FI61642B - SUSPENSION OF SUSPENSION OF SULFID MILLS - Google Patents

Description

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^ 45) Patent granted September 10, 1932

Patent Meddelat V ^ (51) Kv.lk.3 / lnt.CI.3 B 03 D 1/02 SUOMI — FIN LAND <*) Pttannlh «k« imn - PKMtaMMuiing 732067 (22) H «k« mltpllvl —AMWenlngfdaf 17.07 .73 (23) The beginning of the cloud— Glltljhttsdtf 17.07.75 (41)

Patent and Registration Board ______-. . . .. ....

„. . (44) Nihtivlkelpsnon | » Date of publication. - οη ο0

Patent- and registerstyrelsen '' AmMnn uttagd och uti.tkrift «n puuicarad dl. u;>. Oe: (32) (33) (31) Pyy4 «ty« Toiksus-Bvjtrd priority 01.08.7¾ USA (US) 1 + 939 ^ 6 Proven-Styrkt (71) American Cyanamid Company, Wayne, New Jersey, USA (US) (72) Donald Edwin Zipperian, Tuscon, Arizona, James Allen Jones, Tuscon,

Arizona, Thomas Brian Buza, Tuscon, Arizona, USA (7¾) Oy Kolster Ab (5 * 0 Aqueous solution suitable as a collector solution for the recovery of copper from sulphide ores by flotation -

The invention relates to an aqueous solution which is suitable as a collecting solution for recovering copper from sulphide ores by foaming and which consists of an aqueous solution of a dithiophosphoric acid derivative in which thiocarbamate has been dissolved.

There are numerous organosulfur compounds of varying structures. They have many different uses depending on their nature and characteristics. Organosulfur compounds are typically used in the manufacture of artificial silk and cellophane, as insecticides, as fungicides, and as foaming agents in mineral enrichment. Certain organosulfur compounds are water soluble, while others are not. In many cases, the lack of water solubility prevents the widespread use of such organic compounds. In many applications, it is desirable to use mixtures of different types of sulfur compounds because of the increased efficiency. However, the incompatibility of different types of sulfur compounds and the lack of water solubility of certain sulfur compounds make it difficult to use mixtures of different types of organosulfur compounds. In this case, it is usually necessary to add the different types of sulfur compounds separately; and in addition, extensive additional treatment is required to provide a uniform mixture. In many cases, the maximum efficiency of the mixture is not achieved due to the incompatibility of the various sulfur compounds.

Alkali metal or ammonium salts of dialkyl dithiophosphates are water-soluble organic sulfur compounds that have been used for many years as blowing agents in mineral enrichment. N-alkyl, O-alkyl thionocarbamates are water-insoluble oils that also have typical uses for organosulfur compounds, such as as a blowing agent in mineral enrichment. The different solubility properties of these different types of compounds do not suggest that these compounds could be used as a single mixture.

The invention is characterized in that the solution contains 35 to 50% by weight of an alkali metal salt of dialkyl dithiophosphate having the formula

S

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SM

wherein M is an alkali metal or ammonium ion and R and R 'represent an alkyl group containing 2 to 3 carbon atoms, and 65 to 50% by weight of water, that the solution contains thionocarbamate of the formula

S

n R 1 NH-C-OR * "wherein R" and R, M represent an alkyl group having 1 to 6 carbon atoms, and that the thionocarbamate is present in an amount sufficient to provide a weight ratio of dialkyldithiophosphate solution to thionocarbamate of between 30:70 and 95: 5 · The solubility of N-alkyl, O-alkyl thionocarbamate in aqueous solutions of alkali metal or ammonium salts of dialkyl dithiophosphates is very unexpected for a number of reasons. N-alkyl, O-alkyl thionocarbamates are insoluble in aqueous solutions of alkali metal alkyl xanthates. Thiophosphates are insoluble in allylamyl xanthate, which is a water-insoluble oil similar in nature and application to thionocarbamates. Toluene, an organic solvent, was found to be immiscible with dithiophosphate solutions in proportions in which thionocarbamates are miscible. The range in which the various thionocarbamates mix with dithiophosphate solutions varies with each type of individual compound.

The collecting reagent of the invention is used in flotation at about 0.5 to 50 grams per ton of ore.

Typical alkali metal or ammonium salts of dialkyldithiophosphoric acid used in accordance with the invention include sodium diethyldithiophosphate, sodium diisopropyldithiophosphate, sodium diisobutyldithiophosphate, sodium diisoamyldithiophosphate, 0,0-bis (1,3-bis) (1,3-bis) . f i corresponding compounds such as ammonium and potassium salts. Alternatively, acid 3 61642 can be called phosphorodithionic acid and the esters can be identified as Ο, Ο esters. All dithiophosphates used according to the invention are water soluble.

Typical thionocarbamates used in accordance with the invention include isopropylmethylthionocarbamate, isopropylethylthionocarbamate, isobutylmethylthionocarbamate, and the like. The first alkyl radical mentioned in the nomenclature is attached to an oxygen atom and the second to a nitrogen atom. Thus, the alkylthiocarbamic acid is identified and its ester is specified by the first named alkyl radical. The compounds are sometimes referred to as thionecarbamates, but for consistency labeling thionocarbamate is preferred. All thionocarbamates used according to the invention are water-insoluble oils.

In preparing the compositions of this invention, an aqueous solution of a dialkyl di-thiophosphate salt is prepared. In general, such a salt is prepared as about 35 to 70% by weight of an aqueous solution, depending on the solubility limit of the dialkyldithiophosphate salt used. The thionocarbamate is soluble in a concentrated, usually at least about 25% by weight dialkyldithiophosphate salt solution.

In preparing the compositions of the invention, the oily, water-insoluble thionocarbamate is mixed with an aqueous solution of a concentrated dialkyl dithiophosphate salt until dissolution occurs. The amount of thionocarbamate used in the preparation of the mixture is generally in such a range as to provide a solution ratio of said dialkyldithiophosphate salt to said thionocarbamate of between about 5:95 and 95: 5. Table I below gives the solubility values of certain thionocarbamates for certain solutions of the dialkyl dithiophosphate salt.

Table I

Solubility of certain thionocarbamates in aqueous solutions of dialkyl dithiophosphate salt.

Volume Ratio - The ratio of dithiophosphate salt solution to thionocarbamate

Dithiophosphate salt Iso-Iso-Iso content of the salt propylpropylbutyl (%) methyl ethyl methyl

Sodium 0.0, bis 35 k0: 60 70:30 1 * 0: 6θ (1,3-dimethylbutyl)

Sodium diisoamyl 35 U0: 60 70:30 U0: 60

Sodium diisobutyl 50 50:50 60: 1 + 0 Ηθ: 6θ

Sodium diisopropyl 50 U0: 60 '6θ · Λθ 60: 1 + 0

Sodium diethyl 50 90:10 90:10 90:10 616 4 2

It is generally preferred to prepare the solutions so that the solubility of the dialkyldithiophosphate salt is at or near maximum and to add thiocarbamate in the required weight ratio desired for the intended application. Thus, a high concentration of dialkyldithiophosphate salt minimizes shipping costs and the desired concentration of thionocarbamate minimizes treatment, requiring only dilution to be used.

The compositions of this invention eliminate the need for the separate addition of two ingredients when simultaneous use is desired, thus generally reducing the number of process steps required for simultaneous use. The mixtures give the thionocarbamates in the addition to the desired form, an aqueous solution form which was not previously available. The form of the aqueous solution is desirable in many applications where it is compatible with the process being carried out and thus eliminates the problems associated with uniformly dispersing normal oily, water-insoluble thionocarbamates.

In certain cases, the compositions of the invention provide improved efficacy over the separate use of either component or the separate but simultaneous addition of each individual component. Thus, the compositions of the invention not only eliminate the process steps and handling difficulties typically associated with the use of thionocarbamates, but can also provide better efficacy in eliminating such prior problems.

A particular application in which the solutions of this invention are preferred is application as a collecting reagent for the enrichment of ores with valuable constituents by foaming. A common solution of thioocarbamate and dialkyl dithiophosphate provides advantages in foaming metal sulfides such as sulfides of copper, zinc, lead, platinum, nickel and molybdenum ores. The advantages are the reduction of process steps when using the combined solution and this can increase the recovery of the desired metals while maintaining a high concentration concentrate.

The collecting reagent is used in an amount that gives the best metal yield while maintaining a high metal content. In general, this amount ranges from about 0.5 to about 50 grams of collector reagent per ton of ore, preferably from about 2.5 to about 25 g / t. The amount of use will vary depending on the ore to be considered, the composition of the collecting reagent solution and the processing equipment used. Optimum usage can be easily determined experimentally? 61642

The invention is illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated.

Examples 1-12

Sets of solutions were prepared using the following substances: (1) isopropylmethylthionocarbamate (2) isobutylmethylthionocarbamate (3) sodium diisoamyldithiophosphate

Compounds 1 and 2 were in the form of oils without diluents, while Compound 3 was in the form of a 35% aqueous solution. In various examples, compounds 1 and 2 were mixed with a solution of compound 3 in a volume ratio of thionocarbamate to dithiophosphate solution of 80/20 to 20/80. The examples obtained are the following:

Volume ratio (25 ° C)

Example 1 2 3 4 5 6

Compound 1 20 30 40 60 70 80

Compound 3 80 70 60 40 30 20

Example 2_ 8_ 10 11 12

Compound 2 20 30 40 60 70 80

Compound 3 80 70 60 40 30 20

In each example, a stable solution was obtained in which the thionocarbamate was completely dissolved.

Examples 13-32

Sets of solutions were again prepared using the following substances: il) isopropylmethylthionocarbamate (2) isobutylmethylthionocarbamate (5) sodium diisopropyldithiophosphate (6) sodium 0,0-bis (1,3-dimethylbutyl) dithiophosphate (7) sodium diisophosphate

Compounds 1 and 2 were in the form of oils without diluents while Compound 6 was in the form of a 35% aqueous solution and Compounds 5 and 7 were in the form of a 50% aqueous solution. The examples obtained are as follows: 6 61642

Volume ratio (25 ° C)

Example 15 14 15 16 17

Compound 5 30 40 60 70 80

Compound 1 70 60 40 50 20

Example 18 19 20 21 22

Compound 6 30 40 60 70 80

Compound 1 70 60 40 30 20

Example 25 24 25 26 27

Compound 6 30 40 60 70 80

Compound 2 70 όθ 40 30 20

Example 28 23 50 51 52

Compound 7 30 40 60 70 80

Compound 1 70 60 40 30 20

In each example, a stable solution was obtained in which the thionocarbamate was completely dissolved.

Examples 55-36

Sets of solutions were prepared using the following substances: (2) isobutyl methylthionocarbamate (7) sodium diisobutyl thiophosphate

Compound 2 was in the form of an oil without diluents while Compound 7 was in a 50% aqueous solution. The examples obtained were as follows:

Volume ratio (25 ° C)

Example 22 21 21 2 £

Compound 7 40 60 70 80

Compound 2 60 40 30 20

In each example, a stable solution was obtained in which the thionocarbamate was completely dissolved.

Examples 37-40

Sets of solutions were prepared using the following substances: (4) isopropylethylthionocarbamate (5) sodium diisopropyl dithiophosphate (7) sodium diidobutyl thiophosphate

Compound 4 was in the form of an oil without diluents, while compounds 5 and 7 were in 50% aqueous solutions. The examples obtained were as follows: 61642

Volume ratio (25 ° C)

Example% 8 and $ 8

Compound 5 70 80

Compound 4 30 20

Example 59 40

Compound 7 70 80

Compound 4 30 20

In each example, a stable solution was obtained in which the thionocarbamate had completely dissolved.

Example 41 In this example, the volume ratio (25 ° C) of the compound of the previous Example 4 and the compound of Example 1 was prepared at 20/80, respectively. The result was a stable solution in which the thionocarbamate was completely dissolved.

Comparative Example A

Attempts were made to dissolve thionocarbamates in xanthate solutions. The following substances were used;

Ksantaatlt

Sodium ethyl xanthate - 50% aqueous solution

Sodium isobutyl xanthate - 50% aqueous solution

Potassium amyl xanthate - 50% aqueous solution

Tionokarbamaatlt

Isopropylmethylthionocarbamate 11i Isopropylmethylthionocarbamate 11i Isobutylmethylthionocarbamate (All thionocarbamates contained oils that had not been diluted)

Mixtures of all xanthate solutions and all thionocarbamates in volume ratios of 40/60 to 70/30, respectively, at 25 ° C gave biphasic mixtures, i.e., a solution of thionocarbamate in aqueous xanthate solution did not flow.

Comparative Example B

Attempts were made to prepare solutions of allyl amyl xanthate (a water-insoluble oil) for the following substances: sodium diopropyl dithiophosphate - 50% aqueous solution sodium 0,0-bis (1,3-dimethylbutyl) dithiophosphate - 35% aqueous sodium diisobutyl - 50% aqueous solution of sodium diisoamyl dithiophosphate - 35% aqueous solution * 61642

The volume ratios of xanthate and dithiophosphate solution 60/40 to 30/70, respectively, at 25 ° C were prepared in different series. Two phases were obtained in each series, that is, a solution of xanthate in an aqueous solution of dithiophosphate was not obtained.

Comparative Example C

The procedure of Comparative Example B was again followed except that the xanthate used in Comparative Example B was replaced with toluene. In the volume ratios of toluene and dithiophosphate solution 60/40 to 30/70, respectively, two phases were obtained.

Examples 42 to 44

Sodium diethyldithiophosphate was used as a 50% aqueous solution as a solvent for the following three thionocarbamates without diluents in the form of an oil: isopropylmethylthionocarbamate isopropylethylthionocarbamate iBobutylmethylthionocarbamate

The solubility limit of each thionocarbamate in weight percent in the dithiophosphate solution was determined at 25 ° C. The results were as follows:

Example Thionocarbamate Weight (jo) 42 isopropylmethyl-5 43 isopropylethyl-4 44 isobutylmethyl-5

Example 45

A crushed and ground ore sample containing $ 0.68 of copper (primarily chalcosite) was treated by the standard laboratory foam support method using different collection reagents at varying concentrations. The lowest acceptable pre-concentrate that can be processed into final concentrate with existing plant equipment was $ 10 Cu for this ore. The pooling reagents used, the concentrations used and the results obtained are given in Table 11: 9 below. «61642

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The varying results of copper yield and copper content were plotted to share the benefits of the solution of this invention in the flotation process.

Figure 1 shows a comparison of the potency of isopropylmethylthionocarbamate alone and an equal total volume of a 50:50 aqueous solution of isopropylmethylthionocarbamate and sodium diisobutyldithiophosphate according to the present invention. The optimum content of isopropylmethylthionocarbamate alone is 26.5 grams per ton of milk and this gives a maximum copper yield of about 82.5 ° C with a copper content of $ 10 or more. The optimum concentration of the solution of the invention is about 21.5 g / t with a maximum copper yield of about 8317 ° C with a copper content of $ 10 or more.

Figure 2 shows a comparison of the potencies of sodium diisobutyl dithiophosphate alone and the same solution according to the invention described in connection with Figure 1.

The optimum concentration of sodium diisobutyldithiophosphate alone is about 18 * 5 g / t and this gives a maximum copper yield of about $ 82 with a copper content of about $ 10 or more. The results of the solution according to the invention are described in connection with Figure 1.

Figure 3 shows a comparison of the individual additions of sodium diisobutylthiophosphate in aqueous solution and isopropylmethylthionocarbamate in oil without diluents, 50 to 50 for the two substances, and the potency of the solution according to the invention described in connection with Figure 1. The optimum concentration of the two separately added substances was about 16 g / t and the maximum copper yield becomes about 80.9 i ° with a copper content of $ 10 or more. The results of the solution according to the invention are described in connection with Figure 1.

Considering the potency of the solution of the invention compared to thionocarbamate alone, the solution of the invention gives a higher yield of copper at the lowest acceptable copper content of the concentrate at a lower effective application rate than can be achieved with tinnocarbamate alone, as shown in Figure 1.

Considering the potency of the solution of the invention compared to dithiophosphate alone, the solution of the invention gives a higher yield of copper at the lowest acceptable copper content of the concentrate, as shown in Figure 2.

Considering the potency of the solution of the invention compared to the separate additions of the two substances, the solution of the present invention gives a higher yield of copper at the lowest acceptable concentration of copper concentrate, as shown in Figure 3.

11 61642

Comparing the efficacy of the separate additions of the two substances (Fig. 3) for the use of thionocarbamate alone (Fig. 1), it can be seen that better results are obtained with thionocarbamate alone. Similarly, when comparing the efficacy of the separate additions of the two substances (Fig. 3) to the use of dithiophosphate alone, it is seen that better results are obtained with dithiophosphate alone. This is an unexpected additional feature of the invention.

Example 46

Ore containing copper and molybdenum with $ 0.4 Cu and 0.04 i »Mo was crushed and wet ground to a flotation fineness. This ore slurry was then placed in a laboratory flotation machine and adjusted to pH 10.8 with lime. The ore was then cured for one minute with collector reagent. A mixture of methyl isobutylcarbinol and alcohols having six and eight carbon atoms was used as the frother, with a total amount of 30 grams per ton of ore. Air was blown into the mixture and the foam was removed at a constant loading rate for five minutes. The copper and molybdenum content of the obtained pre-concentrate was analyzed and the weight percentage of the obtained concentrate was determined.

Using the above procedure, a total of four sections were performed, in which a different collector reagent was evaluated in each section. Table III gives the collection reagents used and the results obtained.

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Example 47

Following the procedure of Example 45, yet another set of size reagents was evaluated. Collecting reagents used And the results obtained are given in Table IV.

Example 48

Following the procedure of Example 45, another set of collector reagents was evaluated. The pooling reagents used and the results obtained are given in Table Y.

The results of Examples 46-46 further demonstrate the utility of solutions of thionocarbamates and dithiophosphates in achieving optimal recovery of metal content, provided that an extensive experiment is performed to select a suitable combination for the ore in question.

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Claims (1)

16 61 64 2 Claim: An aqueous solution which is suitable as a collecting solution for recovering copper from sulphide ores by foaming and which consists of an aqueous solution of a dithiophosphoric acid derivative in which thiocarbamate has been dissolved, characterized in that the solution contains 35 to 50% by weight. an alkali metal salt of a dialkyldithiophosphate having the formula S RO-P-OR 'SM wherein M is an alkali metal or ammonium ion and R and R * represent an alkyl group having 2 to 8 carbon atoms, and 65 to 50% by weight. water, that the solution contains thionocarbamate of the formula SR 1 NH-C-OR "'wherein R" and R "1 represent an alkyl group having 1 to 6 carbon atoms, and that the thionocarbamate is present in an amount sufficient to provide a dialkyldithiophosphate solution, and thionocarbamate weight ratio between 30:70 and 95: 5.