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 . The processes comprise reacting sea water, sea bitterns and/or sea (22) Filed: Jun. 22, 2010 salts with hydroxide and/or calcium oxide.

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Patent Application Publication Jan. 13, 2011 Sheet 4 of 4 US 2011/0008243 A1

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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 with distiller entirety. waste of sodaash industry or 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 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 chloride, or Sylvite is mainly used obtained by processing bittern by following the steps as a , either as single fertilizer or in combination with described. other plant nutrients. is also used in sev (0013 BR 8107507 described recovery of 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 (the mother liquor remaining after the 1st crop of NaCl chemicals like potassium hydroxide and potassium carbon from ). The process involves NaCl and CaCO ate. removal by evaporation and , 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 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. dominantly kainite and further comprising sodium chloride. 0029. In certain embodiments, the processes provided In certain embodiments, the Sodium chloride is present as herein comprise evaporating Sulfate free bitterns to provide coarse particles. In certain embodiments, the kainite and carnallite. In certain embodiments, canallite is further pro sodium chloride mixed salt is reacted with Ca(OH) and/or cessed to provide Sylvinite. In certain embodiments, Sylvinite CaO to yield a slurry comprising CaSO4.2H2O, Mg(OH), is further processed to yield Sylvite, KC1. NaCl and KCl. In certain embodiments, the slurry comprises 0030. In certain embodiments, the processes further com coarse NaCl and fine particles comprising CaSO4.2H2O, prises leaching Sylvinite in water at about 80-100° C. or Mg(OH), and KCl. In certain embodiments, the fine particles higher temperature to leach potassium chloride in solution. are removed from the coarse particles by screening and fil Sodium chloride remains as solid. Since, the solubility of tration. In certain embodiments, KCl from the fine particles is potassium chloride increases with temperature and the solu leached to provide a solution containing KCl. In certain bility of sodium chloride is not affected with temperature embodiments the KCl solution is evaporated to yield high change, the Solid sodium chloride is separated and the hot grade Sylvite, KC1. Solution comprising potassium chloride is cooled to obtain 0023. In certain embodiments, the reaction of kainite and potassium chloride. NaCl mixture with CaO and/or Ca(OH) is carried out at near 0031. In certain embodiments, the processes further com boiling temperature to provide a slurry containing CaSO4. prise mixing Sylvinite in water from about 0°C. to about 10° 2H2O, Mg(OH), NaCl and KC1. The slurry when filtered C. Sodium chloride dissolves and potassium chloride remains yields solids containing CaSO4.2H2O, Mg(OH), and NaCl, as Solid. The Solid comprising potassium chloride is centri and a filtrate containing a concentrated Solution of predomi fuged and separated. nantly KC1. In certain embodiments, the filtrate is cooled to an 0032. In certain embodiments, potassium chloride ambient temperature to provide Sylvite, KC1. obtained in the processes provided here is used as a fertilizer 0024. In certain embodiments, the reaction of kainite and or a component in a fertilizer. In one embodiment, Sylvinite NaCl mixture with CaO and/or Ca(OH) is carried out to obtained by the processes provided herein is used as a low provide a slurry containinig CaSO4.2H2O, Mg(OH), NaCl Sodium salt. and KCl. In certain embodiments, the solids are filtered and the filtercake is leached at an elevated temperature to obtain 5. BRIEF DESCRIPTION OF THE DRAWINGS KC1. In certain embodiments, the leaching is carried out at a temperature of greater than about 40°C., 50° C., 60° C., 70° 0033 FIG. 1 provides a flow diagram for the reaction of C., or 80°C. In certain embodiments, the leaching is carried calcium hydroxide with kainite-NaCl mixture and water at out at a temperature of between about 40°C. to 100°C., about near boiling temperature to provide a slurry comprising 40° C. to 80° C., about 40°C. to 70° C., about 50° C. to 100° CaSO4.2H2O, Mg(OH) and excess NaCl, and a solution C., about 60° C. to 100° C. or about 70° C. to 100° C. comprising about 22% KCl and about 17% NaCl by weight 0025. In certain embodiments, the reaction of kainite and based on total weight of the solution. The slurry is filtered to NaCl mixture with CaO and/or Ca(OH) is carried out in the remove CaSO4·2H2O, Mg(OH) and the excess NaCl salts. presence of a Sylvinite solution. In certain embodiments, the The solution is cooled to provide potassium chloride. The reaction of kainite and NaCl mixture with CaO and/or cooled Sylvinite brine comprising about 11% KCl and about Ca(OH) is carried out in the presence of a saturated solution 20% NaCl is returned to the reaction mixture. of NaCl containing small amounts of KC1. In certain embodi 0034 FIG. 2 provides a flow diagram for the reaction of ments, the saturated solution of NaCl allows dissolution of the Ca(OH) with kainite-NaCl mixture and water at ambient KCl in kainite yielding a slurry of CaSO4.2H2O, Mg(OH) temperature to provide a slurry comprising CaSO4·2H2O and and NaCl solids and a saturated solution of Sylvinite. The Mg(OH). The slurry is filtered to provide Sylvinite solution US 2011/0008243 A1 Jan. 13, 2011

which can be evaporated in Solar crystallization ponds or in Ca(OH). In certain embodiments, the end Sylvinite solution house to provide Sylvinite that can be processed further to is further processed to obtain Sylvinite and/or Sylvite. provide KC1. 0048. As used herein Sylvite refers to high grade potas 0035 FIG. 3 provides a flow diagram for the reaction of sium chloride. In certain embodiments, the purity of potas Ca(OH), with kainite-NaCl mixture and Sylvinite solution at sium chloride is about 40%, 50%, 60%, 70%, 80%, 90%, ambient temperature to provide a slurry comprising of fine 95%, 99% or more. In certain embodiments, the purity of KC1, CaSO4·2H2O and Mg(OH) and coarse NaCl. The potassium chloride is about 90%, 95%, 99% or more. slurry is screened to remove the coarse NaCl, the fines are 0049. As used herein, gypsum refers to CaSO4·2H2O. filtered and further leached to provide KCl solution which can 0050. As used herein, epsomite refers to MgSO.7HO. be evaporated by Solar crystallization ponds or in house to 0051. As used herein, harvesting refers to collecting salts provide KC1. from the pond. 0036 FIG. 4 provides a flow diagram for the reaction of 0052. As used herein, bitterns refer to concentrated mag Ca(OH), with kainite-NaCl mixture and saturated NaCl solu nesium water or brine remaining after sodium chloride has tion containing KCl at less than Saturation. The reaction is been precipitated. carried out at ambient temperature to provide a slurry com 0053 As used herein, pond refers to a ground area con prising of fine CaSO2HO and Mg(OH), and coarse NaCl fined by dykes from all sides to contain water, bitterns or salts and a saturated Sylvinite solution with both NaCl and KCl. obtained at various stages in the processes provided herein. The saturated Sylvinite solution is further processed to yield 0054 As used herein, predominantly refers to about 40% Sylvite or KC1. or greater. In one embodiment, predominantly refers to greater than about 40%, 45%, 50% 55%, 60%. 65%, 70%, 6. DETAILED DESCRIPTION OF THE 75%, 80%, 85%, 90%, 95% or 100%. In one embodiment, INVENTION predominantly refers to about 40%, 45%, 50% 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%. For 0037 Provided herein are processes for production of example, "kainite predominantly containing KSO.MgSO4. compositions comprising potassium chloride from sea water, MgCl,.6HO' means the amount of KSO, MgSO, MgCl, sea bitterns and/or sea salts. 6HO double salt in kainite is more than about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 6.1 Definitions 100%. In another example, “carnallite predominantly con taining MgCl2.KC1.6HO' means the amount of MgCl2.KC1. 0.038. Unless defined otherwise, all technical and scien 6HO double salt in carnallite is more than about 40%, 45%, tific terms used herein have the same meaning as is commonly 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or understood by one of ordinary skill in the art. All patents, 100%. applications, published applications and other publications 0055 As used herein, % purity of potassium chloride are incorporated by reference in their entirety. In the event refers to the amount of potassium chloride in the product. The that there are a plurality of definitions for a term herein, those process provided herein provide at least about 80% pure in this section prevail unless stated otherwise. potassium chloride. In certain embodiments, the purity of 0039. As used herein, natural water or water refers to water potassium chloride is about 40%, 50%, 60%, 70%, 80%, from any natural Source, such as ocean, Sea, brackish, lakes, 90%. 95%, 99% or more. In certain embodiments, potassium Such as Salt lake or regular underground water. chloride obtained by the processes provided herein is about 0040. As used herein, oceans and sea refers to all the 90%. 95%, 99% or more pure. connected seas with currents, and are home to living sea 0056. As used herein, near or shy of boiling temperature beings. refers to about 100° C. 0041 As used herein, terminal lakes are lakes receiving 0057. As used herein kainite-NaCl refers to a waters but do not have a way to let any water out, but by mixture of kainite and NaCl. In certain embodiments, the evaporation. The Salton Sea is an example of a terminal lake. kainite-NaCl sea salt comprises predominantly kainite. In 0042. As used herein, a crystallization pond is a pond in certain embodiments of the processes herein, the kainite which salt crystallizes. The Dead Sea is an example of a salt NaCl sea salt is reacted with CaO and/or Ca(OH) to obtain crystallization pond. Sylvinite and/or Sylvite. In certain embodiments, the total 0043. As used herein, kainite refers to a hydrated salt amount of kainite in the kainite-NaCl sea salt is about or predominantly containing KSO, MgSO.MgCl2.6H2O. greater than about 40%, 45%, 50%, 60%. 65%, 70%, 75%, 0044 As used herein, carnallite refers to a hydrated salt 80%, 85%, 90%, or 95%. predominantly containing MgCl2.KC1.6H2O. 0.058 As used hereincarnallite-NaCl sea salt refers to a 0045. As used herein, Sylvinite refers to a mixture of mixture of carnallite and NaCl. In certain embodiments, the potassium chloride and Sodium chloride at all ratios. carnallite-NaCl sea salt comprises predominantly carnallite. 0046. As used herein, Sylvinite solution refers to a solution In certain embodiments of the processes herein, the carnal comprising KCl and NaCl. In certain embodiments, the syl lite-NaCl sea salt is reacted with CaO and/or Ca(OH) to vinite solution is saturated with respect to both NaCl and KCl. obtain Sylvinite and/or Sylvite. In certain embodiments, the In certain embodiments, the Sylvinite solution is saturated total amount of carnallite in the carnallite-NaCl sea salt is with respect to NaCl, and under saturated with respect to KC1. about or greater than about 40%, 45%, 50%, 60%. 65%, 70%, In certain embodiments, the Sylvinite solution is under Satu 75%, 80%, 85%, 90%, or 95%. rated with respect to both NaCl and KCl. 6.2 Processes 0047. As used herein end Sylvinite solution refers to a Sylvinite solution that is obtained after a reaction of kainite 0059 Provided herein are processes for production of NaCl sea salt or carnallite-NaCl sea salt with CaO and/or compositions comprising potassium chloride from sea water, US 2011/0008243 A1 Jan. 13, 2011

sea bitterns and/or sea salts. In one aspect, the processes tion comprises about 22% KCl and about 17% NaCl by comprise evaporation of sea water or sea bittern to obtain a weight based on total weight of the solution. The slurry is mixed salt containing kainite and sodium chloride. In certain filtered to remove CaSO4.2H2O, Mg(OH) and the excess embodiments, kainite starts precipitating when sea water or NaCl salts. In certain embodiments, the solution is cooled to bitterns reach magnesium concentration of about 3.5% or provide potassium chloride. In certain embodiments, the greater by weight based on total weight of bitterns. In certain cooled Sylvinite brine comprising about 11% KCl and about embodiments, kainite precipitates when the magnesium con 20% NaCl is returned to the reaction mixture. centration of bitterns is between about 3.5% to about 8% by weight based on total weight of bitterns. In certain embodi 0063. In certain embodiments, the process for production ments, kainite precipitates when the magnesium concentra of sylvinite is conducted as schematically represented in FIG. tion of bitterns is between about 3.5% to about 6.7% by 2. As illustrated in FIG. 2, the reaction of the CaO and/or weight based on total weight of bitterns. In one embodiment, Ca(OH), with kainite-NaCl mixture in presence of water is kainite precipitates when the magnesium concentration of carried out at ambient temperature to provide a slurry com bitterns is about 3.5%. 5%, 6%, or 6.5% by weight based on prising CaSO4·2H2O and Mg(OH). The slurry is filtered to total weight of bitterns. In one embodiment, kainite precipi provide Sylvinite solution which can be evaporated in solar tates when the magnesium concentration of bitterns is about crystallization ponds or in-house to provide Sylvinite that can 3.5%. 5%, 6%, 6.5%, 6.7%, 7%, 7.5% or 8% by weight based be processed further to provide KC1. on total weight of bitterns. 0064. In certain embodiments, the processes provided 0060. In certain embodiments, the processes provided herein comprise evaporation of sea water or sea bittern to herein use kainite and Sodium chloride mixed Saltas a starting obtain a mixed salt comprising kainite and sodium chloride. feedstock for production of potassium chloride compositions. In certain embodiments, the sodium chloride is present as In certain embodiments, the kainite and sodium chloride coarse particles. In certain embodiments, the kainite and mixed salt comprises about 6-8% Mg. In certain embodi sodium chloride mixture is reacted with Ca(OH) and/or CaO ments, the kainite and Sodium chloride mixed salt comprises to yield a slurry comprising CaSO4.2H2O, Mg(OH), NaCl about 9-13% or about 10-12% K. In certain embodiments, the and KCl. In certain embodiments, the reaction of kainite and kainite and sodium chloride mixed salt comprises about 7-10% or about 7.5-9% Na. In certain embodiments, the sodium chloride mixed salt with calcium hydroxide or cal kainite and sodium chloride mixed salt comprises about cium oxide is carried out in presence of Sylvinite Solution. In 28-30% SO. In certain embodiments, the kainite and sodium certain embodiments, the slurry comprises coarse NaCl and chloride mixed salt comprises about 20-24%. Cl. In certain fine particles comprising CaSO4.2H2O, Mg(OH), and KCl. embodiments, the kainite and sodium chloride mixed salt In certain embodiments, the fine particles are removed from comprises about 18-22% or about 18-20% water. In certain the coarse particles by Screeening and filtration. In certain embodiments, the kainite and sodium chloride mixed salt embodiments, KCl from the fine particles is leached to pro comprises about 0.5-2% or about 1-2% insolubles by weight. vide a solution containing KCl. In certain embodiments the In certain embodiments, the kainite and sodium chloride KC1 solution is evaporated to yield high grade Sylvite, KC1. mixed salt comprises about 8% Mg, about 9.5% K, about 0065. In certain embodiments, the process for production 6.5% Na, and about 30% SO. In certain embodiments, the of sylvinite is conducted as schematically represented in FIG. kainite and sodium chloride mixed salt comprises about 3. As illustrated in FIG. 3, the reaction of CaO and/or 7.72% Mg, about 11.65% K, about 8.10% Na, and about Ca(OH), with kainite-NaCl mixture and Sylvinite solution is 29.13% SO about 22.46% C1, about 19.94% water and conducted at an ambient temperature to provide a slurry com about 1% insolubles by weight. prising of fine KC1, CaSO4.2H2O and Mg(OH) and coarse 0061. In certain embodiments, the process comprises NaCl. The slurry is screened to remove the coarse NaCl, and reacting kainite and Sodium chloride mixed salt with calcium the fines are filtered. In certain embodiments, KCl from the hydroxide and/or calcium oxide and water, including sea fine particles is leached to provide a solution containing KC1. water, to obtain a precipitate comprising calcium sulfate and In certain embodiments the KCl solution is evaporated to . In certain embodiments, the reaction yield high grade Sylvite, KC1. is conducted at a temperature of at least about 80° C. or 0066. In certain embodiments, the reaction of kainite and higher. In certain embodiments, the reaction is conducted at a NaCl mixture with CaO and/or Ca(OH), optionally in pres temperature of at least about 80°C.,90° C., 100° C. or higher. ence of Sylvinite Solution, is carried out at near boiling tem The precipitate is removed to obtain a clear Solution compris perature to provide a slurry containing CaSO4.2H2O, ing Sylvinite. In one embodiment, the solution is cooled to Mg(OH), and NaCl. The slurry when filtered yields solids obtain precipitate of potassium chloride. The potassium chlo containing CaSO4.2H2O, Mg(OH), and NaCl, and a filtrate ride precipitate is separated from brine. In one embodiment, containing a concentrated solution of predominantly KCl. In the brine is recycled to the feedstock. In certain embodiments, certain embodiments, the filtrate is cooled to an ambient the solution comprising Sylvinite is evaporated to obtain Syl temperature to provide Sylvite, KC1. vinite. In one embodiment, the Sylvinite is further processed 0067. In certain embodiments, the reaction of kainite and to obtain Sylvite, potassium chloride. NaCl mixture with CaO and/or Ca(OH) is carried out to 0062. In certain embodiments, the process for production provide a slurry containinig CaSO2HO, Mg(OH), NaCl of sylvite is conducted as schematically represented in FIG.1. and KCl. In certain embodiments, the solids are filtered and As demonstrated therein, the reaction ofCaO and/or Ca(OH), the filtercake is leached at an elevated temperature to obtain with kainite-NaCl mixture in presence of water is conducted KC1. In certain embodiments, the leaching is carried out at a at near boiling temperature to provide a slurry comprising temperature of greater than about 40° C., 50° C., 60° C., 70° CaSO4.2H2O, Mg(OH) and excess NaCl, and a solution C., 80° C., 90° C., 100° C., 110° C., or 120° C. In certain comprising KCl and NaCl. In certain embodiments, the solu embodiments, the leaching is carried out at a temperature of US 2011/0008243 A1 Jan. 13, 2011

between about 40°C. to 120°C., about 40°C. to 80°C., about comprises about 11-14% SO. In one embodiment, the car 40° C. to 70° C., about 50° C. to 120° C., about 60° C. to 120° nallite and sodium chloride mixed salt comprises about 26 to C. or about 70° C. to 120° C. 29% Cl. In one embodiment, the carnallite and sodium chlo 0068. In certain embodiments, the reaction of kainite and ride mixed salt comprises about 37-40% water. In one NaCl mixture with CaO and/or Ca(OH) is carried out in the embodiment, the carnallite and sodium chloride mixed salt presence of a Saturated Solution of NaCl containing Small comprises about 8.32% Mg, about 8.04% K, about 3.6% Na, amounts of KC1. In certain embodiments, the Saturated solu about 13.33% SO, about 27.82% C1, and about 38.89% tion of NaCl allows dissolution of KCl in kainite yielding a water. In one embodiment, the process comprises reacting slurry of CaSO4.2H2O, Mg(OH), and NaCl solids and a satu carnallite and epsomite mixed salt with calcium hydroxide rated solution of sylvinite. The saturated solution of sylvinite and/or calcium oxide in presence of water, including sea is further processed to yield either Sylvinite or KC1. The filter water, to obtain a precipitate comprising calcium sulfate and cake can be washed and can be used for sheet rock boards. magnesium hydroxide and a solution comprising Sylvinite. In 0069. In certain embodiments, the processes provided certain embodiments, the reaction of carnallite and epsomite herein use kainite and Sodium chloride mixed Saltas a starting mixed salt with calcium hydroxide and/or calcium oxide is feedstock for production of potassium chloride compositions. carried out in presence of Sylvinite solution. In certain In one embodiment, the kainite and sodium chloride mixed embodiments, the reaction is conducted at a temperature of at salt comprises about 8% Mg, about 9.5% K, about 6.5% Na, least about 80° C. In certain embodiments, the reaction is and about 30% SO. In one embodiment, the process com conducted at a temperature of at least about 80°C., 90°C., prises reacting kainite and Sodium chloride mixed salt with 100° C. or higher. The precipitate is removed to obtain a clear calcium hydroxide or calcium oxide and Saturated or under Solution comprising Sylvinite. In one embodiment, the solu saturated Sylvinte , to obtain a precipitate compris tion is cooled to precipitate Sylvite, potassium chloride. ing calcium sulfate and magnesium hydroxide. In certain Potassium chloride is separated from brine. In one embodi embodiments, the reaction is conducted at a temperature of at ment, the brine is recycled to the feedstock. In certain least about 80° C. In certain embodiments, the reaction is embodiments, Solution comprising Sylvinite is evaporated to conducted at a temperature of at least about 80°C., 90° C. obtain Sylvinite. In one embodiment, Sylvinite is further pro 100° C. 120° C. or higher. The precipitate is removed to cessed to obtain potassium chloride. obtain a clear Solution comprising Sylvite, KCl. In certain 0074. In certain embodiments, the Sylvinite precipitate or embodiments, the Solution is cooled to obtain a precipitate of Sylvinite obtained by evaporation comprises at least about potassium chloride. The potassium chloride precipitate is 10% potassium chloride by weight based on the total weight separated from brine. In certain embodiments, the brine is of solids. In certain embodiments, the Sylvinite precipitate or recycled to the feedstock. In certain embodiments, the solu Sylvinite obtained by evaporation comprises at least about tion comprising Sylvite is evaporated to obtain Sylvite, KC1. 20% potassium chloride by weight based on the total weight 0070. In certain embodiments, the process for production of solids. In certain embodiments, the Sylvinite precipitate or of sylvinite is conducted as schematically represented in FIG. Sylvinite obtained by evaporation comprises at least about 4. As illustrated in FIG. 4, the reaction of CaO and/or 30% potassium chloride by weight based on the total weight Ca(OH), with kainite-NaCl mixture and saturated NaCl solu of solids. In certain embodiments, the Sylvinite precipitate or tion containing KCl at less than Saturation is carried out at an Sylvinite obtained by evaporation comprises at least about ambient temperature to provide a slurry comprising of fine 40% potassium chloride by weight based on the total weight CaSO4.2H2O and Mg(OH) and coarse NaCl and a saturated of solids. In certain embodiments, the Sylvinite precipitate or Sylvinite solution with both NaCl and KC1. The saturated Sylvinite obtained by evaporation comprises at least about Sylvinite solution is further processed to yield Sylvite or KC1. 50% potassium chloride by weight based on the total weight 0071. In one aspect, the processes provided herein com of solids. In certain embodiments, the Sylvinite precipitate or prise evaporation of sea water or sea bittern to obtain a mixed Sylvinite obtained by evaporation comprises about 10% to salt comprising predominantly carnallite, and further com about 50%, about 20% to about 50%, about 30% to about prising epsomite and sodium chloride. In one embodiment, 50%, or about 40% to about 50% potassium chloride by the carnallite, epsomite and Sodium chloride mixed salt is weight based on the total weight of solids. In certain embodi used as the starting feedstock for production of potassium ments, the Sylvinite precipitate or Sylvinite obtained by chloride. In certain embodiments, the carnallite and epsomite evaporation comprises about 10%. 20%, 30%, 40%, 42%, mixed salt starts precipitating when bitterns reach magne 45%, 50% or more potassium chloride by weight based on the sium concentration between about 6.5% to 8% by weight total weight of solids. In certain embodiments, the Sylvinite based on total weight of bitterns. precipitate or Sylvinite obtained by evaporation comprises 0072. In certain embodiments, carnallite and epsomite about 10-70% or more, 20-70% or more, 30-70% or more mixed salt precipitates when the magnesium concentration of potassium chloride by weight based on the total weight of bitterns is between about 6.5%, 7%, 7.5% or about 8% by Solids. In certain embodiments, the Sylvinite precipitate or weight based on total weight of bitterns. Sylvinite obtained by evaporation comprises about 50-95% or 0073. In one embodiment, the carnallite and sodium chlo more, 70-95% or more, 80-95% or more, 90% or more, 95% ride mixed salt comprises about 8.3% Mg, about 8.0% K. or more potassium chloride by weight based on the total about 3.6% Na, and about 13.3% SO. In one embodiment, weight of solids. the carnallite and Sodium chloride mixed salt comprises about 0075. In certain embodiments, the brine obtained after 7-10% or 8-10% Mg. In one embodiment, the carnallite and separating Sylvinite precipitate comprises less than about sodium chloride mixed salt comprises about 7-10% or 7.5-9% 50% potassium chloride by weight based on the total weight K. In one embodiment, the carnallite and sodium chloride of the brine. In certain embodiments, the brine comprises less mixed salt comprises about 2.5-4% or 3 to 4% Na. In one than about 40% potassium chloride by weight based on the embodiment, the carnallite and sodium chloride mixed salt total weight of the brine. In certain embodiments, the brine US 2011/0008243 A1 Jan. 13, 2011

comprises about 5% to about 50%, about 10% to about 40%, epsomite and sodium chloride, wherein the method com or about 20% to about 40% potassium chloride by weight prises: reacting the mixture with calcium hydroxide and/or based on the total weight of the precipitate. In certain embodi calcium oxide in presence of water to obtain a precipitate and ments, the brine comprises about 10%, 20%, 25%, 30%, 35%, a solution, wherein the solution comprises Sylvinite; and 36% or 40% potassium chloride by weight based on the total recovering Sylvinite from the Solution. In certain embodi weight of the brine. In one embodiment, the brine is further ments, the process further comprises recovering potassium evaporated to obtain potassium chloride. In one embodiment, chloride from Sylvinite. the brine is returned to the starting feed stock. 0080. In certain embodiments, the evaporation of sylvinite 0076. In certain embodiments, bitterns comprising mag solution provides Sylvinite in form of a hard crystalline bed. nesium in an amount of about 3.5% to about 6.7% by weight Sylvinite can be harvested using techniques known to one of based on total weight of bitterns are used in the processes for skill in the art. Exemplary harvesting techniques are production of potassium chloride provided herein. In one described in US Publication Nos. 2008/022O127 and 2009/ aspect, the processes comprise reacting bitterns comprise 0041900. In one embodiment, the hard crystal bed of Sylvin magnesium in an amount of about 3.5% to about 6.7%. In one ite is broken by a cutting machine. Any suitable cutting embodiment, bitterns comprise about 2.5-4% Mg. In one machine can be used. The Sylvinite crystals are broken to the embodiment, bitterns comprise about 2.5-4% K. In one desired size and stock piled with the use of regular heavy embodiment, bitterns comprise about 3.5-5% Na. In one equipment, Such as motor graders. embodiment, bitterns comprise about 5.5-7.5% SO. In one I0081. In certain embodiments, Sylvinite obtained in the embodiment, bitterns comprise about 13-16% Cl. In one processes provided herein is milled to obtain homogenous embodiment, bitterns comprise about 65-70% water. In one particles of Sylvinite. The milled Sylvinite is dissolved in embodiment, bitterns comprise about 3.2% Mg, about 3.1% water at about 80-100° C. or near boiling temperature to leach K, about 4.8% Na and about 6.7% SO. In one embodiment, bitterns comprise about 3.20% Mg, about 3.09% K, about potassium chloride and leave behind most of solid sodium 4.76% Na, about 6.68% SO, about 14.56% C1, and about chloride. Sodium chloride is separated to obtain a solution 67.72% water. In one embodiment, the processes comprise comprising mostly potassium chloride. Sodium chloride can reacting bitterns with calcium hydroxide or calcium oxide to be used, for example, as deicing salt. obtain a precipitate comprising calcium Sulfate and magne I0082. The solution comprising potassium chloride is sium hydroxide. The reaction can be conducted at any tem cooled to crystallize potassium chloride which is washed in a perature. counter current wash leg to remove mother liquor. The 0077. In one embodiment, the reaction is conducted at a washed potassium chloride is centrifuged to remove liquids. temperature of at least about 80°C. In another embodiment, I0083. In one embodiment, Sylvinite is mixed in water at the reaction is conducted at a temperature of at least about 80° about 0°C. All of the sodium chloride and a part of the KCl in C., 90° C., 100° C., 120° C. or higher. The precipitate is Sylvinite dissolve and a part of the potassium chloride removed to obtain a clear Solution comprising Sylvinite. In remains as Solid. The solid comprising potassium chloride is one embodiment, the solution is cooled to obtain a precipitate centrifuged and separated. of potassium chloride. Potassium chloride is separated from 0084. In certain embodiments, an anti-caking agent is brine. In one embodiment, the brine is recycled to the feed added in a solution form to the centrifuged cake. The anti stock. In certain embodiments, solution comprising Sylvinite caking agents are added to provide a free-flowing product. is evaporated to obtain Sylvinite. In one embodiment, Sylvin The wet centrifuge cake is dried to provide potassium chlo ite is further processed to obtain potassium chloride. ride. 0078. In certain embodiments, the process for production I0085 Exemplary anti-caking agents include, but are not of Sylvinite from sea water or sea bittern comprises evaporat limited to sodium hexacyanoferrate (II) (YPS), potassium ing the sea water or sea bittern to obtain a mixture comprising hexacyanoferrate (II) trihydrate (also known as potassium kainite and sodium chloride; reacting the mixture with cal ferrocyanide or YPP), tricalcium phosphate and magnesium cium hydroxide and/or calcium oxide in presence of water to carbonate. In another embodiment, anti-caking agents obtain a precipitate and a solution, wherein the Solution com include silicates, propylene glycol and polyvinyl alcohol. In prises Sylvinite; and recovering Sylvinite from the solution. In one embodiment, the anti-caking agent is YPS. The anti certain embodiments, the process for production of Sylvinite caking agent can be added in an amount Sufficient to prevent from a mixture comprising kainite and sodium chloride, formation of lumps or to keep potassium chloride in free wherein the method comprises: reacting the mixture with flowing form. In certain embodiments, the amount of anti calcium hydroxide and/or calcium oxide in presence of water caking agent YPS added to potassium chloride is less that to obtain a precipitate and a solution, wherein the Solution about 20 ppm by weight. In certain embodiments, the amount comprises Sylvinite; and recovering Sylvinite from the Solu of anti-caking agent YPS added to potassium chloride is less tion. In certain embodiments, the process further comprises that about 20, 18 or 15 ppm by weight. recovering potassium chloride from Sylvinite. 0086. In certain embodiments, the reaction with calcium 0079. In certain embodiments, the process for production hydroxide and/or calcium oxide removes at least about 80% of Sylvinite from sea water or sea bittern comprises evaporat sulfate by weight based on total weight of sulfates in the ing the sea water or sea bittern to obtain a mixture comprising starting material. In certain embodiments, the reaction carnallite, epsomite and sodium chloride; reacting the mix removes at least about 80%, 90%. 95% or 99% sulfate by ture with calcium hydroxide and/or calcium oxide in presence weight based on total weight of Sulfates in the starting mate of water to obtain a precipitate and a solution, wherein the rial. In certain embodiments, the reaction removes from about Solution comprises Sylvinite; and recovering Sylvinite from 80% to about 100%, about 90% to about 100%, or about 95% the solution. In certain embodiments, the process for produc to about 100% sulfate by weight based on total weight of tion of Sylvinite from a mixture comprising carnallite, Sulfates in the starting material. US 2011/0008243 A1 Jan. 13, 2011

0087. In certain embodiments, the reaction with calcium hydroxide and/or calcium oxide and water removes at least about 80% magnesium by weight based on total weight of magnesium in the starting material. In certain embodiments, Wt 9% the reaction removes at least about 80%, 90%. 95% or 99% Insolubles 1.OO magnesium by weight based on total weight of magnesium in Mg 7.72 the starting material. In certain embodiments, the reaction K 11.65 removes from about 80% to about 100%, about 90% to about Na 8.10 100%, or about 95% to about 100% magnesium by weight SO 29.13 based on total weight of magnesium in the starting material. C 22:46 0088. In certain embodiments, kainite and carnallite HO 1994 double salts used for production of potassium chloride are produced by processes known to one of skill in the art. In one 0093. The Kainite-NaCl mixture was reacted with embodiment, kainite and carnallite double salts are produced Ca(OH) to obtain a slurry containing gypsum and Mg(OH) by Solar evaporation of sea water or sea bitterns. as solids and Sylvinite in dissolved form. The slurry was 0089. In certain embodiments, potassium chloride filtered to remove gypsum and Mg(OH). Sylvinite solution obtained by the processes provided herein is at least about was evaporated to provide Sylvinite bed. 40% pure. In certain embodiments, potassium chloride obtained by the processes provided herein is about 50% to (0094 Sylvinite Harvesting about 99% or higher, about 50% to about 90% or higher, (0095. The hard crystal bed of Sylvinite was broken by a about 50% to about 80% or higher, or about 60% to about cutting machine. The Sylvinite crystals were broken to the 90% pure or higher. In certain embodiments, potassium chlo desired size and stock piled with the use of regular heavy ride obtained by the processes provided herein is about 40%, equipment, Such as motor graders. 50%. 60%, 70%, 80%, 90%, 95% or about 99% or more pure. (0096 Sylvinite Processing In certain embodiments, potassium chloride obtained by the (0097. The harvested Sylvinite was trucked and fed to the processes provided herein is about 90%. 95% or about 99% or milling plant where the Sylvinite was milled to insure homog more pure. enous crystal size of the product. The milled Sylvinite was 6.3 Methods of Use dissolved in water at near boiling temperature for the leaching 0090. In certain embodiments, the process provided of potassium chloride. The precipitate containing sodium herein produce industrial grade potassium chloride. In certain chloride was separated by centrifugtion and could be used as embodiments, potassium chloride produced herein can be deicing salt. The Solution containing mostly potassium chlo used as a fertilizer or as a component of a fertilizer. In another ride and some sodium chloride was cooled to crystallize embodiment, potassium chloride is used in dyes, soaps, deter potassium chloride. Potassium chloride was washed in a gents, food, pharmaceuticals and as a starting material for counter current wash leg to remove mother liquor. The preparing other potassium chemicals like potassium hydrox washed potassium chloride was Subjected to a centrifugation ide and potassium carbonate. In certain embodiments, Sylvin step to remove liquids. An anti caking agent YPS was added ite produced herein can be uses as a low sodium salt, espe in a solution form to the centrifuges cake in less than about 20 cially Suitable for persons suffering from hypertension and ppm by weight. The wet centrifuge cake was dried to provide heart diseases. The low sodium salt provided herein can be used as a salt Substitute in food products or as a table salt in the commercial grade potassium chloride. salt shaker for tabletop use for sprinkling on prepared foods. Additionally, the low Sodium salt compositions provided 7.2 Example 2 herein can be used in commercial food manufacturing pro cesses, for example, to Salt the processed foods. Representa Production of Potassium Chloride from Kainite tive foods include Soups, vegetables, meat, poultry, fish, NaCl Mixture cheese, breads, Snack foods, such as potato chips, pretzels, peanuts, seeds, corn chips, tortilla chips, crackers and bread 0098 Kainite-NaCl mixture is reacted with Ca(OH), and Sticks. water at about 100° C. Mg(OH) and calcium sulfate precipi 0091. It is understood that the foregoing detailed descrip tate with excess NaCl. The solids are removed and the hot tion and accompanying examples are merely illustrative, and liquid containing Sylvinite is separated. The hot liquid when are not to be taken as limitations upon the scope of the Subject cooled to ambient temperature yields potassium chloride as matter. Various changes and modifications to the disclosed precipitate. The precipitate is separated and processes to embodiments will be apparent to those skilled in the art. Such obtain potassium chloride. The cooled liquid is returned to the changes and modifications, including without limitation reaction mixture. those relating to the methods of use provided herein, may be made without departing from the spirit and scope thereof. Patents, patent publications, and other publications refer 7.3 Example 3 enced herein are incorporated by reference. Production of Sylvinite from Carnallite-NaCl Mix 7. EXAMPLES ture 7.1 Example 1 Production of KCl, from Kainite-Sodium Chloride 0099 Sea bitterns containing about 6.5% Mg were evapo Mixture Kainite Production rated into a evaporation pond where the bitterns evaporated 0092. The kainite-sodium chloride mixture obtained from till the Mg, concentration reached 8 to 8.5% Mg. sea water evaporation served as a starting feed block for the 0100. In the process of evaporation, a mixture of carnal production of KC1. The mixture had the following composi lite-epsomite and sodium chloride precipitated with the fol tion (amounts in weight%): lowing composition (in weight percent): US 2011/0008243 A1 Jan. 13, 2011

containing gypsum and Mg(OH) as Solids and an end Syl Vinite solution. The slurry was filtered to remove gypsum and Mg(OH). The Sylvinite solution was evaporated to provide Mg 8.32 K 8.04 Sylvinite bed of crystals. Na 3.6 0107 Sylvinite Harvesting SO 13.33 0108. The hard crystal bed of Sylvinite was broken by a C 27.82 cutting machine. The Sylvinite crystals were broken to the HO 38.89 desired size and stock piled with the use of regular heavy equipment, Such as motor graders. 0101 The carnallite-epsomite-halite mixture was sepa 0109 Sylvinite Processing rated from solution. The mixture was reacted with Ca(OH) to 0110. The harvested Sylvinite was trucked and fed to the remove Sulfates and magnesium. The slurry containing gyp milling plant where the Sylvinite was milled to insure homog sum and Mg(OH), as solids was obtained. The solids were enous crystal size of the product. The milled Sylvinite was separated and the liquid containing Sylvinite was evaporated dissolved in water at near boiling temperature for the leaching to provide Sylvinite in solid form. of potassium chloride. The undissolved solids containing 0102 The Sylvinite was leached at 0°C. to obtain potas Sodium chloride were separated by centrifugation and sold as sium chloride as solid and most of the sodium chloride in deicing salt. The Solution containing mostly potassium chlo Soution. The Solid was centrifuged and dried to obtain com ride and some sodium chloride was cooled to crystallize mercial grade potassium chloride. The Solution was Solar potassium chloride. Potassium chloride was washed in a evaporated or heated to 30° C. to precipitate the sodium counter current wash leg to remove mother liquor. The chloride. washed potassium chloride was Subjected to a centrifugation step to remove liquids. An anti-caking agent YPS was added 7.4 Example 4 in a solution form to the centrifuges cake in less than about 20 ppm by weight. The wet centrifuge cake was dried to provide Production of KCl from Sea Bitterns commercial grade potassium chloride. 0103) Sea bitterns having the following composition is used (in weight%): 7.6 Example 6 Production of Potassium Chloride from Kainite NaCl Mixture Mg 3.20 K 3.09 0111 Kainite-NaCl mixture was reacted with Ca(OH) in Na 4.76 presence of Sylvinite solution at about 100° C. Mg(OH) and SO 6.68 calcium sulfate precipitates with excess NaCl. The solids C 14.56 were removed and the hot liquid containing Sylvinite was HO 67.72 separated. The hot Sylvinite Solution was cooled to an ambi ent temperature to yield potassium chloride as precipitate. 0104. The bitterns are reacted with Ca(OH) to remove The precipitate was separated and processed to obtain potas Sulfates and magnesium. The slurry containing gypsum and sium chloride. The cooled Sylvinite solution was returned to Mg(OH) as solids was obtained. The solids were separated the reaction circuit. and the liquid containing Sylvinite was evaporated to provide Sylvinite in solid form. Sylvinite is processed as shown above 7.7 Example 7 in Examples 1 or 2. Production of Sylvinite from Carnallite-NaCl Mix 7.5 Example 5 ture Production of KCl, from Kainite-Sodium Chloride 0112 Sea bitterns containing about 6.5% Mg were evapo Mixture Kainite Production rated into a evaporation pond where the bitterns evaporated till the Mg, concentration reached 8 to 8.5% Mg. 0105. The kainite-sodium chloride mixture obtained from 0113. In the process of evaporation, a mixture of carnal sea water evaporation served as a starting feedstock for the lite-epsomite and sodium chloride precipitated with the fol production of KC1. The mixture had the following composi lowing composition (in weight percent): tion (amounts in weight%):

Mg 8.32 Wt 9% K 8.04 Na 3.6 Insolubles 1.OO SO 13.33 Mg 7.72 C 27.82 K 11.65 HO 38.89 Na 8.10 SO 29.13 C 22.46 0114. The carnallite-epsomite-halite mixture was har HO 1994 vested from the crystallization pond. The mixture was reacted with Ca(OH) in the presence of Sylvinite solution to remove 0106. The kainite-NaCl mixture was reacted with Sulfates and magnesium. The slurry containing gypsum and Ca(OH) in presence of a Sylvinite solution to obtain a slurry Mg(OH) as solids was obtained. The solids were separated US 2011/0008243 A1 Jan. 13, 2011

and the liquid containing an end Sylvinite solution was evapo described in some detail by way of illustration and example rated to provide Sylvinite in solid form. for purposes of clarity of understanding, it will be readily 0115 The Sylvinite was leached at 0°C. to obtain potas apparent to those of ordinary skill in the art in light of the sium chloride as solid and most of the sodium chloride in teachings of this invention that certain changes and modifi solution. The solid was centrifuged and dried to obtain com cations may be made thereto without departing from the spirit mercial grade potassium chloride. The cooled solution was or scope of the appended claims. Solar evaporated or heated to precipitate sodium chloride. What is claimed is: 7.8 Example 8 1. A process for production of Sylvinite and/or Sylvite from sea water or sea bittern comprising: Production of KCl from Sea Bitterns a) evaporating the sea water or sea bittern to obtain a 0116 Sea bitterns having the following composition is mixture, wherein the mixture comprises predominantly used (in weight%): kainite and further comprises Sodium chloride; b) reacting the mixture with calcium hydroxide and/or calcium oxide in presence of a Sylvinite Solution to obtain a precipitate and an end Sylvinite Solution; and Mg 3.20 c) recovering Sylvinite and/or sylvite from the end Sylvinite K 3.09 Na 4.76 Solution and/or the precipitate. SO 6.68 2. A process for production of Sylvinite and/or Sylvite from C 14.56 sea water or sea bittern comprising: HO 67.72 a) evaporating the sea water or sea bittern to obtain a mixture, wherein the mixture comprises predominantly 0117. The bitterns are reacted with Ca(OH), to remove carnallite and further comprises epsomite and sodium Sulfates and magnesium. The slurry containing gypsum and chloride; Mg(OH), as solids was obtained. The solids were separated b) reacting the mixture with calcium hydroxide and/or and the liquid containing Sylvinite was evaporated to provide calcium oxide in presence of a Sylvinite Solution to Sylvinite in solid form. Sylvinite is processed as shown above obtain a precipitate and an end Sylvinite Solution; and in Examples 1 or 2. c) recovering Sylvinite and/or sylvite from the end Sylvinite Solution and/or the precipitate. 7.9 Example 9 3. A process for production of sylvite from sea water or sea bittern comprising: Production of Sylvite, KCl a) evaporating the sea water or sea bittern to obtain a 0118. The kainite-NaCl mixture as in Example 5, was mixture, wherein the mixture comprises predominantly reacted with Ca(OH) in the presence of asylvinite solution to kainite and further comprises Sodium chloride; obtain a slurry containing fine particles of gypsum, Mg(OH) b) reacting the mixture with calcium hydroxide and/or and KCl and coarse NaCl solids. The slurry was screened to calcium oxide in presence of a Sylvinite Solution to remove the coarse NaCl then filtered to remove gypsum, obtain a precipitate and an end Sylvinite Solution; and Mg(OH) and KCl solids. The KCl was leached from the fine c) recovering Sylvite from the end Sylvinite solution. particles. The Sylvite solution was evaporated to provide 4. A process for production of Sylvite from sea water or sea Sylvite bed of crystals. bittern comprising: a) evaporating the sea water or sea bittern to obtain a 7.10 Example 10 mixture, wherein the mixture comprises predominantly carnallite and further comprises epsomite and sodium Production of Sylvite, KCl chloride; 0119. In the process described in Example 9, the slurry b) reacting the mixture with calcium hydroxide and/or was filtered to provide a filter cake of Mg(OH), CaSO. calcium oxide in presence of a Sylvinite Solution to 2H2O, KCl and NaCl from which KCl was leached at elevated obtain a precipitate and an end Sylvinite Solution; and temperature to provide a solution containing KC1. The KCl c) recovering Sylvite from the end Sylvinite solution. solution was evaporated to provide a Sylvite bed of crystals. 5. The process of claim 1, wherein the evaporation of sea 0120 Sylvite Harvesting water or sea bittern in step 0121 The hard crystal bed of Sylvite was broken by a a) is continued till the sea water or sea bittern comprises cutting machine. The Sylvite, KCl crystals were broken to the between about 3.5% to about 6.7% magnesium by desired size and stock piled with the use of regular heavy weight. equipment, Such as motor graders. 6. The process of claim 1, wherein the reaction in step b) is 0122) Sylvite Processing conducted at a temperature of at least about 80°C. 0123. The harvested Sylvite was trucked and fed to the 7. The process of claim 1, wherein the reaction in step b) is milling plant where the Sylvite was milled to insure homog conducted at a temperature from about 80° C. up to about enous crystal size of the product. The milled Sylvite was 1000 C. washed, filtered and dried. 8. The process of claim 1, wherein the step c) is followed by 0124 All publications, patents and patent applications leaching KCl from the Sylvinite at an elevated temperature to cited in this specification are herein incorporated by reference obtain a leached solution. as if each individual publication or patent application were 9. The process of claim 8, wherein the leaching step is specifically and individually indicated to be incorporated by followed by cooling or evaporation of the leached solution to reference. Although the foregoing invention has been recover KC1. US 2011/0008243 A1 Jan. 13, 2011

10. The process of claim 1, wherein the Sylvinite solution in 22. The process of claim 2, wherein the reaction in step b) step b) is saturated with respect to NaCl and KC1. is conducted at a temperature of at least about 80°C. 11. The process of claim 10, wherein the end Sylvinite 23. The process of claim 2, wherein the step c) is followed solution in step b) is saturated with respect to NaCl and KCl. by leaching KCl from the Sylvinite at an elevated temperature 12. The process of claim 1, wherein the Sylvinite solution in to obtain a leached solution. step b) is saturated with respect to NaCl and under saturated with respect to KC1. 24. The process of claim 23, wherein the leaching step is 13. The process of claim 12, wherein the end Sylvinite followed by cooling or evaporation of the leached solution to solution in stepb) is under saturated with respect to both NaCl recover KC1. and KCl. 25. The process of claim 2, wherein the Sylvinite solution in 14. The process of claim 1, wherein the Sylvinite solution in step b) is saturated with respect to NaCl and KC1. step b) is under saturated with respect to both NaCl and KCl. 26. The process of claim 25, wherein the end Sylvinite 15. The process of claim 14, wherein the end Sylvinite solution in step b) is saturated with respect to NaCl and KC1. solution is saturated with respect to both KCl and NaCl. 27. The process of claim 2, wherein the Sylvinite solution in 16. The process of claim 1, wherein the Sylvite is about step b) is saturated with respect to NaCl and under saturated 90% to about 99% pure. with respect to KC1. 17. The process of claim 1 further comprising adding an anti-caking agent to the Sylvite. 28. The process of claim 27, wherein the end Sylvinite 18. The process of claim 17, wherein the anti-caking agent solution in stepb) is under saturated with respect to both NaCl is sodium hexacyanoferrate (II). and KCl. 19. The process of claim 1, wherein in step b) the mixture 29. The process of claim 2, wherein the Sylvinite solution in is reacted with calcium hydroxide. step b) is under saturated with respect to both NaCl and KC1. 20. The process of claim 1, wherein in step b) the mixture 30. The process of claim 29, wherein the end Sylvinite is reacted with calcium oxide. solution is saturated with respect to both KCl and NaCl. 21. The process of claim 2, wherein the evaporation of sea 31. The process of claim 2, wherein the Sylvite is about water or sea bittern in step a) is continued till the sea water or 90% to about 99% pure. sea bittern comprises between about 6.5% to 8.5% magne sium by weight. c c c c c