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Naar het herleidbaar meten van waterstof voor de energietransitie
Annarita Baldan, Heleen Meuzelaar, Stefan Persijn, Marcel
Workamp
Botlek studiegroep bijeenkomst
Delft, 21 november 2019
Contents
▪ Introduction energy gas transition
▪ EMN for Energy Gases
▪ The role of hydrogen in the energy transition
▪ Metrological developments in hydrogen for vehicles
▪ Metrological developments in hydrogen and hydrogen enriched natural
gas for gas grid
▪ Conclusions
2
Drivers
3
✓ Paris agreement and 2018 IPCC report urging for more carbon reduction
actions “now”
✓ European legislation: RED II target 2030 - 32% share of renewable
energies in global consumption
Energy gas diversification:
- Foreseen complex energy mix in the next decades: natural gas, LNG,
biogas, biomethane, hydrogen and any future renewable gas
- Ensure the compliance with quality, efficiency, safety requirements
- Guarantee energy gas exchange between countries and trade
How can metrology support the energy transition?
▪ Challenge
Reliability and robustness of measurement results to address the energy transition
beyond national boundaries and beyond a single technology
▪ Solution
European coordinated effort to interface and collect stakeholder needs and to address
these needs in the most efficient way at metrological, standardization, and policy level
European Metrology Network for Energy Gases
4
Who we are
5
EMN Members:16 European NMIs/DIs have
signed the MoU
VSL, NL - Chair
NEL, GB – vice-Chair
BAM, DE – SC
LNE-LADG, FR - SC
NPL, GB - SC
PTB, DE - SC
RISE, SE - SC
BFKH, HU
CEM, ES
FORCE, DK
GUM, PL
IMBiH, BA
IPQ, PT
LNE, FR
TUBITAK, TR
VTT, FI
EMN for Energy Gases FACT SHEET
❑ Under EURAMET
❑ Facilitate energy transition
❑ Focus on metering of energy gases
❑ Conventional fluids and fluids related to (emerging) renewable/ sustainable energy sources
❑ Cross-cutting character; Complementarity of measurement services for
▪ gas composition
▪ gas flow
▪ temperature and humidity
▪ pressure
▪ density
▪ material data
▪ Particles
▪ material testing
6
With kind permission of Air Liquide
EMN Stakeholders and EMN event
▪ National, European and international
associations dealing with energy gases
▪ Energy gas producers
▪ Transport and distribution sector
▪ Manufacturing industry
▪ Research groups and academia
▪ Testing laboratories
▪ Standardisation TCs (CEN, ISO)
▪ Policy makers and regulatory bodies
7
Hydrogen production
8
▪ Water Electrolysis
− Pure H2
− Used for fuel cells and feedstock
− Expensive
▪ Steam Methane Reforming
− Fuel grade H2
− Large scale for heating, industry
− Requires CCS
− Relatively cheap
Source: Hydrogen Roadmap Europe, 2019 - www.fch.europa.eu
Role of hydrogen (H2) in the energy transition
9
Increasing renewables share leading to imbalances of power supply & demand
SOURCES OF ENERGY BACKBONE OF ENERGY SYSTEM
Infrastructure needs to go through a major transformation
Global buffering capacity based on mostly fossil sources
Carbon needs to be reused to decarbonize feedstock
Some energy usage applications are hard to electrify via the grid or with batteries:▪Transport▪ Industry▪Residential heating
END USES
H2 H2
H2CCS
H2 +CCU
H2
H2
H2
Electricity
Hydrogen
TodayFuture
Energy vectors
Source: Hydrogen Council - https://hydrogencouncil.com/
10
Identified measurement needs
11
▪ H2 as a fuel for transport:
− reference methods for impurities analysis
− sampling protocol at the HRS
− flow metering at the HRS
▪ H2 as energy gas in the gas grid (H2 or H2 enriched natural gas):
− reference methods for impurities and sampling protocol at the H2 source and in the grid
− flow metering for trading and fiscal metering
▪ H2 for industries:
− reference methods for impurities analysis according to the application requirement
▪ H2 as storage in P2G:
− evaluation of H2 quantity in the storage
High-quality H2 as fuel for vehicles
12
▪ Hydrogen fuel cell vehicles can play a major role in
the challenge of meeting EU’s 2050 climate goals
▪ Fuel cells require highly purified hydrogen
→ ISO 14687- 2
▪ Dilemma: lack of available measurement
standards and methods
▪ EMPIR MetroHyVe project
(2017 – 2020)
Source: WaterstofWerkt.nl
The challenge: H2 purity analysis
13
▪ Hydrogen fuel purity requirements as specified in ISO 14687-2 range from 300 µmol/mol down to 4 nmol/mol
Species Maximum
Concentration
(μmol/mol) (ppm)
Water 5
Total hydrocarbons 2
Methane 100
Oxygen 5
Helium/Nitrogen/Argon 300
Carbon Dioxide 2
Carbon Monoxide 0.2
Total sulphur
compounds
0.004
Formaldehyde 0.2
Formic acid 0.2
Ammonia 0.1
Total halogenated
compounds
0.05
H2 purity analysis: a real challenge
14
✓Highly sensitive analyzer
✓Reference materials and calibration
✓Suitable materials
▪ sample cylinders
▪ sampling lines, reducers, flow meters
▪ analyzer
Formic acid AmmoniaFormaldehyde Hydrogen chloride
0.2 µmol/mol 0.2 µmol/mol 0.1 µmol/mol 0.05 µmol/mol
To obtain robust and
accurate measurements
of reactive impurities in
hydrogen
System to quantify reactive H2 impurities
15
CHOOH
NH3
CH2O
Dynamic generation of
reference gas mixtures
Laser-based
spectroscopic
techniques
(CRDS)
SI-traceable
reference
gas mixture
Development of measurement standards
16
Gravimetric method (ISO 6142-1)
▪ Dynamic dilution system using
mass flow controllers
▪ Static gravimetric preparation
Dynamic methods (ISO 6145)
▪ Permeation using a magnetic
suspension balance (MSB)
CHOOH NH3CH2O
▪ Calibrated and passivated MSB
(TA Instruments)
− Temperature ± 0.02 ℃
− Pressure ± 0.1 mbar
− Flow rates ± 1.5 mL/min
− Stabilization period ± 3 days
▪ Permeation rate (𝑞𝑚) =
mass loss per unit of time
Permeation-based gas generation method (ISO 6145-10)
17
System to quantify reactive H2 impurities
18
CHOOH NH3CH2O
Dynamic generation of
reference gas mixtures
Laser-based
spectroscopic
techniques
(CRDS, TDLAS)
SI-traceable
reference
gas mixture
Method validation for H2 impurity
analysis → ISO 21087
Robustness
Analytical instrument:mid-infrared CRDS spectrometer
19
▪ Operating range λ = 2.3 - 5.1 µm
▪ Power up to 3 Watt
▪ Line width ≤ 0.001 nm
Optical parametric oscillator (OPO)
Cavity Ring Down Spectroscopy (CRDS)
▪ 2-5 km path length in compact cell
▪ Coated cell
CHOOH NH3CH2O
2700 2800 2900 3000
0
1
2
3
4
5
abso
rptio
n co
effic
ient
(10
-6 c
m-1
)
Frequency (cm-1)
HCl 50 ppb
HF 50 ppb
H2O 5 ppm
CO 200 ppb
Formaldehyde 200 ppb
Formic acid 200 ppb
NH3 100 ppb
H2S 4 ppb
CO2 2 ppm
Performance of validated methods
Specification
level
Measurement
range
L.o.Q. Uncertainty (at the specification
level)
Potential cross-
interference
0.2 µmol/mol 7 nmol/mol – 20
µmol/mol
7
nmol/mol
4% No
0.2 µmol/mol 20 nmol/mol – 10
µmol/mol
20
nmol/mol
8% No
0.05 µmol/mol 1.5 nmol/mol – 50
µmol/mol
1.5
nmol/mol
5% No
0.1 µmol/mol 1- 11 µmol/mol
Under
investigation
Under
investigati
on
Under
investigation
water
20
CH2O
CHOOH
NH3
European measurement campaign of hydrogen from different production processes
21
Hydrogen purity was analyzed against the ISO standard 14687-2. VSL
analyzed the challenging compounds hydrogen chloride, formaldehyde, formic
acid & ammonia by spectroscopic techniques.
Outcome:
▪ No contaminants above ISO 14687-2 threshold in H2 from SMR with PSA.
▪ No contaminants above ISO 14687-2 threshold in H2 from PEMWE with
TSA.
▪ Sampling contamination may lead to false positive.
SMR=steam methane reforming
PSA=pressure swing adsorption
PEMWE =proton exchange membrane (PEM) water electrolyzer
TSA=temperature swing adsorption
European measurement campaign of hydrogen from different production processes
22
https://www.sciencedirect.com/science/article/pii/S0378775319311632
Results of the campaign are summarized in a recent, open access paper:
Flow metrology for hydrogen vehicles
▪ For transparent sales of gaseous fuels at refueling stations, the flow meter and
measuring system must be certified according to OIML-R139 “Compressed gaseous
fuel measuring systems for vehicles”.
▪ OIML-R139 stipulates maximum permissible errors (MPEs)
− 2018 version now includes separate accuracy classes for hydrogen, to allow for quicker roll
out of hydrogen
▪ Traceable test methods are not yet available (infant stage)
23
Flow metrology for hydrogen vehicles – Challenges
▪ In principle, measuring of delivered mass is easy:
− Weigh storage tanks
− Connect to hydrogen refueling station
− Fill tanks
− Disconnect
− Weigh again
▪ Reality: challenges for the development of a test rig for
hydrogen refueling stations
− Pressure rises from approx. 10 to 700 bar during a refill
− Temperature rises from -40 to 85 °C
− Hydrogen is precooled to allow for faster filling
− Explosion danger in case of leaks: ATEX directive
24
Flow metrology for hydrogen vehicles – development of VSL’s Hydrogen Quantity Standard
▪ Based on weighing the delivered amount of hydrogen
− Traceability to mass (kg)
▪ 3 tanks of 2 kg capacity each
− Individual tanks can be selected using valves
▪ Wireless transmitters for temperature and pressure
− No connections to the “real world”, lower uncertainty
▪ Temperature sensitive safety valves for protection in
case of fire
▪ Currently being built
25
Flow metrology for hydrogen grids - general
▪ Flow meters are expected to deviate significantly when used with hydrogen or hydrogen
enriched natural gas:
− Low viscosity and density make hydrogen a difficult gas to measure
− Calibration with air or natural gas will not suffice
▪ Infrastructure and available standards are layed out for natural gas
− Effects of hydrogen on durability of gas meters?
− Type testing and verification → Measuring Instrument Directive (MID):
− How to comply with the MID with respect to traceability?
Lack of compliance with MID for all flow meters in the grid!
26
Flow metrology for hydrogen grids: Objective 1
27
?
Evaluation of instrument compliance to specs (MID/documentary standards) when
hydrogen and hydrogen enriched natural gas is used
Flow metrology for hydrogen grids – objective 2
▪ For the natural gas transportation net (8 – 60 bar), calibrations of natural gas meters are
traceable to primary standards
▪ Harmonization of traceability chains through the EuReGa-consortium ensure reliable custody
transfer across EU borders
− VSL (NL), PTB (DE), CESAME Exadébit (FR), FORCE Technology (DK)
28
▪ VSL is preparing the primary standard (Gas-
Oil-Piston-Prover) for use with hydrogen and
hydrogen enriched natural gas
‒ First tests planned in 2021 as part of the EMPIR-
project NEWGASMET
Conclusions
▪ VSL is working at the development of a measurement infrastructure for hydrogen as renewable energy gas for vehicles and for the gas grid
− MetroHyVe
− Hydrogen
− NewGasMet
▪ Methods and reference materials to ensure the quality of hydrogen (for fuel cells) are in advanced stage:
− The developed methods are sufficiently sensitive to analyse hydrogen samples according to the new ISO 14687-2
− Robust and selective methods
− Compatibility interaction is biggest challenge (in decreasing order: CHOOH, HCl, NH3, CH2O)
− Further research needed to address other impurities and solutions that will speed-up the analysis time
▪ The primary standard for flow measurements of hydrogen at refuelling stations is in development (high pressure – low temperature)
▪ Traceability of flow meters for measurement of hydrogen and hydrogen enriched natural gas in the gas grid at this moment still lacking. Dedicated research is in start phase
29
CHOOH NH3CH2O
