CA2086788C - Process for increasing the yield during the flotation of potash salts - Google Patents

Process for increasing the yield during the flotation of potash salts Download PDF

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Publication number
CA2086788C
CA2086788C CA002086788A CA2086788A CA2086788C CA 2086788 C CA2086788 C CA 2086788C CA 002086788 A CA002086788 A CA 002086788A CA 2086788 A CA2086788 A CA 2086788A CA 2086788 C CA2086788 C CA 2086788C
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Prior art keywords
flotation
concentrate
floated
salts
modifier
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Expired - Lifetime
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CA002086788A
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French (fr)
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CA2086788A1 (en
Inventor
Fritz Hagedorn
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K+S AG
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K+S AG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/02Froth-flotation processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/0043Organic compounds modified so as to contain a polyether group
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/006Hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/008Organic compounds containing oxygen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/01Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • C01D3/08Preparation by working up natural or industrial salt mixtures or siliceous minerals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/007Modifying reagents for adjusting pH or conductivity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/02Collectors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/04Frothers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02Ores
    • B03D2203/04Non-sulfide ores
    • B03D2203/10Potassium ores
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00Engines characterised by air compression and subsequent fuel addition
    • F02B3/06Engines characterised by air compression and subsequent fuel addition with compression ignition

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Paper (AREA)
  • Physical Water Treatments (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The process for the flotation of potash salts, using conditioning agents in the pre-flotation and post-flotation stages, is optimized. The starting material is at first floated with a partial quantity of the collector and a first pre-concentrate is formed; then the remainder of the collector as well as the frothing agent and the modifiers, especially non-polar substances, are added and a second pre-concentrate is generated.

Description

Froth flotation is widely used throughout the potash industry to isolate the sylvite (=potassium chloride) from the crude salt extracted by mining techniques. The crushed crude salts are suspE~nded in saturated salt solutions. Long-chain aliphatic amines containing 12 - 20 C-atoms are used as the flotation agents. In addition, frothing agents and in many cases non-polar substances are used as adjuvants. The frothing agents are usually alcohols or polyethylene glycol and the non-polar substances (also referred to as modifiers in the following} are liquid hydrocarbons, in particular oils of a wide range of types.
It is known that the output of coarse grains is promoted by the addition of non-polar substances. In the conventional process, the non-polar substances are added to the slurry before the first amine' charge (approximately 2/3 of the total amount}. The remaW ing amount of amine is added after approximately one third of the necessary flotation time has elapsed ("Erzmetall" 25 [1972], 298}.
It is further known that when processing coarsely spathic raw salts with maximum grain sizes of 2 mm, better results can be achicwed if the salts are me c:hanically comminuted into two fraci~ions of greater/smaller than 0.8 mm prior to flotation. The fraci:ions are separately conditioned, and the oil is added to the coarse fraction. Next, t:he two fractions are floated either togei:her or separately.
According to East German Patent DD-PS 147 059, the flotation charge is also mechanically separated into a coarse-grained and a fine-grained fraction.
To start with, the coarse material is separately floated.
Following that, the fine-grained fraction is mixed with the residue of the coarse material and also floated.
German Patent Specification DE-AS 11 85 552 also deals with the problem of floating coarse grain sizes. In that patent, the coarse-grained fraction is separated by classification or screening and then advantageously floated with a special mixture of amines. In this case, too, the non-polar substances are added before the amine.
It is known from German Patent DE-PS 34 35 124 that when fine salt from the decomposition of carnallite is floated, the decomposed potassium chloride having a grain size of less than 0.04 mm can be separated from the raw salt component if flotation is carried out with an appropriate amount of amine (50-200 g/t).
After conditioning has again been carried out using 50-150 g/t amine, the associated sylvite can be floated from the crude salt component.

~~~~~~8 There has been no lack of attempts to attain better flotation of the coarser grains by adapting the hydrodynamic conditions in the flotation apparatus, optimizing the combination of reagents and by flotative aftertreatment of the flotation residue. These measures have resulted in a certain increase in yield.
Nevertheless, the percentage of coarse sylvite remaining in the residue and not removed by flotation is relatively high.
This gives rise to the need to improve the yield by adequately waterproofing the coarse KC1 fractions, using as little amine as possible, while avoiding complex and costly separation of the crude salt into grain-size categories, and also avoiding separate flotation.
The process according to the invention is based on the .following discoveries:
- It was first discovered that the non-polar substances have no effect during the flotation of fine-grained salts (smaller than 0.1 mm).
- It Was further found that the non-polar substances do not act independently but are co-adsorbed with the amine.

- It was also found that the bulk of the amine - and thus also of the non-polar substances - is adsorbed onto the fine-grain fraction because of the large surface area.
- It has been shown that when flotation is carried out, the fine and medium-sized fractions are the first to float up because of their lower weight (post-conditioning is therefore carried out with amine).
- As a result the co-adsorbed non-polar substances enter into the froth together with the fine-grained fraction at the start of the flotation. Thus, during the subsequent flotation of the coarse fraction, where they are exclusively needed to reinforce the hydrophobic effect, they are not available in adequate amounts.
This situation led to the development of the process according to the invention, which is characterized by the specific and optimum use of the non-polar substances, i.e. the modifiers.
' At the start of flotation, the crude salt is conditioned by using a relatively small amount of amine (10-30 g/t). The bulk of the fine-grained fraction, whose flotation is in any case unaffected by the non-polar substances, is the first to float up.

After that, the flotation adjuvants, namely the frothing agent and modifier (non-polar substances, such as tar oil or diesel oil) and the remainder of the amine (approx. 30 - 70 g/t crude salt), are added to the slurry. The premature removal of the non-polar substance with the fine-grained material is prevented in this way. Instead, the modifier ends up through coadsorption with the amine on the surface of the coarser grains where it contributes to reinforcing the hydrophobic effect. As a result, the stability of the bubble/grain units is reduced so that the coarser grains are better removed and the yield increases.
The invention is further explained on the basis of the following examples:
In each of these examples, two crude salts are floated, once according to the state of the art and once according to the invention.
The quantities of reagents used are identical in the comparative examples.
The increase in yield achieved by using the process according to the invention is impressively confirmed.

Using state-of-the-art techniques, a yield of only 84.8 is achieved, but using the process according to the invention, the yield increases to 94.7.
The amount of concentrate is practically the same.
Example 1 Flotation salt: Sylvinite, grain size less than 1.0 mm, 16.8 K20 Flotation solution: NaCl and KC1, saturated, 25°C
a) Conventionalflotation Flotation agent: 70 g/t stearyl amine Frothing agent: 10 g/t "Flotol B" (trademark) Modifier: 40'g/t tar oil Result:
Pre-concentrate: 51.3 K20 Residue: 2.5$ Ki0 Yield: 89.7 b) Flotation according to the invention:
First stage of pre-flotation Flotation agent: 20 g/t stearyl amine Second stage of gre-flotation Flotation agent: 50 g/t stearyl amine Frothing agent: 10 g/t "Flotol B"*
Modifier: 40 g/t tar oil Results:
Pre-concentrates I + II 50.7 K~O
Residue 1.5~ K20 Yield 93.7 Example 2 Flotation salt: Sylvinite, grain size less than 1.0 mm, 19.2 KZO
Flotation solution: NaCl and KC1, saturated, 25°C
a) Conventional flotation Flotation agent: 70 g/t stearyl amine Frothing agent: 10 g/t "Flotol B"*
Modifier: 40 g/t tar oil Result:
Pre-concentrate: 52.3 K20 Residue: 4.2% K20 Yield: 84.8 *Trademark b) Flotation accordincr to the invention:
First stage of pre-flotation Flotation agent: 20 g/t stearyl amine Second stage of pre-flotation Flotation agent: 50 g/t stearyl amine Frothing agent: 20 g/t "Flotol B"*
Modifier: 40 g/t tar oil Results:
Pre-concentrates I + II 52.0 K20 Residue 1.5~ KZO
Yield 94.~~
Example 3 Flotation salt: Hard salt, 12.6 KZO; 15.0 kieserite Flotation solution: Hard salt solution, saturated ' a) Conventional flotation Flotation agent: 90 g/t stearyl amine Frothing agent: 20 g/t "Flotol B"*
Depressing agent: 80 g/t "Depramin"*
Modifier: 40 g/t tar oil *Trademark Result:
Pre-concentrate: 50.4 K20 Residue: 3.4~ Ki0 Yield: 78.4 b) Flotation according to the invention:
First stacte of pre-flotation Flotation agent: 30 g/t stearyl amine Depressing agent: 80 g/t "Depramin"*
Second stage of pre-flotation Flotation agent: 60 g/t stearyl amine Frothing agent: 20 g/t "Flotol" B*
Modifier: 40 g/t tar oil Results:
Pre-concentrate 49.0 K20 Residue 1.4o Ki0 Yield 91.7 *Trademark

Claims (2)

1. A process for the flotation of potash salts to isolate the sylvite (KCl) from crude salt as crushed crude salts suspended in saturated salt solutions, using flotation agents (collectors) in the form of long-chain aliphatic amines containing 12 to 20 carbon atoms, frothing agents, selected from alcohols and polyethylene glycol, and modifiers in the form of non-polar agents selected from liquid hydrocarbons, wherein initially in a pre-flotation stage a disposable residue and a pre-concentrate are generated, and in a post-flotation stage this pre-concentrate is broken down, by renewed application of the flotation process, into a final concentrate and middlings, characterized in that the starting material is first floated using a partial quantity of the collector in the amount of to 30 g/t, thereby producing a first pre-concentrate, and then the rest of the collector in the amount of 30 to 70 g/t, as well as the frothing agent and the modifier are added, thereby producing a second pre-concentrate, which both obtained pre-concentrates are jointly processed by flotation to give the final concentrate.
2. A process according to claim 1, characterized in that the crude potash salts are floated and a tar oil or diesel oil is used as a modifier.
CA002086788A 1992-01-15 1993-01-06 Process for increasing the yield during the flotation of potash salts Expired - Lifetime CA2086788C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4200810.7 1992-01-15
DE4200810A DE4200810C2 (en) 1992-01-15 1992-01-15 Process for increasing the yield of potassium salt flotation

Publications (2)

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CA2086788A1 CA2086788A1 (en) 1993-07-16
CA2086788C true CA2086788C (en) 2002-10-29

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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1185552B (en) * 1963-09-18 1965-01-21 Kali Forschungsanstalt Gmbh Process for the extraction of coarse-grained, high-percentage potassium chlorine from coarsely ground potash crude salts containing sylvine intergrowths by foam flotation
DD147059A1 (en) * 1979-11-05 1981-03-18 Helmut Koehler PROCESS FOR FLOTATION OF CALISALS
DE3435124C2 (en) * 1984-09-25 1987-03-05 Kali Und Salz Ag, 3500 Kassel Process for the production of potassium chloride with more than 55 wt.% K↓2↓O from the fine decomposition salt of carnallite decomposition

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DE4200810C2 (en) 1994-05-05
DE4200810A1 (en) 1993-07-22
CA2086788A1 (en) 1993-07-16

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