VOLUME 55 NUMBER 1 JANUARY 2011 Platinum Metals Review www.platinummetalsreview.com E-ISSN 1471–0676 © Copyright 2011 Johnson Matthey PLC http://www.platinummetalsreview.com/ Platinum Metals Review is published by Johnson Matthey PLC, refiner and fabricator of the precious metals and sole marketing agent for the six platinum group metals produced by Anglo Platinum Limited, South Africa. All rights are reserved. Material from this publication may be reproduced for personal use only but may not be offered for re-sale or incorporated into, reproduced on, or stored in any website, electronic retrieval system, or in any other publication, whether in hard copy or electronic form, without the prior written permission of Johnson Matthey. Any such copy shall retain all copyrights and other proprietary notices, and any disclaimer contained thereon, and must acknowledge Platinum Metals Review and Johnson Matthey as the source. No warranties, representations or undertakings of any kind are made in relation to any of the content of this publication including the accuracy, quality or fitness for any purpose by any person or organisation. E-ISSN 1471–0676 •Platinum Metals Rev., 2011, 55, (1), 1• Platinum Metals Review A quarterly journal of research on the platinum group metals and of developments in their application in industry http://www.platinummetalsreview.com/ JANUARY 2011 VOL. 55 NO. 1 Contents 55 Years of Platinum Metals Review 2 An editorial by Jonathan Butler Palladium-Based Alloy Membranes for Separation of High Purity 3 Hydrogen from Hydrogen-Containing Gas Mixtures By Gennady S. Burkhanov, Nelli B. Gorina, Natalia B. Kolchugina, Nataliya R. Roshan, Dmitry I. Slovetsky and Evgeny M. Chistov CAFC9: 9th Congress on Catalysis Applied to Fine Chemicals 13 A conference review by José M. Fraile and Clara I. Herrerías The Role of Process Parameters in Platinum Casting 20 By Ulrich E. Klotz and Tiziana Drago 10th Scientific Bases for the Preparation 28 of Heterogeneous Catalysts A conference review by Jennifer Houghton “Metathesis in Natural Product Synthesis” 33 A book review by Valerian Dragutan and Ileana Dragutan “Platinum 2010 Interim Review” 41 Haren Gandhi 1941–2010: Contributions to the Development 43 and Implementation of Catalytic Emissions Control Systems By Martyn V. Twigg 34th Annual Conference of Precious Metals 54 A conference review by Richard Seymour BERLIN–PM’2010 59 Publications in Brief 63 Abstracts 65 Patents 68 Final Analysis: Electrolytic Etching for Microstructure 71 Detection in Platinum Alloys By Paolo Battaini Editorial Team: Jonathan Butler (Publications Manager); Sara Coles (Assistant Editor); Margery Ryan (Editorial Assistant); Keith White (Principal Information Scientist) Platinum Metals Review, Johnson Matthey PLC, Orchard Road, Royston, Hertfordshire SG8 5HE, UK E-mail: [email protected] 1 © 2011 Johnson Matthey doi:10.1595/147106711X548825 •Platinum Metals Rev., 2011, 55, (1), 2• Editorial 55 Years of Platinum Metals Review This year marks the 55th anniversary of the first Another important milestone has recently publication of Platinum Metals Review by Johnson passed, the anniversary of the US Clean Air Act Matthey. In more than five decades of continuous Extension in 1970, which led to the development of quarterly publication, Platinum Metals Review has pgm-based technologies for the control of automo- covered a wide range of industrial and scientific tive exhaust emissions. By 1975 model year, plat- uses of the platinum group metals (pgms), empha- inum-based autocatalysts fitted to cars in the US sising the metals’ unique properties in applications were instrumental in reducing carbon monoxide ranging from automotive emissions control and and hydrocarbon emissions by 90 per cent com- efficient industrial processes to anticancer drugs. pared with 1970 models. 1976 model year cars went Platinum Metals Review also covers new applica- on to use two separated pgm-based catalysts to also tions of the pgms, and regularly features articles on control NOx emissions. By the early 1980s the first new and emerging technologies such as fuel cells practical systems to use platinum/rhodium three- and hydrogen energy.This issue continues these tra- way catalysts to control all three legislated pollu- ditions, featuring subjects as diverse as palladium- tants were in production. based membranes for the production of high-puri- Almost every country in the world now has auto- ty hydrogen and platinum casting techniques for motive emissions regulations which necessitate the the jewellery industry.With pgm science more rele- use of pgm autocatalysts and this application is cur- vant than ever at this time, it gives me great pleas- rently the single biggest demand sector for plat- ure to be managing this prestigious and respected inum, palladium and rhodium. Progress on the journal. development and implementation of pgm catalysts 2011 also marks a number of important anniver- for vehicle emissions control is covered in this saries for the Johnson Matthey group: the 160th issue in our ‘Appreciation’ of one of the pioneers of anniversary of George Matthey joining the compa- autocatalysts, Dr Haren Gandhi of Ford, by another ny which was to become the partnership Johnson autocatalyst pioneer, Dr Martyn Twigg of Johnson and Matthey and eventually Johnson Matthey PLC, Matthey. and the 150th anniversary of the company being Dr JONATHAN BUTLER, Publications Manager approved as refiners to the Bank of England. It also marks the 85th anniversary of A. R. Powell, then Contact Information head of Johnson Matthey’s Research Department, Johnson Matthey Precious Metals Marketing Orchard Road perfecting a process for extracting and refining the Royston pgms from the ores of the Merensky Reef in South Hertfordshire SG8 5HE Africa. This enabled the successful exploitation of UK the world’s biggest platinum deposits and helped to E-mail: [email protected] develop Johnson Matthey’s close and enduring association with pgms and with the South African company Rustenburg Platinum Holdings Ltd, which later became Anglo Platinum Ltd, the world’s largest primary producer of pgms. 2 © 2011 Johnson Matthey •Platinum Metals Rev., 2011, 55, (1), 3–12• Palladium-Based Alloy Membranes for Separation of High Purity Hydrogen from Hydrogen-Containing Gas Mixtures doi:10.1595/147106711X540346 http://www.platinummetalsreview.com/ By Gennady S. Burkhanov*, Nelli B. Gorina, Palladium-based alloys with yttrium,copper,ruthenium Natalia B. Kolchugina and Nataliya R. Roshan or indium additions were investigated. Their specific Baikov Institute of Metallurgy and Materials Science, hydrogen permeability, strength, linear thermal expan- Russian Academy of Sciences, Leninskii prospect 49, sion in hydrogen and corrosion resistance in a number 119991 Moscow, Russia; of gas media were determined.This allowed effective *E-mmail: [email protected] membrane elements to be developed using mem- branes made from these alloys, which are used for the Dmitry I. Slovetsky and Evgeny M. Chistov separation of high purity hydrogen from hydrogen- containing gas mixtures. Membrane elements with Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii prospect 29, 93.5 wt% palladium-6 wt% indium-0.5 wt% ruthenium 119991 Moscow, Russia alloy membranes were developed by the authors’ research group, and their technical characteristics are described. Introduction Hydrogen is an attractive alternative fuel to meet ever- growing energy requirements while reducing the reliance on oil and gas, with their attendant environ- mental and resource problems. By contrast, hydrogen is potentially an inexhaustible, clean and environ- mentally sustainable resource. One way to produce high purity hydrogen is by separation from hydrogen- containing gas mixtures produced by catalytic or chemical manufacturing processes. Hydrogen production volumes vary widely,depend- ing on the end use application.These can range from several cubic metres per hour (m3 h−1) for micro- and nanoelectronics and portable energy sources such as fuel cells, to tens or hundreds of m3 h−1 for transport and small stationary energy sources, tens of thou- sands of m3 h−1 for the chemical industry and metal- lurgical applications, and hundreds of thousands of m3 h−1 for large stationary energy installations and hydrogen production plants. Recent progress in hydrogen power engineering means that the demand for high purity hydrogen 3 © 2011 Johnson Matthey doi:10.1595/147106711X540346 •Platinum Metals Rev., 2011, 55, (1)• (>99.9999 vol%) is increasing rapidly.The pressure There has been growing interest in the develop- swing adsorption method is most frequently used in ment of palladium-based alloy membranes for hydro- the USA (1). However, this method is energy inten- gen separation. Analysis of published scientific and sive as high volumes of adsorbents are used, and patent literature shows a large increase in the number some of the separated hydrogen is used for adsor- of patent and non-patent publications related to pal- bent regeneration, reducing the efficiency of the ladium membranes in recent decades (see Figure 1). process for hydrogen purification.Therefore,the best However, the analysis also shows that the commer- method for the production of high purity hydrogen cial preparation of inexpensive high purity hydrogen is currently by separation via selective diffusion remains problematic due to the lack of efficient through metallic membranes made from palladium- palladium-based membrane