(Doi 10.1007 - 978!94!017-1538-6 - 18) Hignett, Travis P. - Fertilizer Manual - Potash Fertilizers

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XVIII Potash Fertilizers

In traduction and phosphorus (the three primary nutrients) are


required in much larger quantities than are the other
elements. In order to attain the maximum effective-
Potash was first mined commercially as carnallite ness, these primary nutrients have to be supplied to
ore in the Stassfurt region of Germany in 1861 soon crops in essentially the same proportions as they exist
after the investigations of Liebig indicated that potas- in most plant life, where the ratio of nitrogen to
sium salts might be used advantageously as a chemical potassium is about 2:1. Thus, among the commercial
fertilizer. Within 2 years, 14 plants had come into fertilizers, about half as much potash is used as ni-
operation. In 1864 the total production was 110,000 trogen, except when the soil is capable of supplying
tons of salts, and this value gradually increased to potash. Thus, the ever-increasing use of nitrogen
about 3 million tons in 1900 and to about 44 million fertilizers necessitates the application of potash in
tons in 1978-79 (calculated as 60% K2 0 product). similarly increasing quantities.

Potassium is the seventh most abundant element The physiological functions of potassium in plants
in the earth's crust. In addition to being an essential include at least the following:
constituent of plant and animal life, it occurs in very
low concentrations in rocks and soils; in the oceans,
lakes, and rivers; and in the saline residues of salt
lakes. The most widespread economic source of potash l. Promotion of carbohydrate metabolism or forma-
is the evaporite deposits--sedimentary deposits formed tion, breakdown, and translocation of starch.
by the evaporation of seawater under very arid con-
ditions ( 1). Commercial deposits, such as those in the 2. Promotion of nitrogen metabolism and the syn-
Elk Poi~Basin in western Canada, required the flow thesis of protein in green plants.
of large amounts of seawater into a lagoon where the 3. Control and regulation of activities of various
dissolved salts precipitated in the inverse order of essential mineral nutrients.
their solubilities, first calcium carbonate, calcium sul-
4. Neutralization of the physiologically important or-
fate, anhydrite, and sodium chloride, followed by the
ganic acids.
highly soluble potassium and magnesium salts when
the seawater reached about 100 times its original 5. Activation of various enzymes.
concentration.
6. Promotion of the growth of young meristems.
The principal potash evaporite minerals of com- 7. Control of stomatal movement and internal water
mercial importance are sylvite, langbeinite, kainite, relationships.
and carnallite. Sylvinite, a mixture of potassium
chloride and sodium chloride crystals, is the easiest
to process and is mined in the largest quantities. It
normally occurs in layers, underlain and overlain with About 95% of all potash mined is used as fertili-
sodium chloride. The sylvinite occurs in more than zers (2). The other 5% is used in various industrial
one stratum. applications. A higher purity (99. 92% KCl) chemical
grade of potash is used by the chlor-alkali industry
AU North American potash mines recover sylvinite. in the electrolysis of KCl-water solutions to form
Two mines in the United States also produce lang- chlorine and potassium hydroxide (KOH), commonly
beinite, which is sold as a source of water-soluble called caustic potash. Caustic potash is used in
magnesium as well as potassium and sulfur. One pro- liquid soaps, textiles, greases, catalysts, engraving,
ducer also reacts langbeinite with potassium chloride alkaline batteries, and rubber fabrication. A substan-
to produce potassium sulfate and the waste product tial amount of caustic potash is further processed to
magnesium chloride. Potassium chloride or sulfate is form potassium carbonate and other potassium com-
also recovered from brine deposits. pounds. More than half of the potassium carbonate
produced annually is used in glass manufacture.
Carnallite (KCl· MgCl 2 • 6H 2 0) is more difficult to Caustic potash is also used in relatively small amounts
process, but it is refined in Europe, Israel, and the to make potassium phosphates for special fertilizers
U.S.S.R. to recover its potassium chloride. such as liquid fertilizers for foliar application. Small
quantities of agricultural grades of muriate of potash
Kainite (KCl· MgS0 4 • 3H 2 0) occurs in several are used with sodium chloride and other chemicals as
European mines, usually in combination with other fluxes in the secondary smelting of aluminum and
potash ores. magnesium. Muriate of potash is included in drill
muds used in oil well drilling.
The purpose of this chapter is to state the im-
portance of potash, to review its mineralogy and prin- Mineralogy of Potash Ores
cipal deposits, to give an overview of the processes
for refining it, to indicate trends in its products, to
report price levels and typical production costs, and Potassium accounts for 2. 35% of the earth's crust,
finally to summarize world potash commerce and where it is mixed mainly with deposits of sodium com-
consumption. pounds. But it is also found in feldspars, muscovite
(white mica), granite, and gneiss. Sedimentary rocks
comprise about 5% of the earth's crust. The sand-
Agronomic and Industrial Significance of Potash stones contain about 1. 1% potassium, shales about
2. 7%, and limestones about 0.27%. Potassium, a mono-
Although some 17 elements are normally required valent alkali metal, does not occur in nature because
to support healthy plant growth, nitrogen, potassium, it is highly reactive and has a strong affinity for

T. P. Hignett (ed.), Fertilizer Manual


© Springer Science+Business Media Dordrecht 1985 225
other elements. It has a melting point of 63. 5°C, a Silicates and other nonsoluble minerals (except
specific heat of 0. 177 cal/mole/°C, and a specific alunite) are not included in the tabulation above.
gravity of 0 . 86. Potash deposits can be classified into three basic types
according to the mineralization of the principal hori-
Potassium mineral deposits are usually the result zons, namely:
of evaporation of water from landlocked seas that have
become separated from the main oceanic body and from 1. Carnallitic mineralization including a carnallite-
which the contained salts have gradually precipitated. kieserite-halite zone, a carnallite-anhydrite-halite
In some cases inland seas have evaporated to form zone, and a carnallite- halite zone.
such deposits. Potassium and other alkali metals were
brought into the oceans and inland lakes by river 2. Sylvinitic mineralization, including a sylvite-
water that leached these materials from rocks and kieserite-halite zone, a sylvite-anhydrite-halite
soils. Sodium is leached more easily from soils zone, and a sylvite-halite zone.
because potassium becomes fixed to clay particles in 3. Kainitic mineralization, containing sulfates, chlo-
soil. rides, and a kainite-langbeinite-picromerite-
glaserite-polyhalite zone.
Salts crystallize in an inverse ratio of their solu-
bilities; the order of deposition usually is calcium
ca,rbonate, magnesium carbonate, calcium sulfate, so- World Potash Reserves
dium chloride, magnesium sulfate, magnesium chloride,
and finally potassium chloride. Other conditions alter
the deposition, and they may account for the various World potash reserves are enormous and sufficient
strata encountered. to meet requirements for many centuries to come. The
U.S. Bureau of Mines in 1978 estimated the reserves
The mother liquor or bittern of seawater after of potash at about 12 billion 1 tons of K2 0 at 1976 do-
the moderately soluble salts have precipitated is rich mestic mine prices, with total resources at 132 billion
in magnesium chlorides and sulfates and smaller tons (3). The fact that potash can be recovered from
amounts of potassium and bromine. seawater means an additional, almost unlimited, but
more costly, resource of this material.
Bittern salts of marine origin include:
Enormous quantities of potash are present in
Sylvite KCl Canada and the U.S.S.R. These two countries to-
gether probably represent more than half the world's
Carnallite KCl·MgCl 2 ·6H 2 0 reserves and about 80% of the world's resources. The
Kieserite MgS0 4 ·H 2 0 remaining known reserves are distributed among the
United States, Europe, the Middle East, Thailand, the
Poly halite 2CaS0 4 • MgS0 4 • K 2 S0 4 • 2H 2 0 Congo, and South America. An estimate of world
Langbeinite K 2 S0 4 • 2MgS0 4 potash reserves and resources is given in table 1
which was taken from a recent U.S. Bureau of Mines
Boracite 5MgO·MgC1 2 ·7Bz03 report (3). A similar estimate has been published by
The World Bank ( 4). A brief description of each
The minerals associated with brines of lake beds deposit follows ( 5, 6).
include other minerals such as those found in Searles
Lake in California. In the U.S. Bureau of Mines classification, "re-
serves" are described as ores that can be recovered
Halite NaCl at or near the current market prices; whereas, "re-
sources" are potentially minable ores which, because
Hank site 9Na 2 S0 4 ·2Na 2 C0 3 · KCl of cost or other constraints, could not necessarily be
Trona Na 2 C0 3 ·NaHC0 3 ·2H 2 0 recovered at current prices but might be at a later
date (3). The World Bank estimates use a similar
Borax Na 2 B 4 0 7 ·10H 2 0 classification. The necessary data for making such
Glaserite 3KzSO• · Nazso. estimates are not always available or may be subject
to different interpretations. Locations of the major
The following potash minerals are found in na- potash deposits are indicated in figure 1.
ture. The most important is sylvite which is usually
found mixed with sodium chloride; the mixture is
called sylvinite. Other ores being used in fertilizer Canada
potash production are carnallite, langbeinite, niter and
kainite. Saskatchewan--The development of the vast
potash deposits in the Devonian Prairie Evaporite
formation in Saskatchewan and adjacent Alberta and
Manitoba has been the most important event in the
Mineral Com1>0sition % KzO potash industry in the last three decades. Three main
potash zones in this evaporite have been defined.
Chlorides Zone 1 (Esterhazy), the lowest, attains a maximum
Sylvite KCl 63.1 thickness of about 21 m and consists of a central syl-
Carnallite KCl·MgC1 2 ·6H 2 0 17.0 vinite region surrounded by carnallite-rich mineraliza-
Kainite KCl·MgS0 4 ·3HzO 18.9 tion. Zone 2, the Belle Plaine member, reaches a
Hanksite KCl·9NazS0 4 ·2NazC03 3.0 maximum thickness of 23 m with a central sylvinite
Sulfates region, but the center carnallite zone is narrower than
Polyhalite K2 S0 4 ·MgS0 4 ·2CaS0 4 ·2H 2 0 15.5 in Zone 1. Zone 3, the Patience Lake member, is over
Langbeinite K2 S0 4 ·2MgS0 4 22.6 24 m thick, and the carnallite mineralization sur-
Leonite K2 S0 4 ·MgS0 4 ·4Hz0 25.5 rounding the sylvinite is narrower still. In general,
Schoenite Kzso.·Mgso.·6HzO 23.3 the grade in all three zones increases toward the
Krugite K2 S0 4 ·MgS0 4 ·4CaS0 4 ·2H 2 0 10.7 south from 20% to 30% K 2 0 and is comparable in all
Glaserite 3K 2 so.·NazS0 4 42.6 three. The depth of the Prairie Evaporite ranges from
Syngenite K2 S0 4 ·CaS04•H 2 0 28.8 660 m along its northern edge to 3,050 m at the inter-
Aphthitalite (K, Nal2S04 29.8a national boundary.
Kalinite K2 S0 4 ·Alz(S04)3·24Hz0 9.9
Alunite Kz•Als(OH)lz•(S04)4 11.4 Seven organizations operate 10 mines in Saskat-
Nitrates chewan with an aggregate annual capacity of 8. 0 mil-
Niter KN03 46.5

a. Assuming equimo1ecu1ar proportions of K and Na. 1. In this manual the term "billion" is equivalent to 1,000 million.

226
TABLE 1. ASSESSMENT OF WORLD POTASH RESOURCES (MILLION TONS OF K20) 8

Other Total
Location Reservesb Resources Resources

North America
Canada 9,000 58,000 67,000
U.S.A. 180 ~ ~

Total 9,180 63,260 72,440

South America
Chile 9
Peru 0 9
Brazil 45 ~

Total 54 243

Europe
France 35 145 180
Germany, Democratic Republic 270 4,260 4,530
Germany, Federal Republic 180 3,080 3,260
Italy 9 27 36
Spain 27 154 181
U.S.S.R. 1,800 43,500 45,300
United Kingdom 45 ~ ~

Total 2,366 51,391 53,757

Asia
Israel and Jordan 218 870 1,088
China, Peoples Republic of 9 9 18
Laos 18 27 45
Thailand --.22 ~ ~

Total 300 9,921 10,221

Africa
Congo 0 180 ~

Total 0 180 180

Oceania
Australia 0 18 18

TOTAL 11,900 125,013 136,913

a. U.S. Bureau of Mines. 1978. "Potash," Mineral Conunodity Profiles MCP-11, (Converted from short to metric
tons).
b. At average 1976 domestic mine price.

lion tons . One of the mines is a solution mine; the United States
others are shaft mines. Total resources may be
74 billion tons of K2 0, of which 18 billion tons may be North Dakota--The Prairie Evaporite formation
economically recoverable--5 billion by conventional underlies 20,700 km 2 of the North Dakota-Montana
mining and 13 billion by solution mining (3, 6). section of the Williston Basin at depths of 2, 000-
4, 000 m. This is an extension of the Canadian de-
Maritime Provinces--The evaporite deposits of ad- posits. The ore beds are thick and high grade, but
jacent parts of Nova Scotia and New Brunswick have the depth would require expensive solution mining.
been known since the beginning of the 20th century; PPG Industries reported in 1976 that tests of the
gypsum and rock salt have been mined for many years. effectiveness of solution mining would be made at
Potash was discovered in the Nova Scotia salt deposits depths of 3,000-3,600 m which is about twice the
in 1919 and again in 1939, but the low grade and un- depth of the Kalium solution mine in Canada. (Kalium
favorable mining conditions discouraged further is a subsidiary of PPG Industries.)
interest. More intensive exploration started in 1965.
Economic reserves have been found in an adjacent area New Mexico--A sedimentary basin of Permian age
of New Brunswick in the Moncton Basin at a depth of covering some 104,000 km 2 in western Texas and
about 600 m. The potash zones range from 3 to 15 m southeastern New Mexico has been outlined by explor-
in thickness, and the average grade is 21%-30% K2 0. atory drilling. The most abundant mineral is poly-
One mine is currently (1979) under construction, and halite, but minable sylvinite occurs in the area around
plans for a second mine and refinery have been an- Carlsbad. At least 60 potash layers have been en-
nounced. The combined capacity of these two projects countered, of which 11 ore zones are significant. The
is expected to be 2 million tpy or more of muriate of productive zones are located 250-610 m below the sur-
potash. A favorable factor is the location within face, dipping gently southeast, and are between 1.5
50 km of the deepwater seaport of St. John. and 3 m thick in the mining area. The ores are syl-
vinite with more than 3% water-insoluble material and
Potash deposits have also been found in New- two mixed ore beds containing sylvite and langbeinite.
foundland, and exploration is expected to continue Reserves are estimated to be about 85 million tons of
there and in Nova Scotia. K20.

227
16

I. CANADA[Sookot.:h•wonl
2. CANAOA\N-II<~,_.;u)
3.USA\NewMuicol
4.U.SA(Utah)
5.U5.A(Cololornoa)
6.6RAZIL[Se•'ii'""J
7.CHILE(A""'f"gcnto)
8.fNGLAND(Cia-lclnd)
9.SPAIN(Catalotuo,No•orro}
10. FIANCE [AIMu[

l
Jl.ITALY(Socolrl
12. GUM.t.NY(Ol.G.!. FRGI
13.uSSJI.[WeotiJ..o.,..)
14.US.S.R [B,.Ioru.. og)
15.u.s.s.R.\Uralo]
16.uss.R (SiH<~a)
17. JOli),I,N&I51AEl\Deo4S.o)
18. CONGO (Poonta NoN-•)
\9.£THIO,IA(0...,.kil)
20. CHINA (lob (h.,..t..loo)
21. THAILANO[Khoret Ple-j
22. AUSUALIA (Lok. Me L...4)

Source: The World Bank.

Figure 1. World Major Potash Deposits.

Seven mines are in operation in New Mexico. trucked to a flotation plant. Standard potash and
Five recover only sylvite, one recovers only lang- compacted granular muriate of potash are produced.
beinite, and one recovers both. The average grade
of the ore is about 16% K2 0.
California--Searles Lake covers an area of about
Utah--The Cane Creek potash deposits near Moab 104 km 2 and is a remnant of a much larger fresh
in southeast Utah lie at depths of around 1, 200 m. water lake. Today, it is a mud and sand flat within
The sylvinite horizon which is exploited is 3-4 m which are two superimposed crystal bodies of mixed
thick, and it contains 25%-30% K2 0. The formation is salts permeated with concentrated br:L.>es. The upper
highly faulted and folded. It is estimated that reserves layer from which the potash is obtained averages 20 m
of 200 million tons of potash-bearing salts are present thick and has a total area of 31 km 2 • The upper
in a 31 km 2 area. brine contains about B% K2 0. Muriate and sulfate of
potash are produced together with nonferti!izer
One mine is in operation in the area. It was products.
originally a shaft mine, but because of difficulties
caused by faulting, it was converted to a solution
mine in 1972. Water pumped into the mine becomes Central America
saturated in 300-350 days and attains a temperature
of 32°-33°C after which it is pumped into a series Mexico--Potassium minerals have been reported in
of evaporation ponds. A sodium and potassium the Isthmus of Tehuantepec and the Yucatan Peninsula.
chloride mixture is slurried from the ponds to the Carnallite is the most prevalent, but sylvinite is also
original refinery for recovery of potassium chloride. present. These deposits are not yet being mined, but
exploration indicates that they may be economically
The Great Salt Lake in Utah covers a variable promising.
area between 2,600 and 5,200 km 2 . It is a remnant
of ancient Lake Bonneville. The Bonneville Salt Flats
in western Utah are another remnant of Lake Bonne- South America
ville. They are a desert deposit of salt or mud flats
impregnated with a saturated or nearly saturated Brazil--The potash deposits of northeast Brazil
brine. A 1-m top layer of hard-packed salt is are estimated to contain 500 million tons of sylvinite
underlain by a layer of fissured clay beneath which and 6 billion tons of carnallite at depths in excess of
lies the brine. The brines which contain about 2.4% 550 m. Although plans have been announced for re-
K2 0 are pumped to evaporation ponds. covery of these deposits, near-term commercialization
is hampered because of difficult access and its loca-
Two plants are in operation in this area. In one tion.
plant brine from the northern part of the Great Salt
Lake is carried by canal to 7,000 ha of evaporation Peru--Brine deposits have been located in the
ponds. Sodium chloride, sodium sulfate, and a western half of the Sechura Desert Region of northern
mixture of kainite, carnallite, and schoenite are Peru. It is estimated that 30 billion tons of brines
successively crystallized. Schoenite is crystallized in circulate in the desert sediments and that they contain
settling tanks and converted to potassium sulfate. 17 million tons of KCl and 146 million tons of MgC1 2 .
No plans for exploitation are currently under consid-
In another operation brines in the Bonneville eration.
Salt Flats are recovered from a 35,000-ha area in
about 145 km of ditches from which they are pumped Chile--The nitrate deposits of Chile are located
into 3,000 ha of evaporation ponds. Following a short on the plateau lying between the coastal range and
(about 3 months) evaporation season, sylvinite is the Andes, principally in the Atacama Desert in

228
northern Chile. The deposits which vary in thickness are found in three separate basins. The Mulhouse
from a few centimeters to several meters are patchy, Basin is a source of the present production where the
poorly stratified layers of red-brown gravel cemented beds are 400-1,100 m below the surface. The upper
together with sodium nitrate and other soluble salts. zone contains 20%-25% K2 0 as sylvite 1-3 m thick, and
Potassium salts·, mainly nitrate, are recovered as a the lower bed is 2-5 m thick with 15%-20% K2 0 as
byproduct from sodium nitrate production. The com- sylvite. Total resources for the French deposits are
position and processing of the Chilean ore are de- estimated at about 300 million tons. The potash de-
scribed in more detail under the heading "Sodium posits also extend across the French border into the
Nitrate" in chapter VIII. Buggingen district of Germany, but mining has now
ceased in this area.
Africa Federal Republic of Germany--In West Germany,
the Kali und Salz mines the Zechstein deposits in the
Congo--During the course of exploratory work in southern Werra district and the north German plain
the Congo Basin between Pointe Noire and Brazzaville, near Hannover. Kali-Chemie has a mine nearby at
an area of approximately 4.1 km 2 of salt and potash Friedrichshall where it mines hartsalz (a rock com-
deposits was outlined in 10 evaporite cycles. Carnal- posed of sylvite, halite, anhydrite, and/or kieserite)
lite beds are regular and extensive with a cumulative at about 900 m depth. Muriate of potash and a 12%
thickness of up to 90 m. The zones are located a- K2 0 product, magnesia- kainite, are produced at
round Holie-St. Paul where sylvinite occurs in three Friedrichshall. All the mines of the Hannover region
beds at relatively shallow depths (90-120 m) with K2 0 exploit the highly concentrated potash beds of salt
contents at a range of 20%-35%. There are two beds domes in the Permian Zechstein evaporites.
containing sylvinite averaging about 20%-21% K2 0.
Large-scale mining operations were started in 1969, No further changes are anticipated in the potash
but floodin.g of the mine has terminated production. production capacity of this country in the next few
There are no known plans to resume it. years.

Ethiopia--The evaporite deposits of the Danakil Democratic Republic of Germany--VEB Kombinat-


Depression contain substantial reserves of potash as kali operates mines in four groups;
sylvinite, carnallite, and kainite. In the area south
of Dallal, the potash horizon has been found at 730 m. Kalibetrieb Werra
The prospected potash bed is 3-15 m thick and con- Kalibetrieb Zielitz
sists of sylvinite grading downward into carnallite, Kalibetrieb Sud-Harz
kieserite, poly halite, and kainite. The deposit has Kali und Steinsalzbetrieb Saale
not yet been exploited although several feasibility
studies have been carried out in the last few years. Various ores are mined to produce muriate and sulfate
of potash as well as kieserite and minor amounts of
Morocco--The potash reserves in the Khemisset miscellaneous products. The total annual production
Basin extend over an area of more than 31 km 2 . The is now slightly over 3 million tons of K2 0. In the
principal ore is carnallite which occurs in two beds early 1980s with the Zielitz mine operating at full
1-10 m thick. There are also low-grade sylvinite capacity plus other minor expansions, the East German
deposits. No exploitation has yet taken place. potash industry should have a capacity of nearly
4 million tons of K 2 0 ( 7).

Middle East England--All four Zechstein evaporite cycles have


been found in the coastal areas between Durham and
Israel and Jordan--The Dead Sea lies between Scarborough and have been correlated with the German
Israel and Jordan and now covers an area of about deposits. The evaporite beds thicken from the north-
700 km 2 to a maximum depth of 400 m. It is fed by west and south to a central area around Whitby and
the Jordan River and natural springs, but it has no Scarborough where the lower, middle, and upper
outlet. The potassium resources of the Dead Sea are evaporites occur. In the Whitby area sylvinite de-
being exploited by Israel, and plans call for exploita- posits occur at depths of 1, 000-1,200 m and at
tion by Jordan also. 1, 500 m. One mine is in operation at a depth of
1, 160 m where the ore grade is 27% K2 0. The opera-
Solar evaporation is utilized to crystallize halite, tion has been hampered by a badly faulted seam, but
followed by carnallite. The latter salt is harvested production is gradually incr;easing.
and converted to muriate of potash. Bromine is also
recovered as a byproduct. The Dead Sea is estimated Denmark--Potash-bearing evaporite beds have
to contain over 1 billion tons of K2 0 of which about been found to be up to 0. 46 m thick in North Jutland
20% may be economically recoverable (3). at depths of 800-1,300 m.

Pakistan--Pakistan possesses potential for potas- Poland--The eastern extension of the Zechstein
sium reserves, both in bedded salts and brine. The formation from Germany contains bedded potassium
salt bed occurrences thus far reported are sporadic deposits in the vicinity of Klodawa. The known
zones of sylvite and langbeinite in salt mines. The deposits contain low-grade (8% K2 0) carnallite ores
area of potash -rich beds is believed to include the that are 500-1,600 m in depth.
greater part of the Salt Range and the Potwar and
Indus Plains. The brine occurrences were discovered Spain--In Spain there are up to four potash beds
in the Punjab province during oil-drilling operations. which contain carnallite and sylvinite ore within the
The brine is hot and under great pressure and is range of 15%-29% K2 0 in the area between Barcelona
saturated with carnallite. It contains about 7% KCl, and Pamplona. These mines are operated at depths
17% MgCl2 , 3% CaCl 2 , 2% NaCl, and fractional percen- of 300-500 m. Further west, the deposits are mined
tages of boron and bromine compounds. Utilization in an area south of Pamplona. These beds ·also con-
of the brine to recover KCl and other soluble products sist of carnallite and sylvinite, but they are less
has been proposed, but no definite plans have been faulted than those in the Catalonian field. Two
made. potash beds occur in the Navarre district at depths
of 130-650 m. The upper seam contains principally
carnallite with an average grade of 14% K 2 0. The
grade of the sylvinite bed is 18%-20% K 2 0. Four
mines are in operation in Spain.
France--The Alsace potash occurrences lie in a
faulted depression of about 210 km 2 between the Rhine Italy--Potash deposits in Italy are found only in
River and the Vosges mountains. Two sylvinite beds Sicily. It is one of the few areas of the world where

229
kainite is the principal ore mineral although some syl- of potassium chloride and sodium chloride. The shaft-
vite and carnallite occur in the ore mined. The four room -and-pillar method of mining is generally prac-
mines in operation produce potassium sulfate and ticed. Long-wall mining is used in limited instances.
potassium-magnesium sulfate. Solution mining technology is well developed and is
practical on a limited scale; the cost of energy re-
quired is the main deterrent. Shaft mining is generally
U.S.S.R. practiced when the ore body is less than 1, 300 m from
the surface. At greater depths solution mining is
In the U.S.S.R. potash is produced in three necessary. Potash is also recovered in much lesser
main regions: the north Urals, southern Byelorussia, (juan tities from brines, such as those in the Great Salt
and the western Ukraine. Sylvinite occurs in the Lake and the Dead Sea.
first two of these regions, while both sylvinite and
kainite are mined in the Ukraine. Muriate of potash
is the principal product. Actual production in the Shaft Mining
U.S.S.R. in 1975 was 8. 7 million tons of K 2 0 from the
following sources: Shaft excavation and construction are generally
conven tiona! and costly. In Canada the Blairmore zone
Byelorussia 3.8 of high water pressure and unstable formations neces-
Urals 4.3 sitated freezing the material to be removed before the
Ukraine 0.6 shaft could be excavated and tubbed. Similar diffi-
culties were experienced in Yorkshire.
These three major projects will probably increase
the Russian potash production significantly during the The success of underground room-and-pillar
next 10-15 years. mmmg is dependent on the character of the ore body;
thick, flat beds are preferred. A thin sylvinite or
The deposits near Stebnik and Kalush in the west other potash-bearing ore zone necessitates mining
Ukraine contain hartsalz, sylvinite, kainite, and lang- sodium chloride above and/or below the sylvinite, and
beinite. These deposits are inclined, and mining in this dilutes the ore grade. Equally difficult and ex-
steeply dipping beds is common. pensive is a badly faulted mine, which also results in
the excavation of an undue amount of debris in order
Additional potash deposits are present in east to operate mobile equipment or to install conveyor
and south Russia. In Siberia, comparatively deep- belts.
bedded deposits are known at Irkutsk, Krasnoyarsk,
and Yakutsk. Widespread mineralization exists north The proportion of ore removed (rooms) during
and east of the Caspian Sea, and several beds of the initial mining depends upon mine depth, roof con-
potassium minerals have been found in salt deposits dition, and other factors. Primary mining often re-
in Turkmenistan. Total resources are estimated at moves in the range of 40%-50% of the ore. Secondary
45 billion tons of K 2 0, of which about 1. 8 billion tons mining can increase the removal to the 80%-90% range.
is currently classified as reserves ill-
Ammonium nitrate and oil mixtures have virtually
displaced dynamite as the blasting agent because they
Asia result in a substantial cost saving. Improved drill
patterns increase the yield per charge and thereby
China--Potash has been recovered from salt lakes further reduce cost. More recent installations use
in China for several years, and production from continuous mining machines having the capability of
underground mines began in the early 1960s. Potash up to 5 tons of ore per minute.
is also recovered from underground brine seams and
from sea salt operations. Over 3, 000 salt lakes are Mechanical loaders gather the fragmented ore,
found in northwest China in Tsinghai Province. Lake whether dislodged by blasting or by continuous
Cha-erh-han is one of the lakes from which potash is miners. Conveying from the mine face to the hoist
recovered. The brines which occur in Szechuan Pro- shaft has traditionally been by railcars. Belt haulage
vince have been processed for many years to recover is rapidly replacing rails, thus reducing labor and
potash. other costs, especially as the distances increase from
mine face to hoist shaft. Mine maintenance and other
There are deposits of potash in west central underground services are usually rendered from facil-
China containing 10%-20% K 2 0. These are currently ities located underground. Working conditions, in-
being exploited. cluding temperature, freedom from harmful dust,
utility services, and mechanization, are nearly ideal
Thailand--A potash deposit has been discovered in most potash mines.
in northwest Thailand extending into Laos. This de-
posit is essentially carnallite which lies at depths be- Ore storage and facilities for primary crushing
tween 80 and 400 m. Sylvite is also present in some to a maximum of about 15 ern are located at the hoist
areas. Only a small area of the potential deposits has shaft. The crushed ore is automatically loaded into
yet been explored, but it is believed that the deposits skips for hoisting to the surface.
may be extensive. The deposit has been estimated to
contain 10 billion tons of K2 0, of which 60 million has
been classified as reserves (3).
Solution Mining
Australia--Several extensive evaporite basins have This method of mining involves the application of
been found in Australia. Lake McLeod in western phase chemistry as well as large amounts of increas-
Australia contains about 6. 5 billion tons of rock salt
ingly expensive energy. Techniques include investi-
below the dry surface of the lake. Underground gations of the salt solution, brine flow, selective
water dissolves the salt and produces a saturated extraction of KCl from .sylvinite, and control of cavity
brine which contains 3% K 2 0. Langbeinite was re-
geometry. Advantages are reportedly that the method
covered from the brines in a plant that was recently (1) avoids the construction of shafts which are also
destroyed by a typhoon. There are no known plans costly and ( 2) permits the mining of land or marine
to rebuild it. deposits without regard to overburden and at depths
not feasible by shaft mining. With solution mining the
preferred approach is to employ rnultiwells circulating
the solvent between the wells. Most of the solution can
take place from the cavern roof. Achieving a high
Potash is very largely extracted from under- level of dissolved potassium chloride per unit of sol-
ground deposits of sylvinite, primarily mixed crystals vent is the key to efficiency. One technique to assist

230
in controlling contact of the brine with the potash ore 7. Harvesting the flotation concentrate from the top
is to inject diesel fuel to blanket the brine. Drilling of the rougher cells. The concentrate contains
costs for identifying the ore zone as well as for pro- some sodium chloride as well as a high percentage
duction holes are high; yet, solution mining is an es- of the sylvite in the raw ore. For that reason it
tablished technology. is introduced into a "cleaner" flotation circuit
which further refines the sylvite. The unfloated
A hole is drilled to a level near the upper level particles from the cleaner circuit can be and
of the potash strata and is then cased down to this usually are recycled to the rougher cells.
level. A pipe is placed in the casing to a level below
the lower level of the potash strata. An aqueous 8. Drying the sylvite either in a rotary dryer or in
medium is pumped between casing and pipe to the a fluid bed dryer.
potash bed where a cavity is established. When the 9. Screening the dried sylvite according to the sizes
cavities of two adjoining cased holes meet, water un- chosen to be marketed.
saturated with regard to potassium chloride and sodium
chloride is added through one cased hole, and the 10. Compacting the off size material from the screen-
saturated solution is withdrawn through the other. ing operation. Screened-out fines are processed
The concentration of the solution can be partially con- through a compactor which produces "flakes" of
trolled by the rate of pumping which determines the potash. These flakes are crushed to the desired
retention time in the cavity, which can be very size, and the fines and oversize are recycled to
lengthy. the process.

Both flotation and compaction involve the applica-


Brine Recovery tion of considerable chemistry and mechanics. There
is, however, substantial art to achieving high recov-
The recovery of potash from natural brines is eries, good production rates, and stable particles in
practiced in a few locations, most notably the Dead each chosen size range of products.
Sea where the net evaporation rate is exceptionally
high. At both the Dead Sea and the Great Salt Lake, Beneficiation of sylvinite ores by flotation
brine is taken from that part of the lake where reten- (figures 2 and 3) necessitates conditioning the ores
tion has been longest and, thus, the brine concentra- with selective collectors and depressing agents before
tion is the highest. Brines can be accumulated from they enter the flotation cells. Amines are used to
certain "dry" lakes by ditching and accumulating make potassium chloride more hydrophobic; a blinder
brines that move laterally through the soil to the is used to depress slime flotation; and an alcohol
ditches from which the brine can be pumped to solar serves as a frothing agent.
evaporation ponds.
A clay and slimes impurities range of 3. 5%-4. O%
requires more extensive mechanical de sliming. Above
this recoveries decrease, and this necessitates more
Beneficiating - Refining equipment to recover slime-entrained sylvite.

Beneficiation of Sylvinite Ores Flotation techniques for removing insoluble slimes


from potash ore can become complex. One arrange-
There are three principal methods of beneficiating ment is four flotation stages for insoluble flotation and
sylvinite ores: flotation, heavy-media separation, and one cell for potash rougher and cleaner flotation. Re-
solution-crystallization (8). agents for insoluble slime flotation can include
Superfloe 127-Aero 870 at a rate of about 68 g of each
Froth Flotation--This method of refining is the reagent per ton of ore. Armeen TD at about 100 g
most widely practiced and the most economical method and Barrett's oil 634 at about 45 g/ton can be used in
of recovering sylvite (KCl) from sylvinite, a mixture potash rougher flotation while about 20 g each of
of potassium chloride and sodium chloride crystals with Armeen TD and Barrett's oil 634 can be used in potash
some attendant clay and clay slimes. Flotation, as the cleaner flotation. High insolubles removal is encour-
name suggests, is a method of floating off either the aged by recycling potash cleaner tails back to insolu-
potassium chloride or the sodium chloride on a froth. ble flotation.
Flotation of the potassium chloride is the preferred
commercial method. Slimes have been removed from low-grade ores
containing 5% water insolubles using nonionic or cat-
The steps in flotation of sylvite from sylvinite ionic polyacrylamide flocculants and cationic, anionic,
after the ore is hoisted include the following: and/or nonionic collectors. Subsequent potash flota-
tion recovers a high percentage of the potash.
1. Crushing and classifying.
2. Adding a saturated brine of NaCl and KCl to Heavy Media Beneficiation--This modification of
produce a pulp containing 50%-75% solids. the. beneficiation technique is especially useful in pre-
serving large potassium chloride crystals which may
3. Wet grinding the ore to a size that liberates the be classified without further processing to products
sylvite from the sodium chloride crystals. This for use in blended mixed fertilizers or for direct
size varies according to the size of the crystals. application (8). The process utilizes the difference
4. Adding the chosen sylvite conditioning agents in specific gravity of sylvite (KCI) and halite (NaCI).
usually including an amine to make the potassium Halite is the more dense (specific gravity 2.13 versus
chloride more hydrophobic. A blinder is also 1. 98 for sylvite); therefore, in a liquid of intermediate
added to depress slime flotation and an alcohol to specific gravity, halite will sink and sylvite will float.
act as a frothing agent. U.S. patent No. 3,638,791 to International Minerals
and Chemical Corp. describes this technique as "Ore
5. Diluting with brine to 20%-25% solids. beneficiation by treatment with a heavy media, e.g. ,
6. Introducing the sylvite-containing brine into a an aqueous liquor and a very finely divided weighting
series of rougher flotation cells, providing agita- agent, typically magnetite or ferrosilicon of minus
tion and introducing air which adheres in the 200-mesh. The efficiency of the magnetite separation
form of bubbles to the sylvite particles and operation is restored by treating the rinse liquor in a
causes them to float to the surface. The sylvite second hydrocyclone. The density of the rinse liquors
float is raked off mechanically from the top of is much less than the density of the ore constituents,
the flotation cells. This flotation process in the and the ore constituents in the wash liquor report to
rougher cells is repeated usually through five the hydrocyclone underflow while the overflow com-'
cells. prises a suspension of the finely divided weighting

231
SLIMES

r:='~
AIR
CLASSIFIERS

OOMPACTION
PLANT
BRINE
STORAGE

GRANULAR
CLASSIFYING BULK

TAILS POND
~~ld~~.£~g:Q~
TO MARKET

CONDITIONING

Source: Amax Chemical Corporation.

Figure 2. Simplified Flowsheet of Potash Refining System Using Flotation.

SYLVINITE agent in the liquor. This liquor is suitable for sep-


ORE FROM STORAGE aration in the magnetic separator at high efficiency.
The underflow is treated to separate ore impurities
from the weighting suspension. This may be accom-
plished by means of a fine screen."

Solution-Crystallization--Dissolution of the ore


with recovery of KCl by crystallization is necessarily
used in solution mining. lt is also used to some
extent for beneficiating shaft-mined ore. Its advan-
tages are that it can utilize ores with a high percent-
age of insoluble materials such as clay, and it
produces a high-grade (62%-63% K2 0) product tf,at is
fully soluble and hence suitable for use in liquid fer-
tilizers. The beneficiation process is based on the
solubilities of NaCl and KCl in hot and cold water
which are:

Solubility, g/100 ml of Water


at 20°C at 100°C

KCl 34.7 56.7


NaCl 35.4 39.1

The data shown above are the separate solubili-


ties of KCl and NaCl. For solutions containing both
salts, the solubility of NaCl decreases slightly as the
temperature increases. Thus, when a brine that is
saturated with both NaCl and KCl at 20°C is heated to
100°C, it is capable of dissolving substantial amounts
of KCl but no NaCl.
MURIATE OF POTASH
TO PRODUCT STORAGE
Figure 4 shows a typical flow diagram of a solu-
tion-crystallization process. Sylvinite ore is crushed
Figure 3. Diagram of Flotation Process for Recovery of Muriate of Potash. to minus 3-mesh and washed with a cool, saturated

232
ORE disadvantage of carnallite ores is their low grade;
even pure carnallite (KCl· MgC1 2 ·6H 2 0) contains only
17% K 2 0. A second disadvantage is that dissolution
and recrystallization methods must be used which are
energy intensive, A third disadvantage is the large
volume of byproduct magnesium chloride solution which
is likely to pose a difficult disposal problem. The
magnesium chloride can be hydrolyzed to magnesium
oxide at elevated temperatures.

Magnesium oxide is useful as a material for manufac-


ture of refractories and other purposes, but disposal
of HCl is another problem.

In spite of its disadvantages, ores or brines con-


taining carnallite are processed to recover KCl in sev-
eral countries including Spain, Israel, and East and
West Germany and may be utilized in the future in
developing countries such as Brazil, Thailand, Congo,
Jordan, and Pakistan.

Processing methods vary widely and depend on


what accessory minerals are associated with the car-
naliite. Halite (NaCl) is a common accessory mineral,
and there are various other combinations as mentioned
in the preceding description of world potash deposits.
Because of the wide variety of carnallite-containing
ores, no attempt will be made to describe any specific
beneficiation process in detail. A recent article sum-
marizes methods for treating carnaliite ores (9).

There are two general types of processes: cold


leach and hot leach. Cold leach processes are carried
out at 20°-25°C. Carnallite ore, which usually con-
tains some NaCl, is leached with water or dilute brine
which dissolves MgC1 2 preferentially. Actually, KCl
Source: U.S. Bureau of Mines.
dissolves and reprecipitates as the MgC1 2 content of
the solution increases. The rates of dissolution and
recrystallization affect the size of the crystals; rela-
Figure 4. Diagram of Solution-Crystallization Process for Recovery of tively coarse crystals which may be separated from
Muriate of Potash. the MgC1 2 solution by centrifuging are preferred. If
the ore contains insoluble material such as clay, it
remains in suspension in the solution. The mixture
NaCl-KCl solution. Most of the ~lay is carried off in of NaCl and KCl crystals may be separated by either
the solution to a desliming step where the clay is dis- of two previously described methods that are used for
carded as tailing. The clarified solu lion is then refining sylvinite--by flotation or by a hot leach which
heated and used to dissolve the KCl from the washed dissolves the KCl preferentially. The MgC1 2 solution
ore. As mentioned earlier, NaCl is not soluble in the is clarified and then evaporated to a high concentra-
hot brine, and the undissolved NaCl is discarded as tion to recover potash by crystallizing carnallite which
tailing. The brine is then cooled, crystallizing KCl is recycled. The MgC1 2 solution can then be dis-
which is separated from the brine, washed, and dried. carded or utilized.
The remaining brine is recycled. When a high-purity
product for chemical use is desired, the crystalline Alternatively, carnallite ores may be treated by
KCl is redissolved and recrystallized to provide a a hot leach at about 100°C which dissolves both MgC1 2
double-refined product containing more than 99.9% and KCl and also any NaCl that may be present. The
KCJ. hot solution is clarified to remove solid impurities and
then cooled and evaporated; after the KCl and NaCl
Electrostatic Beneficiation--This method of bene- crystab are recovered, one of the above-described
ficiating potash utilizes mutual triboelectric charg-ing sepa,ration techniques is employed. Part of the
of the salt components. This can be done by heating mother liquor, which has a high MgC1 2 content, is
the material to 300°-700°C, followed by cooling to diluted, heated, and returned to the hot leach step.
100°-200°C, or by treatment with specific conditioning The remaining mother liquor is evaporated further to
agents. These agents selectively alter the electrical recover the remaining KCl as carnallite and then
properties of the individual minerals to separate one discarded.
or more components from a salt mixture. Preferred
agents are aliphatic and aromatic monocarboxylic acids, The Dead Sea brine typically contains 11 . 5 g/liter
ammonium salts, or aliphatic monocarboxylic acids. of KCl. The concentration of the other salts in
The raw material is ground, conditioned, and treated grams/liter is MgCl 2 , 130; NaCl, 87; CaC1 2 , 37; and
in a heating apparatus with air of a specific moisture MgBr 2 , 5. At the Dead Sea Works in Israel, brine
content and simultaneously triboelectrically charged by from the sea is first fed into large shallow ponds cov-
friction. A charged residue and a preconcentrate are ering about 155 km 2 where the brine is concentrated
obtained in the preseparator. by solar evaporation until about 90% of the NaCl crys-
tallizes. The brine is then transferred to a second
series of evaporation ponds where the carnallite crys-
Beneficiation of Carnallite Ores and Brines tallizes and is recovered by dredging. The brine is
then pumped as a slurry to the refinery. The car-
Carnallite ore is the source of a small percentage nallite slurry is treated by a cold leach process similar
of the world's potash supply even though there are to that described above to separate KCl and NaCl from
large deposits of such ores in many regions. One the brine. Both flotation and hot leach processes are

233
used to separate NaCl from KCl. The KCl is dried 79.3 tons of potassium-magnesium sulfate is re-
and marketed in several grades differing mainly in quired for 100% conversion
particle size; all grades contain 60%-61% KCl. The
99.1 tons of potassium-magnesium sulfate is re-
grades are granular (compacted), coarse (crystalline),
11 standard' rr "fine' It and 11 highly soluble. I!
quired for 80% conversion

The firm also markets table salt, industrial salt Alunite--Alunite [K 2 ·Al 6 (0H) 12 • (S0 4 ) 4 ] is a po-
(NaCJ), and bromine compounds. Part of the brine tential source of potassium sulfate, alumina, and sulfur
remaining which contains MgCl 2 and CaCl 2 is used to dioxide byproduct. The economics of its production
produce HCl for phosphoric acid production and re- hinges on the value of the alumina. Technology has
fractory grade MgO, and part of it is returned to the been developed in the U.S.S.R. (10, 11). A major
Dead Sea. operation utilizing a large alunite deposit in south-
western Utah has been intensively investigated tech-
nically and economically without reaching any satisfac-
Beneficiation and Utilization of Sulfate Ores tory solution to date, mainly because of the lower cost
of alumina from Australia.
Langbeinite--Langbeinite (K 2 S0 4 ·2MgS0 4 ) is
separated from sylvite and halite by selective washing, It was proposed that the alunite ore would be
froth flotation, or heavy media. The langbeinite may mined in an open pit operation. The ore, after it has
be marketed as such as a source of K, Mg, and S, or been stockpiled, would be crushed to minus 2-mm size
it may be converted to other products. Potassium sul- before drying and further grinding of the ore that is
fate is produced by reacting one molecule of langbein- coarser than 14-mesh. This would be roasted to con-
ite with four molecules of muriate of potash (figure 5). vert the potassium to a salt soluble in water or dilute
alkali. Leaching would follow to recover potassium
sulfate solution. Washed, filtered solids would be
transferred to a Bayer-type plant for alumina
LANGBEINITE FINES MURIATE FINES recovery.

In a Bayer alumina plant, the filtered solids are


digested with caustic soda to dissolve alumina. Alu-
mina is precipitated as aluminum hydrate followed by
calcining. To recover sulfuric acid from the sulfur
dioxide stream, a double absorption acid plant is in-
stalled. The sulfuric acid can be used in the manu-
facture of the concentrated phosphates or other prod-
ucts using massive quantities of sulfuric acid.

Production of 1 million tpy of alumina (Al 2 0 3 )


would require about 10 million tons of alunite ore and
would yield about 500,000 tons of potassium sulfate
and nearly 800,000 tpy of sulfuric acid. The magni-
tude of the coproducts tends to limit the potential for
the production of alumina from alunite.

Complex Sulfate Ores--Complex mixtures of potash


ores have been successfully beneficiated in Russia
(10, ll). These ores may contain any or all of the
following minerals: anhydrite, epsomite, halite, kai-
nite, kieserite, langbeinite, poly halite, and sylvite,
along with clay. Extraction of potassium salts from
such ores becomes quite complicated because the
Note: LomiJbeinite and muriate fines are
concentrate products from the mineralogical forms of the various components are
Jon9beinite leach and sylvite flo- unstable, and the chemical composition of the group
totron circuits.
as a whole varies considerably. The process used to
extract the ore depends upon the various proportions
Source: U.S. Bureau of Mines. of the different minerals present. For example,
whenever potassium sulfate is the desired product,
free sylvite and kainite must be present in the same
Figure 5. Diagram of Process for Production of Potassium Sulfate from molecular proportions or the potassium chloride must
Langbeinite and Muriate of Potash. be added if there is an excess of kainite. Ideally,
the reaction is:

Potassium magnesium sulfate is produced by refining


langbeinite. The reaction to produce potassium sul-
fate from langbeinite is: When the ore is deficient in sylvite, schoenite is
produced.
(1) K2 S0 4 ·2MgS0 4 + 4 KCl 3K 2 S0 4 + ZMgCl2'~
langbeinite mur. of potassium magnesium 2KCl·MgS0 4 ·3H 2 0 K 2 S0 4 ·MgS0 4 ·6H 2 0 + MgCl 2
potash sulfate chloride (kainite) (schoenite)

(2) 2(K 2 S0 4 ·2MgS0 4 ) + 2KCl 3(K 2S0 4 ·MgS0 4 ) + MgCl 2 (In both equations above the interaction of the solvent
langbeinite mur. of potas. magnesium mag. has been omitted.) Thus, the product varies between
potash sulfate chloride potassium sulfate and schoenite according to the com-
position of the ore.
*Discarded.
A new method for extracting potassium compounds
from Carpathian ores that contain several minerals is
For each 100 tons of potassium sulfate being extensively tested on an industrial scale at
Kalush. A flowsheet of the process is shown in
56.7 tons of muriate of potash is required for figure 6. In this process natural ore containing about
100% conversion 9% potassium is ground and leached in two steps, with
70.9 tons of muriate of potash is required for a hot "synthetic kainite" solution (described later) in
80% conversion dissolving tanks. The leach dissolves epsomite, kai-

234
n y-
,...._---, r - - ~~~~~~~~RES: KAINITE, SYLVITE, EPSOMITE,
~~xi~ ~~~~F DIS SOLUTION f-s:;.;o:;.;o:;.;I;.;U;.;M;;;;_SA:;.;L..;T;.;s......;AN..;D......;c,;.L;;.A~Y;.;..:......;.:..:..:...;:..:........;.:..:...,.j DORR
PRELIMINARY----.---+!
REDUCTION
CHAMBER IKCI, MgCI 2 ,K 2 S04 , MgS0 4 ,No 2 S0 4 1

CLAY
SED lMENT
SETTLER
,.
INSOLUBLE ORES:
WATER AND MINERALS
RECOVERED FROM
SEDIMENT i
LANGBEIN IT£ COUNTER- WASHED CLAY

I
POLYHALITE CURRENT TO DISCHARGE
SATURATED
HA L1 T E WASHER Mg504 , K2S0 4

WA1ER

SYNTHETIC
KAINITE
SCHOE NITE LIQUOR
VACUUM I-
CRYSTALLIZATION

SLURRY OF SCHOE NITE


PURGE
(K2S04, Mg504 , 6 H 2 0)

,._,;.......;;__:.___-ILI EVAPORATION
KCI,MgCI2 SLURRY

SCHOENITE

1------.tCENTRIFUGE-

WATER

I SODIUM
SULFATE AND
I
SCHOENITE
POTASSIUM
SULFATE
MAGNESIUM LIQUOR END PRODUCT END PRODUCT
IEND PRODUCTS I

Source: Phosphorus and Potassium, 59, 1972.

Figure 6. Flowsheet for the Processing of Carpathian Polymineral Ores.

nite, and sylvite as well as any other readily soluble The potassium sulfate is removed as an end
mineral, but langbeinite, halite, and poly halite are product by centrifugation, and the hot liquor is re-
practically insoluble in this liquor. If the ore con- cycled to the settling tanks.
tains significant quantities of langbeinite and polyha-
lite, then the residue from the leaching process should
be treated to recover them. The ore as mined nor- The thickened slime from the settling tanks con-
mally contains about 15% clay which remains suspended tains salty clay which is washed with a countercurrent
in the hot leach liquor until it is clarified in Dorr flow of water in a washer to minimize losses of potas-
settling tanks. As the liquor begins to cool, potas- sium. This washing liquor along with the filtrate from
sium salts begin to crystallize out. Normally, potas- the schoenite filtration is sent to the dissolving tanks
sium chloride and sodium chloride would precipitate to act as a solvent for the original ore.
first, but since the desired product is schoenite, the
precipitation of these chlorides is inhibited by the During the conversion of kainite to schoenite
addition of a solution that is saturated with magnesium (second equation above), magnesium chloride is also
and potassium sulfate. (This solution is obtained from formed. If the concentration of this magnesium chlo-
the later decomposition of part of the schoenite to ride were allowed to increase indefinitely, the process
form relatively pure potassium sulfate.) This, in would not function properly. To circumvent this
effect, leaves a solution that is saturated with respect problem, a part of the schoenite filtrate is withdrawn
to schoenite but unsaturated with respect to the and sent to an evaporator where enough of both sodi-
chlorides. Under these circumstances, only schoenite um and potassium are removed to maintain a constant
will precipitate. concentration of these materials in the system. The
remaining slurry is recycled to the dissolving tanks
as "synthetic kainite." The concentrated magnesium
chloride liquor is used to make products that require
The clarified liquor, plus the added sulfate solu- magnesium.
tion, is cooled in a vacuum crystallizer to 20°C. The
schoenite so formed is thickened and filtered. Part This process permits the use of Carpathian ores
of the filtered schoenite is mixed with water to pro- to produce several commercially valuable products,
duce potassium sulfate according to the reaction: such as potassium sulfate, potassium-magnesium sul-
fate, potassium chloride, sodium sulfate, and mag-
nesium chloride liquors.

235
Production of Potassium Sulfate by Ther-mal Processes phate rock followed by neutralization with limestone or
lime (see chapter XVI). A CaCl 2 solution is a by-
product of this reaction and may pose a disposal
Mannheim Process problem. In the United States the principal use for
the byproduct HCI is for acidulating oil wells to in-
This process for the manufacture of potassium crease oil recovery. The K 2 S0 4 plant may be built in
sulfate from potassium chloride and sulfuric acid in- an oil field to minimize transportation of HCI. Other
volves a two-stage reaction. The following first re- possible fertilizer-related uses for HCl are to produce
action is exothermic: ammonium chloride (see chapter VIII) or to produce
phosphoric acid by a solvent extraction process (see
KCl + H 2 S0 4 ~ KHS0 4 + HCl chapter XIII).

However, the second reaction is endothermic:


Uses of Potassium Sulfate

The sulfate or other nonchloride forms of potash


The first reaction proceeds at a relatively low are preferred for fertilizing certain crops for which
temperature to produce potassium bisulfate (KHS0 4 ) the quality may be adversely affected by chloride.
which is heated in a Mannheim furnace to complete the Examples are tobacco, potatoes (in some cases), and
second reaction. The process is used in Belgium and grapes. Also nonchloride potash sources are needed
the United States. in areas where chloride accumulation in the soil is a
problem as in the Netherlands or in many arid regions
where chloride salts in irrigation water accumulate in
the soil. Potassium sulfate may be preferred because
In this process, the finely ground potassium of its sulfur content where soils are deficient in both
chloride is briq uett.ed, dried, screened, and then potassium and sulfur.
charged into a conversion chamber. Hot sulfur diox-
ide from a sulfur burner flows into the chamber to-
gether with enough excess air and water vapor to Production of Potassium Nitrate 2
complete the reaction which is:

Southwest Potash Process


·--------~-----

In practice, the gas flows through a series of Potassium chloride is slurried with 65% nitric acid
conversion chambers which are charg·ed and discharged which has been previously chilled to prevent a re-
batch wise. The flow of the S0 2 -containing gas 1s action occurring before the slurry is fed into the re-
such that it first contacts a converter in which the actor (figure 7) (12). In the reactor, which operates
potash has most nearly been converted to K 2 S0 4 , and at about 25 psig ( 1~76 kg/cm 2 ), the slurry is heated
the gas lastly flows through a converter containing a with nitric acid vapor to about 75°C) \Vhcrcupon r~c­
fresh charge of KCl briquettes. action takes place, according to the following equation:

3KCl + 4HN0 3 ~ 3KN0 3 + CI 2 + NOCl + 2H 2 0

HCl Utilization Some 90~) of the chlorine is removed in gaseous


form. Because of the extreme corrosiveness prevailing
Both the Mannheim and Hargreaves processes
produce byproduct hydrochloric acid which must be
utilized or disposed of. In Belgium the HCl is used ) Th1s section has hccn abstracted from_P}1osph9~~~~ ~~-~s~J_n, volume 52,
to mal<e dicalcium phosphate by reaction with phos- with the permission of the British Sulphur Corporation(];!_.

65% KCI from to barometric


HN0 3 Recycle gas(NOCI, N0 2 CI plus N 2 0 4 ,CI 2 ,8rCil condenser
BrCI
bleed nitric acid

~ stream absorption lowers


,condense
totol
II quef1ed
gases
Cl2 99.5%
N02 Cl liquid
NOCI C l2
BrCI I to
N20 4 storage
lsi r--2nd
fractionating
column

81%
HN0 3 .,.
.fY
Lld.I
chlorine
fractionating
column 55%
HN0 3

62%HN03

Source: Phosphorus and Potassium, 52, March/April, 1971.

Figure 7. Flow Diagram of Southwest Potash Process for Production of Potassium Nitrate.

236
in the reactor, this vessel, which is in fact an agitat- practical to concentrate the solution up to 81% nitric
ed autoclave, has to be fabricated from titanium and acid; the weak acid vapors in the overhead fraction
lined with acid-resistant brick. are subsequently concentrated to around 62% HN0 3 in
a second distillation column. Bottoms from the first
The solution from the reactor flows to the chlo- acid distillation column are fed to a battery of vacuum
ride-stripping column where it is heated with more crysta1lizers where potassium nitrate is precipitated
nitric acid vapor to its boiling point of around 150°C. and separated by a centrifuge. The product is dried
This treatment takes the reaction to completion and and may be stored direct or melted and prilled at
gives rise to a stripped solution containing less than 340°-350°C in a 35-ft (10. 7-m) tower. Both technical
10 ppm of chlorine. For this degree of completion to grade (99. 3%) and an agricultural grade (99%) potas-
he obtained, it is necessary to maintain an excess of sium nitrate are produced for the process.
nitric acid corresponding to a concentration 'of 55% in
the solution.
IMI Process
The gaseous mixture, containing nitrosyl chloride
and chlorine, coming from the agitated reactor, is ox- The alternative to a high-temperature, distil-
idized in the gas reactor by means of hot nitric acid lation-based process for manufacturing potassium ni-
at a concentration of at least 80% at 150°C. The re- trate by direct acid attack is solvent extraction at
action which takes place yields nitrogen dioxide and relatively low temperature. At low temperatures, the
more chlorine as follows: potassium nitrate formation reaction proceeds, with
the aid of solvent extraction and with no side reac-
NOCl + 2HN0 3 -" \Cl 2 + 3N0 2 + H 2 0 tions occurring, according to the equation:

Water formed in the oxidation is condensed and KCl + HN0 3 _, KN0 3 + HCl
fed to the primary reactor. The chlorine and nitrogen
dioxide are separated into liquid products; the chlo- In this way the solvent extraction route obviates some
rine is fed to storage, while the nitrogen dioxide is of the intense corrosion problems which are an inher-
oxidized with air and absorbed in water to produce ent feature of the process previously described.
65% nitric acid. This oxidation step is characterized However, solvent extraction installations, with the
by the following chemical equation: associated regeneration facilities, are fairly expensive;
thus, the economic advantage of reduced corrosion is
at least partially offset.

The overall reaction throug-h the process is given In this process developed by Israel Mining In-
by: dustries, potassium chloride, together with stoichio-
metric quantities of chilled 60%-70% nitric acid, is fed
into the first of a series of conversion reactors at 5°-
100C (figure 8). Recycled brine and solvent are also
ln the gas section of the process, two distillation added. The reaction between potassium chloride and
columns are used to separate the pure chlorine from nitric acid is, under normal circumstances, reversible,
pure nitrogen dioxide. Chlorine is removed from the but in this case because of the presence of solvent,
top of the first column and nitrogen dioxide from the the reaction goes almost entirely to completion.. Po-
bottom of the second column while in the wet section tassium nitrate is produced in the solid phase. Both
the potassium nitrate-nitric acid solution is concen- hydrochloric acid and the unreacted nitric acid dis-
trated in the acid distillation column. It has been solve into the solvent phase and are removed, while

wash
water
water

brine circuit
:solvent
water cooler 1water
fRII' .J
?>-...,
HCI r---------l_
I ~ I _ _)IQ/ __ _
I I

rj
K N0 3 isteam 1mull i pie
bulk 1 effect
storage 1L _______ 1 evaporator

22% HC I

Source: Phosphorus and Potassium, 52, March/April, 1971.

Figure B. Flow Diagram of \MI Process for Production of Potassium Nitrate.

237
the potassium nitrate crystals are separated, by de- Refinement of muriate of potash to produce the
cantation and centrifugation, and dried for storage. chemical grade is achieved by redissolving and recrys-
Part of the product is melted and prilled. tallizing an already crystallized potassium chloride.

The remainder of the process is concerned with Most chemical-grade potash is used in the pro-
the treatment of the solvent phase to recover hydro- duction of potassium hydroxide (KOH). The process
chloric acid of reasonable purity and to recycle the entails electrolysis of a KCI brine to yield KOH and
solvent-nitric acid mixture to the reactor system. chlorine. The main use of caustic potash is in the
Both hydrochloric and nitric acids are soluble in the manufacture of liquid soaps which are becoming in-
solvent, but fortunately the distribution coefficients creasingly popular. Other uses are in textile opera-
differ sufficiently for the hydrochloric acid to be re- tions, greases, catalysts, engraving, alkaline bat-
moved separately in a countercurrent liquid-liquid ex- teries, and rubber fabrication. In addition to direct
traction system. The hydrochloric acid is utilized to use of caustic potash in liquid soaps or other prod-
produce phosphoric acid by the IMI solvent extraction ucts, a substantial tonnage is used in the production
process as described in chapter XIII. of potassium carbonate (K 2 C0 3 ) and other potassium
compounds. More than half of the potassium carbon-
ate is used in glass manufacture. Some potassium
Other Processes carbonate is carbonated further to form potassium
bicarbonate, KHC0 3 , used largely in foods and medi-
Potassium nitrate may be recovered as a coprod- cine. KOH is also used to make potassium phosphates
uct in certain nitrophosphate processes as described for use in specialty fertilizers.
in chapter XV.
About 4% of the world potassium consumption is
for industrial applications, as follows:

Waste Disposal
Detergents and soaps 35%
Glass and ceramics 25%
The beneficiation of sylvinite results in byprod- Textiles and dyes 20%
uct sodium chloride containing a small amount of po- Chemicals and drugs 13%
tassium chloride. The waste product slurry usually is Other ~
pumped to a storage area bounded by an earthen re-
taining wall to oolidify gradually as the entrained 100%
water evaporates. A few mines are located where the
slurry can be pumped to an ocean or river. The
latter disposal method is coming under increasing en- Refined potassium chloride is shipped in bags or
vironmen tal criticism and banning. The refining of in bulk form in modified hopper cars called sparger or
other potash ores incurs other byproduct salts that solution cars. An ticaking agents are not added to
are treated similarly. If sufficient solid, level land is chemical-grade KCI since they may cause explosions in
available near the refinery, the cost of containment is the electrolytic cells. With a sparger car the chemi-
not excessive. However, suitable land is not always cal-grade potassium chloride is slurried out of the car,
available, and this presents a serious problem. Also, and with a solution car it is fully dissolved and
the net evaporation rate differs with salts, and this pumped out of the car. Table 2 gives the product
affects the time required for solidification. characteristics of a typical chemical-grade potassium
chloride. Note that it is guaranteed to contain a
Carnallite byproduct liquor contains primarily minimum of 99.9% KCI.
MgCI 2 . One ton of carnallite ore produces 0. 3-0.5 m 3
of brine. Byproduct liquors from potassium sulfate
production also contain largely MgC1 2 . Utilization of
MgCJ 2 by hydrolysis and calcination is practiced in TABLE 2. POTASSIUM CHLORIDE (CHEMICAL GRADE)
Israel. The reaction is:

MgC1 2 + H 2 0 7 MgO + 2HCI Com12onent Unit Guaranteed :r~


The MgO is useful for production of refractories, KCl % 99.9 (min.) 99.92
and the HCI is used to produce phosphoric acid by the K20 % 63.12 (min. ) 63. 13
IMI solvent extraction process. · H20 (@ 105°C) % 0.07 (max. ) 0.02
H20 (@ 700°C) ~' 0.67 (max. ) 0.30
Water insoluble ppm 75 (max.) 12
Acid insoluble ppm 75 (max.) 8

Chemical Grade Potash Sodium, Na ppm 150 (max.) 100


Bromine, Br ppm 700 I(max.) 600
Sulf.'lte, so 4 ppm 10 (max.)
Chemical grade potash, a highly refined potassium Calcium, Ca ppm 10 (max.)
chloride, is used almost entirely in the production of Calcium and
chlorine and potassium hydroxide (KOH), commonly Magnesium, Ng ppm 30 (max.)
called caustic potash.
Iron, Fe ppm 5 (max.) 2
High purity of chemical grade potash is important Lead, Pb ppm 3 (max.) 0.5
for at least three reasons: Copper, Cu ppm 0.5 (max.) 0.05
Nickel, Ni ppm 0.5 (max.) 0.05
1. Certain unacceptable impurities in the chemical Chromium, Cr ppm 0. 1 (max.) 0.01
grade potassium chloride are carried forward in Molybdenum, No ppm 0. I (max.) 0.01
the process into the caustic potash. Vanadium, v ppm 0. 1 (max.) 0.01
Titanium, Ti ppm nil (max.) 0.01
2. Efficiency of caustic potash manufacture in an
electrolytic cell is impaired by undue presence of
diluents.
3. Presence of heavy metals causes release of hy- Bulk Density, Loose--I,04I kg/m 3
drogen in the electrolytic cells in the presence
of chlorine, giving rise to the formation of ex- Color - White
plosive mixtures.

238
Potash Particle Size PARTICLE SIZE DISTRIBUTION

During much of the history of potash production


in Europe and North America, particle size was of
little consequence. Each company shipped for agricul-
tural purposes the size range most easily produced,
approximating what is now classified as "standard"
grade (13). Agricultural potash was then either ap-
plied asa straight material or used in production of
"pulverized 11 or later 11 ammoniated 11 nongranular com- z 60
0
pound fertilizers. In the early 1950s when granula-
tion of compound fertilizers was being developed in :;J
z
the United States and the initial equipment proved to <i
1-
be sized too small, Southwest Potash Corporation in- w

if'"'
troduced "coarse" grade as an aid to granulation. 40
Coarse potash is now offered by most North American
producers; its particle size is mainly between 0. 8 and
2. 0 mm. The use of larger particle size muriate of
potash did assist in the agglomeration wanted and
thereby reduced the recycle of particles finer than
the bottom size screen being used. This practice led
to increased production rates in many plants with
undersized equipment. Granulation units installed
during the latter 1950s or later in Europe, the United
States, Japan, and other countries were better engi-
TYLER SCREEN MESH
neered with respect to incorporating "standard" grade
potash materials into granular compound fertilizers. Source: AMAX Chemical Corporation.

The advent of "bulk blending" in about 1960 led


Figure 9. Particle Size of Granular and Coarse Potash in Comparison with
to the introduction of "granular" materials. This
Granular Phosphates Available in the United States.
trend was fostered by the introduction of granular
diammonium phosphate, largely in the 6- to 14-Tyler
mesh (1. 2- to 3. 3-mm) range. As the trend to bulk
blending in small plants located in immediate consuming
areas developed, the demand for large particle size used to produce a semicoarse particle at most West
materials increased similarly. Bulk blending is most German plants.
commonly practiced in the United States and Canada,
but its use is growing in Latin America and some
other regions. Granular potash is also preferred for In the German Democratic Republic, the Unter-
direct application. breizbach plant has granulating facilities to produce
about 250,000 tons annually on a K 2 0 basis. This
Both "coarse" and "granular" grades of potash product ranges from 0. 5 to 4. 0 mm but can be
are used by bulk blenders. However, the "coarse 11 screened at Wismar, a port, to 0. 5-l. 5 mm and 1. 5- to
grade does not match well the particle size of nitrogen 4. 0-mm fractions for export.
and phosphate materials commonly used in bulk blend-
ing, leading to unsatisfactory analysis control of The potash industry in the U.S.S.R. intends to
bulk-blend mixtures (see chapter XXII). increase the proportion of granulated product to 75%
of total output. Only about 1. 0 million tpy was pro-
Gradually the potash industry, in North America duced in 1977. Both U ralkali and B yeloruskali mines
especially, is increasing its granular grade compaction have compaction units.
capacity. Likewise, blend plant owners are recogniz-
ing the need for using potash of a size that is similar
to that of the other materials in the mixture and, Price Differential for Grades
therefore, are more generally choosing "granular" pot-
ash. Figure 9 illustrates the similarity of "granular" The following prices ar~ illustrative of the vari-
potash to other granular materials and the dissimilarity ous "grades" of muriate of potash offered by North
of "coarse" grade potash. Studies at the National American producers ( 14):
Fertilizer Development Center, Muscle Shoals, Alabama,
demonstrate that all materials in a blend mixture
should be within ±10% range of particle size on each
screen size to avoid undue segregation. Price (Feb. -June 1977) 3
Typical Siz£ $/~hart Tone
In Germany, where potash was first produced, Grade Range, mm Un1t of KzO $/kg of KzO
the kieserite, carnallite, and insoluble anhydrite are
Standard less than 0.8 0.80 0.088
finely grained, and the crystals are intergrown, mak- Coarse 0.8-2.0 0.84 0.093
ing separation by grinding and flotation almost impos- Granular 1.2-3.3 0.86 0.097
sible. Crystallization is the principal method of bene- Soluble 62'%,-63% K2 0 less than 0. 8 0.86 0.097
ficiation used in Germany. Some flotation units are
a. List price from Phosphorus and Potassium, 83:14 (1976L f.o.b.
now in use. More recent crystallization units installed mine in Canada.
in Europe are capable of producing a rounded grain b. Specifications vary somewhat from one producer to another.
of about 1-mm diameter. Compaction of fine particles Short-ton unit of K20 ;; 20 lb (l'.t of short ton).
to granular size range has been introduced in Europe.
In North America coarse grade and, with certain ores,
some granular potash can be produced by flotation.

In North America granular grade ranges in size The prices shown above amount to a premium for
between 1. 2 and 3. 3 mm. In France compacted potash granular potash over a standard of about $4 per met-
ranges between 0. 8 and 5. 0 mm. A screened fraction ric ton of muriate of potash containing 60% K 2 0.
sold as "granular" is 1. 5-5.0 mm with the major per- "Soluble" potash commands a similar premium; it con-
centage of particles between 1. 8 and 4. 0 mm. tains no insoluble impurities and is used mainly in
fluid fertilizers. A fine particle size is preferred for
The West German plants have compaction units rapid dissolution or, in the case of suspensions, to
for "granular" grade D_:32. Swenson crystallizers are prevent rapid settling.

239
The premium for granular potash has varied con- smooth rolls. The shape of the briquettes may be
siderably since 1976. In mid-1979 the premium for long and narrow like a cigar. The briquettes are then
international sales of granular Canadian or European crushed and screened to recover the desired size.
potash was about $10/ton, but for sales within North
America the premium varied from $10 to less than $5/ The roll compaction machines consist essentially
ton, presumably in response to supply and demand of a set of two, powered, inward-turning rolls. One
factors. roll has a fixed bearing; the other is floating in a
slide arranged so that it can be forced toward the
Sulfate of potash also is offered in standard and fixed roll by hydraulically actuated pistons acting on
granular sizes; the price of the granular grade in the bearing blocks. The material to be compacted is
1976 was about $8. 60/ton more than the standard fed continuously into the nip of the rolls from above.
grade. For potassium magnesium sulfate, the premium Very high pressure can be exerted on the material as
for granular grade was $6. 60/ton. Granular potash it is forced or drawn between the rolls where a mo-
products may be obtained by screening flotation prod- mentary phase change to a plastic flow condition takes
uct or by roll compaction as described elsewhere in place. The crystals are fused together into an almost
this report. However, granular sulfate of potash is continuous sheet of product which is ejected beneath
produced only by compaction. the rolls. The void content of the sheet may approach
zero, and the thickness may vary from 1/8 in to
3/4 in (0. 3-1.9 em), depending on the feed texture
Granulation of Potash Salts and compaction machine in use. Compaction machines
vary in size (table 3), but the mechanism of com-
Granulation of fine potash salts is carried out on paction is the same. One of the very few in-depth
a commercial scale by compaction. Some other methods studies on compaction has been published by
have been tried, but there is no known commercial B. E. Kurtz and A. J. Bardunhn ~-
use. A typical f!owsheet of a roll compaction unit for
producing granular muriate of potash is shown in
figure 10. The feed is fine potash plus recycled fines Factors affecting compaction of potash are as
follows:

Feed Texture--The optimum particle size distri-


bution lies on the slope of approximately 8% plus 14-
mesh to 8% minus 200-mesh. This includes minus 12-
mesh fines and dust recycle from the compaction
circuit, in addition to fresh crystalline feed. Exces-
sively coarse crystalline feed may result in a weaker,
grainy-textured sheet. A high minus 200-mesh con-
teni. increases the void content in the sheet and pro-
duces severe mechanical stresses on the drive gears
-CO
GRANULATING
of the compactor due to "chattering" in which the
rolls vibrate and slip under load. Segregation can
COMPACTING MILL be a serious problem. It is minimized by using a
MILL
-CO OVERSIZE
RETURNED
small volume feed bin so that fresh feed is constantly
blended with recycled material.

Feed Condition--An oil or amine residual film on


the crystal from previous treatment inhibits fusion of
the surfaces and results in weak sheet and heavy re-
cycle to the rolls. The film can be removed by high
temperature drying. Some producers add a small a-
mount of moisture to the feed; others find that trace
UNOE RSIZE RETURNED GRANULAR
PRODUCT additives, such as starch, improve the quality of the
product.

Source: Allis Chalmers. Feed Temperature--Optimum feed temperature


without water-cooled rolls is 120°-150°F (49°-65°C).
Higher temperatures result in additional maintenance
Figure 10. Simplified Flowsheet for Granulation of Potash by Roll
Compaction.
problems throughout the plant. Hot feed (300°-500°F)
(150°-280°C), however, can be compacted into an ex-
tremely dense sheet at somewhat lower pressures when
from the process. The feed is preheated in a the high temperature conditions can be tolerated.
steam-heated conveyor and fed to a hopper above a
pair of smooth rolls. The rolls turn toward each Methods of Introduction--Feed to compactors can
other and compress the material into a continuous be introduced either by gravity or with assistance by
sheet. The sheet is broken into flakes by a "flake force feeding screws.
breaker." The flakes are screened to remove fines
and then fed to two "granulating mills" in parallel. High bulk density of the feed is important to
The granulating mills are corrugated rolls with sharp- successful compaction when rolls are fed by gravity.
edge corrugations designed to break the flakes in such The density, however, is altered drastically by the
a way as to form a maximum percentage of the desired presence of air entrapped in the material, and the
particle size. Other types of crushers, such as cage quantities of this air must be decreased to tolerable
mills, may be used. The product from the primary levels. The deaeration of feed might be accomplished
mills is screened to remove fines (which are recycled by vibration of the feed hopper above the rolls, by
to the compactor), product size (1. 2-3.3 mm), and vacuum, or by mechanical stirring. In varying de-
oversize (which goes to a third granulating mill). grees, all of these methods help by decreasing the
The product from the mill is screened to recover more void content of the feed. Some operators claim that
product size. Oversize is recycled to the mill, and deaeration and increased bulk density resulting there-
fines are recycled to the compactor. Of the total from are quite effectively obtained by using a high,
throughput, 40%-60% is recovered as granular prod- shaft-like hopper directly over the rolls.
uct, and the remainder is recycled as fines to the
compactor. Force feeding utilizes one or more vertical
screws to introduce feed into the angle of nip under
In a similar process, the incoming potash is pressure. This serves two purposes, namely, it
formed into briquettes by pressing the material be- assists in displacement of the entrapped air and in-
tween rolls that have matching pockets rather than creases the coefficient of friction between the feed

240
TABLE 3. ROLL COf1PACTION NACHINES IN CURRENT USE

Ail is-Chalmers Komarek-Greaves


--------
Humboldt
-- ---- Vulcan-Koppers

Roll diamelf'r, 61 71 91 102

Roll width, em 61 69 119 127

RP~I 24 42 25 14

Peripheral speed, m/min 46 94 72 47

Rol1 construction Cast iron-alloy Casl iron roll Cast steel. Nonobloc body
shell. Solid 2 11 alloy shell. Internal V.'ater and shaft. Water
stf'Pl shaft. Hollow shaft. cooling. cooled under
roll surface.

Bearings Sleeve or roller Roller Roller Roller

Motor capacity (kW) 149-221, 373 2 X 186 448

Applied pressure, kg/em 3,575 3,932 4, 182 5,362

Feeding method Either gravity Tapered-screw, Hydraulic Five 22-kW


or vertical twin twin-force variable-speed, hydraulic motor-
screw force feeder tv./in-force driven force
feeder. (4: 1 ratio). feeder. feeders.

Throughput, tph 27 45 77 91

Approximate production
rate (6 x 14 mesh), tph 11 20 26 27

mater·ial and smooth surfaces of both rolls. The turer of large diameter rolls utilizes a grating immedi-
benefits claimed for the force feeding method are: ately above the angle of nip. The air is drawn down
into the rolls instead of escaping above with some
turbulent effect. The resulting sheet leaves the rolls
( 1) decreased sensitivity of compaction rolls to fluctu- as longitudinal strips.
ations in texture of the feed; (2) increased angle of
nip, which is reflected in increased thickness of the The flowsheet (figure 10) shows a 24 by 24 in (61
compacted sheet and higher production rate by the by 61 em) Allis-Chalmers compaction unit running in
compactor resulting therefrom; and ( 3) greater effec- an independent closed-circuit system. The equipment
tiveness of automation by use of screw feeders, e.g. , is common in the industry, and this f!owsheet, al-
by controlling force feeder speed to maintain a specific though not standard, is particularly illustrative be-
loading on the compactor motor or to produce a con- cause of its simplicity.
stant sheet thickness by transducer signal to a vari-
spced force feeder drive. Most recent compaction installations are designed
to recycle all or part of the near sized granular mate-
]{_oll_~_E'Iecl--This variable must be regulated in rial back to the mill product screening plant to re-
relation to feed texture, method ot its introduction, cover a percentage of the product as coarse or stan-
and roll diameter. High- speed rolls generally produce dard-grade products.
a thinner sheet with less recycle, but they are sensi-
tive to feed texture changes. Slower turning rolls One drawback of roll compaction processes is
( 10-25 rpm) are more stable, but they produce a nar- that the granules may have thin edges or corners
row sheet. that break off in handling to form fines. To overcome
this problem, some producers put the granular prod-
Roll Pressure--All other variables are controlled uct through a tumbler so that fragile edges are bro-
to permit:"the-hlihest possible roll pr"?ssure consistent ken off and can be removed by screening. Also, a
with a sustained operation. This is the most critical treatment with steam has been developed that helps to
factor in the successful agglomeration of free-flowing round the edges. Other particle stabilizing treatments
potash between compaction rolls. Roll pressure on the may involve addition of moisture or brine followed by
potash is normally quoted in pounds per linear inch drying.
and is commonly in the range of 20,000-30,000 lb/
linear in (about 3,500-5,400 kg/linear em). Pressure Granulation by roll compaction can also be applied
is applied to the bearing blocks of the floating roll by to potassium sulfate, ammonium sulfate, and crystalline
a hydraulic system which is either set manually or diammonium phosphates. The process also can be
automatically controlled to maintain optimum pressure. used to granulate some types of compound fertilizers,
as discussed in chapter XIX, and to agglomerate a
Roll Surface--Smooth rolls are standard, with a wide range of nonfertilizer products.
provisiOn for .. sc-raping fused material from the surface.
The rolls may be solid or duct.ed for cooling water, As to the cost of granulation by roll compaction,
but a common practice in the industry is to apply ex- the price differential of about $4-$8/ton for granular
ternal cooling by water sprays, damp sponges, etc. potash salts versus the price of standard grade pre-
Application of moisture results in severe corrosion of sumably reflects an order of magnitude of the cost.
the roll surfaces.

Roll Diameter--Sensitivity to particle size distri- World Potash Production Capacities


butiona~reSidual air content in the feed is
decreased as roll diameter is increased, thereby per-
mitting increased circumferential speed. One manufac- Since the first potash mine was opened in 1861

241
near Stassfurt, Germany, world potash production ( 4). Over 60% of this forecasted increase will be in
capacity has increased to about 32 million tons of K 2 0 the U.S.S.R. The report estimates that the rate of
equivalent in 1979 ( 4), largely as muriate of potash capacity increase will be sufficient to satisfy the in-
and much lesser amounts of potassium sulfate and creased demand at least up to 1982, when the capac-
small amounts of potassium nitrate. The following ity is expected to be 36. 18 million tons of K 2 0.
tabulation summarizes the present (1978-79) capacities
by country.

Prices and Production Costs


World Potash Capacity in 1978-79

Million Historical information in potash prices is not very


Tons K2 0 Percent useful because of the major dip in prices during
1966-72 which resulted from the overambitious devel-
World total 31.96 100 opment of new mining capacity in Saskatchewan and
the U.S.S.R. following:
U.S.S.R. 10.00 31
Canada 7.50 24 1. A worldwide campaign to "feed the world."
German Democratic Republic 3.20 10
2. Discovery of large potash reserves and suitable
German Federal Republic 3.30 10
technology in Saskatchewan and the U.S.S.R.
United States 2.86 9
France 2.39 7 3. Expansion of nitrogen and phosphate production
Spain 0.88 3 which lent encouragement to investment in new
Israel 0.88 3 potash production.
Others 0. 95 3
Figure 11 shows price trends to date for three
major fertilizer materials (16). The potash price,
f. o. b. Vancouver, rose froril$33/ton of 60% K 2 0 muri-
A World Bank report estimates that world capac- ate in 1970 to a maximum of $80/ton in 1974 and then
ity will increase to 39.05 million tons of K 2 0 in 1985 fell below $50/ton in 1977 and rose to about $78/ton

$ /mt
400 400

Diammonium Phosphate
Potassium Chloride
Urea

300 300

E
:::-
~
200 200
"'
a::
....

/' ,;--r-
- - .... --
--'
'- I
100 ) 100
;
;
,.. -.................
,•_.)
--- __ /r - /
\

- -------·--
~,-- .... ..,.. . . .___.. . . --....,- ../ -~-

-·- - -·- - -·-- -·-- ---


---~_c-_-_-_
..... - -
-
0
1968

EXPORT PRICES OF SELECTED FERTILIZER,


1968- 78

Figure 11. Export Prices of Selected Fertilizers, 1968-78 (Potash Prices, f.o.b. Vancouver, Canada).

242
in mid-1979. Note that potash prices rose much less tural soluble grade and chemical grade. The estimated
during the 1973-75 shortage than did most other fer- cost is $219 million which equates to about $194/annual
tilizer materials (17). Noting also the modest increase ton of product expressed in 1977 dollars.
of potash price -c!Uring the past 14 years, it seems
certain that potash prices will have to rise to support Table 5 approximates typical operating costs of
the more rapidly increasing construction costs. On a an operation in Canada as described above. It must
constant-dollar basis, potash price is lower than it be emphasized that ore grade and other conditions are
was 15 years ago. highly favorable in Saskatchewan, and these costs are
lower than many other potash operations, substantially
Table 4 shows the estimated capital cost of a lower than some. On the other hand, the capital re-
plant designed to produce 1. 13 million tpy of product quirements for opening a mine in Saskatchewan are
as muriate of potash at the mine in Saskatchewan. unusually high because of the depth of the deposits
The ore is very high grade and will be used to pro- and the difficult geological formation (high pressure
duce agricultural muriate of potash in all size grades. aquifer) through which the shafts must be con-
Some of the product will be used to produce agricul- structed. Also, the severe climatic conditions increase
the cost of the ore refining plant.

TABLE 4. 1977 CAPITAL COST OF POTASH MINE AND


REFINERY IN SASKATCHEWAN 1.13 MILLION TONS OF On the basis of the premises expressed in tables
4 and 5, there are calculated prices necessary to yield
PRODUCT/YEAR CAPACITY
5%, 10%, and 15% after tax return on investment, as-
Cost, Million suming further the stated 15-year depreciation rate,
U.S. Dollars royalty /taxes, and general and administrative costs.
Facilit
These calculations made with and without the Sas-
katchewan reserve tax, a business expense peculiar
Mine
shafts, 16-ft diameter x 3,000 ft, to Saskatchewan, are shown in table 6.
with hoisting equipment 53.0
It is difficult to compare the investment and
Mine equipment 30.0 operating costs of solution mining with shaft mining
because solution mining is seldom used except where
Subtotal 83.0 shaft mining is infeasible owing to excessive depths
or geological character of the deposit. Also, in solu-
Surface plant 3 136.0 tion mining there is no clear-cut separation of mining
and beneficiation.
219.0
TV A has estimated the energy requirements for
a. Includes eight compactors and a crystallizer three combinations of mining and beneficiation for
circuit. North American conditions, assuming an ore grade of
b. No working capital included. 26% K 2 0 D_lll:

TABLE 5. CANADIAN PLANT, DIRECT OPERATING COSTS

Annual Cost, $/Ton


Cost Product

Mine Personnel
Office 16
Maintenance 74
Production, face 104
Production, backup and utility 42
Total 236 4,786,000 3.51

Plant Personnel
General and administration 48
Supervisory 19
Operating 88
Maintenance 65
Total 220 4,686,000 3.43

TOTAL PAYROLL
(includes 20% fringe benefits) 9,472,000 6.94
General Plant Overhead 643,800 0.48

Mine:
Operating supplies 876,600
Maintenance supplies 3,123,600
Power 957,200
Expendable and miscellaneous 755,500
Total 5, 712,900 4.19

Plant:
Operating supplies 2,830,100
Maintenance supplies 1,146,100
Power 1,587,000
Expendable and miscellaneous 377 800
Total 5,941,000

Total annual direct operating costs 21,769,700 15.97

243
TABLE 6. POTASH PRICE CALCULATION

Basis:
1.12 million tons of product per year capacity
Plant includes eight compactors and a crystallizer
Capital cost, $218.75 million ($192.50/tpy)
Direct operating cost, $15.97/ton
Costs expressed in 1977 U.S. dollars/rot of product
Reserve tax, $15.00/short ton, nondeductible

Costs Including Reserve Tax

Operating $15.95 $15.95


Depreciation (IS-year life) 12.84 12.84
Royalty/taxes 2.20 2.20
Administrative, etc. 2.20 2.20
Reserve tax 0 16.50

Total $33.19 $49.69

Price necessary to yield indicated after tax return on total investment based on current 1977 Canadian taxes:

Price, $/mt, f.o.b. Saskatchewan


%Return on Investment, After Tax Including Reserve Tax Excluding Reserve Tax

73.59 49.50
10 89.82 65.78
15 106.32 82.12

Energy Requirement, World Potash Commerce


GJ/Ton of 60%-62% K2 0
as Muriate of Potash 3
World potash exports in 1976-77 were 13.3 million
Solution mining 6.5 tons K 2 0 and 51% of world potash production. Thus,
Crystallization recovery 5.4 potash is an important item of world commerce. World
potash fertilizer exports increased at an average an-
Total 11.9 nual growth rate of 7.1% over the 10-year period
ending 1975-76. This was 2% faster than the potash
Shaft mining 2.2 production increased on average during this period.
Beneficiation by flotation 1.0 Nine countries export over 99% of all potash materials:
Canada, the U.S.S.R. , East and West Germany,
Total 3.2 France, the United States, Israel, Spain, and Italy,
about as follows:
Shaft mining 2.2
Beneficiation by crystallization 5.4

Total 7.6
Ex;eorter % of Total Ex:eorts
a. I GJ- 0.948 million Btu- 0.239 million kcal.
Canada 40
United States 7
The above energy requirements include both France 4
electrical energy and fuel with the equivalent fuel re- West Germany 6
quirement of electrical energy calculated on the basis East Germany 19
of a conversion efficiency of 33%. It is evident that U.S.S.R. 19
solution mining is energy intensive and, if based on Israel 3
world market prices for oil (about $2/GJ), it would be
uneconomical at current potash prices. However, any
kind of fuel can be used to generate steam and elec-
tricity which are the major forms of energy needed. North American exporters account for about half
Thus, where low-cost coal or natural gas is available, of the exports to lesser developed countries. North
solution mining may be economically acceptable. In American exporters also supply the major portion of
arid climates solution mining may be modified to take the demand in Oceania and Japan. Western European
advantage of solar energy; a relatively dilute solution countries are supplied mainly by trade within the
can be produced at moderate temperature, and most region.
of the evaporation and crystallization can be carried
out in lagoons by solar energy. This is done at the International trade patterns for potash are de-
Texas gulf mine in Utah. termined largely by:

Beneficiation of shaft-mined ore by crystallization 1. Relative transportation costs.


methods also requires a substantial amount of energy, 2. AID and other sales concessions.
but it has the advantage of producing a fully soluble
high-grade (62% K 2 0 or more) product which is pre- 3. Political relationships and the European cartel.
ferred for liquid fertilizers and as an intermediate for
high purity material for industrial uses. Some plants This export pattern has been reasonably stable
prepare a portion of their output by crystallization in recent years but may be altered somewhat if the
for these markets. U.S.S.R. materially increases its exports.

244
Table 7 gives the potash trade in 1976 from nine some\vhat hig·her rate of consumption increase,
exporting countries including Spain to developed, de- reaching 34.5 million tons of K 2 0 in 1985 (4).
veloping, and centrally planned economies (19). Im-
ports in 1976 were divided as follows: 60%to devel- North American potash exports are expected to
oped market economies, 15% to developing market continue to increase primarily from Canada but also
economies, and 25% to centrally planned economies. from Carlsbad, particularly because of its logistic ad-

TABLE 7. POTASH TRADE IN 1976 ('000 TONS K 2 0)

Fed. Rep. Dem. Rep. United


---~o_:.~-~~-~ France Germany_ l_tal_y Spain ~_!many_ U.S.S.R. Canada States Israel 1976 1975

World Total a 476 779 54 239 2,303 L.,304 4,923 848 341 12,268 II, 721

Developed
Markel
Economies 371 )66 16 179 639 597 4.,412 323 273 _!,]}] 6,781

North Ameriba 20 15 4,030 14 48 4,132 3,286


West Europe 283 453 11 150 618 462 25 38 172 2' 213 2,237
Oceania 14 5'• 175 245 210
c
Otlwrs 88 91 14 21 121 303 96 53 787 1,048

Developing
Market
Economies 100 190 38 60 349 104 420 524 68 ___1.185!< ~
Africa 47 I 64 42
Latin America 30 78 4 36 20 I 101 147 471 19 1,088 821
Near East
Africa 25 24 56 85
Asia 10 15 8
Far East
South Asia 91 131 110 335 245
East Asia 19 16 4 163 50 41 296 476
Centrally
Planned
Economies 5 23 1_,_315 J_,_E>_Cl3 91 - 3 038 _]_,_~3

Asia 38 33 91 163 292


h 2,875
E. Europe 23 1, 277 l , .570 2' 971
---------------- --------- ------------ ----------

a. Totals rounded, not .1lways comparable.


b. Yugoslavia included in Wesl Europe.
Includes Japan, South Africa, and Israel.

Source: Jnternat.ional Phosphate industry Association (ISHA) L1_9).

vantage to Central and South America. This adds to


the strategic importance of the Carlsbad location.

World consumption of pot;J.sh fertilizers has


mcreased at an average annual growth rate of about In a recent AMAX study using three published
6% during· the past 20 years. Table 8 gives the re- independent projections of world potash consumption,
gional and world potash consumption for 1962-77, with it was estimated that world consumption will increase
projections to 1985. During this 15-year period, the to about 64 million tons of K 2 0 by the year 2007.
average annual increase of potash consumption for the To supply this demand, production capacity would
world was 6. 8%. have to be increased by at least 41 million tons of
K 2 0 during the period 1976-2007. The 41 million tons
In 1977 world potash fertilizer consumption was of K 2 0 is equivalent to about 68 million tons of
about 23.1 million tons K 2 0. North America, primarily muriate of potash. Since new mines will have to
the United States, consumed 5. 5 million tons and Latin supply most of this added potash, there should be
America, l. 1 million tons. In Asia it is estimated that strong upward long-term pressure on price, sufficient
Japan consumed 655,000 tons; China, 400,000 tons; to justify the investment in ever-increasing potash
India, 360,000 tons; and South· Korea, 200,000 tons operations.
while others used 522,000 tons.
Granular grade is best fitted to the largest and
During the next 7 years, 1977-85, world potash still growing share of the U.S. market. The blending
consumption for fertilizer is projected by TV A to in- of granular materials at small local plants has become
crease about 4. 2% annually from 23.1 million tons K 2 0 standard procedure in much of the major fertilizer use
in 1977 to 32 .I million tons K 2 0 in 1985 (16). In states.
terms of muriate of potash, that would be all increase
of 15.0 million tons of product in the 7 years (see Doth granular and coarse grades of potash are
table 8). To meet this demand, production should be used in bulk- blend mixtures, but educational efforts
about 10% higher than agriculture! consumption in on the benefits of the use of granular grade are in-
order to allow for industrial consumption and the creasing as shown in table 9. Granular grade more
usual 5% gap between production and consumption nearly matches the particle size of other materials
(see chapter I). A World Bank report projects a used in the blended mixtures of solid materials.

245
TABLE 8. REGIONAL POTASH FERTILIZER CONSUMPTION

North Latin Western Eastern


America America Europe Europe U.S.S.R. Africa Asia Oceania World
'000 mt K 2 0- - - - - - - - - - - - - -
!962 2,156.4 193.9 3,474.5 1.244 4 703.0 96.2 683.8 130.3 8,682.6
1963 2,372. 7 210.5 3,663.6 1,247 3 826.0 107. I 758.4 91.3 9,277.0
1964 2,585.8 270.3 3,779.0 1,410.4 901.0 124.4 877.6 128.4 10,076.9
1965 2,694.3 268.6 3,895.4 1,522.4 1,421.0 156.5 924.3 152.5 11,035.0
1966 3,064.1 292.7 3,930.0 1,709.5 1,891.0 158.0 1,066.5 171. 1 12,282.7
1967 3,465.4 326.7 3,941.2 1,929.6 1,902.0 184.4 1,165.6 174.9 13,089.8
1968 3,606.6 366.1 4,231.3 2. 092.4 2,136.0 191.2 1,292.1 157.0 14,072.9
1969 3,698.7 536.4 4,191.8 2,308.7 2,176.0 201.7 1,404.9 175.7 14,693.7
1970 3,835.7 556.5 4,371.1 2,468.0 2,319.0 214.7 1,508.6 194.5 15,468.2
1971 4,022.9 646.5 4,796.4 2,678.4 2,574.0 237.0 1,519. I 196.0 16,670.3
1972 4,120.4 659.3 4,996.2 3,015.9 2,788.0 264.1 1,572.4 193.9 17,610.3
1973 4,398.1 769.6 5. 091.2 3,011.3 3,238.0 294.8 1,750.5 240.5 18,794.0
1974 4,803.2 894.7 5,395.7 3,319.4 3,605.0 308.6 2,118.7 287.9 20,733.2
1975 4,246.1 929.6 4,602.3 3,397.4 3,884.0 343.8 2,182.8 237.9 19,824.0
1976 4,968.2 872.0 4,478.1 3,707.6 5,176.0 326.3 1,814.6 195.7 21,538.4
1977 5,545.6 1,097.1 4,74!.6 3,499.4 5,577.0 350.1 2,002.0 251.5 23,064.2
- -Forecast- - - - - - - - - - - -
1978 5,264.8 1,138.5 4,981.2 3,674.9 5,400.0 376.4 2,364.7 274.0 23,474.5
1979 5,557.4 1,261.5 5,125.2 3,819.0 6,143.0 400.7 2,408.9 283.5 24,999.3
1980 5,743.9 1,362.0 5,269.4 3. 949. 1 6,650.0 426.0 2,501.2 292.9 26,194.6
1981 5,930.5 1,464.9 5,344.7 4,078.1 7,174.0 453.5 2,594.7 302.4 27,342.8
1982 6,117.1 1,570.2 5,434.2 4,207.3 7,714.0 479.0 2,687.1 311.7 28,520.6
1983 6,302.6 1,676.9 5,515.6 4,336.3 8,270.0 506.5 2,775.8 321.0 29,704.7
1984 6,488.2 1,787.4 5,604.7 4,465.4 8,850.0 534. 1 2,868.4 330.3 30,928.6
1985 6,673.8 1,897.3 5,692.9 4,593.4 9,430.0 558.6 2,959.4 339.5 32,145.0

Source: (16)

TABLE 9. AGRICULTURAL SALES OF POTASH BY U.S. AND 3. Singleton, R. H. 1978. "Potash," Mineral Com-
CANADIAN PRODUCERS IN THE UNITED STATES AND CANADA modity Profile MCP-11, U.S. Bureau of Mines,
('000 TONS K20J Washington, D . C .

4. Sheldrick, W. E. , and H. Stier. 1978. "World


Potash Survey," World Bank Working Paper 2. 93,
Granular Coarse Standard Washington, D.C.

1973 1,394 2,141 1,394 5. World Survey 2f Potash Resources, second edi-
1974 1,588 2,241 1,476 tion, 1976. British Sulphur Corporation, Ltd. ,
1975 1,191 2,022 1,046 London, England.
1976 1,665 2,485 1, 174
1977 1,824 2,417 1,119 6. Von Peter, A. 1977. "The Potash Situation -
1973-77 increase--percent 31.1% 12.9% (19.7%) Global Status and Development," Proceedings of
the FAI- IFDC Seminar, Paper No. Tech I/5-1,
New Delhi, India.

AMAX Chemical has successfully promoted the use 7. "G.D.R. Potash- Progress Since 1970." 1977.
of granular grade in blend mixtures through the use Phosphorus and Potassium, 87:40-45.
of the trade name K-Gran and promotional/educational
material explaining the merits of its use. Consumption 8. Mitchell, J. B. 1970. "Three Ways to Process
of the granular grade in North America has increased Potash," Mining Engineering, 22(3): 60-62.
by 31.1% during the 5-year period 1973-77 which in-
dicates that retailers and consumers are becoming 9. "Carnallite: The Other Potash Ore." 1976.
aware of the advantages of this grade (table 9). A Phosphorus and Potassium, 84:39-41.
substantial proportion of the potash used in the
United States and some other countries is for direct
application. For this purpose, either coarse or gran- 10. "Potash, A By-Product of Soviet Alumina-From-
ular grades can be used, but the closely sized gran- Nepheline Process." 1971. Phosphorus and
ular grade is likely to give a more even distribution Potassium, 53:40-41.
pattern when broadcast by mechanical application.
11. "Technical Advances by the U.S.S.R. Potash
Industry." 1972. Phosphorus and Potassium,
59:41-45.

12. "Routes to Potassium Nitrate - Part 2." 1971.


References Phosphorus and l;'otassium, 52:5 2-55.

13. "Sized Potash. n 1977. Phos12horus and Potas-


1. Smith, R. C. 1977. "The Potash Industry," sium, 91:39-43.
Paper presented at the Annual Meeting of Ameri-
can Association of Plant Food Control Officials, 14. "Canada Prices. " 1976. Phos12horus and Potas-
El Paso, Texas. sium , 83: 14.

2. Potash and Potassium Fertilizers. 1966. Chemi- 15. Kurtz, B. E., and A. J. Barduhn. 1960.
cal Process Monograph No. 15, Noyes Development "Compacting Granular Solids," Chemical Engineer-
Corporation, Park Ridge, New Jersey. ~ Progress, 56(1):67-72.

246
16. Harris, G. T., and E. A. Harre. 1979. World 18. Blouin, G. M. 1974. "The Effects of Increasing
Fertilizer Situation and Outlook, IFDC Technical Energy Costs on Fertilizer Production Costs and
Bulletin T-13, International Fertilizer Development Technology," TVA Bulletin Y-84, Tennessee
Center, Muscle Shoals, Alabama 35660. Valley Authority, Muscle Shoals, Alabama 35660.
17. The Commodity Shortages of 1973-74: Case 19. !SMA Potash Statistics. 1977. International
Studies. 1976. United St~National Phosphate Industry Association, Paris, France.
Commission on Supplies and Shortages. For sale
by the Superintendent of Documents, U.S.
Government Printing Office, Washington, D . C .

247

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