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Green Chemistry Green Chemistry View Article Online CRITICAL REVIEW View Journal | View Issue Engineering in direct synthesis of hydrogen peroxide: targets, reactors and guidelines for Cite this: Green Chem., 2014, 16, 2320 operational conditions Juan García-Serna,*a Teresa Moreno,a Pierdomenico Biasi,*b,c María J. Cocero,a Jyri-Pekka Mikkolab,c and Tapio O. Salmib The demand for hydrogen peroxide is booming since it is considered as one of the most environmentally friendly and versatile chemical oxidants available and has a wide range of applications. The annual market, close to 3000 kt per year being produced via the auto-oxidation process (with 2-ethyl anthraquinone (traditional) or amyl anthraquinone for mega-plants), is mostly supplied by the company Solvay (30%), followed by Evonik (20%) and Arkema (13%). Nevertheless, the dream of a direct synthesis process is close to a century old and it has gained momentum in research efforts during the last decade with more than 15 groups active in the world. In this review, we focus the discussion on the targets, e.g. plant tonnage, the reactors and the most feasible industrial operational conditions, based on our experience and point of view using the chemical engineering tools available. Thus, direct synthesis Received 5th August 2013, can be competitive when on-site production is required and capacities less than 10 kt per year are Accepted 6th January 2014 demanded. The total investment cost should be approximately 40.3 ± 12.1 MM$ (in 2012) for a 10 kt per DOI: 10.1039/c3gc41600c year size process to be comparable to the traditional process in terms of costs. Moreover, all kinds of www.rsc.org/greenchem reactors used are hereby discussed emphasizing the pros and cons; the most common ones are batch aDepartment of Chemical Engineering and Environmental Technology, University of Valladolid, Valladolid, Spain. E-mail: [email protected] bDepartment of Chemical Engineering, Åbo Akademi University, Turku/Åbo, FI-20500, Finland. E-mail: [email protected] cDepartment of Chemistry, Chemical-Biochemical Centre (KBC), Technical Chemistry, Published on 07 January 2014. Downloaded by Umea University Library 19/06/2014 12:23:23. Umeå University, SE-90187 Umeå, Sweden Juan García-Serna is a chemical Teresa Moreno obtained her engineer (2000) and an affiliate degree in Chemical Engineer- member of IChemE. He worked ing from Complutense University for Técnicas Reunidas S.A. (Madrid, Spain) and later com- (Madrid) for 2 years (2000–02). pleted her PhD in Chemical He started lecturing in 2001 and Engineering at the University of became a Professor in Chemical Valladolid (Spain, 2011) study- Engineering (2010) at the ing the catalytic direct synthesis Department of Chemical Engi- of hydrogen peroxide in super- neering and Environmental Tech- critical CO2 and the online deter- nology of the Valladolid mination of the product using University (Spain). Prof. García- Raman spectroscopy. She is cur- Juan García-Serna Serna has conducted research in Teresa Moreno rently a Research Scientist in the the High Pressure Processes Industrial Bioactive Technologies Group (hpp.uva.es) since 1998, leading the branch of Chemical Group at Callaghan Innovation (New Zealand) working on the Reaction Engineering and Green Engineering of the group. He has development of processes for adding value to natural materials led and participated in 3 EU, 6 national/regional projects and toward high value products and applications, including the devel- 10+ SME contracts and has published 30+ research papers. opment of sustainable technologies using supercritical fluids. 2320 | Green Chem.,2014,16,2320–2343 This journal is © The Royal Society of Chemistry 2014 View Article Online Green Chemistry Critical Review and semi-continuous modes of operation. However, at the moment, demonstrations of continuous operations as well as carefully determined kinetics are needed in order to scale up the process. Finally, operational conditions, including the catalyst composition (active metal, oxidation state and support), promoters (halides and acids–pH–isoelectric point), solvents, pressure and temperature need to be care- fully analysed. In our opinion, as we try to show here, H2O2 direct synthesis is a competitive process and is ready for larger scale demonstration. Also, more than a hundred patents within the area support this claim, although the barriers of technology demonstration and further licensing are still pending. 1. Introduction Benchmarking against the current amyl anthraquinone high- productivity technology, the last improvement over the tra- Known since the onset of the 20th century when Hugo Henkel ditional ethyl anthraquinone process (both Solvay’spro- and Walter Weber patented the first method for the prietary)4 is not trivial. production of H2O2 via direct synthesis in the presence of Campos-Martin, Blanco-Brieva and Fierro reviewed the water and a suitable catalytic agent in 1914,1 the direct syn- hydrogen peroxide synthesis process analysing the market, thesis of hydrogen peroxide has only become a truly promising applications and the large-scale conventional auto-oxidation alternative to the auto-oxidation route over the last few synthesis process.2 They also reviewed the different emerging decades.2,3 alternatives, such as direct synthesis, photocatalysis, fuel cells, Only during the last decade (from 2004 to 2013 included) plasma reactors (from carbon monoxide, oxygen and water), ca. 70 patents have been granted (more than 30 between 2004 direct reduction of oxygen among others. This work represents and 2006). In light of this, it appears that the technology is an excellent basis to overview the past, present and future well protected but, apparently, there is still scope for develop- hydrogen peroxide technologies. A couple of years later, ment. Therefore, the process could be developed if companies Samanta reviewed the direct synthesis process thoroughly. He found the niche or the eco-efficiency opportunity over the tra- focused on the operational aspects of the direct synthesis by ditional auto-oxidation process (AOP). Moreover, the safety analyzing the factors that affect the secondary reactions, i.e. issues should always be considered in detail. decomposition and hydrogenation.3 He also analyzed the para- An apparently simple reaction, such as the direct reaction meters that influence the selectivity towards H2O2, such as + between hydrogen and oxygen to produce H2O2, is, in fact, solvent, concentration of H ions, palladium oxidation state, much more complex than it seems at first glance. Issues such support, metal additives, H2/O2 ratio and reaction time. An as the requirement of a selective catalyst and three-phase reac- inspiring book chapter was more recently written by Centi, Per- tion conditions, together with the existence of side reactions athoner and Abate affording a longitudinal industrial perspec- that seriously affect the selectivity of the process, i.e. the tive in order to better understand the reactor conditions and formation of water, the decomposition of hydrogen peroxide, fundamental aspects. The authors also reviewed the most and the reduction of hydrogen peroxide, are the most impor- recent patents and open literature on the direct synthesis tant chemical and technical challenges for this process. reaction.5 Published on 07 January 2014. Downloaded by Umea University Library 19/06/2014 12:23:23. Pierdomenico Biasi is an indus- María José Cocero is an indus- trial chemist (2006) and got his trial chemist and a Chartered PhD in chemical engineering Chemical Engineer (IChemE). (2010) from the University of She is Chair Professor in Chemi- Padova. He joined Åbo Akademi cal Engineering (2002) and Head University (Finland) in 2010 and of the Department of Chemical later Umeå University (Sweden) Engineering and Environmental in 2013. He is leading the activi- Technology (2012) at the Valla- ties on H2O2 direct synthesis at dolid University (Spain). Prof. Åbo Akademi University and Cocero founded and has been Umeå University. His specializ- the Head of the High Pressure ation is related to chemical Processes Group (hpp.uva.es) Pierdomenico Biasi reaction engineering and hetero- María J Cocero since 1990. She actively partici- geneous catalysis applied to pates in a number of networks green chemistry. He received grants from different foundations related to supercritical fluids, e.g. the EFCE High Pressure (i.e. Otto A. Malm, Åbo Akademi and Carl Kempe foundations). working party. She has led and participated in 6 EU, 25 national/ He is a coauthor of 15 papers on H2O2 direct synthesis. regional projects and 30 SME contracts, has published 150+ research papers and holds 3 patents. This journal is © The Royal Society of Chemistry 2014 Green Chem.,2014,16,2320–2343 | 2321 View Article Online Critical Review Green Chemistry The three approaches are necessary to understand the hydrogen peroxide synthesis, from the current industrial process to the most promising alternatives. Nevertheless, there has been little discussion on the targets, the reactors and the most feasible industrial conditions to be used. There are still several issues that must be addressed: first, the best tech- niques to cost-effectively study the process from both indus- trial and basic research points of view; second, the recent advancements and protection of the technology via patents; and third, the design criteria for process development, includ- ing a review of the reaction kinetics and mass transfer phenomena. In particular, when discussing the kinetics, we profoundly believe that kinetic studies are the key issue to understand the Fig. 1 Leadership positions in the hydrogen peroxide world market 4 fundamentals, to determine trends with a physico-chemical (values in kt per year). basis and to develop not only industrial processes but also relevant apparatus to be used in laboratory and pilot scales. In this sense, we encourage the researchers in the topic to data from 2010, see Fig. 1). Solvay predicted that, in 2015, the analyze the effects and behavior of the reaction system from market will be based on two strong pillars, i.e. pulp & paper and 4 the view of kinetic mechanisms and transport phenomena.
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