US3891544A - Process for the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof - Google Patents
Process for the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof Download PDFInfo
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- US3891544A US3891544A US378309A US37830973A US3891544A US 3891544 A US3891544 A US 3891544A US 378309 A US378309 A US 378309A US 37830973 A US37830973 A US 37830973A US 3891544 A US3891544 A US 3891544A
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- sodium chloride
- sodium
- potassium
- chloride
- nitrilo
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 75
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 37
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 28
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000008247 solid mixture Substances 0.000 title claims description 8
- 238000011084 recovery Methods 0.000 title claims description 6
- 239000003607 modifier Substances 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 238000005188 flotation Methods 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 12
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 10
- YPIAFFSSQFCMKS-UHFFFAOYSA-N n,n-diacetyl-1-cyanoformamide;hydrochloride Chemical compound Cl.CC(=O)N(C(C)=O)C(=O)C#N YPIAFFSSQFCMKS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 8
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 8
- CVTGEDNIBVTKBJ-UHFFFAOYSA-N 2-[bis(2-amino-2-oxoethyl)amino]acetamide Chemical compound NC(=O)CN(CC(N)=O)CC(N)=O CVTGEDNIBVTKBJ-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PPFPWWIOIBGOIV-UHFFFAOYSA-N C(C)(=O)O.N#CC(=O)NC(=O)C Chemical compound C(C)(=O)O.N#CC(=O)NC(=O)C PPFPWWIOIBGOIV-UHFFFAOYSA-N 0.000 claims description 4
- -1 SODIUM FERRICYANIDE POTASSIUM FERRICYANIDE Chemical compound 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- SSPBKLZIIBOACW-UHFFFAOYSA-N C(C)#N.N#CC(=O)NC(=O)C Chemical compound C(C)#N.N#CC(=O)NC(=O)C SSPBKLZIIBOACW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 claims description 2
- 239000004223 monosodium glutamate Substances 0.000 claims description 2
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000011885 synergistic combination Substances 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 238000009291 froth flotation Methods 0.000 abstract description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 4
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 2
- 230000003292 diminished effect Effects 0.000 abstract description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 2
- 235000002639 sodium chloride Nutrition 0.000 description 30
- 239000007787 solid Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZSBDPRIWBYHIAF-UHFFFAOYSA-N N-acetyl-acetamide Natural products CC(=O)NC(C)=O ZSBDPRIWBYHIAF-UHFFFAOYSA-N 0.000 description 1
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- FQTCUKQMGGJRCU-UHFFFAOYSA-N n,n-diacetylacetamide Chemical compound CC(=O)N(C(C)=O)C(C)=O FQTCUKQMGGJRCU-UHFFFAOYSA-N 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/22—Preparation in the form of granules, pieces, or other shaped products
- C01D3/24—Influencing the crystallisation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/10—Potassium ores
Definitions
- This invention relates to the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof.
- Sylvinite may be of various origin: for example it may be mined, or it may be the solid residue which remains when carnallite is decomposed with water and the magnesium chloride has thereby been dissolved.
- the more valuable component of the sylvinite is the potassium chloride. It is, therefore, customary to separate it from the sodium chloride.
- This invention has the object to improve the separation of potassium chloride and sodium chloride from sylvinite by froth flotation with a view to increasing the yield of potassium chloride.
- sodium chloride crystals habit modifier (herein crystal modifier” for short) is conventional and has a well-defined meaning. It designates a group of substances which, though mostly not interrelated chemically, have this in common that they influence the properties of solid sodium chloride.
- crystal modifier One of the uses to which they are conventionally put is the prevention of caking of sodium chloride, and this is accompanied, at least in some cases, by a change of the shape of the crystals.
- crystal modifiers are substances which, for the purposes of this invention. are to be regarded as crystal modifiers:
- Sodium ferrocynaide potassium ferrocyanide, sodium ferricyanide, potassium ferricyanide, manganese chloride, citric acid, sodium citrate, nitrilotriacetamide hydrochloride, nitrilo-triacetamide hydrosulfate, 3,5-dioxo-l-piperazine acetamide, nitrilodiacetamide monoacetic acid, nitrilo-diacetamide monoacetonitrile, monosodium glutamate, methyl cellulose, gum arabic.
- the required proportion of crystal modifier in the flotation slurry is very small, of the order of l to 500 ppm (parts per million).
- the optimal concentration will be determined for particular working conditions, the parameters to be considered being, for example, the kind of crystal modifier used, the proportion of sodium chloride in the sylvinite to be processed, the concentration of solids in the flotation slurry, the nature of the flotation chemicals used.
- the tops produced by the flotation process in accordance with this invention are so much enriched in potassium chloride that for some uses of the potassium chloride the diminished sodium chloride content is no longer harmful and the refining operation can be omitted altogether.
- the flotation is carried out in a conventional manner, for example, as follows:
- Noramac (trade name for an aliphatic amine acetate)-l00 g. per ton of sylvinite;
- the slurry containing 13 percent by weight of solids, is fed at a rate of 340 m lhour to Denver-type flotation cells from which there are separated:
- the tops In a conventional flotation operation, i.e. in the absence of crystal modifiers, the tops contain about 70 percent of KC] and 30 percent of NaCl (calculated dry), and the bottoms 8 to 1 1 percent of KCl and 89 to 92 percent of NaCl.
- the tops are passed through a series of drum filters and washing tanks (operated in countercurrent) whereby the KC] content is raised to 96 percent.
- the crystal modifier is added to the sylvinite at a suitable stage before the flotation. If the sylvinite is produced by the aqueous decomposition of carnallite, the crystal modifier may be admixed at any stage of this decomposition operation. The crystal modifier will then be found in the solid sylvinite residue.
- the crystal modifier is added at the flotation stage.
- it is admixed to the slurry which contains sylvinite in solution and is saturated with respect to both potassium chloride and sodium chloride, whereafter the slurry should be agitated for a period of time from 5 to 60 Crystal Modifier Added Bottoms amount ppm NaCl KC] dry) nitrilo-triacetamide hydrosulfate 50 94.7 5.3 potassium ferricyanide 25 94.4 5.6 sodium ferrocyanide 5 95.] 4.9 3,5 dioxo-I-piperazine acetamide I 96.3 3.7 nitrilo-diacetamide monoacetic acid I00 95.7 4.3 nitrilo diacetamide monoacetonitrile I00 95.] 4.9
- the crystal modifiers may have a synergistic effect.
- the combination of sodium ferrocyanide (l) with nitrilo-triacetamide hydrochloride (II) achieves a higher enrichment of the tops in KC] with a lesser aggregate quantity of the crystal modifiers than can be obtained with each of them singly (as indicated in the Table above).
- combinations of (I) and (II) gave the following results:
- a method for the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof comprising preparing an aqueous slurry of said solid mixture embodying at least one sodium chloride crystal habit modifier, selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide, potassium ferricyanide, manganese chloride, citric acid, sodium citrate, nitrilotriacetamide hydrochloride, nitrilo-triacetamide hydrosulfate, 3,5-dioxo-l-piperazine acetamide, nitrilodiacetamide monoacetic acid, nitrilo-diacetamide monoacetonitrile, monosodium glutamate, methyl cellulose, gum arabic agitating said slurry and allowing said modifier to act on the sodium chloride for at least five minutes, adding flotation reagents to the slurry, inducing a froth flotation separation to occur, and recovering a potassium enriched fraction from the sodium
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
In the process of separating sylvinite into its components potassium chloride from sodium chloride by froth flotation, in which potassium chloride is recovered in the tops and sodium chloride is left in the bottoms, the potassium chloride yield is increased, and its contamination with sodium chloride diminished, by the pressure of a sodium chloride crystal habit modifier in the flotation system. The modifier can be added to the flotation, or to the sylvinite, or even to carnallite before its decomposition into magnesium chloride and sylvinite.
Description
United States Patent 11 1 Becker et al.
1 PROCESS FOR THE SEPARATE RECOVERY OF POTASSIUM CHLORIDE AND SODIUM CHLORIDE FROM A SOLID MIXTURE THEREOF [75] Inventors: Alan M. Becker; Joseph A. Epstein; Michael S. Lupin; Shaul Zolotov, all
of Beer-Sheba, Israel [73] Assignee: Dead Sea Works Ltd., Beer-Sheba,
Israel [22] Filed: July 11, 1973 [21] App]. No.: 378,309
[30] Foreign Application Priority Data July 28, 1972 Israel 40016 [52] US. Cl. 209/166 [51] Int. Cl 803d 1/02 [58] Field of Search 209/166, 167
[56] References Cited UNITED STATES PATENTS 2,177,985 10/1939 Narris 2091166 [4 1 June 24, 1975 2,288,497 6/1942 Tartaron 209/166 X 2,364,520 12/1944 Cole 209/166 2,365,805 12/1944 Cole 209/166 2,468,755 5/1949 N0err..,..... 209/166 X 2,696,912 12/1954 Atwood 209/166 2,702,121 2/1955 Colin 209/166 2,937,751 5/1960 Schoeld 209/166 3,009,575 11/1961 Kean 209/166 Primary ExaminerR0bert Halper Attorney, Agent, or Firm-Lester Horwitz [57] ABSTRACT 4 Claims, No Drawings 1 PROCESS FOR THE SEPARATE RECOVERY OF POTASSIUM CHLORIDE AND SODIUM CHLORIDE FROM A SOLID MIXTURE THEREOF This invention relates to the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof.
Mixtures of potassium and sodium chlorides are of common occurrence and are an important source of potassium chloride. The proportions of the two salts in these mixtures are not defined and vary within wide limits, but in spite of this fact the mixtures are commonly referred to as sylvinite as if they were a defined mineral, and they will thus be called herein. Sylvinite may be of various origin: for example it may be mined, or it may be the solid residue which remains when carnallite is decomposed with water and the magnesium chloride has thereby been dissolved. The more valuable component of the sylvinite is the potassium chloride. It is, therefore, customary to separate it from the sodium chloride. This is conventionally done by froth flotation in which the potassium chloride forms the froth or tops, and the sodium chloride the bottoms or tailings. The flotation is carried out with the aid of conventional flotation chemicals. As practiced at present it does not achieve a complete separation of the two salts: a minor proportion of potassium chloride is lost in the bottoms, and an even greater proportion of sodium chloride remains admixed to the potassium chloride in the tops. Since for most uses of potassium chloride the contamination with sodium chloride is undesirable, the tops are subjected to a refining treatment with water which dissolves preferentially the sodium chloride but also removes some potassium chloride. Thus, potassium chloride losses occur not only in the bottoms but from the tops as well.
This invention has the object to improve the separation of potassium chloride and sodium chloride from sylvinite by froth flotation with a view to increasing the yield of potassium chloride.
It has been found, in accordance with this invention, that the potassium chloride contents of the tops are increased, and the potassium chloride contents in the bottoms are decreased, if the sylvinite slurry subjected to froth flotation contains a sodium chloride crystal habit modifier.
The term sodium chloride crystals habit modifier" (herein crystal modifier" for short) is conventional and has a well-defined meaning. It designates a group of substances which, though mostly not interrelated chemically, have this in common that they influence the properties of solid sodium chloride. One of the uses to which they are conventionally put is the prevention of caking of sodium chloride, and this is accompanied, at least in some cases, by a change of the shape of the crystals. The following are substances which, for the purposes of this invention. are to be regarded as crystal modifiers:
Sodium ferrocynaide, potassium ferrocyanide, sodium ferricyanide, potassium ferricyanide, manganese chloride, citric acid, sodium citrate, nitrilotriacetamide hydrochloride, nitrilo-triacetamide hydrosulfate, 3,5-dioxo-l-piperazine acetamide, nitrilodiacetamide monoacetic acid, nitrilo-diacetamide monoacetonitrile, monosodium glutamate, methyl cellulose, gum arabic.
The required proportion of crystal modifier in the flotation slurry is very small, of the order of l to 500 ppm (parts per million). The optimal concentration will be determined for particular working conditions, the parameters to be considered being, for example, the kind of crystal modifier used, the proportion of sodium chloride in the sylvinite to be processed, the concentration of solids in the flotation slurry, the nature of the flotation chemicals used.
It has been found, moreover, that especially good results can in some cases be achieved by the combination of several crystal modifiers. Thus, a combination of sodium ferrocyanide and nitrilo-triacetamide hydrochloride produces a particularly great increase of the potassium chloride yield in the tops even if both modifiers are used in very small quantities.
For refining the enriched tops produced by the flotation process in accordance with this invention, much less water is required than hitherto, owing to the lower sodium chloride contents of the tops, and the potassium chloride loss due to the refining operation is accordingly smaller. However, the tops produced in accordance with the invention are so much enriched in potassium chloride that for some uses of the potassium chloride the diminished sodium chloride content is no longer harmful and the refining operation can be omitted altogether.
Except for the addition of the crystal modifiers the flotation is carried out in a conventional manner, for example, as follows:
Sylvinite containing 55 percent by weight of KCl and 45 percent of NaCl, calculated on a dry basis, is fed to a mixing tank at a rate of 58 tons per hour, concurrently with 300 m lhour of a brine containing (in g./liter): KCl-93; NaCl-l24; MgCl -l38; CaCl,-8.4. To the same tank the following flotation reagents are added:
Noramac (trade name for an aliphatic amine acetate)-l00 g. per ton of sylvinite;
Pine oil 80 g. per ton of sylvinite.
The slurry, containing 13 percent by weight of solids, is fed at a rate of 340 m lhour to Denver-type flotation cells from which there are separated:
Tops: 66 mlhour, containing 47 percent of solids Bottoms: 274 m /hour, containing 3.9 percent of solids.
In a conventional flotation operation, i.e. in the absence of crystal modifiers, the tops contain about 70 percent of KC] and 30 percent of NaCl (calculated dry), and the bottoms 8 to 1 1 percent of KCl and 89 to 92 percent of NaCl.
The tops are passed through a series of drum filters and washing tanks (operated in countercurrent) whereby the KC] content is raised to 96 percent.
By one embodiment of the invention the crystal modifier is added to the sylvinite at a suitable stage before the flotation. If the sylvinite is produced by the aqueous decomposition of carnallite, the crystal modifier may be admixed at any stage of this decomposition operation. The crystal modifier will then be found in the solid sylvinite residue.
By another embodiment of the invention the crystal modifier is added at the flotation stage. Preferably it is admixed to the slurry which contains sylvinite in solution and is saturated with respect to both potassium chloride and sodium chloride, whereafter the slurry should be agitated for a period of time from 5 to 60 Crystal Modifier Added Bottoms amount ppm NaCl KC] dry) nitrilo-triacetamide hydrosulfate 50 94.7 5.3 potassium ferricyanide 25 94.4 5.6 sodium ferrocyanide 5 95.] 4.9 3,5 dioxo-I-piperazine acetamide I 96.3 3.7 nitrilo-diacetamide monoacetic acid I00 95.7 4.3 nitrilo diacetamide monoacetonitrile I00 95.] 4.9
In the tops, a considerable increase of the KC] content is achieved by the crystal modifiers. In the following list the enrichment in KC] is indicated in per cent (dry) of the total solids of the tops. Thus, ifin a conventional flotation the KC] content of the tops has been 70 percent, an increase of 3.4 percent means that the KC] content is raised to 73.4 percent, with a concomitant depression of the NaCl content, which means that less washing is required:
enrichment Additive Amount of KC] added ppm in tops, of
total tops manganese chloride ]0 3.4 50 3.0 I50 3.1 400 4.8 sodium citrate I00 6.] 200 7.3 monosodium glutamate O 9.] I00 9.8 methylcellulose 4.7 S0 5.] citric acid 2.] 50 6.7 gum arabic 50 5.2 sodium ferrocyanide 5 5.] I0 56 25 6.5 [50 Ill] 250 10.2 potassium ferrocyanide 2O 5.] potassium ferricyanide l0 5.3 25 8.4 nitrilo-triacetamide hydrochloride 10 10.6 25 9.2 50 l [.8 100 12.7 150 12.4 200 I5] nitrilo-triacetamide hydrosulfate 50 I0. I 100 l2.9 3,5 dioxo-l-piperazine acetamide 100 4.5 nitrilo-diacetamide monoacetic acid 100 5.0 nitrilo-diacetamide monoacetonitrile l 00 l .0
The figures of the above list indicate enrichment of the tops in KC], but not necessarily an absolute increase of the potassium yield. However, even the absolute KC] yield is increased by the addition of crystal modifiers in accordance with the invention, as is shown by the following table:
Additive Amount added Increase in yield ppm of KC] A ll citric acid 25 L0 sodium ferrocyanide 5 1.4 potassium ferrocyanide 20 L5 potassium ferricyanide 25 L9 nitrilo-triacetamide hydrochloride 200 ].0 mtrilo'triacetamide hydrosulfate 50 I .0 mtrilo-triacetamide hydrosulfate l 00 l .4
3,5 dioxo-l-piperazine acetamide 5.7 nitrilo-diacetamide monoacetic acid 100 L0 nitrilo-diacetamide monoacetonitrile l 00 8.2
By a further feature of the invention it is found that the crystal modifiers may have a synergistic effect. For example, the combination of sodium ferrocyanide (l) with nitrilo-triacetamide hydrochloride (II) achieves a higher enrichment of the tops in KC] with a lesser aggregate quantity of the crystal modifiers than can be obtained with each of them singly (as indicated in the Table above). Thus combinations of (I) and (II) gave the following results:
Amount of (l) Amount of (II) KC] enrichment in pp ppm p y We claim:
1. A method for the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof, comprising preparing an aqueous slurry of said solid mixture embodying at least one sodium chloride crystal habit modifier, selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide, potassium ferricyanide, manganese chloride, citric acid, sodium citrate, nitrilotriacetamide hydrochloride, nitrilo-triacetamide hydrosulfate, 3,5-dioxo-l-piperazine acetamide, nitrilodiacetamide monoacetic acid, nitrilo-diacetamide monoacetonitrile, monosodium glutamate, methyl cellulose, gum arabic agitating said slurry and allowing said modifier to act on the sodium chloride for at least five minutes, adding flotation reagents to the slurry, inducing a froth flotation separation to occur, and recovering a potassium enriched fraction from the top and a sodium chloride enriched fraction from the bottom.
2. The method of claim 1 wherein a synergistic combination of two sodium chloride crystal habit modifiers is used.
3. The method of claim 2 wherein a combination of sodium ferrocyanide and nitrilo-triacetamide is used.
4. A method according to claim 1 wherein said mixture is sylvinite produced by the decomposition of carnallite, and said modifier is added during said decomposition.
Claims (4)
1. A METHOD FOR THE SEPARATE FOR THE SEPARATE RECOVERY OF POTASSIUM AND SODIUM CHLORIDE FROM A SOLID MIXTURE THEREOF, COMPRISING PREPARING AN AQUEOUS SLURRY OF SAID SOLID MIXTURE EMBODYING AT LEAST ONE SODIUM CHLORIDE CRYSTAL HABIT MODIFIER, SELECTED FROM THE GROUP CONSISTING OF SODIUM FERROCYANIDE, POTASSIUM FERROCYANIDE, SODIUM FERRICYANIDE POTASSIUM FERRICYANIDE, MANGANESE CHLORIDE, CRITRIC ACID, SODIUM CITRATE, NITRILOTRIACETAMIDE HYDROCHLORIDE, NITRILO-TRIACETAMIDE HYDROSULFATE, 3,5-DIOXO-1-PIPERAZING ACETAMIDE, NITRILO-DIACETAMIDE MONOACETIC ACID, NITRILO-DIACETAMIDE MONOACETONITRILE, MONOSODIUM GLUTAMATE, METHYL CELLULOSE, GUM ARABIC AGITATING SAID SLURRY AND ALLOWING SAID MODIFIER TO ACT ON THE SODIUM CHLORIDE FOR AT LEAST FIVE MINUTES, ADDING FLUTATION REAGENTS TO THE SLURRY, INDUCING A FORTH FLOTATION SEPARATION TO OCCUR, AND RECOVERING A POTASSIUM ENRICHED FRACTION FROM TOP AND A SODIUM CHLORIDE ENRICHED FRACTION FROM THE BOTTOM.
2. The method of claim 1 wherein a synergistic combination of two sodium chloride crystal habit modifiers is used.
3. The method of claim 2 wherein a combination of sodium ferrocyanide and nitrilo-triacetamide is used.
4. A method according to claim 1 wherein said mixture is sylvinite produced by the decomposition of carnallite, and said modifier is added during said decomposition.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IL40016A IL40016A (en) | 1972-07-28 | 1972-07-28 | Process for the recovery of potassium chloride from its mixtures with sodium chloride |
Publications (1)
Publication Number | Publication Date |
---|---|
US3891544A true US3891544A (en) | 1975-06-24 |
Family
ID=11046608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US378309A Expired - Lifetime US3891544A (en) | 1972-07-28 | 1973-07-11 | Process for the separate recovery of potassium chloride and sodium chloride from a solid mixture thereof |
Country Status (7)
Country | Link |
---|---|
US (1) | US3891544A (en) |
CA (1) | CA993125A (en) |
DE (1) | DE2337975C3 (en) |
FR (1) | FR2194648B3 (en) |
GB (1) | GB1405319A (en) |
IL (1) | IL40016A (en) |
OA (1) | OA04451A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4325821A (en) * | 1979-08-15 | 1982-04-20 | Sherex Chemical Company, Inc. | Amine oxide promoters for froth flotation of mineral ores |
US5562943A (en) * | 1994-01-12 | 1996-10-08 | Koh; Hen-Sik | Salt compositions |
US20070099542A1 (en) * | 2005-11-01 | 2007-05-03 | Uni-Charm Corporation | Nursing pad wrapped body |
US20070100310A1 (en) * | 2005-11-01 | 2007-05-03 | Uni-Charm Corporation | Nursing Pad |
CN104058428A (en) * | 2014-07-10 | 2014-09-24 | 青海盐湖工业股份有限公司 | Novel system and method for producing potassium chloride by utilizing carnallite |
CN104384026A (en) * | 2014-10-20 | 2015-03-04 | 山西大学 | Graphic control method for direct floatation of potassium chloride and sodium chloride mixed salt |
CN111302362A (en) * | 2020-04-03 | 2020-06-19 | 天津科技大学 | Large-particle spherical salt and preparation method thereof |
US12043552B2 (en) | 2018-01-31 | 2024-07-23 | Limited Liability Company “Gsm Chemical” | Reactor for separation of sodium chloride and potassium chloride from polymineral sources and method thereof |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106583056A (en) * | 2017-01-09 | 2017-04-26 | 昆明理工大学 | Depressing agent for floating lead and depressing zinc |
CN109574043A (en) * | 2019-02-11 | 2019-04-05 | 青海盐湖工业股份有限公司 | A kind of food grade sodium chloride and its production method |
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US2364520A (en) * | 1943-06-23 | 1944-12-05 | Minerals Separation North Us | Concentration of sylvinite ores |
US2365805A (en) * | 1943-05-15 | 1944-12-26 | Minerals Separation North Us | Concentration of sylvinite ores |
US2468755A (en) * | 1947-05-14 | 1949-05-03 | Armour & Co | Fatty acid amine salt composition |
US2696912A (en) * | 1953-02-02 | 1954-12-14 | Duval Sulphur & Potash Company | Concentrating or separating of the values from soluble ores |
US2702121A (en) * | 1950-01-11 | 1955-02-15 | Public Ets | Methods of froth-flotation |
US2937751A (en) * | 1956-05-23 | 1960-05-24 | Saskatchewan Potash | Flotation reagent |
US3009575A (en) * | 1957-06-28 | 1961-11-21 | Gen Mills Inc | Collection in flotation of sylvite |
-
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- 1972-07-28 IL IL40016A patent/IL40016A/en unknown
-
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- 1973-07-11 US US378309A patent/US3891544A/en not_active Expired - Lifetime
- 1973-07-11 CA CA176,134A patent/CA993125A/en not_active Expired
- 1973-07-12 GB GB3337373A patent/GB1405319A/en not_active Expired
- 1973-07-24 FR FR7326999A patent/FR2194648B3/fr not_active Expired
- 1973-07-26 DE DE2337975A patent/DE2337975C3/en not_active Expired
- 1973-07-27 OA OA54974A patent/OA04451A/en unknown
Patent Citations (9)
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US2177985A (en) * | 1938-03-09 | 1939-10-31 | Benjamin R Harris | Ore dressing |
US2288497A (en) * | 1941-06-18 | 1942-06-30 | Phosphate Recovery Corp | Concentration of potash ores |
US2365805A (en) * | 1943-05-15 | 1944-12-26 | Minerals Separation North Us | Concentration of sylvinite ores |
US2364520A (en) * | 1943-06-23 | 1944-12-05 | Minerals Separation North Us | Concentration of sylvinite ores |
US2468755A (en) * | 1947-05-14 | 1949-05-03 | Armour & Co | Fatty acid amine salt composition |
US2702121A (en) * | 1950-01-11 | 1955-02-15 | Public Ets | Methods of froth-flotation |
US2696912A (en) * | 1953-02-02 | 1954-12-14 | Duval Sulphur & Potash Company | Concentrating or separating of the values from soluble ores |
US2937751A (en) * | 1956-05-23 | 1960-05-24 | Saskatchewan Potash | Flotation reagent |
US3009575A (en) * | 1957-06-28 | 1961-11-21 | Gen Mills Inc | Collection in flotation of sylvite |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4325821A (en) * | 1979-08-15 | 1982-04-20 | Sherex Chemical Company, Inc. | Amine oxide promoters for froth flotation of mineral ores |
US5562943A (en) * | 1994-01-12 | 1996-10-08 | Koh; Hen-Sik | Salt compositions |
US20070099542A1 (en) * | 2005-11-01 | 2007-05-03 | Uni-Charm Corporation | Nursing pad wrapped body |
US20070100310A1 (en) * | 2005-11-01 | 2007-05-03 | Uni-Charm Corporation | Nursing Pad |
US8012138B2 (en) | 2005-11-01 | 2011-09-06 | Uni-Charm Corporation | Nursing pad |
CN104058428A (en) * | 2014-07-10 | 2014-09-24 | 青海盐湖工业股份有限公司 | Novel system and method for producing potassium chloride by utilizing carnallite |
CN104384026A (en) * | 2014-10-20 | 2015-03-04 | 山西大学 | Graphic control method for direct floatation of potassium chloride and sodium chloride mixed salt |
CN104384026B (en) * | 2014-10-20 | 2016-08-17 | 山西大学 | A kind of for direct flotation potassium chloride and sodium chloride salt-mixture figure regulation and control method |
US12043552B2 (en) | 2018-01-31 | 2024-07-23 | Limited Liability Company “Gsm Chemical” | Reactor for separation of sodium chloride and potassium chloride from polymineral sources and method thereof |
CN111302362A (en) * | 2020-04-03 | 2020-06-19 | 天津科技大学 | Large-particle spherical salt and preparation method thereof |
CN111302362B (en) * | 2020-04-03 | 2021-05-07 | 天津科技大学 | Large-particle spherical salt and preparation method thereof |
WO2021196535A1 (en) * | 2020-04-03 | 2021-10-07 | 天津科技大学 | Large-particle spherical salt and preparation method therefor |
US11365127B2 (en) * | 2020-04-03 | 2022-06-21 | Tianjin University Of Science And Technology | Large-particle spherical salt and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE2337975A1 (en) | 1974-02-07 |
FR2194648B3 (en) | 1976-07-09 |
OA04451A (en) | 1980-03-15 |
DE2337975C3 (en) | 1979-05-03 |
GB1405319A (en) | 1975-09-10 |
FR2194648A1 (en) | 1974-03-01 |
CA993125A (en) | 1976-07-13 |
DE2337975B2 (en) | 1978-09-14 |
IL40016A0 (en) | 1972-09-28 |
IL40016A (en) | 1975-05-22 |
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