'US009932277B2 2) United States Patent (10) Patent No: US 9,932,277 B2 Kweeder et al. (45) Date of Patent: Apr. 3, 2018 (34) METHOD FOR PRODUCIN SULEATE NITRATE MMONIUM (56) References Cited US. PATENT DOCUMENTS. (73) Inventors: James A. Kweeder, Mortstown, ND (Us); Raymond G. Wissinger, pace aiee pa 25398 Morristown, NI-(US) DBWONTS A+ 41988 Shorter, J 423396 S2gs95 A 111968 Cook et al S088) A ‘1/1967 Geotey eat (73) Assignee: AdvanSix Resins & Chemieals LLC, Papper tcl Sows? A 11992 Maver 34066 BL 2 Eyal Bow.t8) 82 Eigbsmith etal (*) Notice: Subject to any disclaimer, the term ofthis 200210095966 AL* Higherith ta m0s9 patent is extended of adjusted under 35 200710086380 AI 52007 Kueeer tal ann70199357 AL 82007 Kweoder et SO1OUDETLAD AL 22010. Stovens et (Coutinved) USC. 15446) by 529 days (21) Appl. Now 1286.40 FOREIGN PATENT DOCUMENTS (22) Filed: Nov. 1, 2011 B tsa a2 11205 “ Prior Publication Data n Isao A220 0120131972 AL May 31,2012 (Continue) (OTHER PUBLICATIONS Related U.S. Application Data EPA, “Aminoniam Nita,” I. 1993, pp, $31 198.39 retrieved (60) Provisional application No. 61/409:333 filed om Nov. joy worm cpm gov ache apt2 HOS FinaleD83. pon 2, 2010, Apr 25,2014" (Continved) coer Primary Examiner — Anthony 3 Zimmer C05C imo (2006.01) ker Danie eee mean (78) Atoms, got. Fir Fase Bako Danis cose x00 Gon601) (2) US.cL 6) ABSTRACT cbc COSC 10 2013.01), COI 1246 The present technology provides methods and processes of (2013.01); COSC 700 201301) producing ammonium sulfate nitrate 1:2 double sats by (58) Field of Clamsification Search Combining ammonium sulfite solution, nitric acid and ee tgiB 17996 COI 1/24; COIC 1/245; ammonia in an aqucous reaction mixture. The methods OIG Ie COLD 906 COLD SOR, include reacting the aqueous resetion mixture, followed by COSC. 100; COSC 00; COBB 31/28 Moving Water 10 form the ammonium sulfate nitrate 13 usr 71/84, 58,59, 60, 423/388, 396, 397 double salt. See application file for complete search history. 33 Claims, 1 Drawing Sheet nme ‘Provu for Proeton of Ammonium Sulfate NitrateUS 9,932,277 B2 Page 2 66) References Cited USS. PATENT DOCUMENTS. 201000254850 AL 10°2010 Koester FOREIGN PATENT DOCUMENTS. @ 1onn976 2s 2008 re Isoskeo A 42010 i foasate ASV 20K, GB o01es ALL 193 Gs yosawn A "1988 GB 79x90 A 71988 cB ws i922 ® Mss A 1967 ® 2ooisai7 A 82004 ® SoowoTase A 42008 P Sousaals A 1201, Ru p79) 4 2008 wo 20100089K7 AD — 12010 wo 2olz06146o AY 52012, (OTHER PUBLICATIONS vemational Search Report and Writen Opinion dated Jun. 29 2012 in International Application No, PCTUS2OLL0S8994 foun the International Searching Authority, Ando, J, “Increase in Weight and Depraation of Granulated Fatlizer Compounds Containing Nivates and Sulfate” SMA. ‘Technical Meeting Prague, Czechoslovakia, Intemational Assocs tion of Manufictrers of Superphosphates and Felis Com- pounds, dated Sep. 1974 4 popes Ammonium slate nts new German nitogsnousfeilzer”™ Expriment Station Recon (US Dept of Agriculture, 1920, 4 216, Abc ony VA. Sokolov, “The equibvium and formation of complexes in the fem 120" NIKNOMNIHG}2SO4-" Bull. cad. Se. URSS, {Classe Se. math Na, Ser. Chim, 1938, No. 1, 123-5, Abstract oly. IK. Bahl, al ~“Ternarysysem: NHANO3_(NHA)2S04 112038 250.” Journal of the Indian Chemical Society, 1981, 18, 307-8, ‘Abst only Jn Tue, "medods for production and physeiochemical rope ties of ammonia nitrate salle.” Preemyst Chemicon 1976, S8(12), 611-4, Abstract ony ‘Malguori Ast al. Contbution tothe knowlalge of complex izing componcts, La Chimica e indus, 1964, sl. 46,No, Go pp 760 Ando, Miya, & Akiyama, Compounds in Mixed nitrate Fer tlizers ant the Behavior, The Chemical Society of pan, 1974, No.9, pp. 1617-41622 Janpei Ando, et a, System of Ammonium Nitrate and Feclier Sas, Journal ofthe Society of Chemical Industry, 1970, vo. 73 No. 12, p, 26142618, DOF IO, 1246 nikkasil998 73.12.2014, ‘Montjo-Bemanlo, J. M. ea Stnctures of Relevant Ammonium Sats in Ferlizers,Stuctural Science, Acta Crstallgraphicn See ion B 66(3388-368, Jun. 2010 Yukio’ Date, Equilibrium of _ QNHS)2S04_NHNOS— NISOSNH2—120 System at 25° C1960, vol 63, NO. Up 1913-1916, DOLLO.1246iikdassl99863.11 1913, Zapp, Keto al Ammonium Compounds. Ullmann's Eneyclo- polls of indostial Chemisty. 263-287, um 15, 2000. {No idenied author) "Ammonium Sulphate Nivate Production: Review of Commesally valable Processes” Niuopen, $3:27-30, Mayan. 1968 Dato, A. M. The Manafctre of Inorganic Frilizer Chemi cal Industry Pres, 178-17, Dee. 3, 1958 (ith pana anlation), Dice Action issud in CN Application No. 2011800527315, dated San. 29, 2016, 15 pages (vith English tanltion), * cited by examinerUS 9,932,277 B2 Apr. 3, 2018 U.S. Patent OVeIZIN o7eFNG UNtTuouury Jo UoToNporg 1oj ssod0Ig gut onpolg NS + zt euOUTy OL a pee oN uowrieg arEAg WhOUYUS 9,932,277 B2 1 METHOD FOR PRODUCING AMMONIUM, SULFATE NITRATE RELATED APPLICATION ‘This application claims the benefit of U.S. Provisional Application Ser. No. 61/308,333 entitled "METHOD FOR PRODUCTION OF AMMONIUM SULFATE NITRATE" filed Nov. 2, 2010, which application is incorporated by reference herein in its entirety FIELD OF THE INVENTION ‘The present technology relates to the production of ‘ammonium sulfate nitrate (ASN) composites useful as fer tilizers DESCRIPTION OF RELATED ART Ammonium sulfate nitrate (ASN), one of the first syn thetic fertilizers, has been in continuous use for nearly 100 _yeurs providing the important primary and secondary nuts ‘ents, nitrogen and sulfur. Nitrogen is provided in part, through the nitrate ion, desirable because it is realy adsorbed by many plants and promotes early growth. AS historically used, the term “ammonium sulfate nitrate” has not refered toa specific chemieal compound with elements in fixed proportions. Rather, it has heen used w describe various mixtures of ammonium nitrate and ammonium sul- file, The Association of American Plant Food Officials (AAPECO), which has assumed the role of monitoring and defining ferilizers, has attempted to bring order 10 the ‘nomenclature, APPECO has defined ASN ss double salt of smmonium sulfate and ammonium nitrate ia ual mols proportions having a nitrgen content not ess than 26%. An ‘equal molar mixture of ammonium sulfate and ammonium nitrate has 2 nitrogen content of 26.4% Despite the AAPECO definition, the name, ammonium sulfite’ nitate, has been used to designate many combi tions of ammonium sulfite and ammonium nitrate. See for Instance, RS. Meline, 1. Aric. Food Chem, 16(2), 235-240 (1968), where one product has a 30% nitrogen content. US. Pat, No, 2.795.495 to Steiale et al. describes ammonium sulfate aitrate as having an ammonium sulfaelammoninm nitrate mole ratio of 1:2 not 1:1, Great Britain Patent No. 798,690 states that the proportion of ammonium sulfate is not ertial and may be used in any proportion nocessary 10 ‘obtain the desired nitrogen level. The use of such terminol- ‘ogy has led to confusion between pure double salts and mixtures. Additionally, the order of the words, sulfate and nitrate, are sometimes interchanged inthe literature ‘A double salt isa distinet compound. Double salts con- sisting of (NH,)2SO,*2(NHNO,) and _(NH)280,¢3 (NHLNO,) (hereinafter the 122 double salt and the 1:3 double salt respectively) have been isolated and confirmed The 1:3 product was isolated from aquedus solution and reported as early as 1909 (Reicher etal, Chemish Week- blad., 3. Ganuary), $1-56 (1909). Seheinemakers et al. reported in 1910 in the same publication (Volume 6, 1910, pages 51-56) the isolation of & 1:2 double salt as wel as the 1:3 double salt from aqueous solutions. The existence of 1:2 and 1:3 double salts have been confirmed by Nikonova (le. ): oh, Kogyo Kagaku Zasshi, 63(11), 1913-1916 (1960): Emons et a, Wisenschatlliche. Zeitschrift Techn, Hocksch ‘Chem. Leuna-Merseburg, 14(3) 295-290 (1972); and Smith ‘etal, J. Agr Food Chem. 10, 7-78 (1962), among others 0 o 2 Reported manufacturing processes for ammonium sulfate nitrate describe preparation of uniform fertilizer granules Most products are simply mixtures of ammonium sulfite ‘and ammonium nitrate rar than specific crystal stctures ince the reported chemical compositions do not rellest any specific compound. An exception is US. Pat. No. 2,762,609, ‘whieh elaims 2 process forthe manufacture ofthe 1:2 double salt by reacting nitric and sulfuric acids with ammonia in a ‘o:stage neutralization proces. Inthe fist stage, nitric acid is neutralized with ammonia to form a concentrated aamo- ium nitrate solution, Inthe second stag, the smmoninm sitate solution is reacted with sulfuric acid and adalitional ‘ammonia, forning a soluion of ammonium aitrate and ‘ammonium sulfate, The ASN product is then recovered by ‘removal of water from the reaction mixture. While effective ‘his process i inherently more complex and expensive than ‘one which employs single-stage neutralization. Another known mettod for producing ASN is based on the addition of solid ammonium sulfate and water to molten ‘ammonium nitrate, a8 described in U.S. Pat, No, 6,689,181 to Highsmith etal, which deseribes (a) charging materials comprising ammonium sulfate particles, ammonium nitrate and water toa melting device, wherein the molar ratio of ‘ammonium slfte to ammonium nitrate is about 0.9:1 to bout I.1:1 and the water is more than 2 wt. % to about 10 ‘wt % of the charged materials; (b) melting the smmoniam nitate and dissolving a least a portion of the ammonin sulfate partiles at a temperature of about 180° C. to aber 210° C:(e) reacting the charged materials ata temperature ‘of about 180° C. to about 210° C.; and (d) solidifying the product at a cooling rate of atleast about 100° Cm, Such ‘4 method tends to require vigorous agitation to properly tisperse the ammonium sulfate paricles in the ammonim nitrate melt and careful temperature contralto avoid pos sible explosion of ammonium nitrate. The vigorous mixing could create gas bubbles in the molten ammonium nitrate, ‘whieh potentially increases th risk of explosion SUMMARY OF THE INVENTION ‘The present technology relates to processes for producing ammonium sulfate nitrate double salts that facilitate intimate ‘mixing of ammonium nitrate and ammonium sulfate without ‘the complexity and high cost of rworstage neualization, oF the potential hazards of working with molten ammoninm In some embodiments the presen techaology relates toa method of producing an ammonium sulfate nitate 1:2 double salt in which ammonium sulfite, nitric acid and a source of ammonia are combined in an aqueous solution to {orm a reaction mixture. The reaction mixture ix heated to a temperature from about 160° C. to about 180° C. and is allowed to undergo a reaction for atime period suliient to orm an intermediate mixture. Suficent water is removed trom the intermediate mixture to fom the sumonium sul- {ite nite 1:2 double salt. In some embodiments, the present technology relates toa rmethod of producing an ammonium sulfate nitrte 1:2 ‘double salt in which ammonium sultite, atric acid and @ source of ammonia are combined to form an agueots reaction mixture. The nitric acid and the source of ammonia are reacted in the presence of the ammonium sulfate to form ‘an aqueous solution of ammonium nitrate and ammoniam sulfate. The water content of the aqueous solution of amma-