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Advanced Green Gas Technology

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Advanced Green Gas
Technology
Presented at the EDGaR closing conference, Amsterdam,

18 – 19 March 2015

L.P.L.M. Rabou

March 2015
ECN-L--15-016
Advanced Green Gas Technology

Luc Rabou
Amsterdam, March 19, 2015

www.ecn.nl
Advanced Green Gas Technology

Luc Rabou
Amsterdam, March 19, 2015

www.ecn.nl
 Motivation

• Gas is and will be an essential part of our energy supply

• Reduction of CO2 emissions requires renewable substitute (bio-SNG)
• Cost and availability of biomass make it essential to develop
efficient & versatile conversion technology

L.P.L.M. Rabou 3
March 19, 2015
 AGATE 1 + 2 & Synthetic Methane
• ECN L. Rabou, E. van Dijk, W. Haije, M. Saric, J. Dijkstra P
Dry biomass gasification => CH4 O
H2 + CO2 ( + …...)=> CH4 S
• RUG ST/OC H. Heeres, A. Kumalaputri, V. Hornillos, A. Phua T
Wet biomass gasification => CH4 E
• RUG CIO S. Palstra, H. Meijer R
14C analysis for “green” gas
S
• DNV GL H. Roeterink Cost price and gas quality
• Hanze M. Barankin LCA P2G, µCHP
• TUD P. Aravind Solid oxide fuel cell/electrolyser

L.P.L.M. Rabou 4
March 19, 2015
 CH4 production from dry biomass

1. Gasification: conversion of solid biomass to producer gas

2. Producer gas cleaning: removal of dust, tar, catalyst poisons
3. Producer gas conversion to CH4, CO2 and H2O
4. Upgrading to gas grid specifications

ESME: ECN System for Methanation

L.P.L.M. Rabou 5
March 19, 2015
 Gasification
Quick biomass heating to 750 – 850 °C

Producer gas CO, H2 , CO2, CH4, CxHy , H2O, N2

+ NH3, HCN, CxHyN
+ H2S, COS, CxHyS
+ dust + Cl-compounds
Char carbon-rich residue
Lab-MILENA
- Char combustion provides heat for process
- Gas cooling can be used for steam/E production

L.P.L.M. Rabou 6
March 19, 2015
 Low or high temperature gasification
MILENA Component Vol % (dry) Energy % Efficiency‡ % ‡ heatingvalue
gas CO + H2 60 40 77 X + H2 => CH4
CH4 13 27 100
C2H2 0.3 1 81
C2H4 4.2 14 89 C2H2 + C2H4 + C3H6
C2H6 0.3 1 96 + C6H6 + C7H8
C3H6 0.1 0.5 90
≡
C6H6 1.0 8 90
± 25% of producer gas
C7H8 0.1 1 91 heating value
Tar 0.3 6 91
CO2 + N2 20

L.P.L.M. Rabou 7
March 19, 2015
 Gas cleaning
Dust and tar removal OLGA
(tar = aromatic hydrocarbons, heavier than benzene)

Removal of catalyst poisons

focus on organic sulfur compounds

Hydrogenation of unsaturated hydrocarbons

(Pre)reforming of aromatic hydrocarbons (BTX)

L.P.L.M. Rabou 8
March 19, 2015
 Catalytic gas cleaning (1)
Hydro De Sulfurization (HDS) catalyst

- Opens ring structure containing S atom

=> produces H2S or COS (to be removed)

- Breaks down organic N compounds,

including HCN, but not NH3
Lab-reactors with
- Adds H2 to unsaturated hydrocarbons adsorbents
Lab-HDS (AGATE 2)
=> produces e.g. C2H6, C3H8

HDS test rig built and operating conditions optimized in AGATE 1

L.P.L.M. Rabou 9
March 19, 2015
 Catalytic gas cleaning (2)
Pre-reforming catalyst
- Converts aromatic hydrocarbons (BTX)
with steam into CO and H2 Requires heat
- Acts also as methanation catalyst Produces heat

Prone to carbon deposition

Critical for system performance (degradation)
Lab reforming + methanation

Test rig built and operating conditions optimized in AGATE 2

L.P.L.M. Rabou 10
March 19, 2015
 Methane production (nickel catalyst)
Main methanation reaction: CO + 3H2 <=> CH4 + H2O (+ heat)
Equilibrium shifts to CH4 at high pressure and low temperature

Other reactions: C2H6 + H2 => 2 CH4 (+ heat)

C3H8 + 2 H2 => 3 CH4 (+ heat)

H2 shortage calls for water gas shift: CO + H2O <=> CO2 + H2 (+ heat)
or H2 from another source (P2G)

L.P.L.M. Rabou 11
March 19, 2015
 Upgrading

Final product consists of CH4, CO2, H2O and some H2 (+ some N2 and NH3)

CO2 and H2O removal (at 5 – 10 bar)

Yields CH4 with 5% H2, 3-5% N2, and < 0.03% CO

Further compression and final methanation (at 30 – 40 bar)

or H2 separation / acceptation

L.P.L.M. Rabou 12
March 19, 2015
 CO2 removal or P2G?

CO2 + 4 H2 <=> CH4 + 2 H2O (+ heat) Sabatier reaction

Can be applied to pure CO2, biogas or producer gas

• Could double CH4 production in case of biogas and producer gas

• Saves effort for CO2 removal
• Requires 30 – 40 bar pressure for low final H2 content
• Changes system heat management

System analysis, test rig modification and exploratory experiments

in Synthetic Methane

L.P.L.M. Rabou 13
March 19, 2015
 500 hrs ESME performance test
Wood gasification, gas cleaning and 6 bar methanation
29-Sep 30-Sep 1-Oct 2-Oct 3-Oct 4-Oct 5-Oct
~1 m3/hr MILENA
OLGA
### ### ### ### ### ### ### ### ### ### ###

START MILENA
START OLGA
### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ###

producer gas HDS

R11, R12
R13
START HDS

START 500-H TEST

R14
(~3 kW) R15

6-Oct 7-Oct 8-Oct 9-Oct 10-Oct 11-Oct 12-Oct

### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ###

MILENA
OLGA
HDS
R11, R12
R13
R14
R15

13-Oct 14-Oct 15-Oct 16-Oct 17-Oct 18-Oct 19-Oct

### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ###

MILENA
OLGA
HDS
R11, R12
R13
R14
R15

20-Oct 21-Oct 22-Oct 23-Oct 24-Oct 25-Oct 26-Oct

### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ### ###

MILENA
OLGA
HDS
R11, R12
R13
R14
R15
END 500-H TEST SNG

L.P.L.M. Rabou 14
March 19, 2015
 Thanks to team

L.P.L.M. Rabou 15
March 19, 2015
 HDS temperatures

L.P.L.M. Rabou 16
March 19, 2015
 HDS temperature profile

L.P.L.M. Rabou 17
March 19, 2015
 Prereformer temperatures

L.P.L.M. Rabou 18
March 19, 2015
 Prereformer temperature profile

L.P.L.M. Rabou 19
March 19, 2015
 Gas composition

L.P.L.M. Rabou 20
March 19, 2015
 Summary of 500 hrs test
• Temperature profiles show no indication of catalyst degradation
Commercial operation requires >20 times longer
• Final gas composition stable
• Residual CO ~130 ppm (< 300 ppm after CO2 removal)
• Residual H2 ~2% (< 5% after CO2 removal)
• Important step for scale-up of bio-SNG production
 300 m3/h SNG facility to be built in the Netherlands

L.P.L.M. Rabou 21
March 19, 2015
 Conclusion
• Test equipment available for gas cleaning, methanation and P2G tests
• Sulfur removal to 0.1 ppm proven
• BTX (pre)reforming successful
• ESME design for bio-SNG production
• 500 hrs test shows stable performance
• Bio-SNG consortium
for 4 MW system

• Includes CO2 and H2O removal

• Includes high-pressure polishing step
• Aims at > 5000 hrs/year
L.P.L.M. Rabou 22
March 19, 2015
 Thanks to EDGaR sponsors
Dit onderzoek is medegefinancierd door subsidie van het Energy
Delta Gas Research (EDGaR) programma.
EDGaR is medegefinancierd door het Samenwerkingsverband Noord
Nederland, het Europees Fonds voor Regionale Ontwikkeling, het
ministerie van Economische Zaken en de provincie Groningen.
L.P.L.M. Rabou
March 19, 2015
Investing in your future
This research has been co-financed by grants of the Energy
Delta Gas Research (EDGaR) program.
EDGaR is co-financed by the Northern Netherlands Provinces,
the European Fund for Regional Development, the Ministry
of Economic Affairs and the Province of Groningen.
23
 Be prepared to pay more
Current wholesale prices (approximately)
• Natural gas 0.22 €/m3 7 €/GJ 25 €/MWh
• Electricity 11 €/GJ 40 €/MWh
• Wood 50 €/ton 5 €/GJ 18 €/MWh

• Electricity → H2 > 15% loss > 13 €/GJ + electrolyser

• Electricity → H2 → CH4 > 25% loss > 15 €/GJ + electrolyser + methanation
• Wood → → CH4 > 30% loss > 7 €/GJ + gasification + gas cleaning
+ methanation + CO2 removal

=> Optimize efficiency and reduce costs

L.P.L.M. Rabou 24
March 19, 2015
ECN
Westerduinweg 3 P.O. Box 1
1755 LE Petten 1755 LG Petten
The Netherlands The Netherlands

T +31 88 515 4949

F +31 88 515 8338
info@ ecn.nl
www.ecn.nl

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