US 2011 0008243A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0008243 A1 Sadan (43) Pub. Date: Jan. 13, 2011 (54) PROCESSES FOR PREPARATION OF Related U.S. Application Data COMPOSITIONS COMPRISING POTASSUM (60) Provisional application No. 61/219,728, filed on Jun. CHLORIDE 23, 2009. (76) Inventor: Abraham Sadan, Park City, UT Publication Classification (US) (51) Int. Cl. COID 3/04 (2006.01) Correspondence Address: C22B 26/10 (2006.01) JONES DAY (52) U.S. Cl. ..................................................... 423/499.1 222 EAST 41ST ST NEW YORK, NY 10017 (US) (57) ABSTRACT Provided herein are processes for obtaining Sylvinite and/or (21) Appl. No.: 12/820,882 Sylvite from sea water, sea bitterns and/or sea salts. The processes comprise reacting sea water, sea bitterns and/or sea (22) Filed: Jun. 22, 2010 salts with calcium hydroxide and/or calcium oxide. PRODUCTION OF SYLVITE BY COOLING COOLED SOLUTION COOLING Sylvite Patent Application Publication Jan. 13, 2011 Sheet 1 of 4 US 2011/0008243 A1 0NT|000 NOLIITTOS(ETO00 Patent Application Publication Jan. 13, 2011 Sheet 2 of 4 US 2011/0008243 A1 Patent Application Publication Jan. 13, 2011 Sheet 3 of 4 US 2011/0008243 A1 |ODN?SOW (@) Patent Application Publication Jan. 13, 2011 Sheet 4 of 4 US 2011/0008243 A1 @)10X 00HZ-VOSDO (H0)6W|(9) ODO (@) () US 2011/0008243 A1 Jan. 13, 2011 PROCESSES FOR PREPARATION OF desulfated bittern with a concentrated solution of MgCl, to COMPOSITIONS COMPRISING POTASSUM obtain carnallite and further obtaining KC1. This is an expen CHLORIDE sive route due to cost of raw materials and process steps involved. 1. RELATED APPLICATIONS O010 U.S. Patent Publication No. 2003/0080066 dis 0001. This application claims priority to U.S. Provisional closes an integrated process for recovery of high purity potas Patent Application No. 61/219,728, filed Jun. 23, 2009, the sium chloride, and end bittern containing 7.5 g/L bromine. contents of which is incorporated herein by reference in its The process is based on desulftation of brine with distiller entirety. waste of sodaash industry or calcium chloride generated from limestone and acid. The process has limited applicability due 2. FIELD to requirement of distiller waste and the carnallite obtained is contaminated with high extent of NaCl necessitating further 0002 Provided herein are processes for obtaining Sylvin purification. ite (mixture of KCl and NaCl) and/or Sylvite (KCl) from sea O011 PCT International Publication No. WO/2003/ water, sea bitterns and/or sea salts, including, but not limited 064323 discloses a method of producing KCl-enriched low to, kainite (MgSO.KC1.3H2O), and carnallite (MgCl-KCl. Sodium salt from bittern. This process also uses calcium chlo 6H2O). Further provided are compositions prepared by the ride and is expensive. processes and methods of using the compositions. 0012 US 2005/0220697 and WO/2005/063625 describe treatment of carnallite decomposition liquor (CDL) with lime 3. BACKGROUND (CaO) to obtain KC1. The publication describes that CDL is 0003 Potassium chloride, potash or Sylvite is mainly used obtained by processing bittern by following the steps as a fertilizer, either as single fertilizer or in combination with described. other plant nutrients. Potassium chloride is also used in sev (0013 BR 8107507 described recovery of alkali metal eral industries like dyes, Soaps, detergents, food, pharmaceu halides, alkaline earth metal halides, and Mg(OH) from final ticals and as starting material for preparing other potassium brines (the mother liquor remaining after the 1st crop of NaCl chemicals like potassium hydroxide and potassium carbon from seawater). The process involves NaCl and CaCO ate. removal by evaporation and crystallization, Ca(OH) addi 0004. When sea water is evaporated, various sea salts pre tion to permit Mg precipitation and removal as insoluble cipitate. Generally, the order of precipitation of sea salts is as Mg(OH), brine reconcentration, and removal and separation follows: halite or sodium chloride (NaCl), epsomite (MgSO. of a mixture of NaCl and KCl crystals. The process is carried 7H2O), kainite (MgSO.KC1.3H2O), and carnallite (MgCl2. out in a system of agitators, filters, evaporators, grinders, KC1.6H2O)— epsomite (MgSO.7H2O) mixture. Sodium flotation cells, and thickeners. chloride is mixed in all precipitated salts in various quantities. (0014 DE 22 19340 described that mother liquor of salt Potassium chloride does not precipitate from sea water. evaporation pond is reacted with calcium chloride for the Potassium chloride is recovered from sulfate free terminal purpose of desulfating and then evaporated to precipitate lakes like the Dead Sea and Bonneville Lake or is mined sodium chloride and carnallite. The carnallite is subjected to either by Solution mining or by regular mining. In order to a cold decomposition process with water to obtain potassium obtain potassium chloride from sea water, sulfates need to be chloride. removed from the water. (0015 SE 95638 describes processes for extracting NaCl 0005. The removal of sulfate can be achieved by refrigera from sea water as well as, other Substances in their original or tion or cooling of the sea water bitterns to Subzero degrees to changed forms. The processes involves concentration of the remove epsomite, MgSO4.7H2O. The low sulfate bitterns is sea water by freezing the water to form ice crystals that are then evaporated to provide carnallite that can be processed to separated from the solution gradually. The concentrated solu obtain potassium chloride. Refrigeration cannot remove all tion is further processes to obtain sodium chloride and other Sulfates. Thus, potassium chloride obtained by this process is salts. contaminated with Sulfates to Some extent. 0006. In order to achieve complete removal of sulfates, use 0016. Although, there have been many attempts reported of calcium chloride has been tried by several researchers. in the literature to obtain potassium chloride compositions Calcium chloride reacts with epsomite to precipitate gypsum, from sea water, there continues to be a need for cost-effective CaSO2H.O. However, this is an expensive process. and efficient processes for production of compositions com 0007. Several attempts have been reported using carnallite prising potassium chloride and Sylvinite from sea water, bit to obtain potassium chloride. However, carnallite from sea terns and sea salts. water contains epsomite, and potassium chloride obtained from seawater carnallite is contaminated with epsomite. 4. SUMMARY 0008 U.S. Pat. No. 3,099,528 discloses a process to pro duce KCl via Sylvinite obtained from crude carnallite. In this 0017. In certain embodiments, provided herein are pro process calcium chloride is used to desulfate the brine. As cesses for obtaining Sylvinite (a mixture of potassium chlo discussed above, this is an expensive route. ride and sodium chloride) from sea water, sea bitterns and/or 0009 U.S. Pat. No. 7,014,832 reports an integrated pro sea salts. In certain embodiments, provided herein are pro cess for the simultaneous recovery of industrial grade potas cesses for production of Sylvite (potassium chloride) from sea sium chloride and low sodium edible salt with overall KCl water, Sea bitterns and/or sea salts. yield of 90 to 95%. The process comprises removal of sulfates 0018. In certain embodiments, provided herein are pro from bitterns with a solution of calcium chloride; subjecting cesses for removal of Sulfate and magnesium ions from sea the desulfated bittern to evaporation; mixing the concentrated bitterns to provide magnesium and sulfate free bitterns. US 2011/0008243 A1 Jan. 13, 2011 0019. In certain embodiments, provided herein are pro saturated solution of Sylvinite is further processed to yield cesses for removal of Sulfate and magnesium ions from sea either Sylvinite or KC1. The filter cake can be washed and salts, such as kainite and carnallite, to provide magnesium further used in sheet rock boards or disposed off. and sulfate free salts. 0026. In certain embodiments, the processes provided 0020. In certain embodiments, the processes provided herein comprise evaporating bitterns to provide kainite. In herein comprise reacting sea water, sea bitterns and/or sea certain embodiments, kainite is further processed to provide salts with calcium hydroxide and/or calcium oxide to remove Sylvinite. In certain embodiments, Sylvinite is further pro Sulfate and magnesium. In certain embodiments, the Sulfate cessed to yield Sylvite, KC1. and magnesium free sea water or sea bittern is evaporated to 0027. In certain embodiments, the processes provided obtain Sylvinite. In certain embodiments, the Sylvinite is fur herein comprise evaporation of sea water or sea bittern to ther processed to obtain Sylvite. obtain a solution containing a mixed salt comprising pre 0021. In certain embodiments, the processes provided dominantly carnallite and further comprising epsomite and herein comprise evaporation of sea water or sea bittern to Sodium chloride. In certain embodiments, the carnallite, obtain a solution containing a mixed salt comprising pre epsomite and sodium chloride mixed salt is reacted with dominantly kainite and further comprising sodium chloride. Ca(OH) and/or CaO in presence of a Sylvinite solution to In certain embodiments, the kainite and sodium chloride yield an end Sylvinite Solution and a precipitate. In certain mixed salt is reacted with Ca(OH) and/or CaO to yield and an embodiments, Sylvinite and/or Sylvite is recovered from the end Sylvinite Solution and a precipitate. In certain embodi end Sylvinite Solution and/or the precipitate. ments, Sylvinite and/or Sylvite is recovered from the end 0028. In certain embodiments, the processes provided Sylvinite solution and/or the precipitate. herein comprise evaporating bitterns to provide kainite. In 0022. In certain embodiments, the processes provided certain embodiments, kainite is further processed to provide herein comprise evaporation of sea water or sea bittern to Sylvinite. In certain embodiments, Sylvinite is further pro obtain a solution containing a mixed salt comprising pre cessed to yield Sylvite, KC1.