US3442553A - Slurry mining of carnallite - Google Patents

Slurry mining of carnallite Download PDF

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US3442553A
US3442553A US592119A US3442553DA US3442553A US 3442553 A US3442553 A US 3442553A US 592119 A US592119 A US 592119A US 3442553D A US3442553D A US 3442553DA US 3442553 A US3442553 A US 3442553A
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bed
carnallite
salt
solution
slurry
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Kenneth J Kutz
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E A DEVELOPMENT Inc
Texasgulf Inc
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Texas Gulf Sulphur Co
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    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/28—Dissolving minerals other than hydrocarbons, e.g. by an alkaline or acid leaching agent

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  • This disclosure is directed to a process for the slurrymining of a salt bed, such as carnallite, by introducing water into said bed, thereby leaching a soluble salt (magnesium chloride) therefrom and forming a cavity.
  • the leaching of the soluble salt leaves a less soluble salt (potassium chloride) as a slurry in the bottom of the bed, or in a sump below the bed.
  • This less soluble salt is then removed as a slurry entrained by a substantially saturated solution of the soluble salt.
  • This invention relates to a process for slurry mining of carnallite and for recovery of potassium chloride therefrom.
  • Carnallite is a double salt of potassium chloride and magnesium chloride, having the formula This mineral is valuable chiefly as a source of potassium chloride, which is used in the fertilizer industry.
  • the magnesium chloride is at present of comparatively little value. Extensive deposits of this mineral occur in southeastern Utah as well as other locations in the world such as Canada, Ethiopia, East Germany, West Germany, Brazil, and the Congo. In southeastern Utah these deposits may also contain other minerals, for example, about 0 to 20% by weight of sodium chloride, approximately by weight of sylvite (potassium chloride), and small amounts of bromides, sulfates, calcium salts, and water-insoluble materials. These deposits are located at considerable depth below the ground. Since the mechanical strength of carnallite is quite low, mining by conventional methods would be impractical.
  • An object of this invention is to provide a mining process for carnallite in which potassium chloride is obtained and brought to the surface in the form of a slurry of undissolved particles.
  • carnallite is dissolved in an underground bed where it occurs by introducing water or an unsaturated aqueous salt solution into the bed, dissolving the magnesium chloride, and forming a potassium chloride slurry.
  • the particles of potassium chloride forming the slurry are entrained in the magnesium chloride solution and pumped to the surface, where pure potassium chloride is recovered by conventional means.
  • unsaturated aqueous salt solution is defined as an aqueous solution with a sufliciently low salt content so that it will lea-ch out or dissolve magnesium chloride from carnallite, and thus cause the potassium chloride from the carnallite to fallout or form a slurry; this selective solubility results in the decomposition of the carnallite.
  • FIG. 1 is a diagrammatic view, as seen in vertical elevation, illustrating the slurry mining of carnallite in an underground bed;
  • FIG. 2 is a diagrammatic plan view of a carnallite bed, as seen from above, showing the location of wells and the development of cavities in the bed;
  • FIG. 3 is a vertical sectional view illustrating the first phase of operations in which a sump is formed in a salt formation below the carnallite bed in preparation for slurry mining of the carnallite;
  • FIG. 4 is a vertical sectional view illustrating the second phase of operations, in which water is introduced into a carnallite bed and a solution of magnesium chloride and a slurry of potassium chloride particles is formed;
  • FIG. 4A is a vertical sectional view illustrating the second phase of operations, similar to FIG. 4 but showing a modified form of apparatus
  • FIG. 4B is a vertical sectional view illustrating the second phase of operations, similar to FIG. 4 but showing a further modified form of apparatus;
  • FIG. 5 is a vertical sectional view illustrating the third phase of operations, in which the undissolved particles of potassium chloride are brought to the surface;
  • FIG. 6 is a diagrammatic vertical sectional view showing mining technique which is particularly advantageous for obtaining carnallite from steeply inclined beds.
  • FIG. 7 is a plan view of the carnallite bed of FIG. 6, showing the location of wells therein, as seen from above.
  • a carnallite bed 10 is located at substantial depth below the ground -11.
  • a salt bed 12 containing sodium chloride or other water-soluble salt may be located immediately below the carnallite bed 10.
  • the space 13 between the carnallite bed 10 and the surface of the ground 11 may contain a plurality of strata, including sandstone, shale, anhydrites, limestones, dolomites and a number of sodium chloride beds for example. It will be assumed in this description that the stratum immediately over the carnallite bed 10 consists of a material such as anhydrite or shale which is insoluble in water, although the process is also applicable to deposits in which the overlaying stratum is water soluble.
  • a plurality of wells are drilled from the surface of the ground to the carnallite bed.
  • Each well includes a rig or derrick 14, and tubinglS comprising a plurality of concentric or adjacent tubing strings which provide inlet and outlet conduits for introducing aqueous fluids into and removing aqueous fluids or slurry from the wells.
  • tubing 15 The structural details of tubing 15 will be described later with reference to FIG. 3. Both the rigs or derricks 14 and tubing 15 are similar to their counterparts in oil wells.
  • FIG. 1 also illustrates the formation of cavities in the carnallite bed 10 as water or an unsaturated solution is introduced into the bed and brine and slurry are removed therefrom.
  • a plurality of cavities 16, each extending outwardly from a well, comprise the carnallite bed after it has been mined.
  • Pillars 18 of undissolved carnallite which are substantially remnants of removing a plurality of inverted cones, remain in a carnallite bed after it has been mined.
  • FIG. 2 is a plan view showing the location of wells in a carnallite bed being mined.
  • the wells are located in staggered arrangement in a plurality of parallel rows. This gives a maximum recovery of carnallite from the bed.
  • the number and location of wells is chosen to give a maximum recovery of carnallite from the bed 10, consistent with economic considerations. As the number of wells is increased for a given area, the amount of carnallite mined increases, but at greater cost for well drilling.
  • tubing 15 consists of a plurality of concentric tubing strings 20, 21 and 22 of progressively larger diameter.
  • the innermost tubing string 20 and the next adjacent tubing string 21 are vertically movable and form inlet and outlet conduits for liquid or slurry.
  • the outermost tubing string 22 is cemented to the sides of the well in the strata 13 above carnallite bed 10, and ordinarily terminates at the top of carnallite bed 10. This outermost tubing string 22 serves as a protactive casing.
  • Tubing string 21 is also vertically movable, and a stufiing box and slick joint are provided above the surface of the ground and supported by rig 14 for raising and lowering this tube. Initially, when a cavity is being dissolved out in salt bed 12, this tubing string 21 is located so that its tip is several feet below the boundary between carnallite bed 10 and salt bed 12.
  • the first phase of operations is to form a small sump for collection of potassium chloride slurry. This is done by circulating water downwardly in the annulus between tubing strings 20 and 21, and bringing out brine through tubing string 20. For best results the direction of fiow of water and brine is periodically reversed.
  • the tip of innermost tubing string 20 is generally near the bottom of the desired cavity in salt bed 12. Dissolution of carnallite in bed 10 can be prevented at this stage of operations by injecting a thin blanket of a hydrocarbon oil through the annulus between tubing strings 21 and 22 and through the annulus between tubing string 21 and the sides of the well in carnallite bed 10.
  • the use of such a hydrocarbon oil blanket in solution mining operations is conventional.
  • FIG. 4 illustrates the dissolution of carnallite in bed 10 by injection of water or an unsaturated aqueous salt solution into the bed and the removal of magnesium chloride brine therefrom. Where an unsaturated aqueous solution is used, the salt most frequently is magnesium chloride. This operation is carried out after a sump 25 of desired size has been formed.
  • the tip of the innermost tubing string 20 is approximately at the boundary of carnallite bed 10 and salt bed 12.
  • the tip of the adjacent tubing string 21 is raised to a location in the upper half of the carnallite bed after formation of sump 25 and before the start of dissolution of carnallite.
  • Water or an unsaturated aqueous salt solution is then piped downwardly through the annulus between tubing strings 20 and 21.
  • This water or unsaturated aqueous salt solution circulates in the carnallite bed 10 in the immediate vicinity of the tubing 15.
  • the magnesium chloride content of the carnallite is leached out, forming a cavity 16 and giving a magnessium chloride brine solution.
  • Cavity 16 is in communication with sump 25 so that each is in effect a continuation of the other.
  • FIG. 4A illustrates the dissolution of carnallite in a bed 10 by injection of water or an unsaturated aqueous salt solution and the removal of magnesium chloride brine therefrom.
  • the operation depicted in FIG. 4A is the same as that shown in FIG. 4.
  • the tubing 15a in FIG. 4A includes a pair of tubes 20a and 20b surrounded by a pipe 21.
  • the tips of tubes 20a and 20b are at approximately the boundary between carnallite bed 10 and salt bed 12 therebelow. It may be desirable for the tip of tube 20b to terminate slightly higher than the tip of tube 20a as shown.
  • the tip of pipe 21 is raised to a location in the upper half of the carnallite bed after the formation of sump 25 and before the start of dissolution of' carnallite.
  • Water or an unsaturated salt solution may be introduced into the carnallite bed 10 through the space enclosed by pipe 21 and surrounding tubes 20a and 20b.
  • a solution about saturated in magnesium chloride is pumped upwardly through tubes 20a and/or 20b. The direction of flow may be reversed or coursed through difierent combinations of tubings and annuluses if desired.
  • FIG. 4B illustrates the dissolution of carnallite in bed 10 using a modified form of apparatus.
  • the operation depicted in FIG. 4B is the same as that shown in FIG. 4.
  • the apparatus of FIG. 4B includes a pair of tubes 20c and 21, which are surrounded by tubing string 22 which is cemented to the sides of the well. Tubes 20c and 21 may have the same diameter.
  • Water or unsaturated salt solution may be introduced into the carnallite bed through tube 200, A solution about 90% saturated in magnesium chloride is pumped up through tube 21.
  • the direction of flow may be reversed if desired.
  • tubes 20c and 21 are positioned for supplying water or unsaturated salt solution through tube 200 and for removing 90% saturated magnesium chloride brine through tube 21.
  • the tip of tube 20c is in the upper part of cavity 16, and the tip of tube 21a extends into sump 25.
  • Water or unsaturated aqueous salt solution may be supplied at ambient temperature.
  • the beds are typically at a depth of about 6000 feet, and at this depth may be as hot as 40 C.
  • This sensible heat of the ore will help to supply the heat of solution of the carnallite and will raise the temperature of the solution, thereby increasing the capacity of the well. It is most advantageous to supply water in an amount and at a rate to give a solution which is approximately 90% saturated with respect to magnesium chloride.
  • a small portion of the potassium chloride content of the carnallite is also dissolved.
  • Sodium chloride and sylvite, when present, are also dissolved to a small extent. However, the water solubilities of potassium chloride and sodium chloride are much lower than that of magnesium chloride.
  • the resulting solution will contain about 27.3% magnesium chloride and 3.8% potassium chloride, balance water. This compares with 34.3% of magnesium chloride and 26.8% of potassium chloride in the carnallite.
  • sodium chloride present in the carnallite bed
  • the percentage of each salt in a saturated solution would differ from the amounts given here.
  • the resulting solution will contain about 27.88% magnesium chloride, 2.0% potassium chloride, 1.45% sodium chloride, and 68.67% water. It can be seen that only a small proportion of the potassium chloride will be dissolved.
  • the solution as it is pumped to the surface may contain a greater or smaller amount of magnesium chloride, if desired. Dissolution takes place more slowly as saturation is approached, so that it is not usually worthwhile to attempt to form a saturated solution.
  • the solution pumped to the surface must not be too dilute because its holding power for potassium chloride in solution increases with dilution and causes a decrease in slurry recovery of potassium chloride.
  • the third phase of operations is to recover the potassium chloride slurry 26 which collects in the bottom of sump 25.
  • the magnesium chloride brine brought up to the surface is stored in holding tanks or ponds or the like (not shown) which are located above the ground.
  • FIG. 5 illustrates the third phase of operations of this invention, in which potassium chloride particles are brought up to the surface.
  • a substantially saturated solution of magnesium chloride is introduced into the well in the annulus between tubing strings 20 and 21.
  • This phase of operations is carried out most conveniently by placing the tip of the innermost tubing string 20 at or near the top of the slurry bed 26, and placing the tip of the next tubing string 21 at a short distance above the tip of tubing string 20.
  • This provides for fluid circulation which entrains the solid potassium chloride particles in the magnesium chloride solution flowing downwardly between the annulus and the tubing strings 20 and 21.
  • the tips of tubing strings 20 and 21 are moved up or down by an operator as required to obtain maximum potassium chloride removal, which is indicated by maximum density in the slurry brought to the surface and consequently by maximum pressure build-up on the discharge side of the pump which brings the slurry to the surface,
  • the magnesium chloride solution is substantially saturated with respect to magnesium chloride and potassium chloride, to minimize dissolution of potassium chloride. Ordinarily this solution is the solution obtained in the second phase of operations, or a portion thereof, containing a solution of magnesium chloride which is approximately 90% saturated.
  • the solution flowing downwardly into the well entrains potassium chloride particles, which are brought up through tubing string 20 entrained in the magnesium chloride solution.
  • the fluid velocity in tube 20 must exceed the settling rate of the potassium chloride particles in order to bring these particles up to the surface. It is desirable to reverse the direction of flow periodically to prevent plugging of tubing strings 20 and 21 with potassium chloride particles.
  • tubing strings 20 and 21 have been illustrated in FIGS. 3, 4 and 5 as concentric, it will be understood in the art that they may actually be two similar size strings located adjacent to each other within string 22. Such embodiment is illustrated in FIG. 4A.
  • the entire sequence of operations, illustrated with respect to concentric tubing strings in FIGS. 3, 4, and 5, may be carried out with the apparatus shown in FIG. 4A.
  • the wells and tubing strings therein are not necessarily absolutely vertical, in which case each tubing string shown will usually touch the adjacent tubing strings.
  • the second and third phases of operations may be combined in a single operation. In that case water is introduced into the wells, and magnesium chloride brine containing entrained potassium particles is withdrawn.
  • FIG. 6 illustrates an embodiment of the invention which is particularly suitable to the slurry mining of carnallite in steeply inclined beds.
  • a plurality of wells arranged in parallel rows as illustrated in FIG. 7 are drilled.
  • Each of these wells is surmounted by a derrick 14 in the same manner as described with reference to FIG. 1.
  • Tubing 30 containing an inlet conduit and an outlet conduit is placed in the deepest well and extends from the ground downward to the bottom of the carnallite bed 31 or a short distance therebelow.
  • This tubing contains both an inlet conduit and an outlet conduit and may be identical to that shown as tubing 15 in FIG. 1.
  • a sump 33 is formed in a salt bed below carnallite bed 31 at the bottom of the deepest well. After this sump has been formed, water is then introduced through the inlet conduit of tubing string 30 into sump 33. This results in formation of a cavity 34 which gradually grows larger as dissolution proceeds, the stages of growth of the cavity being illustrated by lines 35. Either simultaneously with the introduction of water through tubing 30 or after the cavity has progressed so that it reaches the other wells, water may also be introduced through tubing 32 in these other wells.
  • Magnesium chloride is leached out and removed through the outlet conduit of tubing 30 and may also be removed through outlet conduits in tubing 32. Most of the potassium chloride remains undissolved and forms a slurry which accumulates in sump 33. At intermittent intervals, this potassium chloride slurry is removed through tubing 30 as described earlier in FIG. 5. The potassium chloride slurry particles tumble downwardly along the boundary between the carnallite bed and the salt bed therebelow. Dissolution of carnallite is far more nearly complete in a. steeply inclined bed as shown in FIG. 6 than it is in a level bed or one having a gentle slope as shown in FIG.
  • a steeply inclined bed as described herein refers to one in which the angle at which the bottom of the bed is inclined is steeper than the angle of repose of potassium chloride particles.
  • the angle of repose is the minimum angle at which particles on a slope will retain their position; at steeper angles the force of gravity exceeds the frictional force tending to prevent falling of the particles, and the particles tumble toward the lowest point. This tumbling is precisely the thing desired, since it makes possible the nearly complete dissolution of the carnallite bed with only small pillars remaining.
  • the material directly below the carnallite bed is an insoluble material rather than a water-soluble salt.
  • this sump must be formed in the carnallite bed itself, with the result that a smaller percentage of the carnallite is recovered per well than is the case when the sump can be formed below the carnallite bed.
  • cavity 16 comes to a point at the bottom of the carnallite bed, instead of having a substantial area at this horizon as it has when there is a sump 25.
  • the potassium chloride particles may be recovered by conventional means. For example, centrifugation or filtration can be used to separate the potassium chloride particles from the magnesium chloride solution.
  • the magnesium chloride may be recovered from the solution by solar evaporation, and may be utilized in the manufacture of magnesium metal.
  • Potassium chloride particles may be processed by known techniques including recrystallization in order to obtain a substantially pure and salable product.
  • a process for slurry mining of a salt from a bed containing said salt as the less soluble component of a double salt which forms an incongruently saturated solution to recover the less soluble salt therefrom which comprises:
  • a process for slurry mining of carnallite to recover potassium chloride therefrom which comprises:
  • a process for slurry mining of a salt from a bed containing said salt as the less soluble component of a double salt which forms an incongruently saturated solution to recover the less soluble salt therefrom which comprises (1) introducing water or an unsaturated aqueous salt solution into said bed, thereby leaching the more soluble salt and forming a cavity, said leaching resulting in the formation of a substantially saturated solution of said more soluble salt and a slurry of the undissolved less soluble salt, and withdrawing said solution from said deposit;
  • a process for slurry mining of carnallite to recover potassium chloride therefrom which comprises (1) introducing water or an unsaturated aqueous salt solution into a bed of carnallite, thereby leaching magnesium chloride and forming a cavity, said leaching resulting in the formation of a substantially saturated solution of magnesium chloride and a slurry of undissolved potassium chloride, and withdrawing said solution from said bed;
  • a process for slurry mining of carnallite from a deposit including a bed of carnallite and a bed of a different water-soluble salt therebelow which comprises (1) drilling a well extending from the ground to the bed of said different water-soluble salt;
  • a process for slurry mining of carnallite from a steeply inclined bed thereof which comprises (1) drilling a plurality of wells extending from the ground to a carnallite bed, said wells terminating at different depths corresponding to differences in depth of the bottom of said bed at the respective locations of the wells;
  • a process for slurry mining of a salt from a deposit including a bed containing a double salt which forms an incongruently saturated solution and a bed of different water-soluble salt therebelow, which comprises (1) dissolving a portion of said difierent salt while preventing dissolution of the double salt so as to form a sump in the bed of said water-soluble salt;
  • a process for slurry mining of carnallite from a steeply inclined bed thereof which comprises (1) drilling a plurality of wells extending from the ground to the carnallite bed, said wells terminating at diiferent depths corresponding to differences in depth of the bottom of said bed at the respective locations of the wells;
  • a process for slurry mining of a salt from a steeply inclined bed containing this salt as the less soluble component of a double salt which forms an incongruently saturated solution to recover the less soluble salt therefrom which comprises 1) drilling a plurality of wells extending from the ground to the salt bed, said wells terminating at different depths corresponding to differences in depth of the bottom of said bed at the respective locations of the wells;
  • a process for slurry mining of a salt from a steeply inclined bed containing this salt as the less soluble component of a double salt which forms an incongruently saturated solution to recover the less soluble salt therefrom which comprises (1) drilling a plurality of wells extending from the ground to the salt bed, said wells terminating at different depths corresponding to differences in depth of the bottom of said bed at the respective locations of the wells;
  • a process for slurry mining of a salt from a bed containing said salt as the less soluble component of a double salt which forms an incongruently saturated solution to recover the less soluble salt therefrom which comprises,
  • a process for slurry mining of carnallite from a deposit including a bed of carnallite and a bed of a different water-soluble salt therebelow which comprises,

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3612608A (en) * 1969-10-02 1971-10-12 Occidental Petroleum Corp Process to establish communication between wells in mineral formations
US3895920A (en) * 1970-09-03 1975-07-22 Donald E Garrett Method of producing coarse potash
US3998492A (en) * 1975-05-23 1976-12-21 Bechtel International Corporation Method for selectively extracting magnesium chloride hexahydrate from magnesium chloride hexahydrate bearing materials in situ by solution mining
US4007964A (en) * 1975-09-23 1977-02-15 Ppg Industries Canada Ltd. Preferential solution mining process
US4300801A (en) * 1979-07-06 1981-11-17 Shell Internationale Research Maatschappij B.V. Method of solution mining salts from an underground salt deposit
EP0066972A2 (en) * 1981-05-20 1982-12-15 Texasgulf Inc. Solution mining of an inclined structure
US4504092A (en) * 1981-03-05 1985-03-12 Mines De Potasse D'alsace S.A. Treatment of carnallitic ores

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685438A (en) * 1948-06-30 1954-08-03 Kansas City Testing Lab Process for the solution mining of potassium compounds
US3355212A (en) * 1965-07-02 1967-11-28 Reynolds Metals Co Solution mining of carnallite

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685438A (en) * 1948-06-30 1954-08-03 Kansas City Testing Lab Process for the solution mining of potassium compounds
US3355212A (en) * 1965-07-02 1967-11-28 Reynolds Metals Co Solution mining of carnallite

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3612608A (en) * 1969-10-02 1971-10-12 Occidental Petroleum Corp Process to establish communication between wells in mineral formations
US3895920A (en) * 1970-09-03 1975-07-22 Donald E Garrett Method of producing coarse potash
US3998492A (en) * 1975-05-23 1976-12-21 Bechtel International Corporation Method for selectively extracting magnesium chloride hexahydrate from magnesium chloride hexahydrate bearing materials in situ by solution mining
US4007964A (en) * 1975-09-23 1977-02-15 Ppg Industries Canada Ltd. Preferential solution mining process
US4300801A (en) * 1979-07-06 1981-11-17 Shell Internationale Research Maatschappij B.V. Method of solution mining salts from an underground salt deposit
US4504092A (en) * 1981-03-05 1985-03-12 Mines De Potasse D'alsace S.A. Treatment of carnallitic ores
EP0066972A2 (en) * 1981-05-20 1982-12-15 Texasgulf Inc. Solution mining of an inclined structure
EP0066972A3 (en) * 1981-05-20 1983-03-16 Texasgulf Inc. Solution mining of an inclined structure

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ES347168A1 (es) 1969-01-16
BR6794396D0 (pt) 1973-04-10
DE1288538B (de) 1969-02-06

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