Cryocap

™ CRYOCAP : Cryogenic solution for CO capture, 2 a world premiere Press Kit November 2015

SUMMARY Cryocap™ – a world premiere developed in France ..............................................3 Cryocap™ H technology .....................................................................................4 2 Cryocap™ H – how does it work? .......................................................................5 2 Upgrading the recovered CO ..............................................................................6 2 Cryocap™ H – towards a decarbonized hydrogen sector ..................................7 2 Air Liquide, a player in the energy transition ..........................................................8 Blue Hydrogen, Air Liquide’s commitment ............................................................10 Innovation at Air Liquide .......................................................................................11 Key figures ...........................................................................................................11 Contacts ..............................................................................................................12 2 Cryocap™ Press Kit

CRYOCAP™ – A WORLD PREMIERE DEVELOPED IN FRANCE A technological innovation 2 Cryocap™ is a technological innovation for CO capture methane reforming hydrogen production unit operated by using a cryogenic process (involving low temperatures, Air Liquide in France represents the first industrial deployment 2 around -50°C, to separate gases) that is unique in the world. of the Cryocap™ H technology. Cryocap™ can be adapted to specific applications combining a variety of Air Liquide technologies: the capture Because Cryocap™ is located at the heart of the hydrogen 2 production process – i.e. where the emissions are the most of CO produced by steel plants (Cryocap™ Steel), thermal 2 power plants (Cryocap™ Oxy), or hydrogen production units highly concentrated – it optimizes CO capture compared 2 with conventional solutions, in particular the chemical process (Cryocap™ H ). known as amine scrubbing capture. Today, Cryocap™ is 2 Cryocap™ has resulted in the filing of several patents and the only technique that enables the reduction of the CO illustrates the Air Liquide group’s innovation. Its installation released during the production of hydrogen while also in Port-Jérôme, Normandy, France, at the largest steam increasing this hydrogen production. Towards the decarbonized production of hydrogen The most common process for producing hydrogen is based on steam methane reforming, which involves a chemical 2 reaction between natural gas, mostly composed of methane, and steam, which produces hydrogen and also releases CO . 2 2 [1] Cryocap™H enables to capture a large portion of the CO that is released (from 60% to 90 % ). It can be then liquefied 2 and purified to be finally used to meet the CO needs of local industrial markets (agri-food, water treatment, etc.). This solution represents an important step toward the ultimate goal of producing decarbonized hydrogen. An ambitious project conducted with the support of local and national government agencies Cryocap™ represents an investment for research centers and one of its engineering Air Liquide of around 30 million euros, centers. This geographic proximity of operations, decided in 2012. It also benefited from public researchers, and designers has allowed for financial support of close to 9 million euros, fluid, optimal management of the project. provided jointly by the Haute Normandie Within France, Air Liquide has a strong region, the community of Caux Vallée de ecosystem of innovation that involves 2,000 Seine communes, and ADEME (French people and includes an R&D center, hubs of Environment and Energy Management expertise, a laboratory for new ideas, the Agency) through the Programme i-Lab, and ALIAD, the Group’s venture capital d’Investissement d’Avenir, a government arm in innovative technology startups. In program for investment for the future. 2014, two-thirds of Air Liquide’s spending on innovation was done in France and Air Liquide has chosen to invest in France. additional investments of close to 100 million France constitutes a solid industrial base for euros were decided to accelerate the pace of the Group and also hosts one of its main innovation in France. [1] If hydrogen is used as an energy source in the SMR oven to replace natural gas Cryocap™ Press Kit 3

CRYOCAP™ H 2 TECHNOLOGY The Air Liquide site in Port-Jérôme: the Group’s largest hydrogen production unit in France The Port-Jérôme site, located in Notre-Dame-de-Gravenchon signed a long-term contract with Air Liquide for the supply 3 in Normandy, is the largest SMR (Steam Methane Reforming) of around 50,000 Nm /h of hydrogen for its Esso refinery, hydrogen production unit operated by Air Liquide in France. in Port-Jérôme. At that time, Air Liquide invested 60 million euros in an SMR hydrogen production unit adjacent to the The process of desulfurizing fuels (which is notably required facility of its customer. Operated by the teams of Air Liquide under European legislation) requires large quantities of France Industrie, this unit has been supplying the Esso hydrogen. For this reason, in 2002 the ExxonMobil group refinery with the hydrogen it needs 24/7 since 2005. 4 Cryocap™ Press Kit

CRYOCAP™ H – HOW DOES IT WORK? 2 4 2 1- The reaction between natural gas – essentially composed of methane (CH ) – and steam (H O) requires high temperatures and occurs in a furnace. When it emerges from the reforming oven, the synthesis gas (called syngas) that is obtained, 2 composed mainly of hydrogen (H ) and carbon monoxide (CO), is collected. 2- This syngas then undergoes a catalytic reaction called “shift” that produces a gas mixture that is mainly composed of 2 2 hydrogen (H ) and carbon dioxide (CO ). [2] 3- The gas mixture is then treated in a PSA to produce pure hydrogen ready to be injected into the pipeline to supply the 2 refinery. A waste gas which contents CO in high concentration and some hydrogen is also produced by the PSA. 2 2 4- This is where Cryocap™ H comes in to treat this waste gas and separate the CO from the additional hydrogen. Then 2 the CO is purified to achieve food grade standard. 2 5- The CO is stored in its liquid form and later used to meet the need for continuous supply in certain industrial applications (for carbonating sparkling beverages, for freezing, for agricultural uses, etc.). 2 2 The Cryocap™ H installation in Port-Jérôme has an annual capture capacity of 100,000 tonnes of CO . Cryocap™ technology enables hydrogen production 2 to be increased CO emissions by up to 20% depending during hydrogen production Hydrogen is injected on the configuration are captured through to the neighbouring refinery SMR area of the facilities. liquefaction. to desulfurize fuels. Hydrogen production by natural gas stream reforming. 2 CO storage is then delivered by truck to customers. Natural gas. Cryocap™ area 2 Liquefied CO goes through a series of purifiers enabling to reach food standards. [2] Pressure Swing Adsorbtion Cryocap™ Press Kit 5

UPGRADING THE RECOVERED CO 2 2 2 The concentration of CO in atmospheric air is very low (0.04%). CO is one of the gases sold by Air Liquide around the world. It is recovered from industrial facilities such as fertilizer or bioethanol plants, which emit it during their own processes. 2 The market for CO is a relatively tight one. With the Cryocap™ installation in Port-Jérôme, Air Liquide strengthens and secures its production capacities, as well as improving its ability to satisfy demand. The main applications of CO 2 The agri-food industry: carbonation, Other industries 2 preservation, and refrigerated transport CO is slightly acidic, which makes it suitable for use in water 2 treatment to control pH content and neutralize effluents. It In the form of snow or ice, CO constitutes an extremely powerful and practical source of cold that has a variety can also be used to remineralize drinking water. of uses in the production and shipment of food products, for example to preserve in-flight meals served onboard airplanes In addition, it can be used as a chemical reagent to extract at the correct temperature. the molecules from certain oil and gas products or even for cryogenic cleaning, because it leaves no trace or residue. In its gaseous form, it extends the shelf life of certain 2 2 CO is also present in the composition of certain shielding products by replacing the air in packaging with CO , alone or combined with nitrogen. This helps to cut down on food gases used in welding. waste. It is also used in sparkling beverages, for which Lastly, it can be used to produce theatrical smoke and fog it provides the bubbles, as well as for beverages served in or for other forms of entertainment. restaurants on tap. Used in greenhouse growing, it helps to speed up the process of photosynthesis and improve crop yields. CO is used in various forms: 2 gaseous, liquid, solid… Production Traitement Agricultural Water agricole de l’eau production treatment Chemical industry Industrie chimique Other Beverages industries Boissons 30% Agri-food industry Nettoyage Industrial cleaning 70% industriel Industries Food industry agroalimentaires Soudage Welding Transport réfrigéré Refrigerated transport 6 Cryocap™ Press Kit

CRYOCAP™ H – TOWARDS A DECARBONIZED 2 HYDROGEN SECTOR 2 Cryocap™ H establishes a link between the traditional use of hydrogen – indispensable for producing clean fuels – and its emerging use to charge hydrogen-powered electric vehicles. In doing so, it is reinforcing the Air Liquide’s leadership in technologies designed to protect the environment. The production of hydrogen – at the core of Air Liquide’s business for 40 years Air Liquide’s hydrogen business got its start in the 1970s for the purpose of fueling space rockets and since then has grown constantly, due to environmental regulations concerning fuels as well as the growing trend toward outsourcing hydrogen production by players in the chemical and refining industries. The Group’s Engineering & Construction activity, reinforced by the acquisition in 2007 of the German engineering firm Lurgi, has key hydrogen production processes. Currently, Air Liquide produces around 13 billion m³ of hydrogen annually for the refining and petrochemical industry around the world. Hydrogen applications today Refining and chemical industries Hydrogen energy The hydrogen sector is mainly of interest to oil and gas Hydrogen is a rapidly developing alternative to fossil fuels. It is refineries, which use hydrogen to crack crude oil and to used to power hydrogen fuel cells for stationary applications desulfurize hydrocarbons (around 2/3 of the Group’s total (relay antennas) as well as for clean mobility: forklift trucks, annual sales by volume) in order to produce sulfur-free urban transportation vehicles, and now passenger cars. fuels. The sulfur dioxide that is released by combustion To date, 75 hydrogen charging stations have been engines can provoke respiratory problems in human beings; designed and delivered by Air Liquide around the world. in addition, it is responsible not only for the smog that hovers over many large urban areas but also for the acid rain that causes deforestation and water supply acidification. Moreover, sulfur causes a rapid deterioration in the catalytic converters of vehicles. In 2014, the volumes of hydrogen supplied by Air Liquide to refineries around the world were sufficient to avoid releasing approximately 935,000 tonnes of sulfur dioxide into the atmosphere, which is close to four times the total sulfur dioxide emissions of a country like France. Hydrogen is also used in smaller quantities for the manufacture of numerous chemical (in the nylon, plastics, detergent and paint industries), pharmaceutical, and agri- food (hydrogenation of cooking oils, artificial sweeteners) products, as well as for the heat treatment of metals. Cryocap™ Press Kit 7

AIR LIQUIDE, A PLAYER IN THE ENERGY TRANSITION Air Liquide solutions to protect life and the environment most environmentally-friendly technologies and applications represent more than 40% of the company’s sales. As available. With CryocapTM, the Group is opening up new 2 part of its approach to corporate responsibility, the Group oportunities for reducing the CO emissions released by its is constantly seeking to reduce the environmental impact own production sites and those of its customers around of its production facilities and also to offer its customers the the world. Contributing to lower emissions for Group customers 2 In addition to the CO emissions avoided as a result of the steelmaking, the injection of oxygen into blast furnaces energy performance of its production units, Air Liquide reduces the consumption of coke. Air Liquide estimates supplies numerous products and services that enable its that the use of the oxygen provided for these two 2 2 applications alones enables its customers to avoid CO customers to reduce their own CO emissions and improve their environmental footprint. emissions of around 10 million tonnes a year. Air Liquide enables its customers to produce cleaner via two Air Liquide also participates in several research programs principal applications: in Europe and in the United States that involve the • The desulfurization of hydrocarbons using hydrogen, combustion with oxygen enriched air or pure oxygen, as which reduces the sulfur dioxide emissions (SOx) that well as technologies for capturing this gas after combustion. cause acid rain and allows the catalytic converters on In fact, the combustion of pure oxygen (known as oxy- vehicles to function properly. combustion) results in smoke with a high concentration of 2 CO, which makes its capture possible. This is one of the main • The use of oxygen in furnace burners (glass or cement) 2 technologies that could eventually reduce CO emissions and that significantly lowers their electricity consumption. In thereby lead to a decrease in greenhouse gas emissions. 8 Cryocap™ Press Kit

Hydrogen energy, an alternative to fossil fuels Faced with the energy and environmental The Air Liquide group masters the entire it does not release any greenhouse dual challenge the Air Liquide group has industrial chain (production, storage, gases, particles nor make any noise. been committed for nearly 20 years distribution and use by the final customer) Plus, it takes just five minutes to to the development of solutions, in of this rapidly developing sector. recharge it and it offers an extended particular for clean transportation based driving range of 500 kilometers. on alternative fuels, including biogas and Air Liquide is contributing to the hydrogen. development and use of hydrogen to Even when it is produced using meet the needs of the transportation conventional methods i.e, from Hydrogen is one of the energy solutions sector by supporting the rollout of the natural gas, hydrogen offers a definite being developed to address the clean charging stations needed on a global environmental benefit: for an equal transportation challenges: by combining scale. distance covered, hydrogen electric hydrogen with the oxygen that is vehicles enable to reduce greenhouse present in the air, the fuel cell produces Hydrogen provides real benefits to gas emissions by 20% compared electricity while releasing only water as address urban pollution: not only does a with vehicles powered by internal a byproduct. hydrogen car offer great driving comfort, combustion engines. Cryocap™ Press Kit 9

BLUE HYDROGEN, AIR LIQUIDE’S COMMITMENT With Blue Hydrogen, Air Liquide is moving toward a gradual decarbonization of its hydrogen production dedicated to energy applications. In practical terms, Air Liquide has made a commitment to produce at least 50% of the hydrogen necessary for these applications through carbon-free processes by 2020 by combining: biogas reforming, the use of renewable energies during water electrolysis, the use of the technologies for the capture and upgrading of carbon emitted during the process of producing hydrogen from natural gas. ™ Cryocap in Normandy is part of this initiative. 10 Cryocap™ Press Kit

INNOVATION AT AIR LIQUIDE Innovation is one of the pillars of the Group’s strategy. Innovating enables Air Liquide to open up new markets, creates new growth opportunities and address the major challenges facing society. For Air Liquide, innovation is where scientific expertise meets the entrepreneurial spirit. Air Liquide’s scientific and technological expertise is represented by its Research & Development department, its Engineering & Construction business unit and its centers of expertise, as well as by structures designed to promote entrepreneurship, like the aB&T network, i-Lab, Air Liquide’s laboratory for new ideas, and ALIAD, its venture capital arm. The Group’s innovation ecosystem is backed by an “open innovation” approach. Today, the Group cultivates outside collaboration around the world with customers, universities, research institutes, SMEs and start-ups. KEY FIGURES 6,200 employees contributing to innovation 9 R&D centers worldwide More than 200 industrial and academic partners 15 engineering centers and 3 manufacturing 300 patents filed every year centers worldwide Nearly 60% of innovation spending is dedicated €278 M innovation expenses in 2014 to protecting life and the environment Cryocap™ Press Kit 11

World leader in gases, technologies and services for Industry and Health, Air Liquide is present in 80 countries with more than 50,000 employees and serves more than 2 million customers and patients. Oxygen, nitrogen and hydrogen have been at the core of the company’s activities since its creation in 1902. Air Liquide’s ambition is to be the leader in its industry, delivering long-term performance and acting responsibly. oys - November 2015 T Air Liquide ideas create value over the long term. At the core of the company’s development are the commitment and constant inventiveness of its people. Atteleyn / Air Liquide anticipates the challenges of its markets, invests locally and globally, and delivers high-quality solutions to its customers and patients, and the scientific community. The company relies on competitiveness in its operations, targeted investments in growing markets and innovation to deliver profitable growth over the long-term. Air Liquide’s revenues amounted to €15.4 billion in 2014, and its solutions that protect life and the environment represented more than 40% of sales. Air Liquide is listed on the Paris Euronext stock exchange (compartment A) and is a member of the CAC 40 and Dow Jones Euro Stoxx 50 indexes. echnologies / Jean-Erick Pasquier La Company / P-E Rastoin / Jean-Luc T For any additional information, please contact: Advanced Business and Corporate Communications Air Liquide Caroline Philips +33 (0)1 40 62 50 84 A-pictures / [email protected] Meyssonnier CAP A. Anne Michaud +33 (0)1 40 62 50 59 © Photos : [email protected]