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Integrated process for potassium sulfate and a mixture Of ammonium

chloride/potassium sulfate salts production

Article  in  International Journal of Engineering and Technology · March 2018

DOI: 10.14419/ijet.v7i1.9188

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 International Journal of Engineering & Technology, 7 (1) (2018) 185-197

International Journal of Engineering & Technology

Website: www.sciencepubco.com/index.php/IJET
doi: 10.14419/ijet.v7i1.9188
Research paper

Integrated process for potassium sulfate and a mixture

Of ammonium chloride/potassium sulfate
salts production
Yousef Ahmad Mubarak *

Chemical Engineering Department, School of Engineering, The University of Jordan, Amman-11942-Jordan

*Corresponding author E-mail: y_mubarak@ju.edu.jo

Abstract

Relatively pure and coarse crystalline potassium sulfate of about 52 wt % K2O content and almost chlorine free has been obtained by
reacting commercial potassium chloride and commercial ammonium sulfate in a stirred tank reactor at moderately low temperature. To
increase the yield of potassium sulfate to a reasonable value, an evaporation stage located between the reactor and the crystallizer is used.
The main steps of the production process include dissolution, reaction, evaporation, crystallization, centrifuging, drying, and then cool-
ing. It is found that the best operating parameters to produce potassium sulfate of good quality, quantity, and crystal size are 1:1 as KCl/
(NH4)2SO4 mole ratio, 60 ºC reaction temperature, 1 hour reaction time, about one third of the total water used in the dissolution step is
to be evaporated, 10 ºC crystallization temperature, 1 hour crystallization time, and 160 and 60 rpm agitation speeds in the reactor and
the crystallizer respectively. Applying these operating conditions, a potassium sulfate yield of about 78 % can be achieved. Also, a fully
soluble complex salt as a mixture of ammonium chloride and potassium sulfate is obtained by further treatment of the mother liquor.
Further concentration of the mother liquor by further water evaporation of about 40 wt % and then crystallization of the slurry at 25 oC
can recover up to about 60 wt % of the remaining solid in the mother liquor as a complex salt. The total yield of potassium sulfate is
found to be about 95 wt % and the whole value of the solid product obtained is about 79 wt %.

Keywords: Ammonium Chloride; Ammonium Sulfate; Crystallization; Potassium Sulfate; Potassium Chloride.

1. Introduction 1.1. Potassium sulfate production processes

Potassium as a source of K exists as a single fertilizer like potassi- Historically potassium sulfate has been made primarily from po-
um chloride (KCl), potassium sulfate K2SO4, and potassium hy- tassium chloride and sulfuric acid when the byproduct HCl was
droxide (KOH) or as NPK fertilizers like mono potassium phos- the dominant product. However, over the year the HCl market has
phate (MKP), and potassium nitrate (KNO3). Potassium (K) ferti- had more competition and “natural” K2SO4 with lower capital and
lizer is commonly added to improve the yield and quality of plants operating coasts has begun to dominate its production in some
growing in soils that are lacking an adequate supply of this essen- countries with natural complex salts. Nowadays, potassium sulfate
tial nutrient. Most potassium fertilizer comes from ancient salt can be manufactured by several processes such as: Mannheim
deposits located throughout the world. The word “potash” is a process, yield from natural complex salts, naturally occurring
general term that most frequently refers to potassium chloride brines, the Ochoa process, production of potassium sulfate from
(KCl), but it also applies to all other K-containing fertilizers, such potash and sodium sulfate, production of potassium sulfate by
as potassium sulfate (K2SO4) [1], [2]. reacting ammonium sulfate with potassium chloride. A brief de-
Potassium sulfate is an organic crystalline salt with a chemical scription of these processes in addition to disadvantages will be
formula K2SO4, produced in a crystalline or a powder form. It is given below.
white, odorless, bitter tastes, nontoxic, nonflammable, and soluble
in water. It contains 48 to 54 % potassium (as K2O) and supplies 1.1.1. Mannheim process
18.4 % of sulfate, and it is considered as the second largest ton-
nage of potassium compound and is primarily used as a fertilizer The Mannheim process was originally developed for sodium sul-
[3]. Potassium sulfate is a valuable chemical commodity and it is fate production. For the production of potassium sulfate, sodium
typically employed as a fertilizer especially for certain crops that chloride is replaced with potassium chloride. The required raw
do not tolerate the chloride ions well, also most crops need more materials (potassium chloride (KCl) and sulfuric acid (H2SO4)) are
sulfate than chloride. This fertilizer is a rich source of potassium poured into the center of a muffle furnace heated to above 600 ºC
and sulfur which offers a high concentration of nutrients readily [5]. Potassium chloride reacts with sulfuric acid during the slow
available to plants. Potassium sulfate is also used in the manufac- mixing of the ingredients in the gas heated Mannheim furnace
ture of glass and production of potassium alums [4]. consisting of cast iron muffle with rotating plough which helps to
agitate the mixture. The hydrochloric acid produces during the
reaction is cooled and absorbed into water to produce 33 % hydro-
Copyright © 2018 Yousef Ahmad Mubarak. This is an open access article distributed under the Creative Commons Attribution License, which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
186 International Journal of Engineering & Technology

chloric acid as a byproduct. The precipitated potassium sulfate is can be obtained by out-salting, but this requires a longer res-
cooled, filtered and the lumps are crushed and granulated [6], [7]. idence time and more sophisticated crystallization equip-
The following reactions take place during the production process: ment.
• Dilution of the solution being cooled with water permits ob-
KCl + H2SO4 → KHSO4 + HCl taining quality glaserite, but its yield is only 5 to 10 wt % of
the theoretical. In addition, the refrigeration is so expensive.
KHSO4 + KCl → K2SO4 + HCl • In addition, as a result of evaporation of the glaserite solu-
tions, a thick crust of glaserite, difficult to remove, is
Although the Mannheim process is the most widely process for formed on the apparatus surface, which reduces the heat
K2SO4 production but it has many disadvantages transfer coefficient.
1) Mannheim process needs high production cost.
2) It needs a high temperature (> 550 oC) which means high 1.1.4. Recovery of potassium sulfate from polyhalite
energy consumption.
3) Mechanical problems and some difficulties encountered due The process utilizes polyhalite, water and energy to produce three
to corrosion. main products soluble potassium sulfate, standard potassium sul-
4) The Mannheim kiln is of necessity constructed from special fate, and granular potassium sulfate. Processing polyhalite to pro-
bricks which have high resistance to direct flame, intense duce potassium sulfate by this technique involves crushing, wash-
heat and acid, while the stirrer must be heat- and acid- ing, calcinations, leaching, crystallization, and granulation. This
proof. method can be effective in areas, which have high evaporation rate
and low rainfall and only with brines that contain very high sulfate
1.1.2. Recovery from natural complex salts levels, while in reality lakes with sufficient brine mineral levels
are rare. Potassium sulfate production from such sources is usually
Complex salts containing magnesium sulfate and potassium sul- complex because of the presence of many other salts in significant
fate occur naturally in many potash ores, such as the potash ores proportions, which leads to the use of a combination of a mechan-
that are found in the European deposits and in the Permian Basin. ical type of separation step with a solubility process step in order
The chief natural complex salts that are the source of the potassi- to make the latter more efficient. The recoveries of potassium
um sulfate are; Kainite (KCl.MgSO4.3H2O), Langbeinite sulfate are less than the optimum due to the greatest difficulty
(K2SO4.3MgSO4), and Carpathian polmineral ores. The natural encountered in effecting a clean separation of these several salts
process involves the initial conversion with recycled K2SO4 end because of the presence of the sodium chloride. In most cases,
liquor “mined” kainite or langbeinite to form an intermediate potassium sulfate is not recovered directly from natural brine
product schoenite. All processes are based on intercrystalline reac- sources; however, potassium chloride is commonly recovered and
tions of ion exchange. then used as a raw material for the production processes of potas-
The process comprises four basic units: preparation of the ore and sium sulfate [12], [13].
flotation, production of schoenite and its recovery, leaching of the
schoenite to potassium sulfate, and liquor treatment. The kainite is 1.1.5. Naturally occurring brines
repulped with recycled brine, screened, and directed to ball mills
and hydro-classifiers. Overflows go to a thicker and main filter In this process evaporate minerals comprising mixtures of relative-
and underflows to flotation and filtration. Float material, after ly coarse salts are treated in a manner such that certain salts are
filtration, is combined with the solid fraction from the main filter converted by recrystallization to very finely divided form and then
and directed to the schoenite reactors and separating cyclones. separated from the coarse salts by size classification. The ore
After a two-step hydro-separation, centrifugation, and filtration, should be calcined at 450 °C to remove the water of crystallization
schoenite is directed to the leaching reactors. After decomposition and render the material soluble in a hot water leach. Polyhalite
of the schoenite, product is directed to final centrifuges and a dry- which is a row material in this process crystallizes in the triclinic
er; the overflows are cooled and crystallized. After additional system. There are various operations in this process and the pro-
thickening, the product is centrifuged and dried. The product spec- cess can only be effective in areas which have plenty of water
ification ensures that the K2O content is not lower than 50% and resources. The treatment being especially useful in a process for
the chlorine content is less than 1% [8]. the recovery of potassium sulfate from marine evaporates mixtures
[14]. The main disadvantage of this technique is its high energy
1.1.3. Production of potassium sulfate from potash and sodium and cost are needed in addition to that it requires high rate of
sulfate equipment maintenance.

Potassium chloride can be reacted with various sulfate salts to 1.1.6. Production of potassium sulfate by reacting ammonium
form a double salt that can be decomposed to recover potassium sulfate and potassium chloride
sulfate. The most common raw material employed for this purpose
is sodium sulfate. A saturated solution of sodium sulfate is added In this production process, potassium sulfate is produced by react-
to a saturated solution of potassium chloride to produce glaserite, ing ammonium sulfate and potassium chloride at a temperature of
which is the double sulfate of sodium and potassium. The solution about 30 to 40 °C to produce a slurry containing
obtained can be filtered to remove insoluble matter, and is then K2SO4·(NH4)2SO4 double salt, and reacting this double salt with
subjected to crystallization, such as evaporative crystallization or an aqueous solution containing potassium chloride at a tempera-
cooling crystallization in which glaserite crystallizes out of solu- ture of about 30 °C to produce a slurry containing potassium sul-
tion. The obtained solution is filtered to separate the produced fate. The slurry containing potassium sulfate is subjected to a sol-
potassium sulfate from the mother liquor. The resulting mother ids/liquid separation step to obtain potassium sulfate crystals hav-
liquor undergoes evaporative crystallization in which sodium ing a size in the range of about 20 to about 150 meshes. The fil-
chloride is produced, and then it is separated by filtration from the trate from solids/liquid separator flows to a settler, where this
mother liquor and recovered as a co product [9-11]. The main filtrate is separated into fines, which are recycled back, and an
disadvantages of this method are summarized as follows: overflow liquor; reacting the overflow liquor with sodium sulfate
• This process takes a very long time and this is the most se- and either calcium chloride or calcium sulfate dihydrate at a tem-
rious disadvantage. perature of 30° C to produce a slurry containing syngenite,
• There are numerous problems associated with the sol- CaSO4·K2SO4·xH2O, and passing the slurry containing syngenite
id/liquid separation of glaserite. Since known processes into a solids/liquid separator to produce a filtrate and solid synge-
produce a fine glaserite. Somewhat larger glaserite crystals nite [15], [16].
International Journal of Engineering & Technology 187

After reviewing most of the available commercial potassium sul- that consists of dissolved potassium sulfate and ammonium chlo-
fate production processes and based on the availability of the raw ride is transferred from the reactor to the kettle evaporator as
materials, the advantages, and disadvantages of the mentioned shown in the process flow sheet. Steam will be used in the kettle
processes especially the huge quantity of energy required by most evaporator to rise up the solution temperature from 60 oC up to
of the available production processes and their environmental 100 oC to allow water to be evaporated and hence increase the
effect, it is necessary to seek a more feasible and more environ- concentration of the potassium sulfate in the solution.
mentally friendly production process with less energy consump- Reducing the temperature of the solution after the required amount
tion. of water has been evaporated will bring the solution far away be-
low the crystallization temperature of potassium sulfate. The out-
1.1.7. Description of the present production method put solution from the kettle evaporator (stream 5) will be fed to the
batch crystallizer where the hot solution is cooled down from
Production of potassium sulfate by the present process starts by about 100 oC to the crystallization temperature (varies between 5
charging both commercial potassium chloride (KCl) and ammoni- to 28 oC). Chilled water will be circulated in the jacket of the crys-
um sulfate ((NH4)2SO4) to two separate jacketed dissolution tanks tallizer to cool the solution down to the set crystallization tempera-
to prepare potassium chloride and ammonium sulfate saturated ture; the crystallization temperature must be kept constant for the
solutions. In order to obtain the saturated solutions of both of whole period of the crystallization step.
these materials, it is necessary to raise the temperature of the solu- On completion of the crystallization step, solid potassium sulfate
tion up to 60 oC under an agitation. The two saturated solution crystals will be formed leaving the more soluble compound (am-
(streams 1 and 2) are transferred to a jacketed continuous stirred monium chloride) dissolved in the solution. During the crystalliza-
reactor where the reaction temperature is kept constant for the tion step, the mixture should be agitated with a stirring speed that
whole period of reaction time. The stoichiometric reaction be- is enough to keep the potassium sulfate crystals suspended in the
tween potassium chloride and ammonium sulfate obeys the fol- solution, this will allow for larger potassium sulfate crystals to
lowing reaction equation: grow up. If the agitation speed is not high enough to suspend the
formed crystals, then a fine product will be obtained because the
2KClaq + (NH4)2SO4 aq → K2SO4 s + 2NH4Cl aq (1) formed crystals will settle down and accumulate over each other
hence preventing crystals growth step to take place.
Fig. 1 shows the process flow sheet for the production of potassi-
um sulfate according to the laboratory experimental work carried
out. On completion of the reaction, the resulted solution (stream 3)

Fig. 1: Process Flow Sheet of Potassium Sulfate Production.

The resulting slurry of potassium sulfate crystals and the mother contact with hot air blown into the dryer with a temperature of 122
oC. Potassium sulfate crystals (stream 11) leave the rotary dryer at
liquor flows via stream 8 to the centrifuge where the separation of
potassium sulfate crystals from the mother liquor takes place un- a moisture content of about 0.05 % and at a temperature of 60 oC.
der the very high speed of rotation of the internal basket of the To prevent the dried potassium sulfate crystals from gaining some
centrifuge. The moist potassium sulfate crystals (stream 9) need moisture from the air and then agglomerate while they are in stor-
further drying while the mother liquor (stream 10) is pumped to a age, a cooling step is required to cool down the end product from
storage tank for further processing and recovery. The mother liq- about 55 oC down to room temperature. Dust from both, the rotary
uor contains valuable compounds such as dissolved ammonium dryer (stream 12) and the cooler (stream 13) are sent to a bag filter
chloride and soluble potassium sulfate that must be recovered. to recover any potassium sulfate fine crystals and to clean the exit
To get rid of the excess moisture content within the obtained po- air from solid pollutants. Also, water vapor from the reactor and
tassium sulfate crystals and obtain crystals with the standard spec- the evaporator is collected and condensed to reduce the amount of
ifications, a rotary dryer is used where the wet crystals flow via water consumed.
stream 9 from the centrifuge to the rotary dryer. The wet crystals The mother liquor (stream 16) that contains mainly the dissolved
flow counter-currently into the rotary dryer where they will be in ammonium chloride and the unrecovered potassium sulfate is
188 International Journal of Engineering & Technology

treated as shown in Fig. 2 to obtain a complex salt of both of these temperature and crystallization time. In the present work, five
compounds. The treatment process starts with the further evapora- variables were investigated to achieve the best-operating condi-
tion of water to increase the concentration of the salts in the liq- tions that lead to a maximum yield of K2SO4 with better crystals
uor. The saturated solution (stream 18) is then transferred to crys- quality. These variables are: the reaction temperature (40, 60, 80
tallizer 2 that operates at a temperature of 25 oC to allow the salts and 100 ⁰C), the reaction time (0.5, 1, 2 and 4 hour), the crystalli-
crystal to nucleate and grow up. By the end of the crystallization zation temperature (5, 10, 15 and 28 ⁰C), the crystallization time
process, the suspension (stream 19) is centrifuged to separate the (0.25, 0.5, 1 and 2 hour), and the percentage of water evaporated
solid salt formed from the second mother liquor. The obtained (15, 24 and 32 %). Also, to recover potassium sulfate/ammonium
sold salt (stream 20) is dried using a rotary dryer to remove the chloride complex salt from the main mother liquor, the percentage
excess moisture. of water evaporated and the crystallization temperature were stud-
Many experimental runs were done to determine the best operat- ied. The percentage of water evaporated varied as 0, 15, 30, 40,
ing parameters for producing potassium sulfate by reacting am- and 50 wt % while the crystallization temperature varied as 5, 10,
monium sulfate and potassium chloride. There are many operating 15, 25, and 30 ⁰C.
parameters need to be optimized such as mole ratio of KCl to
(NH4)2SO4, reaction temperature, reaction time, crystallization

Fig. 2: Process Flow Sheet of Mother Liquor Treatment.

= 0.2 wt %, mean particle size = 1.1 mm, loose bulk density =

2. Materials and methods 1040 kg/m3, and color = whitish.

2.2. Experimental procedure followed

2.1. Materials used
The following block flow diagram (Figure 3) summarizes the
A standard potassium chloride (KCl) supplied by the Arab Potash procedure adopted in the experimental work to produce both po-
Company and has the following specifications: purity = 96.6 %, tassium sulfate and the complex salt. Both raw materials were
potassium oxide (K2O) = 61 wt %, moisture content = 0.35 wt %, used as received to prepare the saturated solutions from which the
particle size (90 % minimum) between 0.212-1.7 mm, bulk densi- two products were obtained.
ty = 1300-1358 kg/m3 [17]. Commercial ammonium sulfate
((NH4)2SO4) with the following specifications: ammoniacal nitro-
gen = 21 wt %, water soluble sulphur = 24 wt %, moisture content
International Journal of Engineering & Technology 189

Fig. 3: Block Flow Diagram for Potassium Sulfate and Potassium Sulfate/Ammonium Chloride Complex Salt Production.

yield by about 5 wt %, while increasing the reaction temperature

3. Results and discussion from 40 to 100 oC, increases K2SO4 yield by about 15 wt %. On
the other hand, increasing the reaction temperature from 60 to 100
oC, increase the yield by about 6 wt % only.
In this proposed method two products can be produced; the main The obtained potassium sulfate crystals were all white and shiny
is the crystalline potassium sulfate while the other byproduct is a except the crystals obtained at a reaction temperature of 40 oC; the
mixture of ammonium chloride and potassium sulfate salts. Below K2SO4 crystals were very fine in size and less shiny. Since the
the effect of the operating parameters on the yield, chemical anal- obtained K2SO4 crystals at a reaction temperature of 40 oC are not
ysis, and physical appearance of the products will be presented. acceptable in terms of crystal size and physical appearance, and
since increasing the reaction temperature above 60 oC does not
3.1. Effect of operating parameters on the potassium increase the yield significantly, it is concluded that the best reac-
sulfate production tion temperature to adopt is 60 oC. Figure 4 shows microscopic
graphs of the obtained potassium sulfate crystals obtained by crys-
3.1.1. Reaction temperature effect tallization saturated solutions reacted at different temperatures. All
samples were crystallized at a crystallization temperature of 10 oC.
To investigate the effect of the reaction temperature on the yield
of potassium sulfate, four experiments were carried out at different
reaction temperatures (40, 60, 80 and 100 oC) while all other pa-
rameters were kept fixed at: molar ratio of KCl/(NH4)2SO4 = 1/1,
reaction time = 60 min, crystallization temperature = 10 oC, crys-
tallization time = 60 min, and evaporated water ratio = 15 %. The
effects of the reaction temperature on the potassium sulfate yield
and crystals size are presented in Fig. 3. It is obvious that in gen-
eral, increasing the reaction temperature increases the K2SO4
yield. Increasing the temperature from 40 to 60 oC, increases the
190 International Journal of Engineering & Technology

74

Potassium Sulfate Yeild [wt %]

72

70

68

66

64

62

60
0 20 40 60 80 100 120
o
Reaction Temperature [ C]

Fig. 3: Percentage of Potassium Sulfate Yield as a Function of Reaction Temperature while the other Parameters were Kept Fixed at 60 Min Reaction
Time, 10 OC Crystallization Temperature, 60 Min Crystallization Time and 15 wt % Evaporated Water Ratio.

Fig. 4: Microscopic Images of Potassium Sulfate Crystals Crystallized at 10 oC From Solutions Reacted at A) 40 B) 60 C) 80 D) 100 Oc.

13 wt % only. Further increment in the reaction time does not

3.1.2. Reaction time effect increase the yield significantly and nearly similar yield values
were obtained for reaction times of 1, 2 and 4 hours. Also, it is
To reveal the reaction time effect on the K2SO4 yield, four trials noticed that the amount of K2SO4 nuclei and fine crystals formed
were conducted at 0.5, 1, 2 and 4 hours reaction time while the during the reaction step after 30 minutes was very little compared
other operating parameters were kept constant at: molar ratio of with the amount formed after 60 minutes. As a result of this, a
KCl/(NH4)2SO4 = 1/1, reaction temperature = 60°C, crystallization reaction time of 60 minutes can be considered as the best reaction
temperature = 10°C, crystallization time = 60 minutes, and evapo- time. Fig. 6 shows microscopic graphs of the obtained potassium
rated water ratio = 15 %. Fig. 5 presents the effect of the reaction sulfate crystals by crystallization saturated solutions reacted at 60
time on the yield of the potassium sulfate crystals. The results oC for different times. All samples were crystallized at a crystalli-
show that increasing the reaction time form 30 min to 60 min in- zation temperature of 10 oC.
creases the potassium sulfate yield by about 10 wt % and increas-
ing the reaction time to 120 minutes increases the yield by about
International Journal of Engineering & Technology 191

70
68

Potassium Sulfate Yeild [wt %]

66
64
62
60
58
56
54
52
50
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Reaction Time [hours]
Fig. 5: Percentage of K2SO4 Yield as a Function of Reaction Time while the other Parameters were Kept Fixed at 60 OC Reaction Temperature, 10 OC
Crystallization Temperature, 60 Min Crystallization Time and 15wt % Evaporated Water Ratio.

It is clearly seen in Fig. 7 that decreasing the crystallizer’s temper-

3.2.3. Crystallization temperature effect ature will increase the yield of K2SO4 crystals as a result of the
supercooling which leads to excessive nucleation. Decreasing the
One of the most widely used methods for achieving the supersatu- crystallization temperature from 28 oC to 10 oC increases the
ration essential for crystallization is cooling of a solution. On K2SO4 yield by 20 wt %. Since the difference in the yield values is
completion of the reaction between the potassium chloride and almost negligible (less than 2 wt %) if the crystallization tempera-
ammonium sulfate, the slurry is transferred to the crystallizer to ture reduces from 10 to 5 oC, then there is no need to reduce the
allow further nucleation and growth of K2SO4 crystals and hence crystallization temperature further. Hence, it is believed that 10 oC
increase the yield of potassium sulfate. Knowing that the solubili- might be a suitable crystallizer temperature at which a reasonable
ty of ammonium chloride [18] (39.5 g/100 g water at 25 oC) is amount of K2SO4 can be recovered. The microscopic images of
over three times the solubility of potassium sulfate [19] (12 g/100 Fig. 8 show that increasing the crystallization temperature increas-
g water at 25 oC), and then cooling a saturated solution containing es the size of the obtained crystals, at lower crystallization tem-
both of these salts will allow potassium sulfate to crystallize ini- perature the nucleation rate is high and hence smaller size of crys-
tially. In the present study, slurries from the reactor were cooled at tals will be obtained [23], [24].
different crystallization temperatures to investigate the effect of
the crystallization temperature on K2SO4 yield; the crystallization
temperatures covered were 5, 10, 15 and 28°C. The other parame-
ters were kept constant at: molar ratio of KCl/(NH4)2SO4 = 1/1,
reaction temperature = 60°C, reaction time = 60 minutes, crystalli-
zation time = 60 minutes, and evaporated water ratio = 15 %. The
cooling temperature is known to influence the rate of growth and
size of crystals through its effect on supercooling [20-22].

Fig. 6: Microscopic Images of Potassium Sulfate Crystals Crystallized at 10 OC from Solutions Reacted at 60 oC for A) 0.5 B) 1 C) 2 D) 4 Hr.
192 International Journal of Engineering & Technology

70
68

Potassium Sulfate Yelid [wt %]

66
64
62
60
58
56
54
52
50
0 5 10 15 20 25 30
Crystallization Temperature [oC]
Fig. 7: Percentage of K2SO4 Yield as a Function of Crystallization Temperature; the other Parameters were Kept Fixed at 60 OC Reaction Temperature, 60
Min Reaction Time, 60 Min Crystallization Time and 15 wt % Evaporated Water Ratio.

Fig. 8: Microscopic Images of Potassium Sulfate Crystals Crystallized for One Hour at Different Temperatures A) 5 B) 10 C) 15 D) 28 OC.

while the yield increases by about 16 wt % when the crystalliza-

3.2.4. Crystallization time effect tion time increases from 30 to 120 minutes. Since the increment in
the K2SO4 yield is very small as the crystallization time increases
As expected, the crystal yield increases with time [25], the effect from 60 to 120 minutes and in order to save more energy and to
of crystallization time was studied by setting the crystallization reduce the process time, it is suggested to stop the crystallization
time to 0.25, 0.5, 1, and 2 hours, while the other variables were set stage after 60 minutes. The microscopic graphs obtained (Fig. 10)
at: molar ratio of KCl/(NH4)2SO4 = 1/1, reaction temperature = reveals that reducing the crystallization time will decrease the
60°C, reaction time = 60 minutes, crystallization temperature = final size of the crystals as a result of the insufficient time for
10°C, and evaporated water ratio = 15 %. As expected, increasing crystals to grow up.
the crystallization time will increase the K2SO4 yield as presented
in Fig. 9. The figure reveals that the yield increases by about 14 wt
% when the crystallization time increases from 30 to 60 minutes,
International Journal of Engineering & Technology 193

69

Potassium Sulfate Yeild [wt %]

67

65

63

61

59

57

55
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25
Crystallization Time [hours]

Fig. 9: Percentage of Potassium Sulfate Yield as a Function of Crystallization Time while the other Parameters were Kept Fixed at 60 OC Reaction Tem-
perature, 60 Min Reaction Time, 10 OC Crystallization Temperature and 15 wt % Evaporated Water Ratio.

Fig. 10: Microscopic Images of Potassium Sulfate Crystals Crystallized at 10 OC for Different Periods of Time A) 0.25 B) 0.5 C) 1 D) 2 Hr.

crystallization = 60 minutes. Fig. 11 presents the effect of the

3.2.5. Water evaporation ratio effect percentage of water evaporation on the K2SO4 yield. It can be
clearly seen that increasing water evaporation leads to higher
In order to prepare the two saturated solutions of potassium chlo- yield; the yield increases from 42 to 65 wt % by water evaporation
ride and ammonium sulfate, it is necessary to use a large quantity of about 15 wt % of the total water exist in the solution. By in-
of water to dissolve the solid raw materials at the required temper- creasing the percentage of water evaporation to 32%, about 100%
ature (60 oC). The total percentage of water at the beginning of the increment in the K2SO4 yield can be achieved (about 85 wt % of
reaction stage is about 65 wt % of the total feed. The presence of K2SO4 is recovered); further increase in water evaporation does
this high quantity of water limits and reduces the K2SO4 yield; not increase the yield much. As a result of this conclusion, a 32
hence a very low yield was obtained when this large quantity of percentage of water evaporation will be considered as the best.
water remains in the solution during the crystallization stage. It is This percentage of water evaporation means that around 1.5 tons
necessary to evaporate part of this water to increase the concentra- of water must be evaporated for each ton of potassium sulfate
tion of the salts in the solution and allow the less soluble salt production. This amount of water is considered reasonable if we
(K2SO4) to crystallize at a reasonable crystallization temperature. compare it with the 10 tons of water that must be evaporated per
The effect of the percentage of water evaporation prior to crystal- ton of potassium sulfate as mentioned by Sardisco in his patent
lization was studied by setting the ratio of the water evaporation at [26].
0, 15, 24 and 32%, while all other parameters were set at: molar
ratio of KCl/(NH4)2SO4 = 1/1, reaction temperature = 60 °C, crys-
tallization temperature = 10°C, reaction time = 60 minutes, and
194 International Journal of Engineering & Technology

90.2
80.2

Potassium Sulfate Yield [wt %]

70.2
60.2
50.2
40.2
30.2
20.2
10.2
0.2
0 10 20 30 40 50
Evaporated water ratio [wt %]
Fig. 11: Percentage of K2SO4 Yield as a Function of Evaporated Water Ratio; the other Parameters were Kept Fixed At 60 OC Reaction Temperature, 60
Min Reaction Time, 10 OC Crystallization Temperature and 60 Min Crystallization Time.

3.3.1. Mother liquor treatment

3.2.6. Best operating parameters for K2SO4 production
The mother liquor that contains a considerable amount of
To verify the obtained results in this study, a triplicate identical dissolved K2SO4 in addition to a large quantity of ammonium
experiments were conducted at the obtained best-operating chloride can be treated further to produce ammonium
conditions: molar ratio of KCl/(NH4)2SO4 = 1/1, 60 oC reaction chloride/potssium sulfate slat. In the present study, two main
temperature, 60 minutes reaction time, 10 oC crystallization factors affetcting the yield of the salt were studied; these are the
temperature, 60 minutes crystallization time, and 32 wt % water water evaporation ratio and the crystallization temperature.
evaporation. About 78 wt % of the K2SO4 was recovered as a
white and shiny solid crystals as shown in Fig. 11. The chemical 3.3.2. Effect of water percentage evaporation on the yield of
analysis of the obtained K2SO4 crystals is presented in Table 1. In the complex salt
addition to the chemical analysis, the microscopic graphs shown in
Fig. 12 is another evidence that the obtained crystals are The mother liquor leaves the K2SO4 centrifuge still has a
potassium sulfate crystals which is in agreement with what is reasonable fraction of unrecovered potassium sulfate in addition to
reported in the literature [27], [28]. the whole ammonium chloride. It is crucial to recover these
valuable materials from the solution, different trials were
Table 1: Specifications of the Obtained Potassium Sulfate Crystals conducted to recover as much as possible out of these materials.
Produced at the Best Operating Parameters The recovered salt is a mixture of ammonium chloride and
Element Description potassium sulfate. It has been found that the percentage of
Color White recovered salt is very low if crystallization is applied on the
State Free flowing mother liquor without any water evaporation, the very high
Appearance Shiny crystals
solubility of ammonium chloride prevents the crystallization step
Solubility Fully soluble
K +
43.2 wt % to take place with the existence of the huge quantity of water in
K2O 52.2 wt % the solution. Hence it was necessary to get rid of part of the water
Cl- 0.5 wt % exist in the solution prior to the crystallization step. Keeping the
N -
0.2 wt % crystallization temperature fixed at 25 oC, Fig. 13 shows the effect
SO4-2 55.2 wt % of water evaporation % on the yield of the salt, as shown in the
moisture 0.8 wt % figure, the recovered quantity of the salt is very little (< 10 wt %)
if no water evaporation takes place. Up to 59 wt % of the
dissolved salts in the mother liquor can be recovered if 40 wt % of
the water is evaporated. The percentage of yield may reach 67 wt
% by further evaporation (50 wt % of the water is evaporated) but
the viscosity of the slurry inside the evaporator will be high and
this may cause handling and transferring problems.

Fig. 12: Microscopic Graphs of Potassium Sulfate Crystals Obtained by

Applying the Recommended Operating Parameters.

3.3. Effect of operating parameters on the complex salt

production
International Journal of Engineering & Technology 195

80

70

Complex Salt Yield [wt %]

60

50

40

30

20

10

0
0 5 10 15 20 25 30 35 40 45 50 55
Evaporated water ratio [wt %]
Fig. 13: Percentage of the Complex Salt Yield as a Function of Evaporated Water Ratio. Samples were Crystallized at 25 OC for 60 Min.

Fig. 14: Microscopic Graphs of Complex Salt Crystals Obtained by Crystallizing the Mother Liquor at 25 OC after Water Evaporation of A) 40 wt % B)
50 wt %.

Also, it has been found that the crystals obtained from solutions 6 wt % of the complex salt can be obtained. This additional
with high viscosity are hard to be dried and the flowability of the amount reduces to 3 wt % if the crystallization temperature de-
particles are less compared to crystals obtained from solution with creased from 25 to 5 oC. Since cooling the crystallizer to 5 oC will
less viscosity as shown in Fig. 14. As a result of this, it is decided cost more and needs a longer period of time, it is recommended to
to keep the percentage of evaporation around 40 wt %. use a crystallizer temperature of 25 oC at which about 59 wt % of
the complex salt can be recovered.
3.3.3. Effect of crystallization temperature Table 2 shows the chemical analysis of the complex salt obtained.
Detailed experimental values for the feed, main product (K2SO4)
It has been found that once the solution is concentrated, the com- and the complex salt in addition to the chemical analysis of each
plex salt will start to precipitate even at high temperature. The item and the percentage of yield are tabulated in Table 3. These
effect of the crystallization temperature on the percentage of salt values were obtained by conducting a complete experimental run
yield is presented in Fig. 15. Each point on the curve represents an using the suggested operating parameters to produce potassium
individual experiment, all experiments were conducted by keeping sulfate as well the complex salt.
the percentage of evaporation around 40 wt % while keeping the
crystallization time fixed at 60 minutes and varying the crystalli-
zation temperature. Four crystallization temperatures were tested;
5, 10, 25 and 30 oC. The results show that if the crystallization
temperature reduces from 30 to 5 oC, then an additional amount of
196 International Journal of Engineering & Technology

65
64
63

Complex Salt Yield [wt %]

62
61
60
59
58
57
56
55
0 5 10 15 20 25 30 35
o
Crystallization Temperature [ C]

Fig. 15: Percentage of the Complex Salt Yield as a Function of Crystallization Temperature; the Crystallization Time was Kept at 60 Min and the Percent-
age of Water Evaporation was 40 %.

Table 2: Chemical Analysis of the Obtained Complex Salt Produced From the Main Mother Liquor after 40 wt % Water Evaporation and Then Crystalli-
zation at 25 OC
Element Description
Color white
State Free flowing
Appearance Crystals
Solubility Fully soluble
NH4+: 21.5 %
NH4Cl (63.8 %)
Cl-: 42.3 %
K+: 15.9 %
K2SO4 (35.3%)
SO4-2: 19.5 %
Moisture 0.8 %

Table 3: Chemical Analysis of the Feed and the Obtained Products as Well as the % Yield. the Operating Parameters were: 60 OC Reaction Temperature,
60 Minutes Reaction Time, 10 OC (K2SO4), and 25 OC (Complex Salt) Crystallization Temperature, 60 Minutes Crystallization Time, and 32% (Main
Solution) and 40% (Mother Liquor) Water Evaporation
Mass (g) Composition (g) Theoretical Mass (g) Yield %
Feed 291
KCl (96% purity) 156 52.4% K+ 78.7 K2SO4 174.25 K2SO4 95.4
47.6% Cl- 71.3 NH4Cl 107 NH4Cl 52.5
Other 6 K+ 93.2
(NH4)2SO4 (98% purity) 135 72.8% SO4-2 96 Cl- 52.1
21.2% N- 28 N- 52.4
6.05% H+ 8 SO4-2 96.8
Other 3 Total solid yield 79.1
Main Product 138
K2SO4 135.8 78
43.2% K+ 59.62
55.2% SO4-2 76.18
NH4Cl 1.05 1.0
0.5% Cl- 0.69
0.2% N- 0.28
0.06% H+ 0.08
Moisture 1.1 0.8% H2O 1.1
Complex Salt 86.3
K2SO4 30.5 17.5
15.9 % K+ 13.7
19.5 % SO4-2 16.8
NH4Cl 55.1 51.5
42.3% Cl- 36.5
16.7% N- 14.4
4.8% H+ 4.2
Moisture 0.7 0.8% H2O 0.7

um sulfate at moderately medium reaction temperature. The chem-

4. Conclusions ical analysis of the obtained K2SO4 crystals shows that the product
has about 52 wt % K2O and less than 0.5 wt % chlorine content.
The addition of an evaporation step before the crystallization step
Potassium sulfate with high purity and clarity is produced by re- will increase the K2SO4 yield from about 64 wt % up to 78 wt %.
acting commercial potassium chloride with commercial ammoni- Large crystals of potassium sulfate have better features and have
 International Journal of Engineering & Technology 197

more satisfying aesthetics for the customers; also the separation of ic Ion Substitution, ACS Sustainable Chem. Eng. 5(10) (2017)
these crystals from the mother liquor and drying will be easier. 9076–9085. https://doi.org/10.1021/acssuschemeng.7b01992.
A potassium sulfate yield of about 78 wt % and a reasonable crys- [16] R. Phinney, Method of producing potassium sulfate, patent,
US6315976 B1, 2001.
tal size can be obtained if the production process is carried out at
[17] Potassium chloride specifications.
the recommended operating conditions obtained from the experi- http://www.arabpotash.com/Pages/viewpage.aspx?pageID=30. Ac-
mental study. A reaction temperature of 60 °C, a reaction time of cessed December 26, 2017.
1 hour, a crystallization temperature of 10 °C, a crystallization [18] L. Wang, Q. Xia*, J. Kang, M.X. Du, G.L. Zhang, and F.B. Zhang,
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[19] S. Sawamura, N. Yoshimoto,Y. Taniguchi, Y. Yamaura, Effects of
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of 40 wt % and a crystallization temperature of 25 oC will yield https://doi.org/10.1080/08957959908200298.
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[22] F. Schuth, Nucleation and Crystallization of Solids from Solutions,
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