CA2284967A1 - Method of formulating alkali earth salts - Google Patents
Method of formulating alkali earth salts Download PDFInfo
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- CA2284967A1 CA2284967A1 CA002284967A CA2284967A CA2284967A1 CA 2284967 A1 CA2284967 A1 CA 2284967A1 CA 002284967 A CA002284967 A CA 002284967A CA 2284967 A CA2284967 A CA 2284967A CA 2284967 A1 CA2284967 A1 CA 2284967A1
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- Prior art keywords
- liquor
- sodium bicarbonate
- sulfate
- potassium
- precipitate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
- C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D7/00—Fertilisers producing carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
Methodology for formulating sodium bicarbonate and potassium sulfate. In one embodiment, sodium sulfate and ammonium bicarbonate are reacted to form sodium bicarbonate with the remaining liquor or brine treated with sulfuric acid to remove carbonates with subsequent precipitation of potassium sulfate. A
further embodiment employs ammonium bicarbonate, ammonia gas or carbon dioxide to precipitate sodium bicarbonate. The result of the methods is the production of high quality fertilizer and food grade sodium bicarbonate.
further embodiment employs ammonium bicarbonate, ammonia gas or carbon dioxide to precipitate sodium bicarbonate. The result of the methods is the production of high quality fertilizer and food grade sodium bicarbonate.
Description
METHOD OF FORMULATING ALKALI EARTH 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
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.
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.
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
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.
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.
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) with potassium chloride.
A further aspect of one embodiment of the present invention is to provide a method of formulating food grade sodium bicarbonate and potassium sulfate, comprising 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 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);
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 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.
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) with potassium chloride.
A further aspect of one embodiment of the present invention is to provide a method of formulating food grade sodium bicarbonate and potassium sulfate, comprising 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 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);
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 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.
Having thus described the invention, reference will now be made to the accompanying drawings illustrating preferred embodiments, and in which:
Figure 1 is a process flow diagram illustrating a first part of one process according to the present invention;
Figure 1a illustrates a second part of the process illustrated in Figure 1;
Figure 1 b illustrates a third part of the process illustrated in Figure 1;
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 Figure 2b illustrates a third part of the process illustrated in Figure 2.
Similar numerals in the figures denote similar elements.
Referring now to the drawings, Figures 1 through 1 b illustrate the process according to a first embodiment.
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.
Having thus described the invention, reference will now be made to the accompanying drawings illustrating preferred embodiments, and in which:
Figure 1 is a process flow diagram illustrating a first part of one process according to the present invention;
Figure 1a illustrates a second part of the process illustrated in Figure 1;
Figure 1 b illustrates a third part of the process illustrated in Figure 1;
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 Figure 2b illustrates a third part of the process illustrated in Figure 2.
Similar numerals in the figures denote similar elements.
Referring now to the drawings, Figures 1 through 1 b illustrate the process according to a first embodiment.
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 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°C
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.
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 sulfatelammonium 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 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 40°C and combined with solids 65 from filter 66. This solution is passed into vessel 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)ZS04, 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 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.
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 1 c. 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.
Having set forth the process according to this first embodiment, reference will now be made to an example of the process.
BICARBONATE KILL PRIOR TO
POTASSIUM SULFATE PROCESS
Feed - 1 litre @ 1.3 S.G.
360 gll Na2S04 1 st STAGE
Production of NaHC03 Brine Exit at reaction termination:
130g NazS04 10.4% Na2S04 40'C
213.8g (NH4)ZS04 17.1% (NH4)ZS04 1.250 S.G. @ 0.95 I
100g NaHC03 8.0% NaHC03 solution 907a HZO
1350.8 This makes 172g NaHC03 solids SECOND STAGE ESTIMATE
consumes 55g NH3 A) 25.07g NH3 + 64.9g CO2 142.5g CO2 B) 51.2g NH3 + 132.6g COZ
2nd STAGE 0.95 I of brine will dissolve the following:
A) 1 Moles ) Z Moles NazS041 OH20 azS041 OH20 (3328) 6448) 2728 NazS04 16.2% NazS04 148 NazS04 20.7% NazS04 213.88 (NH4)zSO412.8% (NH4)zSO4 13.98 (NH4)zSO410.7% (NH4)zSO4 1008 NaHC03 5.9% NaHC03 1008 NaHC03 5.0% NaHC03 1087C! Hz0 65.1 % H20 1267 HZO 63.4% H20 1672.8 999 X1.275 S.G. and 1.313 I brine ~ X1.300 S.G. and 1.5 I brine 2nd STAGE Final Solution Composition 67.38 NazS04 10% NazS04 OOg NazS04 10% NazS04 118 (NH4)zSO4 18.9% (NH4)zSO4128 (NH4)zSO4 20.2% (NH4)zSO4 318 NaHC03 8% NaHC03 1608 NaHC03 8% NaHC03 1087 Hz0 63.1 % Hz0 1267 HZO 61.8% H20 644.58 Solution 0398 Solution reduction of NaHC03 92.98 reduction of 193.28 NaHC03 .G, 1.265 and makes 1.31 .G. 1.285 and makes 1.6 I
I brine of Solution BICARB KILL
4128 (NH4)zS04 2008 NaS04 + 160 X 98 =93.38 HZS04 1608 NaHC03 84(2) 12678 Hz0 20398 (1.6 1 ) 1.285 S.G.
This becomes:
412g (NH4)ZS04 335g Na2S04 1267g H20 2014g @ 1.265 = (1.61 ) must add Na2S04 to Saturation of 1.30 S.G.
1.61 x 1.30 = 2080 Therefore:
412g (NH4)2S04 400g Na2S04 1267g Hz0 2079g total (1.61) Cooling 4128 (NH4)ZS04 28.7%
116g Na2S04 8.0%
907 H20 63%
1435g Solution Feed to Evaporator NH4C1 330.8 g 21.9 KC1 130 g 8.6%
NaC1 94.7 g 6.3%
x-S04 50 3.3%
H20 907a 60.0 1512g @ 33% NH4CI then: - 2.8% KCI
then: - 2.0% KZS04 Therefore: 330.8 = 1002 g .33 Evaporation Load = 907 - 623 = 2844 0.79t1t NaZS04 add 0.5 t for washing 1.29 t HZO / t Na2S04 KZSO~ Reaction a) K2S04 from (NH4)ZS04 = 412 x 174 = 543g b) KZS04 from NazS04 = 116 x 174 = 142g c) Losses of KZS04 - -43g TOTAL KZS04 642g KCI Recovery a) KCI intermig reaction = 685 x 2 x 74 = 5828 b) KCI lost to tails = 50g c) Therefore: KCI need = 632g KZSO~ yield = 642 x 100 = 93.7%
KCI Conversion Efficiency = 582 x 100 = 92.1 BASIS: One Tonne of Na2S04 feed INPUTS PRODUCT
First Stage 0.153t NH3 0.48t NaHC03 0.396t C03 2.52t H O
Second Stage 6448 Na2S0410H200.53t NaHC03 0.142t NH3 10 0.368t CO
Bicarb Kill + Na2S04 SaturationFilter to Produce clear brine 0.26t HzS04 0.18t Na SO
Cooler to 0 C -BTU's 1.8t Na SO 10H O
Cooler brine 1.14t (NH4)ZS04 28.7%
0.32t Na2S04 8.0%
2.52at Hz0 63%
3.99 t Tota I
KC1 = 1.76t 1.78t K SO
Evaporation to 33% NH4C1 0.92t NH4CI brine 1.29t1t Na2S04 0.08 t KCI SOLIDS
0.05t KZS04 0.28t KCI
1.73t H20 0.08t KZSO
2.78 Total 0.36t Rec cle Lime Process @ 85% off 0.57t Ca0 0.29t NH3 Brine: 0.955 CaCl2 0.08t KCI
0.05t KZSOQ
1.73t H20 2.815t 75 to 90' C
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 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°C.
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.
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)S04, where x = K, Na, recycled to vessel 88.
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.
NO BICARBONATE KILL
Feed -1 litre @ 1.3 S.G.
360 gll Na2S04 1 st STAG E
Production of NaHC03 Brine Exit at reaction termination:
130g Na2S04 10.4% Na2S04 40°C
213.88 (NH4)ZS04 17.1 % (NH4)ZS04 1.250 S.G. @ 0.95 I
100 g NaHC03 8.0%NaHC03 solution 9078 Hz0 1350.8 This makes 1728 NaHC03 solids consumes 558 NH3 142.58 COZ
Resaturation with NaZS04: brine will hold 1508 Na2S04. This brine is then filtered and fed to the second stage NaHC03 crystallizer.
FEED REACTION EXIT BRINE PRODUCT
2808 Na2S04 35.98 NH3 1308 Na2S04 1778 NaHC03 213.88 (NHQ)ZS04 92.98 COZ 3538 (NHQ)zS04 1008 NaHC03 1008 NaHC03 1490.88 14908 1.151 @ 1.32 S.G. 1.285 S.G.
1.151 23.7% NH SO
The exit brine is then cooled to 0'C.
Brine composition is : 5.0% Na2S04 which mean 608 NazS04 precipitates as 1368 of Na2S0410Hz0 precipitate and remove 768 of H20.
Therefore: 907 - 76 = 831 g H20.
Brine composition @ 0'C and 1.26 S.G.
708 Na2S04 3538 (NH4)zS04 1008 NaHC03 831 cLHzO
1354a TOTAL
About 1 litre brine KzSO
a) 708 Na2S0~ x 174 = 85.8 b) 353 NH ~2SOA x 174 = 465.3a EXIT BRINE:
283g NH4CI 21.9%
57g NaCI 4.8%
1198 (KNaHC03) 9.2%
Boil up to 33.0% NH4C1.
Release of NH3 and COZ from evaporator but NH4CI salts out KCI and not the NaCI.
KCI is recovered same as in Example 1.
BASIS: One Tonne Na2~ feed INPUTS PRODUCT
First Stage 0.15t NH3 0.48t NaHC03 0.396t CO2 2.52t H O
Second Stage 0.10t NH3 0.49t NaHC03 0.26t C03 0.42t Na SO
Cooled to 0 C 0.4t of Na SO 10H O
Cooler Brine 0.19t Na2S04 5%
0.98t (NH4)ZS04 26%
0.28t NaHC03 7.4%
2.31 t H20 61.4%
3.76t Total INPUT PRODUCT
KCI 1.62t ~~ 1.8t K SO
Evaporation to 33% NH4CI Brine Solids Circuit Control = 0.7t H20 0.98t NH4C1 0.28t KCI
5t 0.08t KCI 0.08t KZSOa Washing = 0-5 t To evaporator 1.2t HzOlt NazS040.15t NaCI 0.36t 0.19t NaCI from C03 1.57t Hz0 2.97t 10 Lime Process @ 85% efficiency 1.01t CaCl2 0.61 t Ca0 0.08t KCI
0.34t NaCI
1.57t H20 3.Ot 75 - 90'C
CHLORIDE
Feed Solution: from #1 412 g (NH4)ZS04 335 g NazS04 2014 g @ 1.265 = 1.60 I
Cooling to 0'C yields a filtered solution of:
412 g (NH4)zS04 28.7%
116 g Na2S04 8.0%
9. 07 ct H20 1435 g solution This brine is then heated to 25'C where KCI solid is added to produce KZS04.
The exit brine from circuit has the following composition:
the K2S04 NH4CI 330.8 g 21.9 KCI 130 g 8.6 NaCI 94.7 6.3 x-S04 50 g 3.3 % x = Na/K
H20 907 a 60 1512 g This brine is than heated and reacted with lime to recover the ammonia and bypass the evaporator. The KCI reports to the CaCl2 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 CaClz brine can be reduced to as low as 1.0% by adding solid Na2S04 to CaCI2IKCl brine. The potassium is effectively collected as apprecipitated of syngenite (CaS04 ~ KzS04 ~ xHzO) at 0 to 100'C with preferred temperatures of to 30'C so that S04 solubility is kept to minimum and the reaction occurs at a reasonable rate.
CaCl2 Brine composition 20 343.3 g CaCl2 22.5 130 g KCI 8.5 94.7 g NaCI 6.3 50 g x S04 32.% (NaIK) 907 g HZO 59.5%
1525 g 100 140 g Na2S04 addition: Exit BrineExit Cake 234.8 g CaCl2 17.8%
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°C
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.
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 sulfatelammonium 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 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 40°C and combined with solids 65 from filter 66. This solution is passed into vessel 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)ZS04, 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 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.
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 1 c. 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.
Having set forth the process according to this first embodiment, reference will now be made to an example of the process.
BICARBONATE KILL PRIOR TO
POTASSIUM SULFATE PROCESS
Feed - 1 litre @ 1.3 S.G.
360 gll Na2S04 1 st STAGE
Production of NaHC03 Brine Exit at reaction termination:
130g NazS04 10.4% Na2S04 40'C
213.8g (NH4)ZS04 17.1% (NH4)ZS04 1.250 S.G. @ 0.95 I
100g NaHC03 8.0% NaHC03 solution 907a HZO
1350.8 This makes 172g NaHC03 solids SECOND STAGE ESTIMATE
consumes 55g NH3 A) 25.07g NH3 + 64.9g CO2 142.5g CO2 B) 51.2g NH3 + 132.6g COZ
2nd STAGE 0.95 I of brine will dissolve the following:
A) 1 Moles ) Z Moles NazS041 OH20 azS041 OH20 (3328) 6448) 2728 NazS04 16.2% NazS04 148 NazS04 20.7% NazS04 213.88 (NH4)zSO412.8% (NH4)zSO4 13.98 (NH4)zSO410.7% (NH4)zSO4 1008 NaHC03 5.9% NaHC03 1008 NaHC03 5.0% NaHC03 1087C! Hz0 65.1 % H20 1267 HZO 63.4% H20 1672.8 999 X1.275 S.G. and 1.313 I brine ~ X1.300 S.G. and 1.5 I brine 2nd STAGE Final Solution Composition 67.38 NazS04 10% NazS04 OOg NazS04 10% NazS04 118 (NH4)zSO4 18.9% (NH4)zSO4128 (NH4)zSO4 20.2% (NH4)zSO4 318 NaHC03 8% NaHC03 1608 NaHC03 8% NaHC03 1087 Hz0 63.1 % Hz0 1267 HZO 61.8% H20 644.58 Solution 0398 Solution reduction of NaHC03 92.98 reduction of 193.28 NaHC03 .G, 1.265 and makes 1.31 .G. 1.285 and makes 1.6 I
I brine of Solution BICARB KILL
4128 (NH4)zS04 2008 NaS04 + 160 X 98 =93.38 HZS04 1608 NaHC03 84(2) 12678 Hz0 20398 (1.6 1 ) 1.285 S.G.
This becomes:
412g (NH4)ZS04 335g Na2S04 1267g H20 2014g @ 1.265 = (1.61 ) must add Na2S04 to Saturation of 1.30 S.G.
1.61 x 1.30 = 2080 Therefore:
412g (NH4)2S04 400g Na2S04 1267g Hz0 2079g total (1.61) Cooling 4128 (NH4)ZS04 28.7%
116g Na2S04 8.0%
907 H20 63%
1435g Solution Feed to Evaporator NH4C1 330.8 g 21.9 KC1 130 g 8.6%
NaC1 94.7 g 6.3%
x-S04 50 3.3%
H20 907a 60.0 1512g @ 33% NH4CI then: - 2.8% KCI
then: - 2.0% KZS04 Therefore: 330.8 = 1002 g .33 Evaporation Load = 907 - 623 = 2844 0.79t1t NaZS04 add 0.5 t for washing 1.29 t HZO / t Na2S04 KZSO~ Reaction a) K2S04 from (NH4)ZS04 = 412 x 174 = 543g b) KZS04 from NazS04 = 116 x 174 = 142g c) Losses of KZS04 - -43g TOTAL KZS04 642g KCI Recovery a) KCI intermig reaction = 685 x 2 x 74 = 5828 b) KCI lost to tails = 50g c) Therefore: KCI need = 632g KZSO~ yield = 642 x 100 = 93.7%
KCI Conversion Efficiency = 582 x 100 = 92.1 BASIS: One Tonne of Na2S04 feed INPUTS PRODUCT
First Stage 0.153t NH3 0.48t NaHC03 0.396t C03 2.52t H O
Second Stage 6448 Na2S0410H200.53t NaHC03 0.142t NH3 10 0.368t CO
Bicarb Kill + Na2S04 SaturationFilter to Produce clear brine 0.26t HzS04 0.18t Na SO
Cooler to 0 C -BTU's 1.8t Na SO 10H O
Cooler brine 1.14t (NH4)ZS04 28.7%
0.32t Na2S04 8.0%
2.52at Hz0 63%
3.99 t Tota I
KC1 = 1.76t 1.78t K SO
Evaporation to 33% NH4C1 0.92t NH4CI brine 1.29t1t Na2S04 0.08 t KCI SOLIDS
0.05t KZS04 0.28t KCI
1.73t H20 0.08t KZSO
2.78 Total 0.36t Rec cle Lime Process @ 85% off 0.57t Ca0 0.29t NH3 Brine: 0.955 CaCl2 0.08t KCI
0.05t KZSOQ
1.73t H20 2.815t 75 to 90' C
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 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°C.
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.
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)S04, where x = K, Na, recycled to vessel 88.
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.
NO BICARBONATE KILL
Feed -1 litre @ 1.3 S.G.
360 gll Na2S04 1 st STAG E
Production of NaHC03 Brine Exit at reaction termination:
130g Na2S04 10.4% Na2S04 40°C
213.88 (NH4)ZS04 17.1 % (NH4)ZS04 1.250 S.G. @ 0.95 I
100 g NaHC03 8.0%NaHC03 solution 9078 Hz0 1350.8 This makes 1728 NaHC03 solids consumes 558 NH3 142.58 COZ
Resaturation with NaZS04: brine will hold 1508 Na2S04. This brine is then filtered and fed to the second stage NaHC03 crystallizer.
FEED REACTION EXIT BRINE PRODUCT
2808 Na2S04 35.98 NH3 1308 Na2S04 1778 NaHC03 213.88 (NHQ)ZS04 92.98 COZ 3538 (NHQ)zS04 1008 NaHC03 1008 NaHC03 1490.88 14908 1.151 @ 1.32 S.G. 1.285 S.G.
1.151 23.7% NH SO
The exit brine is then cooled to 0'C.
Brine composition is : 5.0% Na2S04 which mean 608 NazS04 precipitates as 1368 of Na2S0410Hz0 precipitate and remove 768 of H20.
Therefore: 907 - 76 = 831 g H20.
Brine composition @ 0'C and 1.26 S.G.
708 Na2S04 3538 (NH4)zS04 1008 NaHC03 831 cLHzO
1354a TOTAL
About 1 litre brine KzSO
a) 708 Na2S0~ x 174 = 85.8 b) 353 NH ~2SOA x 174 = 465.3a EXIT BRINE:
283g NH4CI 21.9%
57g NaCI 4.8%
1198 (KNaHC03) 9.2%
Boil up to 33.0% NH4C1.
Release of NH3 and COZ from evaporator but NH4CI salts out KCI and not the NaCI.
KCI is recovered same as in Example 1.
BASIS: One Tonne Na2~ feed INPUTS PRODUCT
First Stage 0.15t NH3 0.48t NaHC03 0.396t CO2 2.52t H O
Second Stage 0.10t NH3 0.49t NaHC03 0.26t C03 0.42t Na SO
Cooled to 0 C 0.4t of Na SO 10H O
Cooler Brine 0.19t Na2S04 5%
0.98t (NH4)ZS04 26%
0.28t NaHC03 7.4%
2.31 t H20 61.4%
3.76t Total INPUT PRODUCT
KCI 1.62t ~~ 1.8t K SO
Evaporation to 33% NH4CI Brine Solids Circuit Control = 0.7t H20 0.98t NH4C1 0.28t KCI
5t 0.08t KCI 0.08t KZSOa Washing = 0-5 t To evaporator 1.2t HzOlt NazS040.15t NaCI 0.36t 0.19t NaCI from C03 1.57t Hz0 2.97t 10 Lime Process @ 85% efficiency 1.01t CaCl2 0.61 t Ca0 0.08t KCI
0.34t NaCI
1.57t H20 3.Ot 75 - 90'C
CHLORIDE
Feed Solution: from #1 412 g (NH4)ZS04 335 g NazS04 2014 g @ 1.265 = 1.60 I
Cooling to 0'C yields a filtered solution of:
412 g (NH4)zS04 28.7%
116 g Na2S04 8.0%
9. 07 ct H20 1435 g solution This brine is then heated to 25'C where KCI solid is added to produce KZS04.
The exit brine from circuit has the following composition:
the K2S04 NH4CI 330.8 g 21.9 KCI 130 g 8.6 NaCI 94.7 6.3 x-S04 50 g 3.3 % x = Na/K
H20 907 a 60 1512 g This brine is than heated and reacted with lime to recover the ammonia and bypass the evaporator. The KCI reports to the CaCl2 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 CaClz brine can be reduced to as low as 1.0% by adding solid Na2S04 to CaCI2IKCl brine. The potassium is effectively collected as apprecipitated of syngenite (CaS04 ~ KzS04 ~ xHzO) at 0 to 100'C with preferred temperatures of to 30'C so that S04 solubility is kept to minimum and the reaction occurs at a reasonable rate.
CaCl2 Brine composition 20 343.3 g CaCl2 22.5 130 g KCI 8.5 94.7 g NaCI 6.3 50 g x S04 32.% (NaIK) 907 g HZO 59.5%
1525 g 100 140 g Na2S04 addition: Exit BrineExit Cake 234.8 g CaCl2 17.8%
5.25 g KCI 1.1 % 310 g CaS04 ~ KzS04 209 g NaCI 15.9 % + 100 g Hzo 50gxS04 3.8%
807 61.3 The exit brine can be deep well disposed of and cake can be blended into the KZS04 product as binder or further processed to remove the CaS04.
The cake can be reacted with (NH4)ZHC03 from the NaHC03 process feed and the CaS04 reacts quickly to produce a brine of (NH4)2S04 and KZS04 and a filter CaCl3 precipitate which is disposed of. The (NHa)ZS041KZS04 brine is recycled to K2S04 first stage crystallizer.
Although embodiments of the invention have been described above, it is not limited thereto and it will be apparent to those skilled in the art that numerous modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the claimed and described invention.
807 61.3 The exit brine can be deep well disposed of and cake can be blended into the KZS04 product as binder or further processed to remove the CaS04.
The cake can be reacted with (NH4)ZHC03 from the NaHC03 process feed and the CaS04 reacts quickly to produce a brine of (NH4)2S04 and KZS04 and a filter CaCl3 precipitate which is disposed of. The (NHa)ZS041KZS04 brine is recycled to K2S04 first stage crystallizer.
Although embodiments of the invention have been described above, it is not limited thereto and it will be apparent to those skilled in the art that numerous modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the claimed and described invention.
Claims (4)
1. A method of formulating food grade sodium bicarbonate and potassium sulfate, comprising 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 ammonium 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°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;
l) heating liquor from step k) to between 30'C and 40'C; and m) precipitating potassium sulfate by contacting said liquor from step l) with potassium chloride.
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 ammonium 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°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;
l) heating liquor from step k) to between 30'C and 40'C; and m) precipitating potassium sulfate by contacting said liquor from step l) with potassium chloride.
2. The method as defined in claim 1, further including the step of separating precipitated potassium sulfate and washing with potassium chloride.
3. The method as defined in claim 2, further including the step of treating liquor from said step of separating precipitated potassium sulfate with lime to liberate ammonia gas.
4. The method as defined in claim 3, further including the step of recycling said ammonia gas to step g).
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 I) to between 30°C to 40°C; and k) treating said liquor from step j) with potassium chloride to precipitate potassium sulfate;
l) evaporating liquor from step k) to recover potassium values for recycling to step k); and m) drying said potassium sulfate.
14. The method as defined in claim 13, further including the step of treating liquor remaining from step I) with lime and ammonium chloride.
15. The method as defined in claim 14, wherein ammonia gas is liberated and recycled.
16. The method as defined in claim 13, wherein used potassium chloride solution is recycled to step k).
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 I) to between 30°C to 40°C; and k) treating said liquor from step j) with potassium chloride to precipitate potassium sulfate;
l) evaporating liquor from step k) to recover potassium values for recycling to step k); and m) drying said potassium sulfate.
14. The method as defined in claim 13, further including the step of treating liquor remaining from step I) with lime and ammonium chloride.
15. The method as defined in claim 14, wherein ammonia gas is liberated and recycled.
16. The method as defined in claim 13, wherein used potassium chloride solution is recycled to step k).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10396998P | 1998-10-13 | 1998-10-13 | |
| US60/103,969 | 1998-10-13 |
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| Publication Number | Publication Date |
|---|---|
| CA2284967A1 true CA2284967A1 (en) | 2000-04-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA002284967A Abandoned CA2284967A1 (en) | 1998-10-13 | 1999-09-29 | Method of formulating alkali earth salts |
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| EP (1) | EP1121327A1 (en) |
| JP (1) | JP2002527330A (en) |
| KR (1) | KR20010088870A (en) |
| CN (2) | CN1156397C (en) |
| AU (1) | AU751236B2 (en) |
| BR (1) | BR9914543A (en) |
| CA (1) | CA2284967A1 (en) |
| CZ (1) | CZ20011176A3 (en) |
| EA (1) | EA002709B1 (en) |
| HR (1) | HRP20000125A2 (en) |
| HU (1) | HUP0104062A3 (en) |
| ID (1) | ID28729A (en) |
| NO (1) | NO20011851L (en) |
| NZ (1) | NZ510786A (en) |
| PL (1) | PL347098A1 (en) |
| SI (1) | SI20636A (en) |
| SK (1) | SK5002001A3 (en) |
| TR (1) | TR200100960T2 (en) |
| UA (1) | UA73096C2 (en) |
| WO (1) | WO2000021887A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6365122B1 (en) * | 1998-06-22 | 2002-04-02 | William J. Rigby | Process for manufacturing potassium sulfate fertilizer and other metal sulfates |
| US6475458B1 (en) | 1999-10-25 | 2002-11-05 | Airborne Industrial Minerals Inc. | Method for formulating food grade sodium bicarbonate |
| JP4812253B2 (en) * | 2001-08-29 | 2011-11-09 | リグビィ、ウィリアム、ジェイ． | Method for producing potassium sulfate fertilizer and other metal sulfates |
| US7393378B2 (en) * | 2003-02-11 | 2008-07-01 | Airborne Industrial Minerals Inc. | Method for recovering purified sodium bicarbonate and ammonium sulfate |
| JP5404180B2 (en) * | 2009-05-22 | 2014-01-29 | 日立造船株式会社 | Sodium extraction device |
| CN102503636A (en) * | 2011-10-27 | 2012-06-20 | 山西师范大学 | Ammonium chloride agglomerating prilling method |
| FR3007753A1 (en) * | 2013-06-26 | 2015-01-02 | Solvay | PROCESS FOR THE PREPARATION OF ALKALI METAL BICARBONATE PARTICLES |
| CN104556154B (en) * | 2014-12-30 | 2017-04-12 | 东莞市英硫净水服务有限公司 | Comprehensive utilization technology of residual liquid after evaporation of heavy salt water |
| CN109052434B (en) * | 2018-10-19 | 2021-06-04 | 四川金象赛瑞化工股份有限公司 | Method for jointly producing soda ash and composite nitrogen fertilizer by taking mirabilite and ammonium bicarbonate as raw materials |
| CN111895722B (en) * | 2020-09-04 | 2024-03-01 | 江西智联塑化科技有限公司 | Conduction oil cooling device for pentaerythritol stearate preparation |
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| CA2032627C (en) * | 1990-12-18 | 1997-01-14 | Jack S. Thompson | Process for producing sodium carbonate and ammonium sulphate from sodium sulphate |
| CN1044222C (en) * | 1991-12-28 | 1999-07-21 | 邓绍齐 | Method for comprehensive utilization of sodium sulfate containing chromium |
| CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
| CN1041401C (en) * | 1994-11-01 | 1998-12-30 | 何永汉 | Method for production of Lemery salt |
| SK279011B6 (en) * | 1995-04-05 | 1998-05-06 | Považské Chemické Závody | Method for conversion of ammonium sulphate to potassium sulphate |
| US5830422A (en) * | 1995-06-23 | 1998-11-03 | Ormiston Mining And Smelting Co. Ltd. | Method for production of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate |
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| KR20010088870A (en) | 2001-09-28 |
| AU5845799A (en) | 2000-05-01 |
| YU27101A (en) | 2003-10-31 |
| PL347098A1 (en) | 2002-03-25 |
| EA200100340A1 (en) | 2001-10-22 |
| CN1156397C (en) | 2004-07-07 |
| CZ20011176A3 (en) | 2001-09-12 |
| WO2000021887A1 (en) | 2000-04-20 |
| NZ510786A (en) | 2002-05-31 |
| UA73096C2 (en) | 2005-06-15 |
| ZA200001142B (en) | 2000-10-23 |
| JP2002527330A (en) | 2002-08-27 |
| HUP0104062A2 (en) | 2002-04-29 |
| BR9914543A (en) | 2001-06-26 |
| SI20636A (en) | 2002-02-28 |
| TR200100960T2 (en) | 2001-08-21 |
| AU751236B2 (en) | 2002-08-08 |
| NO20011851D0 (en) | 2001-04-10 |
| CN1330612A (en) | 2002-01-09 |
| HUP0104062A3 (en) | 2003-03-28 |
| ID28729A (en) | 2001-06-28 |
| SK5002001A3 (en) | 2001-10-08 |
| NO20011851L (en) | 2001-06-12 |
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| EP1121327A1 (en) | 2001-08-08 |
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