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58THE AIR LIQUIDE ADVANCED TECHNOLOGIES MAGAZINE

www.airliquideadvancedtechnologies.com

Cryogenics : technologies that are part of everyday life

IN BRIEF

Air Liquide: partnering research to expand the realm of possibilities

Ed Sanders: membrane technology has a bright future

FOCUS

Hydrogen-powered logisticsWIDE ANGLE

EXPERT'S VOICE

Cryogenic tanks enable the use of liquid nitrogen to freeze, preserve and transport biological samples.

Extending our range of technologies In concrete terms, this means making cryogenics a driver for innovative solutions, not just in science, but also in medicine and industry. It means finding alternative methods for freight, with vehicles that pollute less thanks to liquid nitrogen and natural gas.

Expanding our markets Logistics hubs using 100 % hydrogen-powered materials handling vehicles are now a reality and a first for Europe! Thanks in particular to the confidence that our customers show in us.

Opening our horizonsAir Liquide is on every continent and the advanced Business & Technologies entity is in Europe, Asia and the USA. Our teams have a common dynamic that resonates all over the world. The recent visit of the Korean President is one of the symbols of this.

This edition of the Cryoscope bears testimony to this dynamic.

Xavier VIGOR CEO of Air Liquide advanced Technologies

Xavier PONTONE Vice-President advanced Business & Technologies Europe

Benoît Potier, Chairman and CEO of the Air Liquide Group, and Korean President Park Geun-hye during her visit to Air Liquide’s Sassenage site.

editorialHORIZONS

Aiming for more eco-responsible practices, taking on new challenges that are firmly rooted in our everyday lives: Air Liquide advanced Business & Technologies is opening up new horizons. What we could only imagine yesterday is now possible.

CRYOGENICS

Technologies that are part of everyday lifeFor nearly 50 years Cryopal1 has been designing, manufacturing and commercializing vacuum lines for cryogenic fluid transfer, and cryogenic tanks with a capacity of 0.5 to 1000 liters.

Countless people benefit from technologies developed by Cryopal without knowing it; in particular people suffering from respiratory failure, who use liquid oxygen storage containers and portables. Or people who use assisted reproductive technology: cryogenic tanks enable the use of liquid nitrogen to freeze, preserve and transport biological samples (sperm, embryos, etc.). The technologies designed by Cryopal are mainly used in the medical, biological and pharmaceutical industries. They are also of interest to industry and research, allowing Air Liquide to remain a driving force in cryogenics within these different sectors.1 Cryopal, Air Liquide entity, was founded in 1968 and recently joined Air Liquide advanced Business & Technologies.

IN BRIEF

03

Air Liquide contributes to meet the energy and environmental challenges we face.

IN BRIEF

BIOGAS

Air Liquide accelerates its development in EuropeAir Liquide has commissioned 12 biogas purification units over the last 12 months in France, the United Kingdom, Hungary and Denmark. Five of these units are operated by Air Liquide.

These plants allow Air Liquide to sign long-term contracts for the production of biomethane intended for the European natural gas network. The biomethane also refuels fleets of natural gas vehicles (NGV).

Air Liquide has designed and built 50 biogas purification units around the world. Transformed into biomethane, it is then injected into natural gas networks. These units have a combined installed capacity of 160,000 m3/h. The biogas purification and distribution industry is an extremely promising form of circular economy that helps to reduce greenhouse gas emissions. It could also provide solutions for the zero-emission transport of tomorrow.

François Darchis, Senior Vice President, member of the Air Liquide group’s Executive Committee supervising Innovation, commented: “These new biomethane production contracts illustrate the ability of Air Liquide to leverage its technologies to incubate new businesses. By positioning on the entire chain from biogas purification to distribution with bio NGV stations, Air Liquide is contributing to meeting energy and environmental challenges.”

VIDEO AVAILABLE ON-LINE

FIRST LOOK

Road freight enters a new eraWhole-heartedly committed to sustainable development, Transalliance has invested in a new breed of trucks. A whole fleet that runs on clean, carbon-neutral fuel. A first for France and Europe.

Road freight has reached a new milestone. On June 21, 2016, a clean multi-energy Air Liquide refueling station opened in Fléville-devant-Nancy, distributing compressed or liquefied natural gas and liquid nitrogen. Air Liquide was chosen to implement this project, as the only company capable of offering this full range of solutions.

The range includes the BlueezeTM solution, which is specially devoted to refrigerated transport. This system cools the air in a truck trailer thanks to the circulation of liquid nitrogen at -196°C, in a totally leak-proof heat exchanger. The benefits are obvious, with 90% less particulates, NOx and CO2 produced; a significant reduction in noise (a major advantage for urban and night-time deliveries); and a lower cost per kilometer.

The alternative energies distributed at this multi-fluid station are accessible to all haulers aiming for cleaner transportation.

EVENTS

Melfi celebrates its 10th anniversary In 2006, Melfi took off on board the Discovery shuttle. Melfi is a super “space fridge”, for which Air Liquide has developed a special motor…

With this NASA-led mission, Air Liquide embarked on a new space adventure. The Discovery shuttle had a cryo-freezer onboard for storing a variety of scientific or biological samples at temperatures as low as -95 °C. Its code name is Melfi (The Minus Eighty degree Laboratory Freezer for ISS). Air Liquide designed and developed its cold-producing turbo engine, which rotates at up to 90,000 revolutions per minute! It was a huge challenge, since it required equipment usually intended for industrial installations to be packed into a very tight space. It was, moreover, constrained by all the parameters of a long-term orbit.

Initially scheduled for use over a two-year period, Melfi is still in activity. This project made Air Liquide part of a very select club of companies capable of designing solutions and equipment that can operate continuously in space.

EVENTS

04 WIDE ANGLE

HYDROGEN ENERGY

100% hydrogen-powered logistics: a first for Europe!

All-hydrogen logistics may already be all the rage in the USA and Canada, but it is also starting to gain traction in Europe with the first large-scale projects. As an example, Prelocentre – which provides a fruit and vegetables logistics service for the Grand Frais chain in France – uses hydrogen to run all goods handling devices in Prelocentre, its warehouse in Saint-Cyr-en-Val near Orléans. A European first!

In a suburb of Lyon, Philippe Giroux makes the most of a quiet moment to read the trade press. An article catches his attention: more and more warehouses in the USA and Canada are using forklift trucks that run on hydrogen. When used in a fuel cell, hydrogen produces clean energy as it combines with air to generate electricity, and water is the only waste emission. Hydrogen can be produced using natural gas – biogas or other – as well as by water electrolysis. As CEO of Prelocentre, the exclusive logistics service provider for the French distributor Grand Frais, Philippe Giroux is very interested!

Hydrogen generates clean energy as it combines with air to produce electricity, and water is the only waste emission.

05

The forklifts can be recharged with hydrogen in just three minutes.

WIDE ANGLE

A new logistics centerThe construction of the Prelocentre logistics center near Orléans was an ideal opportunity to roll out a new system using forklift trucks powered by hydrogen. Right from the planning stage, the company incorporated adaptations to its warehouse in order to run a fleet of forklifts fitted with fuel cells and accommodate the related hydrogen infrastructure. Hydrogen-powered forklifts are no more complicated to operate than battery-powered ones: the batteries in standard electric forklifts are simply replaced with compact fuel cells. Air Liquide is responsible for supplying and maintaining the stock of high pressure hydrogen (450 bar) outside the building and connecting it to the hydrogen station inside the warehouse. The station supplies hydrogen to 46 forklifts, at a pressure of 350 bar. This project is co-financed by the European FCHJU (Fuel Cells and Hydrogen Joint Undertaking) Public-Private Partnership as part of the HyLIFT-Europe project.

Philippe Giroux is confident of success with his project: «I wanted to innovate, but above all, I wanted our new logistics center to benefit from all the advantages of hydrogen energy. Air Liquide has given me that opportunity!»

Full of advantagesHydrogen has many advantages over electricity, offering economic, practical, environmental and technological benefits.

Switching to hydrogen energy in a new warehouse makes sense because it eliminates the need for a costly room to store and recharge electric batteries. This frees up valuable warehouse space as well as saving money!

With hydrogen, several charging stations can be installed at strategic locations in the warehouse, whereas there would be one centralized hub for charging electrical forklifts. Multiple hydrogen charging points limit travel for forklifts, thereby boosting productivity.

Employees’ work is less laborious and there is less risk of accidents because they no longer have to carry the forklifts’ heavy electrical batteries, which weigh several hundred kilos each. The forklifts can be recharged with hydrogen in just three minutes and then they are good to go. This saves precious time every day!

Hydrogen technology allows forklifts to remain in use non-stop. Long stoppages for recharging are no longer necessary. Even better: the performance of fuel cell forklifts is constant throughout use, until the hydrogen runs out. Electrical batteries lose power as the charge runs down.

And finally, the lifespan of a fuel cell is longer: around 10 years, compared with 5 to 6 years for an electrical battery.

What’s next?Prelocentre has only just opened in Saint-Cyr-en-Val, and already it has plans for expansion. The warehouse will soon have more fuel cell forklifts. A second building for Grand Frais is to be constructed nearby, also equipped with fuel cell forklifts. Other major distributors have been impressed by the Prelocentre scheme and are taking a close interest in hydrogen technology for their own logistic centers. One in particular plans to centralize all its former warehouses in one huge logistics hub. These chains have met Air Liquide in order to discuss their projects.

What if all logistics sites in the future used forklifts whose only waste emission was water vapor? The idea is gaining momentum; projects are popping up everywhere and Air Liquide is fully mobilized.

1Find out more: www.fch.europa.eu/project/hylift-europe-%E2%80%93-large-scale-demonstration-fuel-cell-powered-material-handling-vehicles

FUEL CELLELECTRICAL BATTERY

10 years5-6 years

The European HyLift-Europe program1

Prelocentre joined European consortium HyLift to help drive forward its plan for a 100% hydrogen-powered warehouse. The scheme aims to provide large-scale demonstrations of different types of hydrogen-powered forklifts in use, with applications in logistics and at airports. HyLift wants to highlight that the technology is economically viable for end users as well as meeting their operational needs. Nine months after Prelocentre was commissioned, results show extremely positive feedback from the field.

VIDEO AVAILABLE ON-LINE

LIFESPAN

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Can you describe Prelocentre’s business in a few words?

Our logistics center opened in September 2015, with 110 employees, in an industrial zone south of Orléans. Our building devotes 9,000 m2 to the storage of fruit and vegetables at 10°C and 1,000 m2 to refrigerated storage of seafood at 4°C. We work 24 hours a day, 7 days a week, to deliver 70,000 tons of fruit and vegetables to the 64 Grand Frais stores in the west of France.

What made you choose fuel cell forklifts for this warehouse?

We are the logistics service provider for Grand Frais, a well-known specialist in the distribution of chilled and local produce in France. As a partner, I wanted my company to be aligned with our customer’s environmental policy. So when we were setting up a new warehouse, I took the opportunity to make the building eco-friendly. Using hydrogen energy is one part of that. It has many advantages: not only is it sustainable, it’s also competitive and flexible. We don’t need a charging room, so that’s 400 m2 that we can use for storage. On top of that, we eliminate the risks associated with changing batteries, which is a great relief for our material handlers.

Fuel cells also allow us to use our forklifts all day, non-stop. And above all, our personnel are proud to work in the first 100% hydrogen logistics site in Europe! This is also a selling point for Grand Frais.

Why did you choose Air Liquide as the supplier for your hydrogen recharging stations?

I contacted HyPulsion, which was a Joint-Venture between Axane (Air Liquide entity) and Plug Power1 at the time, after reading an article about a practice that’s common in the US and could save my company money: hydrogen in logistics. Our partnership with Air Liquide is going great, my contacts are highly competent and know our business well. Hydrogen technology is easy to adopt, with operators only needing a short training session. Air Liquide even allowed me to join the European HyLift program, and I’m proud to be part of a Europe-wide project.

Philippe Giroux, Prelocentre CEO

questions for…

1 Plug Power, Inc. is a pioneering American company in the hydrogen sector, which produces fuel cells for forklift trucks.

WIDE ANGLE

Other experiences in FranceThere are no fewer than 10,000 hydrogen-powered forklifts in the USA, with a total capacity of 100 million hours of running time powered by fuel cells. Initiatives are gradually appearing in Europe. Air Liquide already supplied a hydrogen recharging station to leading furniture distributor Ikea in 2014, to power around 20 forklift trucks at its logistics hub in Saint-Quentin-Fallavier near Lyon. In early 2015, FM Logistic chose Air Liquide as its partner when deploying hydrogen-powered forklifts at its logistics center in Neuville-aux-Bois near Orléans, and to install a recharging station. Unlike the Prelocentre project, these two operations were undertaken on existing sites, which already used electrical forklifts. The switch will be gradual, with fuel cell forklifts steadily replacing the electrical ones. The two sites are not yet 100% hydrogen.

HYDROGEN-POWERED FORKLIFTS IN THE USA

MILLION HOURS OF RUNNING TIME POWERED BY FUEL CELLS

2012

2014

2015

AIR LIQUIDE HYDROGEN STATIONS FOR MATERIAL HANDLING VEHICLES IN FRANCE

First French logistics hub equipped with hydrogen forklifts, for Air Liquide Welding in Vatry

Hydrogen station for IKEA in Saint-Quentin-Fallavier

Creation of a hydrogen station for FM Logistic in Neuville-aux-Bois

Air Liquide sets up a hydrogen station for Prelocentre in Saint-Cyr-en-Val, the first all-hydrogen warehouse in Europe

10,000100

07

Is this technology for separating gas using polymer membranes new for you?

No, it’s a subject I have been working on for many years. Membrane based gas separation is used in a wide range of applications, from nitrogen inerting of tanks - aeronautics, industry and food processing ; to the recovery of hydrogen, production of biomethane and the purification of natural gas for the clean energy market.

What’s the principle behind it?

Given a partial pressure difference across a membrane, gases selectively cross the membrane based on differences in size, shape, and solubility using the partial pressure as a driving force. For example: oxygen molecules cross the membranes 2 to 9 times faster than larger, less soluble nitrogen molecules. This underlying phenomena enables an OBIGGS1 system to produce a stream of nitrogen-enriched air to inert military and commercial aircraft fuel tanks. It is also the underlying principle for all membrane based separations. The extent of separation is determined by the polymer used for membrane fabrication. Through molecular design of the base polymer, membranes are tailored for specific separations.

Has the technology changed much since its beginnings?

Yes, a lot. Modern membranes are more selective, stronger, and more efficient. The separation layer is thinner too. We have gone from 0.2-micron thick membranes to more efficient 0.05-micron composite membranes. This means we have divided the quantity of membrane modules needed by four. That's a huge saving!

What do you think is the most significant progress?

The coming advances in natural gas conditioning. Until now, membranes required an onerous and costly pre-treatment to protect them from contaminants in the sub-quality natural gas. The acquisition of PoroGen has given us access to composite membranes based on polyether ether keytone (PEEK), a very robust polymer immune to contaminants. PoroGen membranes can replace costly natural gas pretreatment. When combined with highly selective MEDAL2 membranes, pipeline quality natural gas is produced. System footprint and weight are reduced, the separation system has no moving parts and reliability is drastically improved. This is a huge change!

Do these new membranes open up new horizons for Air Liquide?

Exactly. The Air Liquide advanced Separations (ALaS) team’s role is to develop membrane systems to exploit the synergies between the MEDAL and PoroGen technology portfolios. These systems improve efficiency, cost effectiveness and system operability while providing pipeline quality natural gas or renewable biogas to meet future energy demands.

So we are moving towards clean energy with limited environmental impact?

Indeed. The ALaS natural gas systems use no hazardous chemicals and reduce environmental footprint. It’s an interesting option for offshore and remote applications. This technology could help meet the planet’s growing energy needs by providing “clean” natural gas. For example, as a fuel source, CO2 emissions from natural gas combustion are approximately 50% lower than coal-based systems!

How do you see the future?

The prospects for the future exceed the progress achieved! Today’s membranes are limited by the intrinsic separation performance of the polymers used to make the membrane. Membrane materials with disruptive performance have recently been developed. For example, a polymer with 150 times the nitrogen productivity and identical selectivity has been reported. Materials with similar increases in performance have been reported for other separations, further broadening the impact of membrane based separation. Successful development of these materials into membranes and separation systems will greatly reduce the production costs of commodities required for continued world growth and simultaneously address the environmental consequences of the growth. Work to develop these membranes is ongoing. I am very enthusiastic about the future impact of membrane technology and working to develop technology that could benefit our planet’s future!

KEY FIGURES

1MILLION FIBERS FOR A MEMBRANE

1OBIGGS is an autonomous system that generates nitrogen on board planes in order to protect fuel tanks against the risks of explosion.2Air Liquide Advanced Separations is the result of Air Liquide's acquisition of MEDAL and PoroGen.

EXPERT'S VOICE

ED SANDERS

Membrane technology has a bright future

Air Liquide advanced Separations’ Innovation Manager/CTO & International Fellow, Ed Sanders, has new ambitions for 2016: to launch a new clean technology for purifying natural gas, to meet our future energy needs.

“ Modern membranes are more selective, stronger, and more efficient.”

INNOVATION

EXPERIENCE FOR MEDAL

25 years'

MEMBRANE DIAMETERS OF BETWEEN

INCHES1 and 12

METER LONG1

MAXIMUM

08 FOCUS

CRYOGENICS

AIR LIQUIDE: PARTNERING RESEARCH TO

expand the realm of possibilitiesStudying the properties of matter, making objects or fluids levitate, pushing back the limits of nuclear magnetic resonance, developing superconductive materials; The opportunities opened up by the hybrid magnet being built at the CNRS National Laboratory for Intense Magnetic Fields (LNCMI) in Grenoble are vast. Air Liquide contributed to this unprecedented adventure by supplying the cryogenics that the magnet requires.

Intense magnetic fields are a powerful research tool. They make the visible invisible, reveal as-yet unknown properties of matter, produce magnetic resonance images with previously unseen resolutions, grasp the secrets of superconductive materials below critical temperatures, and more. A magnetic field is described as intense if it exceeds 20 teslas1, which is 400,000 times stronger than earth’s magnetic field. These properties are already being used in a wide variety of projects, like NeuroSpin’s medical imaging platform, the experimental ITER nuclear fusion reactor, or the in-depth study of graphene – a very promising material of the future, for the production of flexible flat screens, or the creation of ultra-fast nano-transistors, to a tripling of electric vehicles’ battery capacity. There has even been talk of building a space elevator made from graphene!

The combination of a resistive magnet and a superconductive magnet But in order to exploit the extraordinary properties of intense magnetic fields, you first need to be able to generate them. Only a handful of laboratories in the world have the necessary equipment. The LNCMI is one of them. Every year, researchers from all over the world flock to its site in Grenoble to conduct continuous experiments under intense magnetic fields up to 36 teslas, or to Toulouse, for 90-tesla pulsed magnetic fields. To go even further, the LNCMI is building a magnet in Grenoble capable of generating a magnetic field of 43 teslas. Only a hybrid magnet, made up of an assembly of copper alloy electro-magnets and a superconductive magnet can produce such a powerful magnetic field.

Cryogenics crucial to the 43-tesla magnet Adding a superconducting magnet with no electrical resistance at low temperatures, reduces the energy required to generate intense magnetic fields. For this, the LNCMI sought the help of cryogenics2 expert, Air Liquide. “The ties between the low-temperature research industry and Air Liquide go back to the 1950s,” recalls Luc Ronayette, cryogenics manager for the 43 T Hybrid magnet project, “when TBT was founded by the inventors of the first helium liquefiers, the Frenchmen Louis Weil and Albert Lacaze, before being acquired by Air Liquide.”

Involvement from the early stages of research projects Because Air Liquide has nurtured this special relationship with public research, it is familiar with its needs, enabling it to design suitable equipment very early in projects. “It’s no coincidence that our HELIAL3 helium liquefier was selected by the LNCMI. It is a reliable and robust liquefier that will operate 24 hours/day, 10 months/year,” explains Air Liquide advanced Technologies’ Hydrogen and Helium Product Manager, Simon Crispel. Combined with a sub-atmospheric pumping system, the system will be capable of supplying the magnet with superfluid liquid helium pressurized to 1,200 hPa at a temperature of 1.8 Kelvin. “Its performance exceeds our requirements,” admits Luc Ronayette. “The contract provided for a production capacity of 130 liters of liquid helium per hour. In the trials conducted in the first half of 2015, we reached 150 liters/h.” This previously unseen level of efficiency for this range of helium liquefiers was made possible by the use of 3D turbines. This first for Air Liquide and the LNCMI led them to draft a joint publication4 for the ICEC16-ICMC2016 conference in New Delhi (India).

CRYOSCOPE

Air Liquide advanced Business & Technologies

July 2016 - N° ISSN 2107-4658

Publishing director: Xavier Vigor

Redaction (Brief): ginette Redaction (Wide Angle, Expert's voice and Focus): Catherine Decombe-Joulain

Photos and illustrations: Air Liquide, J. Bastable, CNRS / D. Morel / Laboratoire National des Champs Magnétiques Intenses - Grenoble, L. Deflorenne, Future Biogas, L. Lelong, H. Lucas / S. Guillemin, M. Malakoff, NASA, Utopik photo.

Coordination: Nathalie Simon de Kergunic, Katelyne Braunlich

Graphic design: ginette

Print: atlanticlafab

Distribution: atlanticlafab

Printing: 1950 copies (EN/FR) Legal deposit upon publication.

2 rue de Clémencière - BP 15 38360 Sassenage

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Thanks to all the employees who contributed to this issue: C. Anglade, S. Artuso, B. Baratte, B. Chidaine, P. Crespi, S. Crispel, J. Cristiani, P. Dilly, C. Dubois, A. El Haroussi, C. Franceschini, E. Sanders and L. Tonnellier. Thank you to all of our customers and partners mentioned in this issue of Cryoscope.

1 The tesla is the unit of the magnetic field

2 Cryogenics is the science of temperatures below -150°C or 120 K

3 The HELIAL is a standard helium liquefier designed and built by Air Liquide, financed here by the Rhône-Alpes region and the European Regional Development Fund (ERDF)

4 L. Ronayette, S. Crispel et al. “Cryogenic system for the 43 T Hybrid Magnet at LNCMI Grenoble from the needs to the commissioning”

Significant constraints for the installationAir Liquide perfectly understood the constraints of the LNCMI’s research infrastructure, as Luc Ronayette describes: “Air Liquide had to adapt to our environment in direct contact with the laboratory. Its team started integrating the components of the liquefaction system and their interconnections more than 6 months before the delivery of the equipment to our site. Moreover, Air Liquide had to adapt the connections between the cold box and the compressor using fiber optics rather than electrical cables, which would have been disturbed by the electro-magnetic fields in certain rooms they cross.”

Adding a superconducting magnet with no electrical resistance at low temperatures, reduces the energy required to generate intense magnetic fields.