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LA N

-7

SEIN

and
Processing
S

I X years ago langbeinite was practically unknown in the fertilizer industry. Today it
takes 1% prominent place among the potash and
magnesium base fertilizers. Production of langbeinite in the 1941-42 fiscal year was 28,672 tons,
compared with 85,701 tons during 1945-46.
Langbeinite is a double sulfate of potash and
magnesia, with the formula KzS04.2MgS01, and
is composed of 22.7% KnO, 19.401, MgO, and
57.9% SOs. It has a specific gravity of 2.825
and a hardness of 4.2. It crystallizes in the
isometric system, usually as simple tetrahedrons,
which show a triangular outline on the surface
of the hand specimen or on the walls of the
mine workings. It is more slowly soluble in
cold water than either sylvite or halite, and
much of the langbeinite present in samples
can be recovered by quickly dissolving out the
chloride minerals. It is the hardest of the saline
minerals, and has a conchoidal or irregular fracture with no cleavage.
The geology of the region in which langbeinite
occurs is complex and not fully understood.
Langbeinite is one of numerous salts deposited
during the latter stages of evaporation of a large
Permian sea. In the early part of the Permian
period a shallow sea extended across New Mexico
and western Texas, northward through Oklahoma
and Kansas, and into southeastern Nebraska. The
indications ape that the shore lines of this sea fluctuated over considerable areas. The sea was originally
in open communication with the ocean by way of a
channel extending through Mexico into the gulf.
One theory is that, late in Permian time, the
connections to the sea berame restricted because of the deposition of limestone reefs. The
further growth of these barrier reefs, coupled
with t$e subsidence of certain areas, led to the
formation of large evaporating pans. The area
defining one such pan is generally known as
the Delaware Basin, and it is in the series of
evaporites found in this basin that commercial
deposits of potash salts occur.

6. T. Harley and 6. E. Atwood


International Minerals & Chemical
Corporation, Carlsbad, N. Mex.
The Delaware Basin is a pear-shaped area occupying approximately
15,000 square miles. It covers portions of Eddy and Lea Counties in
southeastern New Mexico and extends as far south as the Glass Mountains
in Brewster County, Tex. It is a t the northernmost edge of the basin
in a relatively small area approximately 25 miles east of Carlsbad,
N. Mex., that potash salts are being mined. This region is the only
portion of the Delaware Basin in which commercial deposits of potash salts
have been found.
The potassium minerals are the products of the last stages of evaporation; consequently the horizons at which they occur are found in the
upper salt strata. The top of the salt is found a t an average depth
of 400 feet below the surface, or an elevation of approximately 2800
feet above sea level. The bittern salts are interbedded with halite and
occur at vertical intervals of approximately 50 feet. The uppermost
bed is found about 750 feet below the surface and contains carnallite
(KCl.MgCL.6HzO). At depths of 800 and 850 feet beds of langbeinite
occur, the lower being associated with considerable sylvite. At 900
feet a stratum of sylvite is found. The stratographic sequence of
these beds indicates that the cycle of deposition was periodically interrupted

43

44

I N D U S T-RI A L A N D E N G I*N E E R I N G C H E M I S T R

T h e only commercial deposits of langbeinite


known to exist in the United States are located a t
Carlsbad, N. Mex. Mining is by room and pillar
method, and operations are carried qut with the
latest type of mechanical equipmynt. There are
no tracks on the level, and haulage is by means
of rubber-tired shuttle cars operated from a
double overhead trolley system and cable reels.
The "ore is undercut and drilled with electric
augers in a manner similar to coal mining practice. The level is equipped with modern electrical
and mechanical shops, which permit almost a
complete repair and maintenance schedule without removal of equipment to the surface. The
finished langbeinite is prepared by simple crushing and washing in fresh water to dissolve the
halite and wash out the clay impurities. The
solid langbeinite is then centrifuged, dried, and
placed in a storage warehouse ready for market.
By hydrating langbeinite and combining i t with
sylvite in a so-called base exchange process, magnesium is eliminated with the substitution of
potassium to make sulfate of potash, containing
90 to 95% potassium sulfate.

and renewed. However, the order in which the bittern salts


occur follows a normal path predictable from available solubility
data.
When attempting to explain the formation of any individual
bed, the theorist is immediately confronted with contradictory
evidence, and no effort is made here to unravel the many structural irregularities which occur in the potash beds. The ultimate
answer as to the genesis of the beds will be obtained only through
intensive geological-geochemical studies, which have as yet made
little progress.

Vol. 39, No. 1

It is opened up by a large hoisting shaft and by a system of 2 to


4 parallel entries driven to connect the various working sections
of the mine. The main set of entries on the level runs parallel
and directly above the main haulage road on the 900-foot level
of the mine. At the intersection of each wofking panel with
this main entry a raise, or ore pass, connects the two levels.
The ore varies in thickness from 4.5 to 6 feet, and about a foot
of salt is mined underneath to give a working height of 6 to 7
feet. Mining is by the room and pillar system with pillars 32 X
32 feet in dimension and rooms and breakthroughs 32 feet wide.
The first step in the mining operation is to undercut the face.
This is done with a Goodman mining machine having a 9-foot
cutter bar. The cut, which is 6 inches wide and about 8.5 feet
deep, is made at the bottom of the face and across its full width.
The purpose of this cut is twofold, first to provide an additional
free face to improve the work of the explosives used, and second
to provide a smooth floor upon which to operate the shuttle cars.
The mining machine has a cutting speed of 5 to 6 inches per
minute and is driven by a 60-horsepower alternating-current
motor. Various types of bits have been used in the cutter chain;
after a long series of tests, this mine standardized on a bit faced
with a Carboloy tip. Each bit can be sharpened fifteen to seventeen times before it is discarded and will do two to five times
as much cutting per sharpening as any bit previously used.
Machines are transported by tractor trucks from one room to
another. Each truck has mounted on it an Aerodyne midget
fan for ventilation of the face while the men are a t work;
The next step is the drilling of the face, with Jeffrey A6 electric auger drilIs. Drilling speed is 28 inches per minute, and
steel and bit wear is not excessive. Three lengths of steel serve
to drill holes up to 11 feet deep. Holes are drilled in the common toe-hole pattern in vertical rows 4 feet apart, each row containing three to four holes, depending on height of face. Such
a round will pull the full depth, give satisfactory breakage, throw

PAN FEEDER AND CONVEYOR

MINING

Langbeinite is dug by standard coal mining methods, someu-hat


modified to meet the physical character of the ore. Only the
higher grade bed, lying at a depth of 800 feet, is being mined.

FER

ONE B'x 25' DEWATERING

FLED
WATER

SANDS

ONEB'x 25' DEWATERING


DORR CLASSIFIER

OVERFLOW

IS' j E T T L l N G CON;
OVERFLOW

I
L--

CENT'RIFUGAL
PUMP

DIAPHRAGM PUMP

36"X 50" BIRD CONTINOUS


CENTRIFUGE

TO USE IN
TAILINGS

1
DISPOSAL

FLIGHT CDNVEYOR

PLANT

5'X 40' ROTARY K I L N

I
BOT.
STORAGE BIN

FINISHED SUL! P O - MAG


9 6 % Q S 0 4 . 2 MC SO4

Dorr Classifier, Final Stage in Langbeinite Washing

Figure 1. Flow Diagram of Langbeinite Washing Section

January 1947

INDUSTRIAL AND ENGINEERING CHEMISTRY.

45

Raymond Pulverizer Preparing Langbeinite for Base Exchange

.
'

the ore away from the rib, and leave little or no overhang in the
face. Langbeinite is so hard that i t was drilled with wet jackhammer-type drills a t first. This was unsatisfactory because
of solution of salt in the water used and the attendant danger of
short circuits. Experimental work was done on alloy-tipped bits
used with the Jeffrey auger drill; after nearly a year of work
Carboloy-tipped bits were adopted for all drilling at a substantial
saving in cost.
Much care has to be exercised in spacing and pointing holes,
but after some practice the drillers become proficient. General
practice is for the face boss or shift boss to locate each one of
the holes and the position of the post by actual measurement.
Blasting is done at the end of each shift with primers which
are assembled underground. The shot firer hauls powder and
primer from the underground magazines to the faces in insulated boxes. Holes are fired electrically, and each round is
connected in series. The shooting circuit is 220 volts of alternating current; it is taken off the transformer serving the section
with power, but through a separate blasting line having locked
switch boxes. Both Du Pont and Hercules powders are used;
the DLIPont is extra D, 40% volume strength, and the Hercules
powder is Hercomite 4X, 40% volume strength. Primers are
made up with unperforated sticks of powder, all other powder
being perforated for better tamping in the hole. Blasting caps
are KO. 6, and delays through KO. 4 are used on this,level of
the mine. Powder consumption is 0.6 pound per ton of langbeinite ore.
The ore and waste are loaded by Joy 11-BU caterpillarmounted conveyor-type machines. These machines have universal application, and can load in narrow or wide headings.

They are electrically driven through a trailing cable connected


with a junction box, which is kept within a short distance of the
working faces. The current is 220 volts, alternating current.
The Joy machine can load out boulders that weigh as much as
1500 pounds; with a good face of broken ore and a plentiful
supply of cars to serve it, a mucking rate of 150 tons per hour
can be maintained.
Haulage on this level is entirely b y rubber-tired shuttle cars,
which operate on a double overhead trolley. This is the first installation of its kind in a nonmetallic mine. The f i s t cars used
were the 42D, holding 7 tons of broken ore. Later the 60Dtype cars holding 10 tons were introduced. The cars are loaded
by a Joy loader and haul the ore to one of the raises; there the
ore is discharged by a conveyor in the bottom of the car. Hauls
as long as 3000 feet have been made by these cars with remarkably
high efficiencies, but best practice is to keep the haul length
down so that the loader can operate continuously. Under these
circumstances the material handled on the level will average 30
tons per man-shift.
In mining langbeinite, 15 to 20% of the material is classed as
waste and left in the mine. This material is loaded onto shuttle
cars by Joy loaders and transported to an abandoned part of the
mine, where it is dumped in front of a second loader which
stacks it in the face over the tail conveyer.
The ore is drawn from a 800-foot level through raises into mine
cars on the 900-foot level, and is hauled to the shaft station
where it is crushed in a Jeffrey 56-inch single-roll crusher to a
maximum of 5 inches in size. It is then passed through storage
bins to an automatic skip loader into the hoisting skips for transfer to surface and the treatment plant.

46

.INDUSTRIAL AND ENGINEERING CHEMISTRY

from the washer runs consistently above 20% in sodium chloride,


whereas the residual solid phase analyzes 96 to 98% langbeinite. The solids are centrifuged and kiln-dried. to become
finished products. The washing section as outlined is shown on
the flow diagram (Figure 1).
The results being obtained with the countercurrent washer
are illustrated graphically in Figures 2 and 3. Figure 2 shows the
grade of the solid phase in its travel through the wash section;
Figure 3, the loss in recovery due to the dissolution of langbeinite.
The data for these curves were taken during treatment of an
ore analyzing 40% langbeinite and rejection of a liquor containing 22% sodium chloride.
Langbeinite production has risen from approximately 200 tons
per day in 1941 to a current daily tonnage of 500. Of this
amount, approximately, 225 tons are consumed in the manufacture of potassium sulfate, and 275 tons are sold under the name
Sul-Po-Mag.

v)

c5

Vol. 39, No. 1

POTASSIUM SULFATE SECTION

60

u
z

3
lL

50

-L

40

0.0

2 .o

WASHTIME

4.0
MINUTES

6 .O

Figure 2. Analysis of Solid Phase during


Travel through Wash Section

REFINING

The beneficiation of langbeinite ore does not present a serious


problem. This mine has been successful in the development of
an efficient fresh-water washing process in which the chloride
gangue salts are dissolved away and leave residual langbeinite.
Although langbeinite is the most soluble salt in the system under
discussion, the rate a t which it dissolves is very slow. This slow
rate, coupled with the relatively fast rate for the gangue salts,
furnishes the basis for the wash process.
Since langbeinite is a soluble salt, the extraction efficiency in
any fresh-water washing process is a function of the rapidity
with which the wash is accomplished. The salt content of the
rejected wash water is also a function of processing time, and,
therefore, optimum performance is obtained only after a delicate
balance is reached between water consumption, equipment
capacity, and extraction efficiency.
This mine utilizes a continuous countercurrent washer, which
gives maximum solution of the gangue salts in minimum contact
time. Briefly this process consists of the following steps: Minerun ore is dry ground by Jeffrey hammer mills operating in closed
circuit with vibrating screens. The crushed product has the
following average screen analysis:
Mesh

Cumulative
% Retained

Mesh

In the potassium sulfate or base exchange section langbeinite


is reacted with sylvite and water to produce potassium sulfate,
of a minimum grade of 90% K2S04, and a waste liquor rich in
magnesium chloride. The process involves the reaction of liquid
and solid phases in the reciprocal salt pair system magnesium
chloride-potassium sulfate-water. The phase reactions are
complicated and can be thoroughly understood only in the light
of certain solubility data. Solubility data on this system have
been obtained independently by dAns ( I ) . vant Hoff @),.and
others, and check within reasonable limits.

Cumulative
% Retained

The crushed ore is then introduced into the wash section


proper, which consists of 140 feet of open launder discharging
into the first of two Dorr dewatering classifiers operating in
series. The feed water is added to the second classifier with
the sands from the first unit. The overflow from the second
classifier is pumped to the feed launder, where it travels to
the first classifier with the new feed. The overflow from this
classifier is the spent liquor and is rejected as waste after a settling
operation for removal of suspended fines, The liquor rejected

a L

:E

z-

i
G

T R A V E L THROUGH
SECOND CLASSI-

6.0

T R A V E L THROUGH

LAUNDER AN0 FIRST


CLASS1 FI E R

0.0

2 .o
WASHTIME

4.0

6 .O

MINUTES

Figure 3. Processing Loss Resulting from


Dissolution of Langbeinite
The base exchange process is a two-step batch operation. I n
the first, referred to as the hydration step, the finely ground
langbeinite is agitated with potassium sulfate mother liquor to
produce schoenite (KzS04.MgS04.6HzO) or leonite (KzSO4.MgS04.4Hz0), depending upon temperature, and a waste liquor
of high magnesium chloride content. I n the second step, filtered
schoenite or leonite is agitated with sylvite and water to produce
potassium sulfate as a solid and a mother liquor for use in the
preceding step.
The essential reactions, although possible in one step, are purposely split so as to yield a higher potassium recovery. In the
two-step process the principal reactions are believed to progress
as follows:

2(K2S04.2MgSO4) f 2KC1
18Hz0 +
3(KsSO,.MgSOb.6H20)

+ MgClt
3(KzSOd.MgSOa.6H20) + 6KC1+
6K2S04+ 3MgCI2 + 18H20

(1)
(2)

INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1947
SYLVITE

T-

JEFFREY

TI

MEASURED

Q.ZffiSO4

--?-

RAYMOND PULVERIZER

ceases in favor of the double salt, glaserite


[K8Na(S04)d. The following analysis of the
mother liquor reflects the maximum tolerance
of sodium in production of potassium sulfate a t 25 C. The stable solid phases
are glaserite, sylvite, schoenite, and potassium
sulfate.

LANGBEINITE
K

4 HYDRATION TANKS
WITH TURBO AGITATOR2

SIDRAGE BIN

47

CENTRlFrGAL PUMP

CENTRIFUGAL

Moles/1000 Moles Wetet

BIRD CONTINUOUS
CENTRIFUGALS
60%MUFllATE
TO STORAGE

15.75
10.0
23.75
9.25
1000

LEONITE CAKE
KaS04 * MG S 0 4 . 4 H2D

+-

Per Cent
5.92

4.75
13.97
4.27
71.09

FLIGHT CONVEYOR

The most outstanding of the variables influencing yields in the base exchange is temperature. The solubility of potassium rises
CENTRIFUGAL PU P
rapidly with any increase in operating temperature, and, consequently, yields suffer. The
THICKENER
extent to which temperature influences rem
covery is seen in the fact that an increase in
UNDERFLOW
OVERFLOW
t
t
operating temperature of 25 C., or a change
QLIVER FILTER CFN TRlFUGAl RJMP
from 25 to 50 C., results in a decrease in yield
I
I
ARCANITE CAKE
MOTHER Liauou
of aDproximately 10%.
The optimum operating temperature in the
t
I
base exchange is believed to be 25
Operation below this temperature would not
t
only introduce cooling costs but would also
FINISFED POTASSIUM SULPHATE
00% u2 s 0,
impair reaction rates. The best results thus
far obtained in the base exchange process
Figure 4. Base Exchange Flow Diagram
show a yield of potassium sulfate, equivalent to 7301, of the total input. Available
Reaction 1 (hydration step) will proceed to much higher magsolubility data indicate these results to be approximately 90%
nesium chloride and lower potassium chloride concentrations
of the possible yields in operation at 25 C.
than will the second (reaction step). In this system potassium
sulfate is stable only at relatively low concentrations of magLITERATURE CITED
nesium chloride accompanied by high concentrations of potas(1) dAns, J., Die Losungsgleichgewichte der Systeme der Salze
sium chloride. Reaction 2 therefore furnishes an ideal liquor
ozeanischer Salzablagerungen, Berlin, 1933.
for the hydration of langbeinite.
(2) Hoff, J. H. vant, Zur Bildung der ozeanischen Salaablagerungen, Berlin, 1905.
The extent to which each of the reactions progresses in a sodium-free system is illustrated in a comparison of typical mother
PRESENTED
before t,he Division of Fertilizer Chemistry a t the 110th Meeting
and waste liquors at 25 C.:
of the AXERICANCHEXICAL
SOCIETY,
Chicago, Ill.
3 REACTION TANKS
WITH TURBO AGITAATORS

c.

Stable Bolid Phases

Mother Liquor
Sohoenite, K~QOP,
KCl

Waste Liquor
Sohoenite
14.82
9.84
5.26
70.08

In the base exchange flow (Figure 4) the reactions progress so slowly that careful selection of equipment is necessary to keep processing time within practical limits. Raymond mills
are used for the reduction of langbeinite. When
the langbeinite is introduced into the hydration
step, i t analyzes 98% -200 mesh. All slurry
tanks are equipped with Turbo agitators for maximum intensity of agitation. Although the sylvite
is more rapidly dissolved than langbeinite, it
must also be kept within certain definite size
limits to prevent interference with the rapidity
of react,ion.
The presence of sodium in the base exchange
system quickly impairs results; beyond certain
definite concentrations of sodium in the reaction step the precipitation of potassium sulfate

Dryer for-Langbeinite