kryo
Advanced desulphurization
required Yes No Yes Yes Yes Yes
Loss of methaneIntroduction – membrane gas separation
• Membranes are appropriate for biogas upgrading because of
• low energy consumption,
• good selectivity and low product lost,
• flexible operation and short start-up time,
• easily engineered modules
• and lower costs.
• High CH4 recovery efficiency can be reached (>96%)
• organic and non-organic membranes
Source: EVONIK Source: IKTS Source: https://www.airliquideadvancedseparations.com/our-
membranes/biogas
Facilitator
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Biomethan | 19.03.2019 | Seite 20Gas separation with inorganic membranes
• inorganic Membranes
• metallic membranes (tungsten, palladium or stainless steel)
onto a porous substrate
• Ceramic membranes consist of metal loxide (aluminum or
titanium) and non-metal (oxides, nitride, or carbide)
• Zeolite membranes are used in highly-selective gas separation
due to highly uniform pore size.
• advantage of the non-organic membranes are
• high thermal, chemical and mechanical stability
• inertness to microbiological degradation
• ease of cleaning after fouling compared to organic counterparts
Facilitator
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Biomethan | 19.03.2019 | Seite 21Gas separation with inorganic membranes
Carbon-Based Membranes
0,34nm
1 µm
Molecular Sieve Carbon Adsorptions Selective Carbon
Membrane Membrane
(MSCM) (ASCM)
Distance between lamella: 0,4 -
SourceIKTS
0,5 nm
Facilitator
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Biomethan | 19.03.2019 | Seite 22Gas separation with inorganic membranes
Carbon based membrane preparation
Ceramic
Support
Al2O2 mono channel tubes
i = 7 mm, a = 10 mm, l = 100 mm
Polymeric inside asymmetric structured
Coating
Precursor
cross section
Polymerisation asymmetric ceramic
membrane (SEM)
10µm
Pyrolysis
Post
Treatment
Source: Fraunhofer IKTS
Facilitator
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Biomethan | 19.03.2019 | Seite 23Gas separation with inorganic membranes
Carbon based membrane - Biogas separation tests
• robust membrane performance in real
biogas
• Permselectivity CO2/CH4 up to 100
• flow rates of CO2 up to 9 m³/(m²h*bar)
feed 4.5bar
96% CH4
50% CH4
50% CO2
69% CO2
Source: Fraunhofer IKTS, DBI
Facilitator
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Biomethan | 19.03.2019 | Seite 24Thank you for your attention!
Dr.-Ing. Burkhardt Faßauer
19.03.2019, Paris
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