(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Orga 2 NET A International Bureau , i 2 (10) International Publication Number (43) International Publication Date 32 November 2012 2.112022) WIPO|PCT Rees (1) International Patent Classification (81) Designated States (uriess otherwise indicated, for every AIC 1/18 (2006.01) Kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR) BW, BY, BZ, CA, CH, CL, CN, CO, CR. CU, CZ, DE, DK, DM, DO, DZ_EC, FE, EG, ES, Fl, GB, GD, GE, GH, GM, GT, HN, 21) International Application Number: PCT/AU2011/001557 (22) Internat ng Date: HR, HU, ID, IL, IN, 1S, JP, KE, KG, KM, KN, KP, KR, LDevember2011 01122011) KZ LA, LC, LK, ER, LS, LT, LU, LY, MA, MD, ME MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, 25) Filing Language: English OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, 26) Publication Language: nals SE, SG, SK, SL, SM, ST, SV, SY, TH, TI, TM, TN, TR, eae oam Fnalish TT,1Z, UA, UG, US, UZ, VC. VN, ZA, ZM, ZW (80) Priority Data DOLIHISTL—16May2011 (16052011) AU_ (84) Designated States (unless otherwise indicated, for every kind of regional protection available: ARIPO (BW, GI, (71) Applicants (or all designated States except US: THE GM RE-LR LS. MW, MZ. NA, RW, SD, SL, SZ, 12, UNIVERSITY OF SYDNEY [AU/AUK Parramatta Rood, —_UG,,2M, ZW), Pasian (AM, AZ. BY, KG, KZ, MD, RU, Sydney, New South Wales 2006 (AU). ORICA INTER: TJ, TM), European (AL, AT, BE, BG, CH. CY, CZ, DE NATIONAL PTE LID [SG/SG}; 78 Shenton Way#06-15 DR, BR, ES, FI, FR, GB,GR, HR. HU, IE, IS, IT, LT, LU, Tower 2, Singapore 079120 (SG). LY, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SISK, SM, TR), OAPI (BF, BI, CF, CG, Cl, CM, GA, GN, GQ, aventors/Applicants for US only): JOHNSTON, Ane GW-ML, MR.NE, SN, TD, TG). thony Matthew [AU/AU|; 3 William Street, Double Bay, Published: "New South Wales 2028 (AU). HAYNES, Brian Scott IAUIAUL; 6 Gladys Avenue, Frenchs Forest, New South ‘Wales 2086 (AU) ™ 3) with ternational search report (rt. 21(3)) (74) Agent: GRIFFITH HACK; GPO Box 4164, Syney, New South Wales 2001 (AU), = © g a 6 a S a 9 S (64 Title: INTEGRATED PROCES 'S FOR PRODUCING AMMONIUM NITRATE ? boy 1 Figure 4 (57) Abstract: A process for producing ammoniue nitrate is disclosed and in which: 8) a gaseous oxidise feed composed at least substantially of ammonia, steam and an oxidising gas is exposed to conditions whereby the ammonia is oxidised to produce a reac ~ ‘ion mixture including nitrogen monoxide and water vapour, 6 the resction mixture is cooled in a heat exchanger whereby the nitro ‘gen monoxide is oxidised, the water vapour is condensed and the products ofthe nitrogen monoxide oxidation react with and are ab sorbed by the coodensed water to form a nitric acid steam, with substantially all ofthe nitrogen monoxide in the reaction mixture being converted to nitric acid, and ¢) the nitric seid stream is reacted with a stream of ammonia in an ammonium nitrate producing sage to form the ammonium nitrate Substantially al of the steam within the oxidiser feed is derived from the ammonium nitrate pro ‘ducing stage, and atleast 10% of the ammonia Within the oxidisr feed is derived and carried by the steam trom the ammoniuen ni trate producing stage. Alko disclosed is ammonium nitrate, in any of its various possible forms, when produced by the disclosed pro -WO 2012/155173 PCT/AU2011/001557 10 15 20 25 30 INTEGRATED PROCESS FOR PRODUCING AMMONIUM NITRATE TECHNICAL FIELD OF THE INVENTION This invention relates to a process for producing ammonium nitrate and which integrates production of nitric acid with the production of ammonium nitrate. BACKGROUND OF THE INVENTION International patent Application No. ___, dated , based on Provisional Patent Application No. 2010905289, lodged in Australia in the names of Optint Pty Limited and University of Sydney on 01 December 2010, discloses an integrated process for the production of ammonium nitrate in which: a) a gascous oxidiser feed composed at least substantially of ammonia, steam and an oxidising gas is exposed to conditions whereby the ammonia is oxidised to produce a reaction mixture including nitrogen monoxide and water vapour, b) the reaction mixture is cooled in a heat exchanger whereby the nitrogen monoxide is oxidised, the water vapour is condensed and the products of the nitrogen monoxide oxidation react with and are absorbed by the condensed water to form a nitric acid stream, and ¢) the nitric acid stream is reacted with a stream of ammonia to form the ammonium nitrate. As disclosed in the referenced Patent Application, separate streams of the ammonia are fed to the nitric acid and ammonium nitrate producing stages. Also, in one embodiment of the disclosed process, steam that is generated in the course of concentrating an ammonium nitrate solution in the ammonium nitrate producing stage is transferred to the nitric acid producing stage to form at least a portion of the steam component of the oxidiser feed or to form a portion of a water or steam component of a starting feed from which the oxidiser feed is derived. AsWoO 2012/155173 PCT/AU2011/001557 further disclosed in one embodiment, a small excess of ammonia may be supplied to the ammonium nitrate producing stage (for the purposes of minimising evaporator corrosion and suppression of the partial pressure of nitric acid in the vapour space of the evaporator) and, as a 5 consequence, a small amount of ammonia (substantially less than 10% of the ammonia component of the oxidiser feed) might be fed to the nitric acid producing stage with the steam. The present Inventors have now determined that, by feeding a 10 substantial excess (i.¢., at least 10%) of ammonia to the ammonium nitrate producing stage, the size of the ammonium nitrate reactor may be reduced, as may be the mixing precision requirement for complete reaction of the nitric acid. Also, it has been determined that the substantial excess of ammonia may usefully be fed from the ammonium 15 nitrate producing stage to the nitric acid producing stage in a steam feed that comprises substantially the whole of that required by the nitric acid producing stage. As also disclosed in the referenced Patent Application, the oxidising gas 20 constituent of the oxidiser feed comprises a gas containing more than about 80% oxygen. However, the present Inventors have now determined that the oxidising gas may comprise air or another oxidising gas mixture that is less rich than 80% oxygen; accepting that the reaction-absorption volume will be substantially larger, but this being 25 compensated by the potential for substantially reduced cost of employing a less oxygen-rich oxidising gas. 30WoO 2012/155173 PCT/AU2011/001557 10 20 25 SUMMARY OF THE INVENTION ‘The present invention may be defined as providing a process for producing ammonium nitrate in which: a] a gaseous oxidiser feed composed at least substantially of ammonia, steam and an oxidising gas is exposed to conditions whereby the ammonia is oxidised to produce a reaction mixture including nitrogen monoxide and water vapour, b) the reaction mixture is cooled in a heat exchanger whereby the nitrogen monoxide is oxidised, the water vapour is condensed and the products of the nitrogen monoxide oxidation react with and are absorbed by the condensed water to form a nitric acid stream, with substantially all of the nitrogen monoxide in the reaction mixture being converted to nitric acid, ©) the nitric acid stream is reacted with a stream of ammonia in an ammonium nitrate producing stage to form the ammonium nitrate, d) at least 80% of the steam within the oxidiser feed is derived from the ammonium nitrate producing stage, and ¢) at least 10% of the ammonia within the oxidiser feed is derived and carried by the steam from the ammonium nitrate producing stage. The present invention may also be defined as providing ammonium nitrate (in any of its various possible forms) when produced by the above process. As employed in the above and following definitions of the invention the term “oxidising gas” is to be understood as including air or other oxidising gas mixture or, desirably, a gas containing more than about 80% and most desirably above 95% oxygen. Also, by “substantially all” of the nitrogen monoxide in the above and following definitions of the invention is meant an amount of nitrogen monoxide greater than 90%, desirably greater than 95% and, most