Hydrogen

Economy
Opportunities for Process Analytics

Unrestricted | © Siemens 2022 | October 2022 | Process Analytics

Agenda

01 The Market

HYCO Plant – Steam Methane Reformer

02 (SMR)

03 Hydrogen Liquefier

04 Hydrogen Purity for Mobility

05 Electrolysis

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 The Market

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What is Hydrogen?
Lightest and most abundant

1.008
H gas
Never alone

Fuel of stars

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Hydrogen
Some interesting facts and figures

$14.1 bn 10 m
Hydrogen plant and equipment investments will China plan 10 million cars by 2050,
grow from US$6.0 bn in 2017 to US$14.1 bn 1,000 hydrogen stations by 2030.
in 2022.
A CAGR of 18.6%.

1807
The first hydrogen car was invented 1807
29.2%
Hydrogen production market will grow
by Francois Issac de Rivaz. Hydrogen was US$426.8 m in 2017 to US$1.5 bn in 2022.
converted to electricity by a fuel cell. A CAGR of 29.2%.
Worldwide production is 70 MtpA.

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Hydrogen
Some interesting facts and figures

Global H2 supply … … meets global H2 demand

Three main technologies to produce H2 Hydrogen market is divided in three sectors
while industry being by far largest one

4% Electrolysis & others3 1% Mobility4,6

• Utilize electricity to split water into hydrogen • Expected growth by green H2
and oxygen, mainly chlor-alkali electrolysis • Penetration of FCV and green fuels
systems are key drivers

48% Partial oxidation & Coal gasification3 9% Energy4,6

Global Hydrogen
• POx as by-product from chemical production Expected growth due to need for
• Coal gasification as part of chemical Demand storage of curtailed renewables
processes in the steel industry 70 m t5 90% Industry6
48% Steam Methane Reforming (SMR)3 • Includes chemical, refineries, metal
Synthesis from steam and natural gas, processing and others
today most economic method • Expected growth due to CO2
emissions regulations

Global demand is set to increase in coming years and Production Techniques will become greener.

Source: 1 Freedonia; 2 https://www.irena.org/-/media/Files/IRENA/Agency/Publication/2019/Sep/IRENA_Hydrogen_2019.pdf p.; 3 2014 FCH GIA; 4 Navigant; 5 IEA 2019; 6 CertifHy

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Hydrogen production, key applications

Industry Key Percentage of Hydrogen 3% 2%

Sector Applications Global H2 Demand Sources
4% 6%
• Ammonia
Chemical • Polymers
• Resins
65% 18% Global
35% Hydrogen 54%
• Hydrocracking 48% Market
Refining • Hydrotreating
25% 30%

• Annealing
Iron &
• Blanketing gas
Steel • Forming gas
Natural Gas Ammonia production

• Semiconductor Oil Chemical Industry/refineries

• Propellant fuel 10%
General • Glass production
Coal Electronic Industry

Industry • Hydrogenation of fats Electrolysis Metal/Glass Industry

• Cooling of generators Food Industry

Source: IRENA based on FCH JU (2016)

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Hydrogen Production

Primary Energy Secondary Energy Conversion Intermediary Product Final Energy Carrier Process Analytics
Potential in all major H2
Solar, Electricity Electrolysis
Wind
production processes:
• Quality – Impurities
Algae from Biochemical
measurement – Final
sunlight Conversion product and Feed
Hydrogen • Safety (O2, H2)
Biomethane
Biogas • Process Control
Biomass
Ethanol (Reactor, Furnace)
Vegetable Oils • Environmental (CEMS)
Thermochemical
Natural Conversion
Gas
SMR
Steam methane
reforming Syngas
Oil
POX
Partial oxidation

ATR
Coal Autothermal reforming

Source: Shell Hydrogen Study © Shell

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What’s next?

Blue Hydrogen
Grey hydrogen whose CO2 emitted during production
is sequestered via carbon capture and storage (CCS).

Main production routes Characteristics

Intensive CO2
+ SMR + CCS
Grey Hydrogen Expensive
Currently, 96% of hydrogen is produced from
fossil fuels via carbon intensive processes. + Coal gasification + CCS Social acceptance

Main production routes Characteristics

Intensive CO2
Steam Methane Reforming (SMR)
Low cost Green Hydrogen
Low or zero-emission hydrogen produced
Coal Gasification Social acceptance using clean energy sources.

Main production routes Characteristics

Zero emissions of CO2
+
Expensive
Electrolysis using renewables
Social acceptance

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Hydrogen
Power-to-X ?

Power Generation Conversion in/out Utilization

H2
Direct utilization w/o storage

Mobility
(H2-Fuel)
>90%
Consumption of hydrogen
Fuel Cell Car
O2 H2 H2-Storage in industries (e.g., ammonia
H2 production and petrol
Solar power + – refineries)1
CH4
Energy
Gas pipeline (Re-Electrification)
Intermittent
H2O
“Convergence” • Storing renewably generated power
generation
PEM-Electrolyzer
Gas-Turbine
• Power generation as island solutions
CH4 Injection
H2
Wind power
Steady • Methanol
generation H2
• Ammonia
Industry
• Fertilizers
(H2-Utilization)
Grid CO2
Methanation/CO2 • Methane
utilization/others Industry
• Polymers/Resigns
Fossil • Steel

H2 drives the convergence between energy and industry markets

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Hydrogen Council
Roadmap

Start of Mass market

commercialization acceptability

Power- In renewables-constrained countries

1 generation In other countries

Transportation Forklifts
4 Medium and large cars
City buses
Vans
Coaches
Trucks
Small cars
Trams and railways Synfuel for freight
Minibuses ships and airplanes
Passenger ships

Industrial Medium-/low industry heat

5 energy High-grade industry heat

Building heat Blended hydrogen heating

6 and power Pure hydrogen heating

Industry Refining Production of methanol, olefines and BTX using H2 and captured carbon
7 feedstock Ammonia, methanol Steel
Decarbonization of feedstock

Today 2020 2025 2030 2035 2040 2045

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Why highlighting this story about Hydrogen plants?

Hydrogen (H2) is globally required for many chemical processes, mostly hydrocracking and
01 ammonia (fertilizer industry)

Today it is produced mostly from fossil fuels: by steam reforming of natural gas (SMR), partial
02 oxidation (POX), autothermal reforming (ATR). There is a need for process control and final product
quality control using our product portfolio: CGA + GC

Today Hydrogen is mostly produced and used locally. It’s not easy: can embrittle many metals and is
03 flammable. Projects are and will be everywhere in the world.

Future: Hydrogen (H2) is the central pillar of energy transformation required for decarbonization and
04 the energy carrier in the future of transportation.
There are requirements for impurities measurement to assure high purity H2.

Water electrolysis is used to produce only 4% of the total ~70 m tpa H2 today, but this technology is
05 expected to significantly grow in the future. Together with Blue Hydrogen this trend will bring plenty
of opportunities for our product portfolio.

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 SMR
Steam Methane Reforming

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HYCO Plant

01 02 03 04
Feedstock Steam Reforming Shift Reaction/ Raw Hydrogen
Purification CH4 + H2O → CO + 3H2 Syngas Heat Recovery Purification
• Hydrogenation of organic • CO + H2O → CO2 + H2 • Pressure Swing Adsorption
sulphur and Chloride • Catalyst: Metal tubes filled (PSA)
• Cold Box to separate
compounds with Nickel
CO2 from H2 • 99.999% pure Hydrogen
• Olefins Removal • Conversion rate influenced
• Tail gas recycled
by temperature, steam/
• Removal of H2S to reformer
methane ratio and pressure
and HCL

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HYCO Plant
Other similar processes

POX ATR
Partial Oxidation Auto Thermal Reforming
Feedstock is coming from Air Separation Unit Mix of POX & SMR – heat

Initial process: Combustion zone: Partial oxidation 2 processes:

• CnHm + n/2 O2 → n CO + m/2 H2 Combustion zone: Partial oxidation
• CO + H2O → CO2 + H2 (Shift) • CnHm + n/2 O2 → n CO + m/2 H2
Steam Reforming zone
Hydrogen purification – identical with additional
• CH4 + H2O → CO + 3 H2
scrubber to remove remaining particles and gas
processing plant to remove contaminant before PSA • CO + H2O → CO2 + H2 (Shift)
(acid gas, NH3 etc.)
Hydrogen purification – identical

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Steam Methane Reforming
Measurement points

CEMS SCR NH3 Shift Converter Control CO Product

A4
AX4
Feed Slip
HT Shift Converter LT Shift Converter
Natural Gas AX9
A9 CO Product
SCR
A1
AX1
AX1 Flue Gas
AX3
A3
Hydrogen Product
SMR Combustion
Control
SMR Feed H2 Product –
AX2
A2 PSA Control
CO A11
AX11

Steam Methane AX6

A6 Separation
Reformer
Syngas CO2 chemical Pressure Swing
(H2 & CO Yield) wash Absorption
Sulfur Acid Gas Removal
removal

AX8
A8 AX10
A10
Desulfurization AX
Control
AX5
A5
Steam Dryer & coldbox
A13
AX13
Fuel Gas CO2 A7
AX7

Fuel Gas A12

AX12
CO2 Product PSA Tail Gas

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Process Analyzers in HYCO Plants
Typical Measurements and AP Portfolio

C1 % SIPROCESS H2 %
Technology Portfolio C2 %
Shift Converters (High Temp)
GA700 CO %
C3 % SIPROCESS
Cold Box GA700 CO ppm
TDL: O2: C4 %
MAXUM Ed. SIPROCESS
Natural Gas (FEED)
10% 3% II C5 % Acid Gas Removal GA700 CO2 ppm
C6+ % H2 ppm
CEMS: MAXUM
N2 % CO Product CH4 ppm
7% CO2 %
Ed. II
N2 %
H2S ppm
H2S: H2 ppm
Moisture: ULTRAMAT O2 % CH4 ppm
10% 20%
Reformer Combustion Control
23 CO %
CO2 Product
MAXUM
Ed. II N2 %
SCR/SNCR LDS6 NH3 ppm CO ppm
O2 % AR ppm
CO ppm MAXUM
PSA (H2 Product) CO ppm
Ed. II
NDIR: ULTRAMAT CO2 % CH4 ppm
CEMS
23 NOx ppm
27% SOx ppm MAXUM
CH4 %
PSA Tail Gas CO %
Ed. II
GC: CH4 ppm H2 ppm
43% H2 % MAXUM
Ed. II
MAXUM Ed. CH4 ppm Fuel Gas BTU
II or
SYNGAS
SIPROCESS CO %
GA700 CO2 %
H2O ppm

Overall Siemens provides a strong portfolio for HYCO plants!

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MAXUM Ed. II Ultra Trace FID
Analysis of CO traces down to ppb levels

PSA Outlet
End-Product

Ultra Trace FID M50 – packed –Methanizer – FID

470 ppb CO in H2 50 ppb CO in H2

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MAXUM Ed. II Densification
Optimization potential by using MAXUM Ed. II for the total solution

1 SMR FEED Serial stream

analysis by GC Stream 1 Stream 2 Stream 3
2 Fuel Gas

3 PSA Tail Gas

4 H2 Product (PSA Outlet)

5 CO Product

Densification

CO Product H2 Product

Sample Parallel stream

Streams analysis by GC

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CGA application at HyCO plants

HyCO plants require several NDIR analyzers

for process control application
• ULTRAMAT 7 module for highly selective measurements
of CO, CO2, CH4 , SO2, NO in ppm or % range. Version
with stacked detectors available (CO/NO and CO2/CO)
• OXYMAT 7 module for measurements
of O2 paramagnetic method
• CALOMAT 7 module for % range H2 in N2 or other gases
• Additionally auxiliary applications available: CEMS with
ULTRAMAT 23 or ULTRAMAT/OXYMAT 6
• LDS6 NH3 ammonia slip application on DeNOx plant

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CGA application at HyCO plants
Example: stacked detectors, EX Zone, Sample: syngas

CO 0 ... 30 %
CO2 0 ... 20 %

CH4 0 ... 10%

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 Hydrogen
Liquefier

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Hydrogen Liquefier

H2 Off gas from

Pressure Wing
Refineries,
Adsorption (PSA) Vacuum jacketed line
Crackers, PDH LH2 transfer

Vent DAQ

MFC
H2 supply
Hydrogen LN2 supply
Liquefier

Backing pump
/TMP

Liquid Hydrogen 5 L LH2 200L Precooler/

Storage H2 Liquefier O-P converter

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Contaminants in High purity gases
N2 in H2

Analyzer MAXUM Ed. II Process GC

Environment MAXUM Ed. II : CI.I, Div.1, B&H2, C, D

Purifier: General Purpose

Separation Micro packed 1/16”

Analytic Backflush

Valve Single 10 port diffusion tight Model 50 diaphragm

valve for combined injection and backflush

Detector Thermistor Thermal Conductivity Detector

Carrier Gas Hydrogen UHP (99.995%)

Purified to >99.9999% with external
Getter purification;
Consumption 3 scfd

Cycle Time 2 minutes

Detectability ~0.2 ppmv (2xSN)

Repeatability +/- 0.22 ppmv at 0.6 ppmv over 4250 analysis

cycle/6 days

Minimum detectability of about 0.2 ppm with a TCD Detector and High Purity Carrier Gas

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 Hydrogen Purity
for Mobility
e.g., Refuelling Station

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New Standard
Hydrogen Purity for Mobility

Impurities Tolerance
limit
GC Technique
(Detector)
Range
(ppm)
ISO
threshold
EN 17124 – 2018
Total hydrocarbons except methane (C1 basis) 2 µmol/mol FID 0.5 – 200 2
Hydrogen fuel — Product
Methane (CH4) 100 µmol/mol FID 5 – 1000 100 specification and quality
Oxygen (O2) 5 µmol/mol TCD 1 – 100 5 assurance — Proton exchange
Helium (He) 300 µmol/mol TCD 50 – 3000 300 membrane (PEM) fuel cell
Nitrogen (N2) 300 µmol/mol TCD 50 – 3000 300 applications for road vehicles
Argon (Ar) 300 µmol/mol TCD 50 – 3000 300
Carbon dioxide (CO2) 2 µmol/mol TCD 1 – 100 2
ISO FDIS 14687-
Carbon monoxide (CO) 0.2 µmol/mol FID 0.05 – 20 0.2
Water 5 µmol/mol N.A.
Hydrogen fuel quality —
Total sulfur compounds (S1 equivalent) 0.004 µmol/mol N.A.
Product specification (revision
Formaldehyde (HCHO) 0.2 µmol/mol N.A. of previous one) to be
Formic acid (HCOOH) 0.2 µmol/mol N.A. published
Ammonia (NH3) 0.1 µmol/mol N.A.
Halogenated compounds (halogen ion eq.) 0.05 µmol/mol N.A.
HCL 0.05 µmol/mol N.A.
H2S 0.004 µmol/mol N.A.

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Monitoring of hydrogen purity

FIDAMAT 6 gas analyzer is suitable for the

determination of the total hydrocarbons.
Version 6-G can be used for following applications:

Example applications with compressed H2:

• Monitoring of leakages of lubricants on hydrogen
compressors to prevent contamination of H2 and as
consequence protection PEM hydrogen fuel cells
• Monitoring the hydrogen after evaporation of liquid H2
and compression at so called ionic piston
compressors which use isothermal compression
(medium, 450 bar or high pressures, 900 bar)

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 Electrolysis

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 Option 2

Electrolysis of water is the separation of water (H2O)

into oxygen and hydrogen gas using electric current

What is electrolysis?

1800 • A DC electrical power source is connected to two electrodes which

are placed in the water
• An electrolyte allows the charge exchange and is the namesake
of the various technologies
William Nicholson and Anthony Carlisle
discovered electrolysis, the separation of water • Hydrogen will appear at the cathode, Oxygen at the anode
Current + 2H2O → O2 + 2H2
into hydrogen and oxygen by direct current • The production rate is proportional to the total electrical charge
and established a new field in chemistry:
The electrochemistry
Facts and figures
• 1 kg hydrogen needs stoichiometrically 9 liter water
• The energy content of 1 kg hydrogen amounts for 39.4 kWh

1888
A method of industrial synthesis of hydrogen
Upper heating value in kWh/kg1

and oxygen through electrolysis was

developed by Dmitry Lachinov.
39 Hydrogen 16 Methane 13 Diesel 13 Gasoline

1 http://www.linde-gas.at/internet.lg.lg.aut/de/images/1007_rechnen_sie_mit_wasserstoff_v110550_169419.pdf

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There are three considerable technologies of water electrolysis

Alkaline Water Electrolysis PEM Electrolysis High temperature

Diaphragm Gas tight membrane Solid oxides
Anode Cathode Anode Cathode Anode Cathode

½ O2 H2 ½ O2 H2 ½ O2 H2

OH- KOH H+ O2-

electrolyte
Water Water
- + - + - steam
+

Electrolyte KOH3 Polymer membrane Ceramic membrane

Circulated medium KOH3 Water Steam
Operational temperature1 60 – 90 ºC RT4 – 80 ºC 700 – 900 ºC
Technical maturity1 Industrially mature Commercially available Lab/demo
Field experience1
Cold-start capability2
Intermittent operation2
Scalability to multi–Mega Watt2
Reverse (fuel cell) mode1

1 Fraunhofer; 2 IndWede; 3 KOH: Potassium hydroxide; 4 Room temperature Existing/ available In development/limited Not possible, not available

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Potential application with CGA
Electrolyzer

H2 in O2 0...2 % vol. (CALOMAT)

O2 in H2 0...2 % vol. (OXYMAT)

O2 H2O + O2 H2O + H2 H2
Gas treatment

Gas/water
H2O
separator
Heat
exchanger SCS

H2O H2O

Stack/module

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 Summary

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Summary

Offerings for challenging applications

• CO and H2S analysis down to <100 ppb MDL
• Trace N2 measurement in H2 with TCD
• Trace hydrocarbons in Hydrogen

Flexible concepts
• The GC hardware concept allows to group multiple
streams efficiently by using serial analysis and/or
parallel application concepts
• All sample streams can be measured with a
minimum amount of GCs (Densification)
• SIPROCESS GA700 – 3 measurements in one analyzer

Total Analyzer Package offered from one hand!

GC and CGA Siemens portfolio allows to cover 90%
of the analyzer application

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Questions and Answers

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Disclaimer

© Siemens 2022

Subject to changes and errors. The information given in this document

only contains general descriptions and/or performance features which
may not always specifically reflect those described, or which may
undergo modification in the course of further development of the
products. The requested performance features are binding only when
they are expressly agreed upon in the concluded contract.

All product designations may be trademarks or other rights of

Siemens AG, its affiliated companies or other companies whose use by
third parties for their own purposes could violate the rights of the
respective owner.

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 Contact
Published by Siemens AG
Frederic Thielland

DI PA S&V MI COE
Oestliche Rheinbrueckenstrasse 50
76187 Karlsruhe
Germany
E-mail [email protected]

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