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WO 2013/138845 Al 26 September 2013 (26.09.2013) P O P C T

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WO 2013/138845 Al 26 September 2013 (26.09.2013) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization I International Bureau (10) International Publication Number (43) International Publication Date WO 2013/138845 Al 26 September 2013 (26.09.2013) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C25B 1/02 (2006.01) C01B 3/00 (2006.01) kind of national protection available): AE, AG, AL, AM, C25B 1/30 (2006.01) C01B 15/01 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, C25B 11/06 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (21) International Application Number: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, PCT/AU20 13/000232 KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, (22) International Filing Date: ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, 12 March 2013 (12.03.2013) NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, (25) Filing Language: English TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, (26) Publication Language: English ZM, ZW. (30) Priority Data: (84) Designated States (unless otherwise indicated, for every 2012901 138 22 March 2012 (22.03.2012) AU kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, (71) Applicant: MONASH UNIVERSITY [AU/AU]; Welling UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, ton Road, Clayton, Victoria 3800 (AU). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, (72) Inventors: MACFARLANE, Douglas; 9 Camperdown MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Street, Brighton East, Victoria 3187 (AU). IZGORODIN, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, Alexey; 9/1 18 Waverley Road, East Malvern, Victoria ML, MR, NE, SN, TD, TG). 3145 (AU). Published: (74) Agent: SMOORENBURG PATENT & TRADE MARK ATTORNEYS; PO Box 515, Ringwood, Victoria 3134 — with international search report (Art. 21(3)) (AU). (54) Title: PROCESS AND CATALYST-ELECTROLYTE COMBINATION FOR ELECTROLYSIS (57) Abstract: The invention relates to a process for electrolysis comprising a cathode and an anode comprising a catalyst, both the cathode and anode at least partly immersed in an electrolyte, the process characterised in that the electrolyte at least partly inhibits further oxidation of a product formed at the anode. Typically the catalyst comprises one or more metal-(Group Vlb) semiconductors, and one or more metal-(GroupVlb))- phosphorous species. PROCESS AND CATALYST-ELECTROLYTE COMBINATION FOR ELECTROLYSIS FIELD OF INVENTION [0001] The present invention relates to the field of electrolysis, particularly water electrolysis including water oxidation or water splitting, [0002] In one form, the invention relates to a process and apparatus for electrolysis. [0003] In one form, the invention relates to a new catalyst-electrolyte combination for electrolysis. [0004] In one particularly preferred aspect the present invention is suitable for electrolytic generation of hydrogen peroxide or radicals capable of forming hydrogen peroxide. [0005] It will be convenient to hereinafter describe the invention in relation to processes for generating hydrogen peroxide, or radicals capable of forming hydrogen peroxide and hydrogen, however it should be appreciated that the present invention is not limited to that use and can be applied to other processes and generation of other products. BACKGROUND ART [0006] It is to be appreciated that any discussion of documents, devices, acts or knowledge in this specification is included to explain the context of the present invention. Further, the discussion throughout this specification comes about due to the realisation of the inventor and/or the identification of certain related art problems by the inventor. Moreover, any discussion of material such as documents, devices, acts or knowledge in this specification is included to explain the context of the invention in terms of the inventor's knowledge and experience and, accordingly, any such discussion should not be taken as an admission that any of the material forms part of the prior art base or the common general knowledge in the relevant art in Australia, or elsewhere, on or before the priority date of the disclosure and claims herein. Hydrogen Peroxide [0007] Hydrogen peroxide (H20 2) is a strong oxidising agent and is considered a highly reactive oxygen species. [0008] Its oxidising capacity is so strong that in concentrated form it is used as a rocket propellant. Its strong oxidising capacity makes it particularly well suited for use as a bleach, cleaning agent and antimicrobial for industrial and domestic use. One of the advantages of hydrogen peroxide is that it is a stronger oxidising agent yet more environmentally acceptable than chlorine based oxidising agents. [0009] The market for hydrogen peroxide is large and continues to expand, for example, from about 1.9 million tonnes in 1994, to 2.2 million tonnes in 2006, to an estimated 4.3 million tonnes 2012. Due to the potential hazardous nature of the processes that involve production, storage and transportation of hydrogen peroxide at high concentration, significant interest recently has been given to the development of alternative production methods, particularly in-situ processes. [0010] Hydrogen peroxide is principally manufactured by the 'anthraquinone process' consisting of the autoxidation of a 2-alkyl anthrahydroquinone (or 2-alkyl-9,10- dihydroxyanthracene) to the corresponding 2-alkyl anthraquinone. For example, the cyclic reaction depicted at equation (1) shows the oxidation of 2-ethyl-9,10- (C dihydroxyanthracene 16 H12(OH)2) to the corresponding 2-ethylanthraquinone (Ci 6H 20 2) and hydrogen peroxide. [001 1] Most manufacturers use the Riedl-Pfleiderer process, which includes the step of bubbling compressed air through a solution of the anthracene. Oxygen in the air reacts with the labile hydrogen atoms of the hydroxy group, giving hydrogen peroxide and regenerating the anthraquinone. The hydrogen peroxide thus generated is extracted and the anthraquinone derivative is reduced back to the dihydroxy (anthracene) compound using hydrogen gas in the presence of a metal catalyst. The cycle is then repeated. [00 ] The overall equation for the process is: → H2 + 0 2 H20 2 equation (2) [0013] The economics of the process depend heavily on effective recycling of the quinone (which is expensive), extraction solvents, and the catalyst and many attempts have been made to improve the economics of the process. [0014] For example Solvay have improved productivity and reduced the cost of production by optimising the distribution of isomers of 2-amyl anthraquinone and pursuing economies of scale. This improved process was implemented in 2008 in a "mega-scale" single-train plant in Zandvliet (Belgium) and another in 20 1 in Map Ta Phut (Thailand). (Hydrogen Peroxide 07/08-03 Report, ChemSystems, May 2009). [0015] Processes for producing hydrogen peroxide directly from the elements has been of interest for many years. However, one of the problems associated with this approach is that the reaction of hydrogen with oxygen thermodynamically favours production of water. · While use of a finely dispersed catalyst is beneficial for promoting selectivity to hydrogen peroxide, the selectivity is still not sufficiently high for commercial development of the process. In an effort to improve the selectivity researchers have developed minute (nanometer-size) phase-controlled noble metal crystal particles on carbon support. Evonik Industries, established a pilot plant in Germany in late 2005 using this catalyst and has claimed that there are reductions in investment cost because the process is simpler and involves less equipment. However, the process has the drawbacks of being more corrosive and unproven and yields low concentrations of hydrogen peroxide (about 5-10 wt% as compared with about 40 wt% via the anthraquinone process). [0016] In 2009, another attempt was made to develop a process for direct synthesis using a gold-palladium nanoparticulate catalyst. (G.J. Hutchings et al, Science 2009, 323, 1037) The catalyst is claimed to have the advantage of reducing hydrogen peroxide decomposition and potentially being an inexpensive, efficient and environmentally friendly process. Hydrogen peroxide tends to decompose spontaneously, and even more rapidly under the influence of the catalysts typically used in direct synthesis. However the use of a gold-palladium nanoparticulate catalyst typically achieves only very low concentrations of hydrogen peroxide (less than about 1-2 wt%). [0017] Attempts have also been made to produce alkaline hydrogen peroxide using a monopolar cell to electrolytically reduce oxygen in a dilute sodium hydroxide solution. (Hydrogen Peroxide 07/08-03 Report, ChemSystems, May 2009). " (Anode) 20H - H20 + 1/20 2 + 2e equation 3(i) ~ (Cathode) H20 + 0 2 + 2e - H0 2 + OH equation 3(ii) (Overall) NaOH + 1/20 2 -» H0 2Na equation 3(iii) [00 8] It was shown recently that significantly lower production costs can be achieved in the system where hydrogen and hydrogen peroxide are produced simultaneously by water electrolysis. (Ando, Y. and Tanaka T., 'Proposal for a new system for simultaneous production of hydrogen and hydrogen peroxide by water electrolysis', International Journal of Hydrogen Energy, 2004, 29(13), 1349-1354). + → 20 2 + 2H + 2e H20 (E0 = 0.69 V vs NHE) equation 4(a) → + 2H20 HOOH + 2H + 2e (E0 - .776 V vs NHE) equation 4(b) → + 2H20 0 2 + 4H + 4e (E = .23 V vs NHE) equation 4(c) + 4H + 4e 2H2 (E0 = 0 V vs HE) equation 4(d) [0019] In order for this system to be viable, however, the water oxidation catalyst should promote formation of hydrogen peroxide and inhibit the oxygen evolution reaction (equation 4(c)) which is the more thermodynamically favourable process.
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