Noble gases 39 39 DERA Rohstoffinformationen Deutsche Rohstoffagentur (DERA) in der Bundesanstalt für Geowissenschaften und Rohstoffe (BGR) Wilhelmstraße 25 – 30 13593 Berlin Tel.: +49 30 36993 226 [email protected] www.deutsche-rohstoffagentur.de DERA Rohstoffinformationen DERA ISBN: 978-3-943566-64-2 (Druckversion) ISBN: 978-3-943566-65-9 (PDF) ISSN: 2193-5319 Noble gases – supply really critical? Impressum Editors: German Mineral Resources Agency (DERA) at the Federal Institute for Geosciences and Natural Resources (BGR) Wilhelmstrasse 25 – 30 13593 Berlin, Germany Tel.: +49 30 36993 226 Fax: +49 30 36993 100 [email protected] Author: Dr. Harald Elsner with a technical contribution by Jürgen Messner and technical support by Dr. Martin Blumenberg as well as by Jan Warstat/NASCO Energie und Rohstoff AG Contact: BGR/DERA Dr. Harald Elsner Federal Institute for Geosciences and Natural Resources (BGR) Stilleweg 2 30655 Hannover, Germany [email protected] Layout: deckermedia GbR Date: October 2018 ISBN: 978-3-943566-64-2 (print version) ISBN: 978-3-943566-65-9 (online pdf version) ISSN: 2193-5319 Reference: ELSNER, H. (2018): Edelgase – Versorgung wirklich kritisch? – DERA Rohstoffinformationen 39: 197 S., Berlin. Cover images: Jolante Duba/BGR Pslawinski/Wikipedia Hannover, 2019 The BGR (Federal Institute for Geosciences and Natural Resources) is the central geoscientific authority providing advice to the German Federal Government in all geo-relevant questions. It is subordinate to the Federal Ministry for Economic Affairs and Energy (BMWi). DERA Rohstoffinformationen Noble gases – supply really critical? Noble gases – supply really critical? 3 Contents Figures 5 Tables 7 Executive Summary 9 Acknowledgements and Feedback 11 1 Introduction 12 2 Noble gases 13 2.1 Properties 13 2.2 Occurrence and genesis 16 3 Production and uses 21 3.1 Production and processing 21 3.1.1 Helium 21 3.1.2 Neon 22 3.1.3 Argon 23 3.1.4 Krypton 24 3.1.5 Xenon 25 3.2 Uses 25 3.2.1 Helium 26 3.2.2 Neon 38 3.2.3 Argon 40 3.2.4 Krypton 41 3.2.5 Xenon 43 3.2.6 Radon 44 3.3 Toxicity 44 3.3.1 Radon 45 3.4 Recycling 47 3.5 Substitution 48 3.6 Chemical requirements on noble gases 50 3.7 Requirements on helium deposits 60 4 Demand 61 4.1 Helium 61 4.2 Neon 62 4.3 Argon 63 4.4 Krypton 65 4.5 Xenon 66 4 Noble gases – supply really critical? 5 Supply 68 5.1 Helium 68 5.2 Neon 75 5.3 Argon 79 5.4 Krypton 81 5.5 Xenon 85 5.6 Projects (helium) 87 6 Supply and demand balance 91 6.1 Helium 91 6.2 Neon 92 6.3 Argon 93 6.4 Krypton 93 6.5 Xenon 94 7 Price trend 96 7.1 Helium 96 7.2 Neon 97 7.3 Argon 97 7.4 Krypton 97 7.5 Xenon 98 Appendix 107 Country profiles 109 Noble gases – supply really critical? Noble gases – supply really critical? 5 Figures Fig. 1: The noble gases helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe) in gas discharge tubes. 11 Fig. 2: Sir William Ramsay (1852–1916), Scottish chemist, who received the Nobel Prize for Chemistry in 1904 for the discovery of the noble gases. 13 Fig. 3: Principle of CO2 purification and separation of helium at the Doe Canyon/Colorado site. 22 Fig. 4: Principle of fractionating distillation with the aid of a rectification column. 23 Fig. 5: Carl Paul Gottfried von Linde (1842–1934), German engineer and founder of today’s Linde AG, who developed the principle of air liquefaction in 1895. 24 Fig. 6: Fluorescent tubes filled with noble gases, forming the respective chemical symbol of the noble gas. 26 Fig. 7: Typical MRI in a Taiwanese hospital. 27 Fig. 8: Zeppelin NT over Friedrichshafen on Lake Constance. 28 Fig. 9: Tungsten inert gas welding in an inert gas atmosphere of argon or helium is suitable for welding all metals and alloys where quality is more important than welding speed. 29 Fig. 10: View into a section of the tunnel of the LHC large hadron storage ring, which depends on constant supercooling of the magnets by means of liquid helium for ist functioning. 33 Fig. 11: High-field magnetic separator, supercooled using liquid helium for separating ferrous minerals from kaolin. 35 Fig. 12: Use of helium by sector in the USA in 2015. 36 Fig. 13: Comparison of global helium use by sectors in 2015. 37 Fig. 14: Illuminated advertising using neon lights at a restaurant in Lustenau/Austria. 38 Fig. 15: Stainless steel is usually welded using the tungsten inert gas method in an inert gas atmosphere of argon or, more rarely, helium. 39 Fig. 16: Refining of a CrMoWVNbN stainless steel alloy in an argon-oxygen decarburisation vessel. 40 Fig. 17: In 2010, 50 of the 6379 windows of New York’s Empire State Building were removed every night, one after the other; the glass interstices coated with a metal film, then filled with a gas mixture consisting of air, argon, and krypton, and subsequently reinstalled. 42 Fig. 18: At night, 4000 watt high-pressure xenon Osram floodlights illuminate the Niagara Falls between Canada and the USA. 43 Fig. 19: Radon concentration in soil air in Germany. 47 Fig. 20: Today, helium is almost exclusively offered in the standard quality 5.0 (99.999% He). 50 Fig. 21: IACX Energy helium plant on the Harley Dome natural gas field with 7.0% He average in Utah. 60 Fig. 22: Global neon demand distribution in 2017. 63 Fig. 23: Global steel production in million tonnes (Mt). 64 Fig. 24: Global turnover in the semiconductor industry in US$ billions. 64 Fig. 25: Global krypton demand distribution in 2017. 65 Fig. 26: Global xenon demand distribution in 2017. 66 Fig. 27: ISO containers for transporting liquid helium at Linde AG’s Unterschleißheim factory. 68 Fig. 28: Important global helium trade flows in 2017. 69 6 Noble gases – supply really critical? Fig. 29: Transport containers filled with 450 litres of liquid helium at Linde AG’s Unterschleißheim factory. 70 Fig. 30: Development of global helium capacities (pure helium only) since 2000. 72 Fig. 31: Generalised map of global helium plant sites. 73 Fig. 32: Development of global helium production since 2000. 75 Fig. 33: Generalised map of crude neon purification plant sites. 78 Fig. 34: In Germany, argon is supplied by a number of companies, here by Linde AG. 79 Fig. 35: In Germany, pure krypton is produced by Linde AG in their Unterschleißheim factory, among others. 82 Fig. 36: Generalised map of crude krypton and crude xenon purification plant sites. 86 Fig. 37: Generalised map of current global LNG facilities. 90 Fig. 38: Helium: supply and inferred demand since 2000. 91 Fig. 39: Crude neon: supply and demand since 2000, including forecast of future development. 93 Fig. 40: Krypton: supply and demand since 2000, including forecast of future development. 94 Fig. 41: Xenon – the most valuable and critical noble gas. 94 Fig. 42: Xenon: supply and demand since 2000 including forecast of future development. 95 Fig. 43: Price trend for crude and pure helium since 1995. 96 Fig. 44: Price trend and forecast for pure neon (wholesale price) in US$/l since 1998. 98 Fig. 45: Price trend and forecast for krypton (wholesale price) in US$/l since 1998. 99 Fig. 46: Price trend and forecast for xenon (wholesale price) in US$/l since 1998. 99 Fig. 47: The krypton and xenon purification plant in Panzhihua, Sichuan Province, of Hunan Xianggang Messer. 117 Fig. 48: In addition to oxygen, nitrogen and argon, the air separation unit in Leuna also produces crude neon, crude krypton/crude xenon and helium. 122 Fig. 49: Generalised map of air separation unit (ASU) sites with argon production in Germany. 125 Fig. 50: Generalised map of air separation unit (ASU) sites with crude krypton and crude xenon production in Germany. 127 Fig. 51: View of part of the crude krypton and crude xenon purification plant at Linde AG’s Unterschleißheim plant. 128 Fig. 52: Just under a quarter of the world’s helium was produced In Qatargas’ huge LNG facilities in Ras Laffan, Qatar in 2017. 138 Fig. 53: Satellite image of Cliffside helium storage facility north-west of Amarillo, Texas, USA. 155 Fig. 54: Production and storage of helium in the USA. 156 Fig. 55: Evolution of sales of pure helium (Grade A) in the USA. 156 Fig. 56: The Crude Helium Enrichment Unit (CHEU) on the Cliffside storage facility north-west of Amarillo, Texas, USA, seen from space. 157 Fig. 57: Generalised map of important helium-bearing natural gas fields and current helium production, transport and storage facilities in the USA. 160 Noble gases – supply really critical? Noble gases – supply really critical? 7 Tables Table 1: Selection of important atomic and physical noble gas parameters. 15 Table 2: Frequencies of noble gases and hydrogen. 17 Table 3: Composition of dry air. 18 Table 4: Natural radionuclides, forming noble gases on decay. 20 Table 5: Formation of noble gases since the origin of the Earth 4.5 billion years ago. 20 Table 6: Guaranteed qualities of helium for different uses or in different degrees of purity. 51 Table 7: Guaranteed qualities of argon for different uses or in different degrees of purity. 54 Table 8: Guaranteed qualities of neon for different uses or in different degrees of purity. 57 Table 9: Guaranteed qualities of krypton for different uses or in different degrees of purity. 58 Table 10: Guaranteed qualities of xenon for different uses or in different degrees of purity.