DE1166113B - Flotation process for inorganic ions - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WTTWl · PATENT OFFICE Internat. Class: B 03 d

EDITORIAL

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German class: Ic- 10/10

1166113
S 63282 VI a / lc
June 3, 1959
March 26, 1964

The invention relates to the recovery of. inorganic ions from solutions by adding the inorganic ions are contacted with an organic reagent to form an insoluble reaction product, and that insoluble reaction product is separated from the solution.

Flotation processes for extracting various minerals from ores have long been common known. These flotation processes essentially consist of crushing the mineral containing ores, conditioning the finely ground mineral with flotation agents and others Additives, from the floating of the treated mineral particles with air bubbles and the extraction of the mineral from the resulting foam.

In contrast, the invention consists in removing ions from solutions in the complete absence of undissolved To obtain mineral particles, e.g. B. also from wastewater from ore separation or from other surface-active substances Waste water containing substances or washing water in which the amount of solid mineral particles is relatively small, so that the resultant from the combination of inorganic ions with the collector Amount of the insoluble reaction product at least 5%, preferably at least 15%, des recovered product.

In general, the method of the invention consists in solubilizing simultaneously Cations or anions together with mineral particles, if any, with vesicles and with anionic and cationic reagents, d. H. Collectors who bring together insoluble products to form, which is transported by the rising bubbles to the surface of the solvent and removed there as a foam concentrate.

Non-metal ions and metal ions can be obtained in the same way by this process. Non-metal ions which can be obtained by the method of the invention are e.g. B. the Ions of silica, polythionates, arsenic acid, thioarsenates, thioarsenites, fluorosilicic acid and Boric acid. The non-metal ions should preferably be in the form of complex anions.

Simple or complex metal ions can be produced in the same way by the method according to the invention be won. Such metals are e.g. B. the alkaline earth metals calcium, strontium and barium, the metals aluminum, manganese, chromium, gallium, germanium, molybdenum, tantalum, hafnium, tungsten, Flotation process for inorganic ions

Applicant:

Felix Sebba; Johannesburg (South Africa)
Representative:

Dr.-Ing. J. Schmidt, patent attorney,
Munich 2, Hermann-Sack-Str. 2

ίο

Named as inventor:

Felix Sebba, Johannesburg (South Africa)

Claimed priority:
^J 5 Great Britain of June 4, 1958 (17 887)

Rhenium, osmium, palladium, copper, silver, gold and platinum, the rare earths praseodymium, lanthanum, Samarium, cerium, terbium, ytterbium and holmium or the actinides such as uranium, neptunium and thorium.

Examples of complex ions are the anionic complex of uranium with sulfate ions, the chloroplationation in water, the complex cyanide ions of metals such as gold, silver, iron or cobalt, Ion complexes of ammonia with metals such as copper, zinc or silver, the complex fluoride ions of metals such as beryllium, also silicates and other complex ions such as molybdates, vanadates or borates.

The collectors used in the process of the invention are generally ionic surfactants Collectors as used in ore flotation processes. These collectors must have at least one hydrophilic (non-polar) and at least one aerophilic (polar) center of activity. They must carry an electrical charge with a sign similar to that of the one to be gained Metal ion is opposite.

A surfactant anionic collector, i. H. a collector that is a surface active agent in aqueous solution Ion with a negative charge,

z. B. a lauric acid soap is used to remove soluble metal cations from the solution. On the other hand, a surface active cationic collector, i.e. H. a collector who is in aqueous solution releases a surface-active positively charged ion, e.g. B. Lauryl pyridinium chloride, used when a metal anion is to be extracted from the solution.

409 540/203

3 4

Cationic collectors, which are necessary for the new process molecule. To prepare for the procedure are mostly compound-withdrawing cationic and anionic collectors with an amine nitrogen. These compounds are are derivatives of vegetable and animal Triz. B. alkyl, aryl and arylakylamines and the deglycerides, preferably vegetable and such speaking amine and quaternary halogen salts. 5 triglycerides obtained from marine animals- arylamines are z. B. picolines, pyridines, quinolines. These triglycerides can contribute to their free fat and their homologues and lower alkyl-substituted acids, which are then known as analogs, Ionic collectors used or for the same examples of cationic collectors, which with grain purpose in the ammonium or alkali metal salts too plex metal anions and non-metallic anions similar purposes can be transferred, Ions react in polar solutions, are z. B. the To obtain a cationic collector, werquaternary Ammonium compounds, such as tridene, convert the fatty acids into methyl-n-octylammionium chloride, trimethyl-n-decyl amines, nitriles or quaternary salts by known processes. It ammonium chloride, trimethyl-n-dodecylammonium- is also preferable that the hydrocarbon chloride, Trimethyl-n-octadecylammonium bromide, tri-chains of these collectors carbon-carbon-dopethyl-n-hexadecylammonium iodide; Mixtures of pel bonds contain. When quaternary amquaternary Salts from tallow fatty acids, from tree monium, diamine or triamine collectors used woolseed oil fatty acids, soybean oil fatty acids and, it is particularly preferable that the sampled coconut oil fatty acids, from fatty acid mixtures of at least one hydrocarbon residue with 8 to Tallow, corn oil, soybean oil, coconut oil, alkyl containing 20-22 carbon atoms, amines, such as diamylamine, didodecylamine-n-decyl- In the term used »insoluble reacamine, n-tetradecylamine, tri-n-octadecylamine, n-octation products «and in similar expressions decylamin and mixtures of amines. Different - "insoluble" does not mean that the "solubility" like collectors are also z. B. ammonium-phenyl- an equilibrium between the ions in the solution nitrosohydroxylamine, 1-n-dodecylpyridinium iodide, 25 and a solid ionic crystal, but rather Octadecyl-beta-oxyethyl-morpholinium bromide, beta-that the reaction product of oppositely ge-stearamidotrimethylammonium methyl sulfate, Octadecylpyridiniumjodid, Octadecyl-alpha-picolinium- are not dependent on unabdecylpyridinium iodide, since they have lost entropy. So bromide, hexadecylquinolinium bromide, decylstyryl- this term refers to products that are attached to pyridinium chloride, dodecylpyridinium phenyl sulfonate, 30 of the interface between solvent and dimethyldodecylphenylammonium phenyl sulfonate, 2- surfaces are adsorbed, d. i.e., the individual product mercaptobenzothiazole derivatives, Numerous imidazo molecules are no longer evenly distributed in the solution lin- and imidazolidine derivatives and dimethyl-n-hexa-, but are mainly on the solution decylbenzylammonium chloride. central vesicle interface localized. The products The anionic collectors are of two types 35 at the interface can be regarded as crystals Types: the oxhydryl compounds, which contain only one product molecule. if Metal or hydrogen with the hydrocarbon part of these crystals in the removed foam of the collector are compressed by an oxygen atom, they form a foam mass, den, and the sulfhydryl compounds, in which the is very insoluble, but no larger crystals the compound contains 40 mediated by a sulfur atom.

will. The Oxhydrylsammler are z. B. carboxylic acids, this insolubility of the

acidic alkyl sulfates, sulfonates and phosphates and reaction products formed in moderate processes

Phosphonates. The sulfhydryl compounds are e.g. B. is correct to a certain extent the effectiveness

Mercaptans, thiocarbonates (xanthates), thioureas of the process. A very high percentage of the and dithiophosphates. Examples of anionic metal ions can be found rapidly from the

Collectors are z. B. the sodium, potassium or Am solution can be removed when the reaction product

monium salts of rosin and its acids, is very insoluble, while the more soluble reac-

the tall oils and animal and vegetable oils; tion products can only be removed to the extent that

Naphthenic acids; Sodium n-octyl sulfate; Potassium-η- as they are adsorbed and removed in the foam,

dodecyl sulfate; the ammonium salt of n-dodecyldi- 50 The rate of collection of ions in the

ethylene glycol sulfate; The sodium salt of crude or solution can often be determined visually, since

Purified petroleum sulfonic acids, beta-phenyl-propionic ion solutions often change color when the ions

acid; Pelargonic acid; Acid mixtures from linseed oil can be removed. So are solutions with blue

Soybean oil, palm oil, corn oil and cottonseed copper ions and copper complex ions or yellow

oil; Monosodium alpha sulfopalmitate; Disodium 55 xanthate ions gradually clearer and finite

alpha-sulfostearate, l, 3-diphenyl-2-thiourea and water-white, to the extent that the ions are removed

Thiocarbanilide. The examples given above for will.

cationic and anionic collectors only provide As already indicated, the _pH value determined by the

represents a selection of the many collectors, some of which solution is the feasibility of the process,

it is known that they are technically usable and 60 because it is known that metal salts in every solution in different

used in flotation processes. are soluble to different degrees, of which the

The required number of carbon atoms in the chemical separation of metals and in the

aerophilic (polar) part or parts of the collector qualitative analytical method use

molecule to give the collector the desired aerodynamic power. Reaction products of the com-

to give hydrophilic properties, complexes Urananions 65 is soluble at a _pH value of 3.9 according to the nature

of the collector different. In general, 5 and at a _pH value of 5.1 are insoluble, when a

up to 24, preferably 8 to 22 carbon atoms is used in certain collectors. Using

at least one aerophilic part of the collector of another collector, they are at a p _H -value

insoluble of 2.0 and at a _pH value of 2.0 soluble. This phenomenon can also be used for separation of a metal ion from others in the solution when the solubility at a certain _pH value are different to some extent.

The ion solvent must of course be able to dissolve the ion to be concentrated and the collector and also be polar enough that the metals and collectors are sufficiently ionized to be Reacts with the collector to form a reaction product which is present in the solvent and Bubble medium is insoluble, can be detected. Suitable solvents are e.g. B. water, anhydrous liquid ammonia, anhydrous lower alkylamines, lower nitroalkanes, anhydrous lower ones aliphatic alcohols and acids, lower liquid alkyl chlorides such as methylene chloride, and anhydrous lower aliphatic ketones and ethers. The preferred solvent for the process according to the invention however, is water.

The concentration of the collector in the solvent is one of several variables that affect its effectiveness of the procedure. In general, the collectors have soap-like properties and form colloid particles when their concentration is increased so much that the so-called critical colloid concentration is achieved. If colloidal particles are present in the solution to a large extent, it will become a colloidal solution or a sol form, which keeps the ion to be removed in solution. In such cases the ascending Bubbles cannot capture a large portion of the metal ions, and this is the effectiveness of the process greatly reduced.

"Colloid particles" are understood here to mean an aggregate that is formed by a number of secondary forces loosely held together molecules, whereby the secondary forces are weaker than the primary valence bonds. Such particle aggregates are often referred to as “micelles”.

The critical colloid concentration is believed to depend on many variables, e.g. B. of the _pH value of the solution, the temperature of the solution to below the melting point of the reaction product, the ionic strength of the solution and the age of the collector solution. In general, the critical colloid concentration of the collectors in aqueous solution is from about 0.1 to about 0.001 mol. For example, the critical colloid concentration of potassium laurate in water is about 0.02 mol, while the critical colloid concentration of potassium myristate in water is 0.006 mol. Expressed in grams, a concentration of 1.5 g / L potassium myristate or approximately 0.019 g / L sodium cetyl sulfate in water would approach the critical colloid concentration.

If there is an excessive amount of collector dissolved in the solvent and colloidal particles form, that is Poor recovery or the process completely unusable; a very strong dilution of the Solution with additional solvent sometimes destroys the colloid particles, and subsequently flotation can take place.

The age and history of the collector will also determine the effectiveness of the procedure. For example, experiments have shown the quantitative recovery of cobalt cyanide ions from aqueous Solutions at concentrations of 1 mg / 1 that the cationic collector sometimes so little were effective in that they reacted only 10% stoichiometrically.

One can overcome this difficulty in part by finding fresh solutions from collector ions in polar carriers, such as ethanol or propanol, where the critical colloid concentration of the ίο Collector's high, collects, and collectible enters the solvent from which the ion is to be recovered. The effectiveness is further increased when a collector solution in a non-polar solvent, e.g. B. petroleum ether, Ethyl acetate or luminous oil, produced, the solvent removed, the collector in a polar Solvent dissolved and the resulting solution immediately into the solution from which the ions are removed should be entered.

As noted, it is preferable to use dilute collector solutions in a polar solvent, which, when ionized, carries a charge to be removed that is opposite to the metal ion, to a solution of metal ions to be added so quickly that practically no colloid formation takes place, and so quickly that all colloid particles are broken up in the soap solution to be added. While the collector to Solution is given, bubbles are driven through the turbidity, so that these the adsorbed molecules carry the reaction product to the surface, where they accumulate or by means of conventional Procedure can be removed.

The rate at which the collector is added is determined, among other things, by the metal ion concentration and the critical colloid concentration. If the metal ion concentration is low, several equivalent collectors can be added to the solution to effect rapid concentration of the metal ion without exceeding the critical colloid concentration of the collector. The amount of collector used in the process will depend on a number of factors, e.g. As the number of reactive radicals in the Sammlermolekeln, the valence of the ion to be detected and the _pH value of the solution. There were purified from 0.1 mg / 1 containing aqueous solutions Kobalticyanidanionen collector at concentrations of about 10 ^-5 to 10 ^-6 mol, and 0.1 mg / 1 containing aqueous copper ion solutions at concentrations of collector 10 ~ ⁵ Mol. This is possible because the metal ions polymerize apparently at around neutral _pH value (6 to 7) and far lower than stoichiometric equivalent amounts collectors are necessary to a given amount of winning metal ion. As can be seen, the range of variation in the amount of collector that is necessary to obtain a given amount of ions is large. It is preferable to use an amount of collector that is from about 0.001 to 10 equivalent collectors to an ion equivalent. In particular, it is preferable to use stoichiometrically equivalent amounts of collectors.

The reaction products that are formed when the above collectors are introduced are removed from the solution by flotation, d. H. get out of the solution with the help of practically non-reacting gas bubbles removed. Usable bladder materials are e.g. B. gaseous

After using excess collector, wipers remove the insoluble Lift the reaction product off the surface of the liquid and transfer it to a suitable vessel. 5 A stream of air can also be used to force the foam into the collection vessel. the Bubbles can also be collected by using a small amount of a superficial solvent run over a weir and through a filter

Foams are well known in the ore flotation art and can be used in the process of the invention can also be used well.

After concentration on the surface and removal, the insoluble reaction products can treated in different ways, depending on the value of the extracted item and the Cost to the collector depends. If that won-

Hydrocarbons such as methane, ethane and butane;
gaseous halogenated hydrocarbons such as
Freons: and gases such as air, carbon dioxide, nitrogen and argon. To remove the insoluble
Reaction products from the solvents used for the ion recovery process of the invention are preferred to the use of air.
In polar solutions they are concentrated
Collector ions apparently at the interface between the solvent and the interior of the bubble. In order to remove the floating foam, it is preferable to use it as much as possible. Method of removing thick and thin small bubbles to use and one possible
long bubble path to the surface to avoid the
to ensure the greatest possible capture of metal ions.
With small reaction vessels it is possible to use the 15th
Decrease the rate of rise of the bubbles and
thereby increasing the effectiveness of the collection,
by imparting a countercurrent movement to the solvent.

The volume of the blown gas is not critical 20 nene ion is much more valuable than the collector, and can be varied widely, depending on the need the collector may not need regained form of the solvent container to become the solvent, and the insoluble reaction product by means of and the mean diameter of the bubbles. can be incinerated and the inorganic material ent-that Volume of the blown gas or the size of either as metal in the case of precious metals or as However, bubbles should in no way be such that the upper mineral oxide is obtained, the surface of the solvent is in great motion. When compared the cost of the reagent

As has already been stated, which are important to the value of the recovered metal, collector ions concentrate at the interface between the solution, it is possible to develop a process for the recovery of the agent and the bubble and rise with the bubbles to develop the reagent, especially if the surface. If the bubbles of subsequent 30 metal can form an insoluble compound. For blowing it can be lifted out of the surface, for example a uranium soap, which is created by means of a cation, a foam in which the insoluble niche quaternary ammonium soap obtained reaction products, the metal soaps, aggregate with an alcoholic solution of a base. This foam is easily removable. If like potassium or calcium hydroxide, however, the blisters are treated to a greater extent by doors. After treatment and brief standing bulence bursts, an insoluble uranium salt is formed, either a relatively high soap concentration close to potassium or calcium uranium, while the soap is formed as the surface of the water, which results in quaternary ammonium hydroxide remaining in solution, This soap forms colloidal solutions again after treatment with borrowed soap molecules, which impairs the recovery of the corresponding acid in the original reagent. j _n an alcoholic solution that is in non-

The speed of the stream of bubbles can change the polar solvents for a new operation be regulated by that the total volume can be prepared.

the bubbles to the extent to which the water and air are used as solvents and decreases

transparency of the water near the surface 45 of bubble media in the preferred embodiment of the solvent increases. When used near the top of the invention.

surface of the water no turbidity occurs, form The effectiveness and selectivity of the process

no colloidal solutions and the speed is determined by many variables, e.g. B. the condensation of the bubble stream can be increased to close to the centering and ionic strength of the collector, the resting point at which a tendency occurs, 50 of the surface of the solvent or of the bubble where cloudy colloids near the surface of the medium, the solubility and ionic strength the metal-liquid form. The formation of cloudy colions and the solubility of the reaction products from loidal solutions reduce the effectiveness of the metal ion and collector and the p _n value of the process and must be avoided. It is pre-solution. The collector ions have electrical charges to maintain the surface of the liquid in a 55 gene, which range from a relatively weak calm state, that is, in a state to relatively strong, resulting from such a factor of moderate turbulence in which the rising gates depends, how the extent of the solvation bubbles are practically completely preserved when respectively hydration and the electron negativity of they break through the surface of the liquid, so molecular residue. The strength of the charge determines that no large amounts of colloidal solution 60 are formed, among other things, in part the speed of the formation. The rate of bubble flow or reaction between the collector ions and the to

winning ions. This fact helps keep one ion apart from the others in the solution can separate. For example, gold usually becomes 65 by leaching with ores containing gold Potassium cyanide obtained. The residue contains uranium and traces of cobalt. Generally will the uranium from the residues with diluted

the total volume of the bubble gas can, as before
above, can be regulated by visual or mechanical determinations of the turbidity of the solutions.

The insoluble reaction products formed in the process can be removed from the surface of the
Liquid as a thin or thick layer of foam, depending

Sulfuric acid leached in the presence of pyrolusite and adsorbed on ion exchange resins. In the Sulfuric acid solution forms an acid-stable cobalt cyanide and is poisoned by the ion exchange resins the resins so strong when passed through that they can no longer be used and must be discarded. So a tiny little amount of cobalt cyanide, usually 1 mg / 1 der, enlarges Solution, meaning the cost of uranium extraction. It was found to remove the cobalt cyanide by contacting the cobalt cyanide with a strongly cationic collector brings and the insoluble product thus formed is floated off. This is due to the fact that the cobalt cyanide are strongly anionic and react easily with the strongly cationic collector, while the weaker anionic uranyl sulfate ions react with the collector at a shorter distance.

The solubility of the insoluble reaction products depends on the branching and the chain length the hydrophobic (aerophilic) chain. This fact can lead to the removal of a cation by FIo- ' tation can be used while another remains in solution. This is how strontium appears through palmitation does not get floated from aqueous solution, but it is floated off by stearation. On the other hand, copper is easily flooded away by the palmitation. Similarly, you can Metals are turned into complexes, reducing their charge and the resulting solubility of the change formed product. This particularly applies to the alkali metals, which are called silicates and similar ions can be obtained. For example, quaternary ammonium collectors are in acidic solutions soluble, while the reaction products of metals that form anion complexes are insoluble and are stable under the same acidic conditions and of unwanted cations present that remain in solution, can be separated.

If the ion to be detected occurs only as a cation, the situation is complicated by the fact that the collector must be anionic, and such collectors are generally salts of weak acids and therefore readily hydrolyze in acidic solution to the insoluble fatty acids, although the fatty acids are introduced by introduction of electronegative substituents, such as chlorine or - SO ₃ H, in the long hydrocarbon chain could make stronger acids. In general, the long chain alkyl sulfonates sufficiently strong acids to be useful in dilute acid solutions, and they must be used at _pH values at which fatty acids are insoluble. In very dilute solutions, it is possible, ions, to obtain such as copper ions, in solutions with a nearly neutral _pH value, and under these conditions even the weakly acidic fatty acids can be used.

It is preferable to use uranyl sulfate, vanadate, molybdate, Chloroplatinate, aurichloride, fluoberyllate, silica, polythionate, chromates and ferrocyanide anions from aqueous solutions with dodecylquaternary chloride and laurylpyridinium chloride as Collect collectors, and copper, cobalt and nickel ammonium complexes along with thorium anions with an alkali laurate soap. To recover detergents from aqueous solutions, it is preferred to use polyvalent metal cations, e.g. B. of aluminum and iron.

example 1

11 solution from a uranium extraction plant with 1 g uranium in the form of uranyl sulfate per liter was poured into a narrow 5-1 beaker with water on 21 diluted. In such a solution, the uranium is in the form of an anionic complex. It ammonia was added until the precipitation of iron just started and the solution was diluted with Sulfuric acid acidified until the precipitate had just gone back into solution. In the lower part of the solution was blown through a sintered glass manifold, and air was blown there was a 25% solution of didodecyldimethylammonium bromide in ethanol, which was also a little Containing propanol, added in portions of 0.1 ecm each. The solution turned cloudy and it pooled a foam on. As the bubbles grew together and burst, the color of the foam became

2o. cream-colored to yellow, which is characteristic of uranium is. The foam was separated from time to time by decanting the liquid. After yourself about 5 l of foam had formed, which required 20 ecm of the solution of the quaternary ammonium salt, Analysis of the solution showed that 97% of the uranium present had been removed. The foam was treated with an alcoholic potassium hydroxide solution and was immediately broken. The lump was broken up by rubbing and it congealed Precipitation from potassium urate. This precipitate was almost iron-free, but contained some manganese, which was present in significant amounts in the treated solution. The reagent used remained in the alcoholic solution and could be used again after acidification.

Example 2

Using the cited in Example 1, the general operation of a number of retrievals various complex metal anions at a slightly acidic _pH value was conducted (5 to 6), wherein different collectors were used as listed in the table below.

Complex
Metal anion Collector NS
lot aum
colour ₅ o uranyl sulfate .... A. plentiful Yellowish Uranyl sulfate .... B. plentiful Yellowish Chloroplatinate .. A. moderate Yellowish Chloroplatinate .. B. moderate Yellowish Cobalt cyanide ... A. moderate Yellowish ₅₅ Cobalt Cyanide ... B. moderate Yellowish Vanadate A. moderate Yellowish Vanadate B. moderate Yellowish Molybdate A. moderate ^ ta ^% ^ JL ^ mJ AA 4 ^ JtJL
Yellowish Molybdate B. moderate Yellowish 6o auricyanide A. moderate Yellowish Auricyanide B. moderate Yellowish Ferrocyanide .... A. moderate Yellowish Ferrocyanide .... B. moderate Yellowish

Collector A is lauryl pyridinium chloride.
Collector B is didodecyldimethylammonium bromide.

Heavily polluted wastewater can contain ferrocyanide anion treated to remove dissolved katio-

409 540/203

to remove niche detergents from it. The cleaning agent and the ferrocyanide are then separated from one another again from the deposited mass, as explained in Example 1.

5 Example 3

11 Solution with approximately 3 mg of cobalt in the form of Cobalt cyanide was placed in a separating funnel and 0.1 ml of 25% strength didodecyldimethylammonium bromide solution in ethanol added, the solution just acidified using methyl red and shaken well. A foam formed. After standing 10 minutes the Let the liquid run off and the foam that remained with a few cubic centimeters of ethyl acetate offset. The foam was destroyed and the soap dissolved. The ethyl acetate was in a quartz vessel separated and then incinerated the soap. The cobalt content in the ash residue became colored metrically analyzed.

Example 4

Just enough ammonia was added to a copper sulfate solution containing about 1 g of Cu ⁺⁺ to dissolve the precipitated copper hydroxide in the form of the cuprammonium complex. Air was bubbled through it and the sodium salt of a higher secondary alkyl sulfonate, known under the trademark Teepol, was slowly added to the solution in 1cc portions. The foam gradually turned greenish and the deep blue color of the cuprammonium ion almost completely disappeared, indicating a very low concentration of copper. The foam mass consisted of copper soap.

Analogously, a number of cations were separated by means of various collectors, such as from the can be found in the table below. was then diluted with 300 ecm of water, which the Test solution revealed. The collector solution was made up of three drops of a distilled mixture of higher fatty acids, obtained from cocoa oil by hydrolysis in 8 to 10 ecm of ethanol and Cooked on an open flame for 1 minute.

The prepared solution containing the Cu complex _{ion, which had a p, r} value of 9.3, was placed in a glass funnel with a rubber rim, 8.4 cm in diameter and 7.6 cm deep, which had a base plate sintered glass with a diameter of 8.4 cm, poured. The air flow was then turned on so that a well-distributed bubble column was obtained, but no excessive turbulence occurred on the surface of the solution, and the collector was gradually added. A moderately blue foamy precipitate of copper soap rose to the surface of the solution and was removed with a spatula until no blue color appeared in the foam. Two more drops of concentrated ammonium hydroxide solution continued to form blue foam. The deposition was complete after about 22 minutes. The final solution showed a ρ ,, value of 8.7.

According to this procedure, further copper ion extractions were carried out under conditions the results of which are given in the table below.

Collector

Monosodium alpha sulfopalmitate

Disodium alpha sulfostearate

Complex
ammonium Collector foam ion Amount of paint Copper .... Potassium palmitate Precipitation greenish Nickel .... Potassium palmitate I.
Precipitation greenish Nickel .... secondary Na moderately greenish Alkyl sulfonate Cobalt .... secondary Na moderately greenish Alkyl sulfonate Cobalt .... Potassium palmitate Precipitation greenish

Distilled mixture
higher fatty acids,

Mixture of fatty acids
with 8 to 18 carbon atoms

Mixture of fatty acids

with 8 to 18 carbon

atoms

Mixture of stearin and!
Palmitic acid j

9.0

4.5

8.9

10.5

8.1

Foam quantity I color

voluminous blue

- blue moderately blue

moderately blue

-. Violet voluminous blue

55

Example 5

A recovery apparatus was made consisting of a 8.4 cm in diameter Glass funnel that was 3 inches deep. The funnel was provided with a rubber rim, the one had such a shape that it formed a drainage trough for the collection of the precipitate To facilitate foam.

Three drops of concentrated ammonium hydroxide solution were added to 20 ecm of copper sulfate solution (with 3 g of CuSO ₄ per liter) in order to generate a complex copper anion, and this solution

Example 6

According to Example 5, a dilute ferrocyanide ion solution was treated which contained about 0.25 g of potassium ferrocyanide in about 300 ecm of water. The pale yellow solution was then acidified with hydrochloric acid and a small amount of air was introduced into the funnel, whereupon a previously briefly boiled solution of approximately 0.1 g of laurylpyridinium chloride in 5 to 10 ecm of ethanol was slowly added. A yellow precipitate formed on the foam layer. After the ion was completely eliminated, the solution had a p _ir value of 3.0.

13 14

The following results were achieved with other collectors in ferrocyanide ion separation:

Collector

solution lot Generated blue. foam colour p _H value moderate yellow 1.9 moderate White 3.1 - Violet * 2.9 - Violet* 3.0 - Yellow purple 3.0 Cream pink 1.6 easy Cream pink 1.9 - Cream pink 1.7

Chloride salt mixture of primary amines with 8 to 18 carbon atoms

Mixture of trimethylalkylammonium chlorides with alkyl radicals of 8 to 18 carbon atoms

Mixture of dialkyldimethylammonium chlorides with alkyl radicals of 8 to 18 carbon atoms

Mixtures of quaternary mono- and dialkylammonium chlorides with alkyl radicals of 8 to 18 carbon atoms

Mixtures of alkyltrimethylammonium chlorides with alkyl radicals 12 to 14 carbon atoms

Chloride salt mixtures of primary amines containing 8 to 18 carbon atoms

Chloride salt mixtures of primary octadecyl and octadecenyl amines

Chloride salt mixtures of primary amines with 16 to 18 carbon atoms, the approximately 2% C14 primary amines with 14 carbon atoms contain

* The color may have been caused by traces of iron, the Berliner

Solutions containing dilute uranium ions can be prepared in the same way. It arise yellow precipitates when using mixtures of alkyltrimethylammonium chlorides consist of quaternary uranyl compounds as collectors.

Dilute nickel nitrate solution that has been made alkaline with ammonia is used after light green foam precipitates obtained using the same deposition method. This can also be done analogously Cobalt ion as an initially blue foam precipitate that turns green after adding a little ammonia precipitate from a dilute cobalt salt solution.

Example 7

To remove calcium from pure tap water, 300 ecm of water was added along with the Collector abandoned in the separator. The collector used consisted of a solution of some Drops of a mixture of stearic acid and palmitic acid in ethanol made with alcoholic potassium hydroxide were saponified. After adding the collector with simultaneous air supply, a light foam containing a precipitate of white calcium soap.

Example 8

To extract metal ions from seawater, a 100 m long pipe is attached to an anchored floating weir, through which a steady stream of air bubbles and the selected collector are passed. The pipe is said to be sunk to a depth of 100 m in a non-turbulent area at a water speed of approximately three knots. The floating weir is designed to encompass the full area from which bubbles can emerge in order to capture all of the precipitation, regardless of the direction of the wind or water current. When three nodes the volume of water passing through the bubble curtain in one hour is, about 55 cbm x 10 ^e. This volume of seawater contains metals in the following order of magnitude:

Copper .. 50 to 500 kg

Lead 220 kg

Zinc 275 kg

Cerium 20 kg

Silver 16 kg

Iron 200 kg

27 kg 5 kg 150 kg

1.5 kg 300 g
Aluminum ... 27500 kg

molybdenum

nickel

uranium

Mercury ..
gold

Since the collectors can each be recovered and reused, it is a continuous one Procedure possible.

Example 9

To 11 a uranium-containing solution that is less than Containing 1 mg of cobalt in the form of cobalt cyanide, 4 ecm of a 15 mg / cem didodecyldimethylammonium chloride in isopropyl alcohol-containing solution added in aliquots of 2 ecm and Air blown through for 1 hour. The collected foam was incinerated and analyzed. There were 0.3 mg cobalt found next to some silica, but no uranium. Another addition from the collector in 2 ecm fractions there was no longer any separation of Kabolt, but some silica. After 10 ecm des Collector's admission, uranium also began to precipitate. This confirms the selectivity of the process, since the uranium content in the uranium-containing solution is approximately 1 g / l. The inventive Process can also be used to clarify and remove silica, which not only if it is present in appreciable amounts, it makes filtration difficult, but also a ion exchange poison because it is adsorbed rather than uranium.

Example 10

To extract the small amount of copper that is still present in the dead rock after flotation is, the ground residues are washed again with water and poured into a with S brought fresh water to the flotation chamber. The water is acidified with sulfuric acid and then diethylxanthate in the form of an alcoholic concentrate added so quickly that the Collector remains below the critical colloid concentration. Air is blown into the flotation chamber. The foam is collected for a while as the copper ions float rather than the copper particles will.

There are many processes known for the purpose of ionizing metals, which only with great difficulty can be floated. The method according to the invention shows that a very good ion recovery together with only a low flotation from these minerals made possible in an economical manner will.

Claims (7)

Patent claims: 1. Flotation process for inorganic ions, characterized in that depending on Charge the ion to be floated to an anionic or cationic collector in one below the Micelle-causing concentration is added and that then the insoluble reaction products floated with blowing in gas and discharged as foam are, the size and speed of the gas bubbles are dimensioned so that a Turbulence of the solution level is largely avoided. 2. The method according to claim 1, characterized in that that a collector is used, the polar moiety of which is approximately 5 to 24, preferably Contains 8 to 22 carbon atoms. 3. The method according to claims 1 and 2, characterized in that the collector in a polar organic solvent is dissolved in the solution. 4. Process according to claims 1 to 3, characterized in that the polar solvent Water and air is used as the flotation gas. 5. Process according to claims 1 to 4, characterized in that for the flotation of Uranyl sulfate, vanadate, molybdate, chloroplatinate, aurichloride, fluoroberyllate, silica, Polythionate, chromate or ferrocyanide ions as collectors of quaternary didodecyldimethylammonium halides or lauryl pyridinium chloride can be used. 6. Process according to claims 1 to 4, characterized in that complex ammonium anions floated by copper, cobalt or nickel or thorium oxide anions with alkali laurates will. 7. The method according to claims 1 to 6, characterized in that the effectiveness the collector is increased by first placing the collector in a non-polar organic Solvent dissolves, drives off the solvent and the collector is now in a polar organic solvent dissolves and the resulting solution immediately in the solution from the ions to be brought to the separation, brings in. 409 540/203 3.64 © Bundesdruckerei Berlin