AU5845799A

AU5845799A - Method of formulating alkali metal salts

Info

Publication number: AU5845799A
Application number: AU58457/99A
Authority: AU
Inventors: Robin Phinney
Original assignee: Airborne Industrial Minerals Inc
Current assignee: Airborne Industrial Minerals Inc
Priority date: 1998-10-13
Filing date: 1999-09-30
Publication date: 2000-05-01
Anticipated expiration: 2019-09-30
Also published as: SI20636A; CZ20011176A3; WO2000021887A1; EA002709B1; CN1515491A; CN1330612A; SK5002001A3; KR20010088870A; HUP0104062A3; JP2002527330A; NZ510786A; AU751236B2; PL347098A1; NO20011851L; NO20011851D0; UA73096C2; CA2284967A1; ID28729A; EP1121327A1; CN1156397C

Description

WO 00/21887 PCT/CA99/00905 METHOD OF FORMULATING ALKALI METAL SALTS TECHNICAL FIELD The present invention relates to a method of formulating alkali earth salts and more particularly, the present invention relates to a method of generating food grade sodium bicarbonate and fertilizer grade potassium sulfate. BACKGROUND ART 10 A significant amount of prior art has been promulgated with respect to the formulation of alkali earth salts. Sodium bicarbonate, as an example, has been prepared in as many different ways as it has been known. Despite this fact, previous unit operations for bicarbonate synthesis have been hampered by inefficient energy use which results directly in increased synthesis costs. As a further limitation, known processes do not make efficient use of the unit operations involved in the preparation of salts. Typically, a single high quality product is formulated with concomitant byproduct formation of a quality inadequate for commercial purposes or that would require too substantial an investment to render them commercially viable. 20 Representative of the prior art is United States Patent No. 3,429,657,issued February 25, 1969, to D'Arcy. The reference discusses a method for recovering and producing potassium salts. In the reference, a potassium bearing brine is reacted with sodium perchlorate to precipitate potassium perchlorate. The potassium is removed by ion exchange with sodium and the free potassium is then combined with chloride, sulfate, nitrate inter alia. INDUSTRIAL APPLICABILITY 30 The present invention has applicability in the fertilizer art.

WO 00/21887 PCT/CA99/00905 2 DISCLOSURE OF THE INVENTION One object of one embodiment of the present invention is to provide a method of formulating food grade sodium bicarbonate and potassium sulfate, characterized in that the method comprises the steps of: a) providing a source of liquid sodium sulfate; b) providing a source of ammonium bicarbonate; c) contacting the sodium sulfate and the ammonium bicarbonate; d) precipitating sodium bicarbonate and forming a liquor; 10 e) precipitating sodium bicarbonate and forming a liquor by contacting the liquor from step d) with sodium sulfate; f) saturating the liquor from step e) with sodium sulfate; g) filtering solids from the liquor of step f); h) contacting the liquor from step g) with sulfuric acid to precipitate carbonates; i) cooling the liquor from step h) to 0*C to form Glauber's salt precipitate; j) heating the liquor from step i) to between 30* to 40*C; and k) precipitating potassium sulfate by contacting the liquor from step j) 20 with potassium chloride. A further object of one embodiment of the present invention is to provide a method of formulating food grade sodium bicarbonate and potassium sulfate, characterized in that the method comprises the steps of: a) providing a source of liquid sodium sulfate; b) providing a source of ammonium bicarbonate; c) contacting the sodium sulfate and the ammonium bicarbonate; d) precipitating sodium bicarbonate and forming a liquor; e) precipitating sodium bicarbonate and forming a liquor by contacting 30 the liquor from step e) with sodium sulfate; f) saturating the liquor from step e) with anhydrous sodium sulfate; g) filtering solids from the liquor of step f); WO 00/21887 PCT/CA99/00905 3 h) contacting the liquor from step g) with at least one of ammonium bicarbonate, ammonia gas or carbon dioxide to precipitate sodium bicarbonate; i) cooling the liquor from step h) to 0*C to a precipitate of sodium bicarbonate and sodium sulfate; and j) precipitating potassium sulfate by contacting the liquor from step i) with potassium chloride. It has been found that following the sodium bicarbonate formulation, significant success in cooling the liquor to 0*C is realized for removing sodium 10 sulfate as Glauber's salt and sodium bicarbonate. Glauber's salt solubility in the system is contemplated by the ammonium sulfate-sodium sulfate phase diagram. By increasing the sodium sulfate in the bicarbonate circuit with increased Glauber's salt recycle, there is a tendency to decrease the bicarbonate solubility and increase the process efficiency. Regarding the conversion of the starting reagents to potassium sulfate, particular success has been encountered by maintaining a mole ratio of five (5) or greater for the potassium and ammonium ions. This ratio ensures high conversion efficiency in the second stage of the process. 20 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process flow diagram illustrating a first part of one process according to the present invention; Figure Ia illustrates a second part of the process illustrated in Figure 1; Figure 1b illustrates a third part of the process illustrated in Figure 1; 30 Figure 2 is a is a process flow diagram illustrating a first part of a variation of the process according to the present invention; Figure 2a illustrates a second part of the process illustrated in Figure 2; and WO 00/21887 PCT/CA99/00905 4 Figure 2b illustrates a third part of the process illustrated in Figure 2. Similar numerals in the figures denote similar elements. MODES FOR CARRYING OUT THE INVENTION Referring now to the drawings, Figures 1 through 1b illustrate the process according to a first embodiment. 10 A source of liquid sodium sulfate 10 dissolved in fresh water and centrate water 12 discussed herein after. The solution is mixed in vessel 14 at 40*C to a specific gravity of 1.30. The solution is filtered in filter 16 which, as an example, may comprise a 5 micron filter. The solids 18 are disposed of while the filtrate 20 is passed into a first sodium bicarbonate crystallization vessel 27. Feeds of water, ammonia and carbon dioxide all denoted by numeral 24 are reacted in vessel 22 in order to synthesize ammonium bicarbonate. Formulated ammonium bicarbonate is centrifuged in centrifuge 26, with the solid product being passed into crystallization vessel 27. A recycle loop 28 recirculates ammonium 20 bicarbonate solids and liquor into reaction vessel 29. The result of the combination in vessel 29 is the formulation of sodium bicarbonate. The mixture is filtered by filter 30 and centrifuged. The sodium bicarbonate is washed with water in vessel 32, centrifuged in centrifuge 34 and the solid retained as food grade sodium bicarbonate. The wash water is returned to vessel 14. The liquor from filter 30 has a specific gravity of 1.25 with the contents including approximately 10.4% sodium sulfate, 17.1% ammonium sulfate, 8% sodium bicarbonate and excess ammonium bicarbonate for reaction with the Glauber's salt (discussed herein after). The liquor is reacted in a vessel 36 at 40 0 C 30 with Glauber's salt formulated in the cooling phase of the process, which will be discussed later, to produce sodium bicarbonate from the excess of ammonium bicarbonate from crystallization vessel 29. Alternatively, the ammonium bicarbonate may be added to the second stage (vessel 36) as solid, slurry or solution.

WO 00/21887 PCT/CA99/00905 5 To the liquor from vessel 36 is added to solid sodium sulfate from source 41 in vessel 40 to formulate a saturated liquor of sodium sulfate/ammonium sulfate. Sufficient ammonium bicarbonate may be present to complete the reaction is solution or some may be added to result in the liquor having a specific gravity of 1.285. The slurry from vessel 40 is filtered with filter 42. The sodium bicarbonate solids 48 are passed to vessel 32 and the liquor 44 is further processed with additional separation of sodium bicarbonate, which is returned to vessel 32. The liquor 44, is then passed to vessel 46 (Figure 1A). Circuit volume from the sodium bicarbonate circuit can be controlled by evaporating the purified sodium sulfate in the 10 feed to produce solid sodium sulfate to ensure circuit saturation. Returning to Figure 1A, vessel 46 contains sulfuric acid to precipitate carbonate compounds. The so treated liquor is cooled to 0*C in chiller 48 to recover Glauber's salt and filtered in filter 50. The recovered Glauber's salt is returned to the sodium bicarbonate crystallization vessel 36. The filtrate contains 25.25% by weight ammonium sulfate and up to 11% by weight sodium sulfate and is passed into a vessel 52 heated to between 30*C and 400C and combined with solids 65 from filter 66. This solution is passed into vessel 20 54 where solid potassium chloride is reacted therewith to formulate a 20% by weight solution of ammonium chloride also containing, by weight approximately, 20.2% ammonium chloride, 6.7% potassium chloride, 4.9% sodium chloride, 2.3% as (x) 2

SO

4 , where x = Na, K, and solid mixed crystals of potassium sulfate with 10% 20% ammonium sulfate. The solution is filtered in filter 56, with the solid fraction containing approximately by weight, 5% potassium chloride, 80% - 85% potassium sulfate, 10% - 15% ammonium sulfate. The solid fraction is combined in vessel 58 with water and potassium chloride brine from vessel 60. The potassium sulfate solid is centrifuged 30 and filtered in filter 62 and recrystallized with a solution of potassium chloride at 25*C. The remaining ammonium sulfate is converted to potassium sulfate. Grades of greater than 98% potassium sulfate are achievable.

WO 00/21887 PCT/CA99/00905 6 In further unit operations, the liquor or filtrate from the potassium sulfate operations and specifically from filter 56 is processed in accordance with the unit operations set forth in Figure 1c. The liquor is evaporated in evaporator in order to concentrate the ammonium chloride liquor such that upon cooling the potassium chloride and residual sulphates are minimized in solution. The solution is filtered with filter 66 with the solid material 67 recycled to vessel 54. The filtrate containing approximately 22% to 30% ammonium chloride is reacted with lime in reactor 68 with liberated ammonia recycled. The calcium chloride formed may be passed to a settler 70 or scrubber 72 depending on intended subsequent uses. 10 Having set forth the process according to this first embodiment, reference will now be made to an example of the process. EXAMPLE 1 BICARBONATE KILL PRIOR TO POTASSIUM SULFATE PROCESS 20 Feed - 1 litre @ 1.3 S.G. 360 g/I Na 2

SO

4 1st STAGE Production of NaHCO 3 Brine Exit at reaction termination: 130g Na 2

SO

4 10.4% Na 2

SO

4 40 0 C 30 213.8g (NH 4

)

2

SO

4 17.1% (NH 4

)

2

SO

4 1.250 S.G. @ 0.95 I 100g NaHCO 3 8.0% NaHCO 3 solution 907q HO 1350.8 This makes 172g NaHCO 3 solids SECOND STAGE ESTIMATE consumes 55g NH 3 A) 25.07g NH 3 + 64.9g CO 2 142.5g CO 2 B) 51.2g NH 3 + 132.6g CO 2 40 WO 00/21887 PCT/CA99/00905 7 2nd STAGE 0.95 I of brine will dissolve the following: k) 1 Moles 3) 2 Moles a 2

SO

4 1 OH 2 0 qa 2

SO

4 1 0H 2 0 :332g) :644g) 72g Na 2

SO

4 16.2% Na 2

SO

4 14g Na 2

SO

4 20.7% Na 2

SO

4 213.8g (NH 4

)

2

SO

4 12.8% (NH 4

)

2

SO

4 213.9g (NH 4

)

2

SO

4 10.7% (NH 4

)

2

SO

4 100g NaHCO 3 5.9% NaHCO 3 100g NaHCO 3 5.0% NaHCO 3 10 1087g HO 65.1% H 2 0 1267a H.,O 63.4% H 2 0 1672.8 1999 1.275 S.G. and 1.313 1 brine 1.300 S.G. and 1.5 I brine 1 2nd STAGE Final Solution Composition 20 ) 167.3g Na 2

SO

4 10% Na 2

SO

4 COg Na 2

SO

4 10% Na 2

SO

4 311g (NH 4

)

2

SO

4 18.9% (NH 4

)

2 SO4 12g (NH 4

)

2 S0 4 20.2% (NH 4

)

2 S0 4 131g NaHCO 3 8% NaHCO 3 160g NaHCO 3 8% NaHCO 3 1087 H.O 63.1% H 2 0 1267 HQ 61.8%H 2 0 1644.5g Solution 2039g Solution Production of NaHCO 3 92.9g Production of 193.2g NaHCO 3 30 3.G. 1.265 and makes 1.31 1 brine S.G. 1.285 and makes 1.6 1 of Solution BICARB KILL 412g (NH 4

)

2 SO4 200g NaSO 4 + 160 X 98 =93.3g H 2 SO4 160g NaHCO 3 84(2) 1267a H,O 40 2039g (1.6 1) 1.285 S.G. This becomes: 412g (NH 4

)

2 SO4 335g Na 2

SO

4 1267q H,O 2014g @ 1.265 = (1.61) 50 must add Na 2

SO

4 to Saturation of 1.30 S.G.

WO 00/21887 PCT/CA99/00905 8 1.61 x 1.30 = 2080 Therefore: 412g (NH 4

)

2 SO4 400g Na 2

SO

4 1267q H,O 2079g total (1.61) 10 Cooling 412g (NH 4

)

2

SO

4 28.7% 116g Na 2

SO

4 8.0% 907 HO 63% 1435g Solution Feed to Evaporator NH4C1 330.8 g 21.9 20 KC1 130 g 8.6% NaC1 94.7 g 6.3% x-S04 50 3.3%

H

2 0 907Q 60.0 1512g @ 33% NH 4 CI then: - 2.8% KCI then: - 2.0% K 2 SO4 Therefore: 330.8 = 1002 g 30 .33 Evaporation Load = 907 - 623 = 284q 0.79t/t Na 2

SO

4 add 0.5 t for washing 1.29 t H 2 0 / t Na 2

SO

4 KSO, Reaction 40 a) K 2

SO

4 from (NH 4

)

2

SO

4 = 412 x 174 = 543g 132 b) K 2

SO

4 from Na 2

SO

4 = 116 x 174 = 142g 142 c) Losses of K 2 S0 4 = -43q TOTAL K 2 S0 4 642g 50 WO 00/21887 PCT/CA99/00905 9 KCI Recovery a) KCI intermig reaction = 685 x 2 x 74 = 582g 174 b) KCI lost to tails = 50g c) Therefore: KCI need = 632g 10 K2SO4 yield = 642 x 100 = 93.7% 685 KCI Conversion Efficiency = 582 x 100 = 92.1% 632 BASIS: One Tonne of Na 2

SO

4 feed 20 Inputs Product First Stage 0.153t NH 3 0.48t NaHCO 3 0.396t

CO

3 2.52t H,O Second Stage 644g 0.53t NaHCO 3 Na 2

SO

4 1 0H 2 0 0.142t

NH

3 0.368t CO, Bicarb Kill + Na 2

SO

4 Saturation Filter to Produce clear brine 30 0.26t H 2

SO

4 0.18t NaSO 4 Cooler to 0*C -BTU's 1.8t NaS0 4 10H 2 0 Cooler brine 1. 14t (N H 4

)

2

SO

4 28.7% 0.32t Na 2

SO

4 8.0% 2.52t H 2 O 63% 3.99 t Total KCI = 1.76t 1.78t K 2

SO

4 Evaporation to 33% NH 4 CI 0.92t NH 4 CI brine o.29tot Na 2

SO

4 0.08 t KCI SOLIDS 0.05t K 2

S

4 0.28t KCI 40 1.73t H20 0.08t K50 2.78 Total 0.36t Recycle Lime Process @ 85% off 0.57t CaO 0.29t NH 3 Brine: 0.955 CaC2 0.08t KCI 0.05t K 2 S0 4 1.73t H 2 0 2.015t K 752to90'C WO 00/21887 PCT/CA99/00905 10 Turning to Figures 2 through 2b, an alternative processing scheme is schematically depicted. In this reaction scheme, prior to the production of sodium bicarbonate, the liquors are saturated with anhydrite. In this embodiment, sodium bicarbonate is produced in crystallization unit 22 and undergoes generally similar steps as set forth for Figures 1 through 1 B. The brine or filtrate is saturated with anhydrous sodium sulfate in vessel 36 and filtered with filter 38 to remove insolubles which are discarded. The filtrate from this operation is reacted 10 with ammonium bicarbonate in vessel 80. As an alternative, the filtrate could be reacted with ammonia or carbon dioxide to precipitate the sodium bicarbonate. The solution is filtered with filter 82 and the sodium bicarbonate remains. The latter is combined with the sodium bicarbonate from filter 30 and then washed, centrifuged and dried. These steps are not shown. The filtrate remaining has a composition of approximately, on a by weight basis, 10% sodium sulfate, 24% ammonium sulfate and 8% sodium bicarbonate. The solution has a specific gravity of 1.285 at 40 0 C. 20 From this stage, the filtrate solution is cooled in a chiller 84 to approximately 0*C in order to produce a filtrate containing approximately, on a by weight basis 5% sodium sulfate, 28% ammonium sulfate and 6% sodium bicarbonate. The solution is filtered with filter 86 and precipitated sodium bicarbonate and sodium sulfate are recycled back to the bicarbonate crystallization vessel 32, while the filtrate is reacted with potassium chloride in vessel 88 to synthesize first stage potassium sulfate in a purity range of about 75% to 90%. The solid potassium sulfate is repulped with potassium chloride brine from vessel 92 in vessel 94. This results in high quality, high grade potassium sulfate. The product is washed with water in a conventional washing stage 96 with recycle to vessel 94. 30 The solution from filter 90 is evaporated in evaporator 98 (Figure 2A) to concentrate ammonium chloride liquor whereby upon cooling the potassium chloride and sulfates are minimized. The solution is filtered using filter 100 with the precipitated potassium chloride and (x)S0 4 , where x = K, Na, recycled to vessel 88.

WO 00/21887 PCT/CA99/00905 11 The filtrate from filter 100 containing ammonium chloride, potassium chloride and potassium sulfate is passed into evaporator 102. The sodium bicarbonate backs the reaction and as a result, ammonia and carbon dioxide are released. These gases are then scrubbed/handled using suitable techniques. The calcium chloride generated is then discarded or sold. EXAMPLE 2 NO BICARBONATE KILL 10 Feed - 1 litre @ 1.3 S.G. 360 g/l Na 2 SO4 1st STAGE Production of NaHC0 3 Brine Exit at reaction termination: 20 130g Na 2

SO

4 10.4% Na 2

SO

4 4000 213.8g (NH 4

)

2

SO

4 17.1% (NH 4

)

2 S0 4 1.250 S.G. @0.951 100 g NaHCO 3 8.0%NaHCO 3 solution 907q HQO 1350.8 This makes 172g NaHCO 3 solids consumes 55g NH 3 142.5g C02 30 Resaturation with Na 2

SO

4 : brine will hold 150g Na 2

SO

4 . This brine is then filtered and fed to the second stage NaHCO 3 crystallizer. FEED REACTION EXIT BRINE PRODUCT 280g Na 2

SO

4 35.9g NH 3 130g Na 2

SO

4 177g NaHC0 3 213.8g (NH 4

)

2

SO

4 92.9g C02 353g (NH 4

)

2 SO4 100g NaHCO 3 100g NaHCO 3 907q H0 907q H,0 1490.8g 1490g 40 1.151 @ 1.32 S.G. 1.285 S.G. 1.151 23.7% (NHA) 2 SO4 The exit brine is then cooled to 0*C.

WO 00/21887 PCT/CA99/00905 12 Brine composition is: 5.0% Na 2

SO

4 which mean 60g Na 2

SO

4 precipitates as 136g of Na2SO410H 2 0 precipitate and remove 76g of H 2 0. Therefore: 907 - 76 = 831g H 2 0. Brine composition @ 0*C and 1.26 S.G. 70g Na 2

SO

4 353g (NH 4

)

2 SO4 10 100g NaHCO 3 831q H,O 1354q TOTAL About 1 litre brine K5SO4 a) 70q NaSO4 x 174 = 85.8 142 20 b) 353q (NH4hSO4 x 174 = 465.3g 132 EXIT BRINE: 283g NH 4 CI 21.9% 57g NaCl 4.8% 119g (KNaHCO 3 ) 9.2% 831q H.O 1290 30 Boil up to 33.0% NH 4 CI. Release of NH 3 and CO 2 from evaporator but NH 4 CI salts out KCI and not the NaCl. KCI is recovered same as in Example 1. BASIS: One Tonne Na,SO, feed INPUTS PRODUCT First Stage 0.15t NH 3 0.48t NaHCO 3 0.396t

CO

2 40 2.52t H 2 0 Second Stage 0.10t NH 3 0.49t NaHCO 3 0.26t

CO

3 0.42t Na 2

SO

4 _ Cooled to 0*C 0.4t of Na 2

SO

4 10H20 Cooler Brine 0.19t Na 2

SO

4 5% 0.98t (NH 4

)

2

SO

4 26% 0.28t NaHCO 3 7.4% 2.31t H.O 61.4% 3.76t Total WO 00/21887 PCT/CA99/00905 13 INPUT PRODUCT KCI 1.62t 1.8t KSO4 Evaporation to 33% NH 4 CI Brine Solids Circuit Control = 0.7t H 2 0 0.98t NH 4 CI 0.28t KCI Washing = 0.5t 0.08t KCI 0.08t K,SO4 To evaporator 1.2t H 2 0/t Na 2

SO

4 0.15t NaCl 0.36t 0.19t NaCI from CO 3 10 1.57t H 2 0 2.97t Lime Process @ 85% efficiency 1.01t CaCl2 0.61t CaO 0.08t KCI 0.34t NaCI 1.57t

H

2 0 3.Ot @ 75 - 90 0 C EXAMPLE 3 - BICARBONATE KILL - NO EVAPORATION OF AMMONIUM CHLORIDE 20 Feed Solution: from #1 412 g (NH 4

)

2 SO4 335 g Na 2

SO

4 1267 a H 2 0 2014 g @ 1.265 1.60 1 Cooling to 0*C yields a filtered solution of: 412 g (NH 4

)

2

SO

4 28.7% 116 g Na 2

SO

4 8.0% 907 q H 2 0 1435 g solution 30 This brine is then heated to 25 0 C where KCI solid is added to produce K 2 S0 4 . The exit brine from the K 2 S0 4 circuit has the following composition: NH4CI 330.8 g 21.9 % KCI 130 g 8.6% NaCI 94.7 6.3 % x-S0 4 50 g 3.3% x = Na/K H,O 907 q 60 1512 g WO 00/21887 PCT/CA99/00905 14 This brine is than heated and reacted with lime to recover the ammonia and bypass the evaporator. The KCI reports to the CaCl 2 brine rather than being recovered in the evaporator. This represents a 15 to 20 % loss of K to the CaCl2 brine. The KCI in the CaCl 2 brine can be reduced to as low as 1.0% by adding solid Na 2

SO

4 to CaCl2/KCI brine. The potassium is effectively collected as apprecipitated of syngenite (CaSO 4 * K 2 S0 4 e xH 2 O) at 0 to 100*C with preferred temperatures of 20 to 30*C so that SO 4 solubility is kept to minimum and the reaction occurs at a reasonable rate. 10 CaCl 2 Brine composition 343.3 g CaCI2 22.5 % 130 g KCI 8.5% 94.7 g NaCl 6.3 % 50 g x SO 4 32.% (Na/K) 907 q H.O 59.5% 1525 g 100% 140 g Na 2

SO

4 addition: Exit Brine Exit Cake 234. 8 g CaCl 2 17.8% 20 15.25 g KCI 1.1 % 310 g CaSO 4 e K 2 SO4 209 g NaCl 15.9% + 100 g H20 50 g x SO 4 3.8% 807 61.3% The exit brine can be deep well disposed of and cake can be blended into the

K

2

SO

4 product as binder or further processed to remove the CaSO 4 . The cake can be reacted with (NH 4

)

2

HCO

3 from the NaHCO 3 process feed and the CaSO 4 reacts quickly to produce a brine of (NH 4

)

2

SO

4 and K 2 S0 4 and a filter 30 CaCl 3 precipitate which is disposed of. The (NHa) 2

SO

4

/K

2

SO

4 brine is recycled to

K

2

SO

4 first stage crystallizer.

Claims

1. A method of formulating food grade sodium bicarbonate and potassium sulfate, characterized in that the method comprises the steps of: a) providing a source of liquid sodium sulfate; b) providing a source of ammonium bicarbonate to precipitate sodium bicarbonate; c) contacting said sodium sulfate and said ammonium bicarbonate; d) precipitating sodium bicarbonate and forming a liquor; e) filtering said sodium bicarbonate; f) saturating liquor from step e) with sodium sulfate; g) contacting said liquor with ammomium carbonate ammonia gas or carbon dioxide to precipitate further sodium bicarbonate; h) filtering precipitated sodium bicarbonate from step g); i) combining sodium bicarbonate precipitate from step e) and h) and washing to form food grade sodium bicarbonate; j) cooling liquor from step i) to 0 0 C to at least form Glauber's salt precipitate; k) treating liquor from step j) with sulfuric acid to convert carbonate minerals to sulfate minerals and release carbon dioxide gas; I) heating liquor from step k) to between 30*C and 40'C; and m) precipitating potassium sulfate by contacting said liquor from step 1) with potassium chloride.

2. The method as set forth in claim 1, characterized in that the method further includes the step of separating precipitated potassium sulfate and washing with potassium chloride.

3. The method as set forth in claim 2, characterized in that the method further includes the step of treating liquor from said step of separating precipitated potassium sulfate with lime to liberate ammonia gas. WO 00/21887 PCT/CA99/00905 16

4. The method as set forth in claim 3, characterized in that the method further includes the step of recycling said ammonia gas to step g.

5. The method as set forth in claim 4, characterized in that the method further includes the step of evaporating filtrate from claim 4.

6. The method as set forth in claim 1, characterized in that said sodium sulfate has a specific gravity of between 1.30 and 1.34 at 40 0 C.

7. The method as set forth in claim 1, characterized in that said liquor from step d) has a specific gravity of 1.25 and contains, by weight, 10.4% sodium sulfate, 17.1% ammonium sulfate, between 8% to 12% sodium bicarbonate and an excess of ammonium bicarbonate.

8. The method as set forth in claim 1, characterized in that said sodium sulfate from step e) comprises Na 2 SO 4 0 10 H 2 0.

9. The method as set forth in claim 1, characterized in that said liquor from step f) has a specific gravity of 1.285 at 40 0 C.

10. The method as set forth in claim 1, characterized in that said liquor from step k) is a saturated liquor of sodium sulfate, ammonium sulfate and sodium bicarbonate.

11. The method as set forth in claim 1, characterized in that said potassium sulfate is generated in a yield of at least 80% with a purity of at least 98%.

12. The method as set forth in claim 1, characterized in that said potassium sulfate is generated in a yield of at least 80% with a purity of at least 98%.

13. A method of formulating food grade sodium bicarbonate and potassium sulfate, characterized in that the method comprises the steps of: a) providing a source of liquid sodium sulfate; WO 00/21887 PCT/CA99/00905 17 b) providing a source of ammonium bicarbonate; c) contacting said sodium sulfate and said ammonium bicarbonate; d) precipitating sodium bicarbonate and forming a liquor; e) precipitating sodium bicarbonate and forming a liquor by contacting said liquor from step d) with sodium sulfate; f) saturating said liquor from step d) with sodium sulfate; g) filtering solids from said liquor of step e); h) contacting said liquor from step f) with sulfonic acid to precipitate carbonates; i) cooling said liquor from step h) to 0*C to form Glauber's salt precipitate; j) heating said liquor from step 1) to between 30 0 C to 40*C; and k) treating said liquor from step j) with potassium chloride to precipitate potassium sulfate; I) evaporating liquor from step k) to recover potassium values for recycling to step k); and m) drying said potassium sulfate.

14. The method as set forth in claim 13, characterized in that the method further includes the step of treating liquor remaining from step 1) with lime and ammonium chloride.

15. The method as set forth in claim 14, characterized in that ammonia gas is liberated and recycled.

16. The method as set forth in claim 13, characterized in that used potassium chloride solution is recycled to step k).