FI79951B - NYA SAMLARE FOER FLOTATION AV MINERALIER. - Google Patents

Description

1 79951

This invention relates to novel collectors for recovering minerals from mineral ores by foaming.

Flotation is a way of treating a mixture of finely divided mineral particles, e.g. powdered ore, suspended in a liquid, whereby some of these solids are separated from other fine mineral particles, e.g.

10 clay and other similar materials in the ore by introducing gas (or generating gas in situ) into the liquid to form a foamy mass containing certain solids on the surface of the liquid and leaving the other solid components of the ore suspended (without foaming). Flotation is based on the principle that the introduction of a gas into a liquid containing solids suspended in various substances causes a portion of the gas to selectively adhere to certain suspended solids and not others, and makes the particles adhered to the gas lighter than the liquid. In this case, these particles rise to the surface of the liquid, forming a foam.

Various substances have been mixed into the suspension to improve the flotation and assembly process. Such added substances are classified according to their function and include, for example; collectors, for sulfide minerals these include xanthates, thionocarbamates and the like; foaming agents which enhance the ability of stable foams to form, e.g., natural oils such as tall oil and eu-30 calyptic oil and the like; modifiers such as activators to induce foaming in the presence of a collector such as copper sulfate; depressants, such as sodium cyanide, which seek to prevent the collector from acting as such on the mineral desired to remain in the liquid, thereby attempting to prevent the substance from migrating up the core and forming part of the foam; pH adjusters for metallurgically optimal results such as lime, soda ash and the like.

5 It is important to keep in mind that additives of the type described above are selected for use according to the nature of the ore in question, the mineral to be recovered and the other additives to be used with them.

10 Understanding the phenomena that make flotation a particularly useful industrial operation is not essential to the practice of the present invention. However, they appear to be largely related to the selective surface affinity of the substances formed by the discrete particles suspended in the liquid containing the retained gas, on the one hand for the liquid and on the other hand for the gas.

The flotation principle is applied to many mineral separation processes, including the selective separation of minerals such as copper sulfide minerals, zinc sulfide minerals, molybdenum sulfide minerals, and others from ferrous sulfide minerals, e.g., pyrite.

Collectors commonly used to recover sulfide-containing precious metals include xanthates, dithiophosphates, and thionocarbamates. Collectors used to recover valuable parts of sulfide-containing minerals are common and widely used. In contrast, the difficulty in recovering valuable parts of oxide-containing minerals is that collectors suitable for recovering valuable parts of such minerals are generally not commercially acceptable.

What is needed are collectors that are useful for recovering a wide range of precious metals from metal-containing ores, including

II

3,79951 Recovery of valuable parts of fidium-containing minerals and valuable parts of oxide-containing minerals. In addition, what is needed are collectors which give high yields in the recovery of valuable parts of the mineral while having good selectivities for the valuable parts of the mineral in the side rock, i. compared to undesirable parts of mineral ore.

The invention relates to a collector for recovering metal sulphides or sulphidated metal oxides from ore 10 by foaming.

The invention is characterized in that R1 -XfR * nN <-R2) a <H) b 15? Ϊ wherein R is -CH 2 -, -C-, -C- or a combination thereof,

OH

n is an integer from 1 to 6 or (R) n is (CH2) BCs where 20 m is an integer from 0 to 6, R1 and R2 independently of one another denote a Cx-22 hydrocarbyl group which may be substituted by one or more hydroxy, amino, phosphonyl -, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano-25, halogen, ether, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbylimino, and R 2 may further be a divalent group bonded by a double bond directly to a nitrogen atom, X is -S-, -O-, -N-R 30 OR 30

N 11 H

-C-S-, -C-N- or -CO-35 R3 is H or a C2.22 hydrocarbyl group which may be subs-substituted; a is an integer 0, 1 or 2; b is an integer 0, 1 or 2; provided that the sum of a and b is 2, except when R 2 is a divalent group bonded directly to the nitrogen atom by a double bond, in which case a = 1 and b = 0, or when (R) n is (CH 2) ) bCh, in which case a + b = 0, and has the condition that when X is

O OR3 Q

Il II I II

-C-S, -C-N- or -CO- so the carbonyl group is attached to R1.

The invention also relates to a process for recovering metal sulphides and sulphide metal oxides from ore, wherein the ore in the form of an aqueous slurry is flotated in the presence of a collector under conditions such that the minerals are recovered in the foam, the collector being a compound of formula R1-X-fR) -n N-fR2 ) a <H) b 0

I II

Wherein R is -CH 2 -, HC-OH, -C-, or a combination thereof, and n is an integer from 1 to 6, or -iR) ^ is - {CH 2> -BC 5, wherein m is an integer from 0 to 6, R 1 and R 2 independently represent C 2-2 hydrocarbyl which may be substituted by one or more hydroxy, amino, phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano, carboxyl, with a hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbylimino group, X X is -S-, -O-, -N-R30 OR3

1 Dl I

-C-S-, -C-N- or -CO- 3 5 79951 R is hydrogen, C1-22 hydrocarbyl, or a substituted C1-4 hydrocarbyl radical, · a is an integer 0, 1 or 2; b is an integer 0, 1 or 2; provided that the sum of a and b is 2, except when R is a 2-valued group bonded directly to the nitrogen atom by a double bond, in which case a = 1 and b = 0 or when - (Rf is, where sa a + b = 0, and with the additional condition that X is 10 O OR3 0

Il II f II

-C-S-, -C-N- or -CO-; then the carbonyl group is attached to R 1.

In a preferred embodiment of the invention, the collector comprises a compound of the formula R 1 X-fCH, * Ne R 2) -2 (n) (H) b 20 wherein R 1 is C 1 -C 22 hydrocarbyl substituted by one or more hydroxy, amino , the phosphonyl or alkoxy radical r 2 has a C 1-8 alkyl, C 1-8 alkylcarbonyl, a C 1-8 alkyl group substituted by an amino, hydroxy or phosphonyl radical or a C 1-8 alkylcarbonyl group substituted by an amino, hydroxy or phosphonyl radical; and X, a, bjan are as defined herein.

The collectors of this invention foam up to a wide range of precious metals, including sulfide ores, oxide ores, and precious metals. Such collectors also provide improved yields of valuable minerals, including mineral oxides, mineral sulfides, and precious metals. It is surprising that not only high recoveries are achieved but also the selectivity for the desired value minerals is surprisingly high.

6,79951 Preferred novel builders of this invention include omega- (hydrocarbylthio) alkylamines; omega- (tetrahydro-karbyylitio) alkylamides; S- (omega-aminoalkyl) hydrocarbon-tytioaatit; N- (hydrocarbyl) alpha, omega alkanediamines; 5- (omega-aminoalkyl) hydrocarbon amides; omega- (hydrocarbyloxy) alkylamines; Omega-aminoalkyylihydrokarbonaatit; or mixtures thereof. More preferred builders are omega (hydrocarbylthio) alkylamines; omega- (hydrocarbylthio) -alkylamide; N- (hydrocarbyl) -alpha, omega-alkanediamine-10-nit, and omega- (hydrocarbyloxy) -alkylamines, or mixtures thereof. Most preferred builders are omega (hydrocarbylthio) alkylamines; omega- (hydrocarbylthio) -alkylamide; N- (hydrocarbyl) -alpha, omega-alkanediamines, or mixtures thereof. The most preferred group of collectors are omega (hydrocarbylthio) alkylamines and omega (hydrocarbylthio) alkylamides.

According to a preferred embodiment, the above formula preferably comprises C 2-4 hydrocarbyl and more preferably C 1-4 hydrocarbyl. is preferably C 1-8 alkyl or C 1-8 alkylcarbonyl, more preferably alkyl or C 1-6 alkylcarbonyl, and most preferably C 1-2 alkyl or C 1-8 alkylcarbonyl. R 1 is preferably hydrogen or C 2-14 hydrocarbyl, more preferably hydrogen or N-hydrocarbyl and most preferably hydrogen. Preferably 25 a is an integer O or 1. Preferably b is an integer 1 or 2. Preferably n is an integer from 1 to 4 and most preferably

min is an integer of 2 or 3. X is preferably -S-, -N-R

3 Tao -0-. More preferably, X is -S- or -N-R. X is most preferably -S-.

Preferred S- (omega-aminoalkyl) hydrocarbon thioates correspond to the formula 0 R1-CS- (CH- ·) · N- (R2) Δ Π a (H) 35 b 1 2 wherein R, R, a, b and n are the same as defined above.

li 7 700C1

/ / / ^ I

Preferred omega- (hydrocarbylthio) -alkylamines or omega- (hydrocarbylthio) -alkylamides correspond to the formula R1-S-tCH2> nNfR2) 2 (H) b wherein R1, R1, a, b and n are the same as as defined above. In those embodiments where X is -S- or 10 0

M

-c-s- R3 are preferred! C ^ _ ^ Q hydrocarbyl.

Preferred N- (hydrocarbyl) -alpha, omega-alkanediamines correspond to the formula R1-N-eCH N- (R2)

I & Π Q

R 3 (H) 20 b 1 2 Ί wherein R, R, R, a, b and n are as defined above.

Preferred N- (omega-aminoalkyl) hydrocarbon amides correspond to the formula

O

R1-C-N-fCH, ·) · N «R2),

I ^ n I D

r 3 (H) a 30 wherein R 1, R 2, R 2, a, b and n are as defined above. In those embodiments where X is O R 3 -N- or -C-N-R 3, the total number of carbon atoms in R 1 and R 2 is preferably 1-23, more preferably 2-16, and most preferably 4-15.

35 β 79951

Preferred omega- (hydrocarbyloxy) alkylamines correspond to the formula R1-O-tCH_ ·) · N- (R2) b Π | d 5 (H) b 1 2 wherein R, R, a, b and n are as defined above.

Preferred omega-aminoalkyl hydrocarbonates correspond to the formula 0 R1-CO-CH9 ·) · N- (R2) 2 n, a (H) b 15 12 wherein R, R, a, b and n are as defined above. defined. In those embodiments where X is

O

II

-CO- or -O- 1 O 1 R is most preferably C 1-4 hydrocarbyl.

b “11

Hydrocarbon here means an organic compound containing carbon and hydrogen atoms. The term hydrocarbon includes the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkyls, aromatics, aliphatic and cycloaliphatic Aralanes and alkyl-substituted aromatics. Aliphatic here means a straight or branched chain and saturated and unsaturated hydrocarbon compounds, i.e. alkanes, alkanes, or alkynes. Cycloaliphatic 30 here means saturated or unsaturated cyclic hydrocarbons, i.e. cycloalkenes and cycloalkanes. The term aromatic herein means biaryl, benzene, naphthenic, phenanthracene, anthracene and two aryl groups joined together by an alkylene group.

9,79951

Cycloalkane means an alkane containing one, two, three or more cyclic rings. Cycloalkene means poly-, di- and polycyclic groups containing one or more double bonds. Halogen 5 means chlorine, bromine or iodine, preferably chlorine.

Hydrocarbyl here means an organic radical containing carbon and hydrogen atoms. The term hydrocarbyl embraces the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cycloaliphatic aralkyl and alkaryl. Aliphatic here means straight or branched, and saturated and unsaturated carbon-hydrogen chains, that is alkyl, alkenyl or alkynyl. Cycloaliphatic herein means saturated and unsaturated cyclic hydrocarbons, i.e., cycloalkenyl and cycloalkyl. The term aryl as used herein means biaryl, biphenylyl, phenyl, naphthyl, phenanthrenyl, anthracenyl, and two aryl groups attached to each other by an alkylene group. Alkaryl as used herein means an alkyl, alkenyl-20 or alkynyl-substituted aryl substituent wherein aryl is as defined above. Aralkyl here means an alkyl, alkenyl or alkynyl group substituted with an aryl group, wherein aryl is as defined above. Alkenearyl as used herein means a radical containing at least one alkene moiety and one aromatic moiety and encompasses radicals in which more than one alkene radical alternates with more than one aryl radical. C 1-2 alkyl includes straight or branched chain groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undesyl, dodecyl, tridesyl, tetradecyl, pentadecyl, hexadecyl, heptadesyl, heptadesyl, , nonadesyl and eicosyl. C 1-6 alkyl means methyl, ethyl, propyl, butyl and pentyl.

10 79951

Cycloalkyl means alkyl groups containing one, two, three or more cyclic rings. Cycloalkenyl means polycyclic, di- and polycyclic groups containing one or more double bonds.

The method of the present invention is also useful for recovering precious metals from metal ores by foaming. Metal ore here means metal as taken from the soil and contains precious metals mixed with side stone. Side stone here means those materials which have no value and which must be separated from the precious metals. This method can be used to make metal oxides, metal sulfides and other valuable metal compounds.

Sulfide ores for which these compounds are useful include copper sulfide, zinc sulfide, molybdenum sulfide, cobalt sulfide, nickel sulfide, lead sulfide, arsenic sulfide, silver sulfide, chromium sulfide, gold sulfide, and uranium sulfide, platinum sulfide, platinum sulfide. Examples of sulfide ores from which metal sulfides can be enriched by foaming using the process of this invention include copper-containing ores such as covellite (CuS), chalcosite (CU2S), chalcopyrite (CuFeS2), vallerite (C ^ Fe ^ S ^), bornite (Cu ^ FeS ^), cybanite (Cu2SF4S5), enargite (Cu ^ (As ^ Sb) S4), tetrahebrite (Cu3SbS2), tenantite (Cu12As4S13), bronchantite (Cu4 (OH) ) 6SO 4), ant-lerite (Cu 3 SO 4 (OH) 4), famatinite (Cu 3 (SbAs) S 4) and burnonite (PbCuSbS 2); lead-bearing ores such as lead flux (PbS); antimony-containing ores such as stibnite (Sb2S3); zinc-bearing ores such as zinc scintillation (ZnS); silver-bearing ores such as stefanite (Ag, -SbS4) and silver luster (Ag2S); chromium-containing ores such as baub-relite (FeSCrS3); nickel-containing ores such as pentlandite ^ (FeNi) Sg ^; molybdenum-containing ores such as molybdenite (MoS2), and platinum- and palladium-containing ores such as cooperite (Pt (AsS) 2).

li 11 79951

Oxide ores for which this invention is useful include ores containing copper oxide, alumina, iron oxide, iron titanium oxide, magnesium alumina, iron chromium oxide, titanium oxide, manganese oxide, tinoxy-5 dia, and uranium oxide. Examples of oxide ores from which metal oxides can be enriched by flotation using the process of this invention include copper-bearing ores such as cuprite (Cu 2 O), teno-rite (CuO), malachite (Cu 2 OH) 2CO 3), azurite 10 (Cu 3 (OH) 2 (CO ^) 2)> attackamide (Cu2Cl (OH) 3), chrysococcal (CuSiO 2); aluminum-containing ores such as corundum; zinc-containing ores such as zincite (ZnO) and smitsonite (ZnCO 2); tungsten-containing ores such as tungsten mite ^ (Fe, Mh) W0 ^ /? nickel-containing ores such as benzenite (NiO); molybdenum-containing ores such as wulfenite (PbMoO 2) and powellite (CaMoO 2); iron-containing ores such as hematite and magnetite, chromium-containing ores such as chromite (FeOC 2 O 2); ores containing iron and titanium, such as ilmenite; ores containing magnesium 20 and aluminum, such as Spinelli; iron and chromium-containing ores such as chromite; titanium-containing ores such as rutile; manganese-containing ores such as pyrolucite; tin-containing ores such as bag terite; and uranium-containing ores such as uraninite; 25 and uranium-bearing ores, such as uranium pitch flash (U3O5 → U3 ° 8 ^ 3a) (U03nH2O).

Other precious metals for which this method is useful are gold-bearing ores such as syl vanite (AuAgTe2) and fish ferrite (AuTe); platinum and palladium-containing ores such as sperrylite (PtAs2); and silver-bearing ores such as hessite (AgTe2).

In a preferred embodiment of the present invention, valuable parts containing ore oxide or sulfide are recovered. In an even more preferred embodiment of the present invention, valuable copper sulfide, nickel sulfide, lead sulfide, zinc sulfide or molybdenum sulfide is recovered. In an even more preferred embodiment, valuable copper sulfide is recovered.

The collectors of this invention can be used at any concentration that provides the desired recovery of the desired precious metals. The concentration used depends in particular on the precious metal to be recovered, the quality of the ore to be foamed, the desired quality of the precious metal to be recovered and the particular valuable fraction of the mineral to be recovered. The collectors of this invention are preferably used in concentrations between 10 and 250 g per ton of ore. , more preferably 10 to 100 g collector per ton of ore to be foamed.

The flotation of this invention generally requires the use of flotation agents. Any blowing agent well known in the art, the use of which results in the recovery of the desired precious metal, is suitable. In addition, it is contemplated that the collectors of this invention may be used in admixture with other collectors well known in the art in the process of this invention.

Collectors known in the art that can be used in admixture with the collectors of this invention are those that provide the desired recovery of the desired value mineral. Examples of useful herein headers are alkyylimonotiokarbo-sulfonates, alkyyliditiokarbonaatit, alkyylitritiokarbonaatit, 25 dialkyldithiocarbamate alkyylitionokarbamaatit, diallyl kyylitiokarbamidit, monoalkyyliditiofosfaatit, dialkyl and diaryldithiophosphate, dialkyylimonitiofosfaatit, tiofosfonyylikloridit, dialkyl, and diaryyliditiofos-sulfonates, alkyl mercaptans, xanthogen ksantaattiesterit 30, mercaptobenzothiazoles, fatty acids and salts of fatty acids, alkyl sulfuric acids and their salts, alkyl and alkaryl sulfonic acids and their salts, alkyl phosphoric acids and their salts, alkyl and aryl phosphoric acids and their salts, sulfosuccinates, sulfosuccinates, primary amines, secondary amines, secondary amines amines, quaternary ammonium salts, alkylpyridinium salts, guanidine and alkylpropylenediamines.

Blowing agents useful in this invention are all blowing agents known in the art that provide recovery of the desired valuable mineral. Examples of such foaming agents are C 1-4 alcohols, tall oils, cresols, C 1-4 alkyl ethers of polypropylene glycols, dihydroxylates of polypropylene glycols, glycols, fatty acids, soaps, alkylaryl sulfonates and the like. In addition, mixtures of such blowing agents can also be used. All blowing agents suitable for the exploitation of mineral ores by foaming can be used in this invention.

Omega- (hydrocarbylthio) -alkylamines or omega- (hydrocarbylthio) -alkylamides can be prepared by the methods described in Berazosky et al. U.S. Patent 4,086,273; FR Patent 1,519,829; or Beilstein, 4, 4th edition, 4th supplement, 1655 (1979). N- (omega-aminoalkyl) hydrocarbon amides can be prepared by the methods described in: Zazio, U.S. Patent 4,326,067; Acta Polon

Pharm. 19, 277 (1962); or Beilstein, 4, 4th edition, 3rd supplement, 587 (1962). Omega- (hydrocarbyloxy) alkylamines and can be prepared by the methods described in GB Patent 869,409; or U.S. Patent No. 3,397,238 to Hobbs. S- (omaga-aminoalkyl) hydrocarbon thioates can be prepared by the methods described in Faye et al., U.S. Patent 3,328,442; or Beilstein, 4, 4th edition, 4th supplement 1657 (1979). omega-aminoalkyl hydrocarbonates can be prepared by the method described in J. Am. Chem.

Soc., 83, 4835 (1961); Beilstein, 4, 4th edition, 4 supplement 1413 (1979); or Beilstein, 4, 4th edition, 4th supplement, 1785 (1979). N- (hydrocarbyl) -alpha, omega-alkanediamines can be prepared by a method well known in the art, exemplified by the method described in East German Patent 98,510.

14 79951

The following examples are intended to illustrate the invention but not to limit the scope of the invention or the claims in any way. * All parts and fractions are by weight unless otherwise indicated.

5 The following examples illustrate the effectiveness of the described flotation methods by reporting the flotation rate constant and recovery rate over an infinite period of time. These numbers are calculated using the following equation, -Kt

10 r ^ RÄ- ^ if-J

where: r is the amount of mineral recovered after time t, K is the rate constant at the recovery rate, and R is the calculated amount of mineral that could be recovered over an infinite period of time. The amount recovered at different long times is determined experimentally and the series of values are placed in the equation to obtain R and K values. The above formula is described in "Selection of Chemical Reagents for Flotation", paragraph 45, pages 907-934, Mineral Processes-2q sing Plant Design, 2nd Edition, 1980, R. Kimpel Dem (Demver).

Example 1 - Copper Sulfide Flotation In this example, several collectors of the present invention are tested for flotation of copper sulfide ore. 500 g of Chilean copper ore, chalcopyrite copper sulphide ore, pre-packaged, is placed in a rod mill with 257 g of deionized water. Copper ore contains 80.2% of particles with a size of about 75 micrometers or less. A certain amount of lime is also added to the bar mill in the next flotation based on the desired pH. The bar mill is rotated after 2Q at a speed of 60 rpm for a total of 360 rpm. The ground slurry is transferred to a 1500 ml cell of an Agitaii flotation machine. The frothing cell is agitated at 1150 rpm and the pH is adjusted to 10.5 by adding an additional 55 lime if necessary.

is 79951

A collector (50 g / ton) is added to the flotation cell, followed by a conditioning time of one minute, during which the foaming agent DOWFROTHz50 (trade name The Dow Chemical Company brand 5) (40 g / ton) is added, followed by an additional conditioning time of one minute. start blowing air into the flotation cell at a rate of 4.5 liters per minute and start the automatic defoaming scraper. Foam samples were taken after 0.5, 1.5, 3, 5 and 8 minutes. The foam-10 samples are dried overnight in an oven along with flotation columns. The dried samples are weighed, divided into suitable samples for analysis, ground to ensure suitable fineness and dissolved in acid for analysis. Samples are analyzed using a DC Plasma Spectrograph-15 instrument.

The collectors tested for flotation of the valuable copper sulfide portion of Chilean copper ore are listed in Table I and the table shows that a large number of compounds within the scope of the invention are effective in recovering valuable copper sulfide. A basic example that does not use a collector at all is included in Table I for comparison. It should be noted that the collectors of the invention shown in Table I were not selected on the basis of optimum performance, but represent an arbitrary selection of compounds that show a significant effect on the recovery and selectivity of valuable mineral moieties.

16 79951 • H cm% • H N (0 4-> 01 (0

Ai> i ^ - (D ^ i w

Oh £ CHW r — r -'- oor- ^ i— CN O oo i ~~ * 0 V / 0) · Η «· - -Γ-1 \ / c / i> 2 (0 II 3 (Ή 3 - ΗΙ-ι I Or-.r ^ - ^ y-jr ^ -cMoo .—.>> 100 O ^ OOO ^ IvO ^ nOOOOO 4-1 ΓΜ · Η 'Η \ sL ·. 1-1 ° - ° _ ° Ο ° Ο ° ° 3 g (Λ · * Ι I Ο Ο Ο Ο Ο θ 'ο "θ' ο" ^ - Μ

._. '-Ϊ́' ίΠοοΊσλ ^ οοοεΝ'- 'C

π-, aO rH ^ OCHr-oocnvOr- · Η. - 3 Μ C ^ Or — r ^ -Jl / lOvOi / ^ ιΐ υ ο: »- - 7” 1 I οοσοοοσοο 2 ^ γΗ 3

<«C

Ή

_ (, -. Ο \ ΗηιΠιϊ0ΟΠΗΝ C

, „2 σιοσ \ σινο <· Γ ^ οοσ \ * 2 2 ο: οοοοοοοοο ^ O -Η 00 '-', ¾> οοοοοοοοο

Ai -Η Ο Η 2 '^ 10'-HiDCTirt ^ -moCCJ ΐ «Ο Ή> (0

Ai HlflCNi-1CMClr-ir-ifOO 3a; -P c / ι tn 3 (0 dj rt I VOC ^ CMOOIOVOOO 5 * £ rJ '^ CsICOONO ^ r ^ vT' p fd rH Jos r ^ - ^ or ^ r ^ <r-sX) r ^ voo fdw

Eh 3 _ ------- - '3Π3 j3 3 ΟΟΟΟΟΟΟΟΟ -PCX · M u -P 3 (0 inCNON'-iCMr-InNu-J ^ O 3 Ai 3

4-1? -HvOcN ^ t ^ cnr ^ u-s-J P ^ -P

(0 -------- 3: (0 4-1 • I—, u-i> jf! -JcoiN - uh - a! + I 3

O 4-> <H

O 3 Φ 3 a; -h Ai O 4-1 2 3 3 3

3 CD -H

3 -P 4-> • H -H 3 ε m 3 -H * H * H 3 rH rH rH 00 3 Ή> 1> 1> 1 (0 g> 1> 1> 1 (0 (0 3 3 3 m 4J oo noo οι ω iä λ iä <u Ai (0

P SH P φ 01 rH

(0 (0 (0 Ai (0 ή

Ai Ai Ai O P O

Ph * H Ή -P Ai 3 | —1 rH rH 01 3

> 1> 1> 1> 1> 1> 1> i> H> 1 0> 1 «J

4J4JP4J4-1P> 1> 1> | 4-1> 1 3 a> oi ai ω <uaj4- »4J-P coioi

>>>>>> 0) 0) 0) (0-H

<0> 3 I 01 -H 0)> i -H>

> 1 3 -P -H

• H -P-P O ^ ^ • H Ή rH -rl 0) rH 0) 3 i — I · Η Ή rH -H> 1 -H ι-H Q> i 00 'I 3 *

> 1 i — I rH> ,, - 4> h i — 1> h * P 1 Q) * rH

> i> i> i> H> HAi> i> i Ό Ai «01 0) P> 1> 1 0)> 1 0)> i 01 10)

QiPPAiPTOPAi rHT3 1 I

rH 0) 3AiQ) Q) OA; a) --P

Oh Λχιορ: ετ3θχΐ - '• h ^ <N

i; 17 79951

Ai I

(¾ K Q) -Η ™ V /, H> tO '-' r ^ Oin <S'jr) ^ - \ / <U-rl> i— ---- - -; z; w.H> 1 r ^ fnoooooovOoo> 3 ·

I -P CO., LTD

c mr * ~>

<N -H rH

M-1 ^ CMrOf ^ vOmavO 5 p, rt co oo ^ r ^ r ^ r ^ tOOr-- H ^ »0-000000 id w> 0C .jj

I -H OOOOOOOO (U

- w ro -Ξ ', —1' T "- CM O SO 00 CM —1 in r- 1 co r ^ '-' OOLricM ^ Tr-oo Π3 1 — I 3liO <rmOOfOin <N * 3 PS oos - - - - - - J3

„OOOOOOOO TS

WC 3 to, q <ti <0 Ovor-ocN ^ ON— · 3 CO Ai αο -. ('- r-OOmvOC'- ο λ; -hPS 0 - 000000 OOOOOOOO β rH Ai .μ O 3 00 - OCN - <T \ OvJ · 3

Ai + j> a: <r <roocoroo \ - o_ 3

"3 ^ oococmcm- cmoo ^ t C

r — I 3 C

3 H

(ti 3 co o co m 1/1 00 - in a-t

In 3 oocoooor ^ uioocr.

v ΟίιΠ'ϊοΟΟί-ΐιοεΝΐ _ Λ

·. «· - w-r.» - · ._ (ti O

.3 OOOOOOOO 3-P

«U -c G

• n - cmco - 0 ^ 00 tiirtS

O ίκίΟίΝΟ ^ 'ίΐ ^' ϊ'ί-ιΛ

2 cmcm <tco- cm <tcn 3 -P

n Ai C 3 w CM3 CICMCNCOCOCOCMCMCN -H (O Ai -P (¾

3 3 C

M 3 A! -B

-h C -P

> ·, -H «ti 3> 1 I I e -p 3 (¾ 00 -p c <d o Λ Λ oo CD -H co

M M M e O

Dj (O (d (d * I

oa: a: to c 00 o G -H -rl CO CD Dj Π -HH -H —I -H CU -P <ti Dj> 1 <E> 1> 1> * H> 1> irH 0) -HH Cd "-P Pu (ti -P -P> -1> iP> i> i Ai CO —i Xl kj) o 1 cu ω -p> 1 cd -p> 1 o ocd> & Hro >> <DC> < DC Ai - C>

CO C CO

O> 1 3 (ti

-P> 1 3 M

C CO CO., LTD

• H -H -H Cd -H C

(H rH Ή (0> C> 1

> 1> 1> 1 CO -H CU O

> 1> 1> 1 -H> rH

CC C C -P -H co CU CU CU O M> 1 m p -nm cu 3 -p

H -H -H -H-C-H-H-H 00 r-H 5> C

rH rH rH rH i> l rH rH rH I CD -H (iti> 1> 1> 1> 1> 1> 1> 1> 1 KW 10 2 rH> 1> 1> 1> 1-P> 1> 1 > 1

PSCCCCDjCCC II I

OO OOCUO (UCU

CCCC-CCPP rHCN 00 18 79951 • r4

• H (N + J M

Ο'ΟΟιΠιΛΓ'ίΟΟΟ'ΤΟΟ (1)> 1.-4 tn otnoomvooomuir · 'Φ -h - en> I r * I r' ^ vOcS'Tr-oof'-O 'p., - 1 ao Lnoou- imovvovotjvoo ·> ►> H ooooooooo jj K -

en 5 OOOOOOOOO

• —l cMoomvjor ~ -jrO'3 · oo cNcsir ~ oofnao <3NCNim 3i o-T ^ icMvomtomo ucc ~ looooooooo

06 S

o <rsO (nmoo <yi »-i ~ Loooinm ^ vooooo

1 ^ -H 06 OOOOOOOOO

'"l. -h looooooooo s Ai ΓΓ H,?; N | rrr ^ .oOvOvO <r> 0 u, Ρ * ϋ ^ οοοηιηοοηοοηο (0 en ^ 2" en rononcomesr-icsin tn 1 2 3 4 5 6' SO i • “L, ooinoooovDMootNio 0 = 1 cNO-oooroooonso

H CSO'i'iNNNvO'O’u-iO

O C - ooooooooo

Ai (Tj U

Ai (O ιΙ '-' νοιΟιηοίΜ'ϊΓΜίΜ 3 Ai I itf vo -'in - o in u "> n cm r — I Ai 3 O; l --r ei cm m en .— ά in <0 3 E- ι Ή

P

> 3

I-I

3 3

Ai • H Ή 4-1 · -! * r4 i-H t — i rt H H -H> i> 1 -n> i> f I — I> i> i O> ι> ί> ι> ι> ίΟ) μ> ι> ι

O 4-> 4J> i4-> 4-> A: A <-P4J

Ai en 33-P φ φ φ φ φ (1) O 0ίΛΧ1 (1) >> 43Λ >>

M

I I

U M

(0 (0

Ai-H Ai-H

• H Ή · γ4ι — t

* —I κ> Ί I — I

in 1> >ί> ~ 1> 1> 1> 1> 1 i »1> 1 ί> Ί 4-1> iC4-l 4J 4-1 4-1> iG4-l 4-1 φ 4J οω φ α) φ 4-> ο φ φ PS> ΦΧ)>>>> ΦΛ>>

I I

2

Ρ Ρ H I

3 λ φ <α u 4 ρ α; μ φ 5 (β · Η · Η · γ4 -Η Αί> Γ4 -H ι — 1 · γ4 | “Η '" ν I — 1 * Γ + ρ4 -γ4 Η Η · Η * Η £> yH £> ι i> ii I-1 ι-Η ϊη <—I <—1-3> ι> i> i> t> <> £ »ι> ι> 1> ι> ι> ιΗ4->> iW tn 4-1 »1> ι Ή 4-1 + 4 ^>,> ιΟ <CAi Ai Λ cc e 6 3 3 4-1 4-1> ιφ ΟΦ Φ Φ ΟΟ Ο 43 XI φ (UGXiXUi jC XlAGXi 19 79951

B

HCM • P Ui X> 1

®} m ^ o. ° ® ° _ S

Q) -H Ό r— r— <0 CO> + * ^ Q) H <0> • H l— * r- ~ oo m _ ^ oo · in vo m -r- Π3 3 'o O O O 3

22 CO * - - - * -4J

\ / -H ° O O O

2 CO 5 I Ή, rt esi rt r-ι CM O OS 3 ΰ r-s oo oo esi in oo 2 H cm 3 i en <r <r cm

X ~ u K

-P O o O O O ”10 T i

• m _ 1 TL

en ^ s 3 2-2, eocM Essen n

T1 m o tn r— G

U i> 200 OO 5 - -H - - ~ e ra en χ o o o o 6

Ui 3 m 0 ^ I <T cm os r- tJ C -H 2 os oo r-en _ M (0 C0 - - - -9

O <a I en cm cm o -P

XX g X x Ό 3 0 oo en m g

rH 3 oo en o σ 'UI

3 H 2 en -r <r cm

+ J 3 o 'o ”0” “o” -H

* s b> »-h \ Q ψ— ^ 3 3 3 200 O <T CM g <

rH - - - _ -p 3 (CJ

n -ien cnm3> i3

n 1 — I -P

£ 3 = 3 -P

Ai -P 3

Jj -P rH

% C O 3 • o 'Ί O> 1> t> 1> 1 t- _ O -P -P -P -P 3 e e

m; m <D <D 0) 0) 30 -H

0 «>> >> C-P-P

X -H -H 3 E en 3

C

|. 00 C -H

• Hl 3 e rH 0-H 3 (0> 1> 1> 1> iQ «-h en -P 00 -P -P -P>, n>,« O) Q) Q) Q) -p (Ö > 1 0) Ai eö

>>> (1) Λ! C ¢) «H

- X (0 iH

(¾ O Ή O

X e Ui C O> 1 3 I -P> 1 3 - lii C en en

Hl I -H 00 Ό> i Iti -H

eno) -H rH I> i> 1 <0> G

Ai 6 -h en 1 Sh ^ xl -P -h en -no) 0 I rl A! N> 1 -H - 0) I H * H> pm> iOicn rH 1 - -h o> 1 e -p-η t) 1> 1 m r- λ; > ιΓ— m n>, o x x> 1 ^ s G Ό -H 0)> 1 I m> i-d e 0) 3 X! -H 0)> 1 en X! 04 · - I> 1> 1 O ® H> 1 en ή 43 rii -h 00— · -px: p 1 o> -h rH (NAi-HiOrH μ C-HX m>, ei en en PS - OH m Q,> 1 Qj-H en o M a - -P> 1 - O> 1 IQX s— II 1 I 3> 1 I Jm -P 2 fö o -H ms

i J3 4J eo ftll - - 'P rH 4-1 CM rH CM

20 79951

•B

* H <N _ _ _ -Ρω ^

>ί> 1 in --J »T

Q)> 1 iH 01

φ -H

U)> t— co cm oo * 0 I oo oo f— is 3

3H 'I O O O + J

»OS - ~ 4-1 HH O O O j

UK rH

3

r— σν vo σν K

oo co o oo 3 I 'T CO CM r- υκ - .11 _ o ° ° Q 3 3 cd ο Ό O c 01 oo vo. .

0 -H K ® o. g “> o o o H 00

M K

3 r- <<r O O

0> * ^ ^ 4J

K Ή CM CM (Π G

K U1 <d 3 <d id 'g to 00 00 ® 7j

«Os 5 m 5 C -P

H - - -H 3

3 O O O Cd p rH

U 3 cd 3

CM 00 CO tj 31 M

* VO. ^ t M C

<f CM CM Γ-H -H

3: cd 4-1 K -P 3 • P 3

G 0) G

-H * H

p - ε -h

3 G K

3 φ 00 M

I G -P P

1> i -Η -H id Φ

• H -P E U3 iH E

rH φ rH Ή> 1 E O oo G 0 tn> 1 '-'Cu cd G Φ

en Oj (0 cd G

O -H cd 01 4- »Cd G

M JQ JG 0) a) cd φ a o -h φ m oi e

0 M G Φ 01 -H

G -PO λ; cd G cd

• H -H 4-1 o Ή Φ K

ε e 01 K> 3 cd - o oi -h ε

- -rH 4-1 o> 1 K

Φ -H rH 01 CO 4->> 1 3 G

4-1 .H> 1 -H G 01>: 0

03> 1 -H> ι X cd cd Ή -H G

• H> i G H Id Cd Cd> 0lG

Ό -P cd T3 M -Γ-l 01 -Η -H

Φ Φ Id tC4J O · Η G 01

> 1 EG G Φ O G -Ρ <d K

• HO Id-PK O K cd Φ

Ό G cd— O φ -P K

10 -P - M oo rH Φ

2 Ό Φ - I Φ Cd -H

- O f -H G Ä (0 ίο W

2 G cm G cd '· η' φ ε il i

1 ε Ή φ rH

CO Id ^ rH H rH CM CO

21 79951

Example 2

The Central African copper oxide ore (Ci 2 O) is subjected to the flotation treatment described in Example 1 using 40 g per tonne of blowing agent, DOWEROTff ^ 250 5 (trademark of The Dow Chemical Company).

The results are listed in Table II, with collectors A and B selected from Table I.

Table II

10

Concentration _Cu_

Collector q / ton pH K_ RR ~ 8 A 160 5.1 2, 48 0.335 0.308 15 A 80 9.5 2.55 0.249 0.234 B 80 9.5 2.91 0.313 0.289 C 160 5.1 4.08 0.135 0 ; 130 20 A - C6H13-S * CH2> 2- ^ 2

O

B - C7H15C-NH * CH2) 2-NH2 C - Sodium isopropyl xanthate, not an embodiment of the present invention

It is well known in the mining industry that existing commercial aggregators such as sodium isopropyl xanthate do not foam oxide minerals very efficiently. It is therefore surprising that collector A, when used at a concentration of 80 g / ton, increases the recovery of valuable copper parts of the ore by 84.4% compared to standard collector C, which was used at a concentration of 160 g / ton, i.e. as much again. Comparing the capacity of collector A, when used at 35,160 g / tonne, with respect to standard C, it can be seen that the recovery of valuable copper parts of the ore increased by 148% 22,79951

The fact that the collectors of the present invention foam a substantially higher amount of valuable fatty parts from the copper oxide ore is an indication that the collectors of the present invention are less sensitive to the form of the metal-containing mineral, i. sulfide or oxide ores compared to existing collectors.

Example 3

Central Canadian sulfide ore containing copper risulfide, nickel sulfide, platinum, palladium, and gold metals was subjected to a series of flotations described in Example 1 using the collectors of this invention and several collectors known in the art. The blowing agent used is DOWEROTh * 1 263 (trademark of The Dow Chemical Company) with a concentration of 3.12 g / ton. Collectors 15 are used at a concentration of 31.2 g / ton. The foams formed were recovered after 0.5, 1.0, 2.0, 4.0, 7.0, 11.0 and 16.0 minutes. The results are listed in Table III, with the collectors selected from Table I.

23 79951: (0: (0

Π -3 · S '30 -j- P

+ j 3 en lt, o: (0 m <o o o o o: (0 u o o o o e g

(1) .... H

CL cvj o -j- o <r - <WO - OO - CN Ή 3 cu - - o - - (0 OOOOO, p en ..... <y (0 O - <3 Oe ^ X -J - r ~ m co - -H cu - oo - - (0 (¾ ooooo 3

-P

(0 <N c \ | O r- * 00 (0 (0

., H 33 O - <3 r- 'O U3 -P

η oo ό uo - - C -P

+ j ..... 0) -P

P C-4 S irt

-HeDlin vO O U0 Ο -P «J

4J - «j r— σν - CO O r — f C C

nil CM -J- <3 - - (0 * H O

U - - - - · -P -P Λ (0

μ'° ° ° C IrHCl-H

> l CTinmCNO n23t!

(il 1 * 3 -3- CM CS O O <l) (0rX -P

- ~ ~ -HO <0 e oo - o p q C (0

(0 0) 0 P

: o oi ^ (^ o P * P tn

331 o O cm oo (0 (0 P O

Moonr · '+ * 6 4-1

o P -P I (0 O

P -P> -P -P

M J, - m O O o -H -H e P -: m -h -: i; i o ni o 3 tn λ: M -p -h ns

H, _li se cc oo ro r ~ - E O 3 .¾ · Ρ Ό "P

d) - i ---- (0> Ci E q

0 X 3 4J -H O) (0 I -H

-¾ X ... n - n m r- + *: <0 tO E -H -H

- - X -Hi -n 3 n. <R CO "P Cl (0 —I -P E

3 Z ~! o r ^ r-CMoP Q) C Cl> i M <0 h ---- 0 a <u (0> ·,, * -h

3 3 0) 0)> 4J Ci H

3 _ 2 ^ 5; ~~ tn 3 M o o ¢)> 1 ^ ® ^ n, * 4- * ai -m - ε> 3

I - O - - - C (0 ΟΦ O 3 CL

0) (O3T3CC-HClO q 3 P, q 3 - P (0 Ci O n S o £ (0-0 3 fOO G Ρ * 0 - *

nT. . . , * 3 H> ra 3> 1 P -H

3 -H 3 Λ CL> i tn

• h (n B 3 X l ro E <n X

U ~ 'D: <r “<r ^ £ X <0 O X o

3, 'i ^ i ^ X G G P> U Φ <D -P

Oi il ”. . . . . : 0 C -H Λ l Λ TO -I

0 C · Ρ Ρ Ο · Ρ I-1 - · Ρ> -ι si— co - in σ \ ο C4J3ASQ) (0I6> i

J ^ Rico n 'cc o - -h 3 3> (0 (0 G

i ® ^ “^“ tnOCfl ^ -HCnCO

. * g -p -p>, e a> <o g i -3- r-oo ^ s-urtU-PGC-PDGi ^ '^

uc - - - - 'y E C -I Λ O U I

luO'i ^ TOvr vo 0: G U co

-it C- ^ r-i + JinCC

• P: (0 -P> O (0 G

, -H ^ E O 0 <0 tn 0 OO

p n: (0 p P -P a <-P

": i« 5.2 o p G c in <o wee

• I- ~ vo r- (0 (0t0Ai (UXa> CL

• · o U ^ Lr · ^ · in ^ r- <-P (0 (0CO-CEn £ O

: -: f> ΰ>; § ^ gS ^ gWenenD-rotHOCZ

o 2§ “7 S ^ -K-ICMCO Ί · in vo

^ 6¾ O

24 7 9 951

Table III describes two novel compounds of this invention, i. The use of OHTEA and NOPA compared to the three optimized standard sizes used in the industry. The ore was multi-constituent and contained 5 different metals. Collectors are comparable in performance in recovering valuable parts of copper ore. The OTHEA collector was clearly superior in the recovery of nickel, platinum, palladium, and gold. In nickel recovery, the R-16 value of OHTEA showed a small increase compared to the Z-21 ^ ^ * marker-10 collector, but a very surprising and significant decrease in pyrrotite recovery, i. 15.5%. Significant improvement was also achieved in the reduction of enrichment bases for platinum and palladium - values were approximately similar for gold.

15 The NOPA collector showed good recovery for copper and nickel compared to the best known collectors used in this field. It showed better efficacy in reducing R-16 pyrrhotite compared to standards. The ratio of nickel yield to pyrrotite yield is clearly better compared to known collectors, i.

30% increase in proportion. The selectivity of NOPA is considerable if the need for smelters is to be reduced because of the high content of unwanted sulfur-containing material in the flotation product.

Example 4 - Copper Sulfide Flotation In this example, various collectors of the present invention are tested for flotation of copper sulfide ore. 500 g of western Canadian copper ore, a relatively high-grade chalcopyrite-type copper sulfide ore containing some pyrite, is placed in a rod mill with 2.54 cm rods, together with 257 g of deionized water, and ground at 420 rpm at 60 rpm. to obtain a particle size distribution such that 25% is less than 100 mesh. Some lime li-35 is also adjusted to the rod mill for the next flotation based on the desired pH. The ground slurry is transferred

II

25 79951 p

Agitair frothing machine for a 1500 ml cell. The frothing cell is agitated at 1150 rpm and the pH is adjusted to 8.5 by adding more lime. The collector is added to the flotation cell at a rate of 5 8 g / ton, followed by a conditioning period of one minute during which the collector, DOWFROTH 250 (trademark of The Dow Chemical Company) is added at a rate of 18 g / ton. After an additional conditioning time of one minute, the air is blown into the flotation cell at a rate of 10 4.5 liters per minute and the automatic defoaming scraper is started. Foam samples are taken after 0.5, 1.5, 3, 5 and 8 minutes. The foam samples are dried overnight in an oven along with flotation coats. The dried samples are weighed, divided into suitable samples for analysis, ground to ensure suitable fineness and dissolved in acid for analysis. Samples are analyzed using a DC Plasma Spectrograph. The results are summarized in Table IV. the compounds used in Examples 1-31 of Table IV are listed separately below: 20 1 *. Without collector 2. C 6 H 13 S * CH 2) 2 NH 2

H O

3. (t-butyl) S (CH2) 2NH2 4. C6H13S <-CH2) 2N-C-C2H5 25

HO

5 · C10H21S "(CH2) 2 ^ 'C2H5 6 * (C4Hg) 2-N- (CH2) 2NH2

HO OH

30 7. (t-butyl tert-(CH2) 2N-C-C2H5 8. CgHigC-NfCH2) 2NH2

HO HO

9 · c4HgS- (CH2) 2N "C_C2H5 10. ci2H25S" ^ CH2 ^ 2N_C-C2H5 26 79951

O _ H O

li. c8h17s- (ch2) 2-c-nh2 12. / QVs- (ch2) 2n-c-ch3

13. C 9 H 17 S- (CH 2) 3 NH 2 14. C 9 H 17 S (CH 2) 2 NCS

5 / - \ * / ch3 15 * 16 · ch3 ch3

H H

10. C8H17S (CH2) 2N 18. C8H17S (CH2) 2N

/ Cx vN = C

H1 / H2N </ N-C-n w

CH3-C-C = C-CH3 15 H

H H / CH3 19. C8H17S (CH2) 2-N 20. C6H13-C-S (CH2) 2N2

N = C-N = C CH CH

20 CV *

HO OH

21. C5H1: 1S (CH2) 3N-C-OC2H5 22. C8H17S-CH2CH2NH2 25 23 * c8H17S (O2) 2 ^ 2 24. C4HgS (CH2) 2NH2-HCl HO OH- 25. C8H17-S (CH2) 2N -CC2H5 26. C2C-OC4 -N- (CH2) 2NH2

30 H HS

27. C5H1; 1S (CH2) C <CH2) NH2 28. CjHjjS (CH2) N-P- (O-CjHj) 2

OH

27 79951

H H

29 · c6h13-s (ch2) 2n-c-po3h2

B

H CH3 5 30. CH3N- (CH2) 2N-CH2-CH (OH) -CH2-O-CH2-CH (C2H5) -C4Hg 31. NH2-CH2-CH (OH) -CH2-O-CH2-CH ( C2H5) -C4Hg

32. C6H13 - S (CH2) C = N

1 * -Not an example according to the invention.

10

Table IV

15 Example- Copper Sidestone Copper Sidestone Select No. _K_ _R_ _K_ R R-8 R-8 Visibility 1 * 2,110,306 1.61 0.068 0.291 0.066 4.4 2 4,190,629 3,630,140 0.606 0.136 4.5 20 3 3.65 0.621 4, 28 0? 121 0.600 0.121 5.0 4 3.79 0.943 2.95 0fi96 0.906 0.189 4.8 5 2.69o, 789 2.37 0.160 0.730 0.148 4.9 6 2.04 0.382 1.88 0 ^ 735 0.358 0.0692 5.2 25 7 3.86 g, 585 3.44 0.118 0.562 0.114 4.9 8 2.36 0.435 2.15 0.0858 0 ^ 409 0.0815 5.0 9 5,160,742 4.43 0.157 0.719 0.153 4.7 10 2.38 0., 499 2.10 0.100 0.469 0.0951 4.9 28 79951

Table IV (continued)

Example- Copper Sidestone Copper Sidestone Selection No. KR K_R R ~ Q Visibility 5 11 4.53 0.869 3.59 0.184 0.838 0.179 4.7 12 2.06 0/148 1.80 0.0895 0.418 0 ^ 0840 5, 0 13 3.90 0.572 3.22 0.126 0.551 0.123 4.5 14 2.120.863 1.59 0.192 0.809 0.179 4.5 15 3.430.534 2.90 0.108 0.513 0.106 4.8 10 16 2.94 0.424 2.45 0.0841 0.408 0.0816 5.0 17 5.00 0.641 4.33 0.148 0.622 0.145 4.3 18 3.51 0.682 3.01 0, 175 0.649 0.168 3.9 19 2.68 0.451 2.29 0.097 0.429 0.094 4.6 20 3.46 0.449 2.96 0.092 0.431 0 (ogo 4.8 15 21 4.58 0.909 3.44 0, 187 0.878 0fi81 4.8 22 4.22 0.540 3.60 0, 124 0.523 0.123 4.3 23 3.61 0.514 2.96 0, 111 0f493 0.107 4.6 24 3.54 0.542 3.21 0.121 0.520 0f117 4.4 25 3.54 0.832 2.73 0.162 0.802 0f156 5fl 20 26 2.14 0.367 1.61 0.080 0.345 0 075 4.6 27 3.62 0.520 2.98 0.119 0.501 0.116 4.3 28 1.97 0.848 1.56 0.180 0.788 0.166 4.7 29 2.41 0.308 2.11 0.0676 0.296 0.066 4, 5 30 2.35 0.340 2.14 0.0702 0.324 0.0676 4.8 25 31 2.25 0.355 2.18 0.0737 0.338 0.0710 4.8 3 2 7.17.0.72 3 5 3 2 0.15 6 0.707 0, 15 5 4.6 1 * Example 29 79951 not according to the invention

Example 4 is similar to Example 1 except that several different compounds within the scope of the invention were tested on a different copper sulfide ore. No attempt was made to optimize the collectors, 5 but all compounds were found to be clearly superior to the fact that no collector was used in the copper recovery. The collectors of this invention show better recovery and selectivity compared to collectors known as standards and optimized for the particular ore under inspection.

Example 5 - Foams of copper sulphide and molybdenum sulphide »p

The homogeneous ore was filled into sacks so that each sack contained 1200 g. Esivaahdotusmenetelmäs-

O

a 1200 g batch is ground with 800 cm of tap water for 14 minutes in a ball mill with a mixed moon ball batch (to obtain a product in which 13% of the particles were + 100 mesh). This slurry is transferred to an agitaij® 500 brand flotation cell 20 equipped with an automatic scraper removal system. The pH of the slurry is adjusted to 10.2 using lime. No further pH adjustments are made during the experiment. The standard blowing agent used is methyl isobutylcarbinol (MIBC). A four to 25 step pre-foaming program is then performed.

Step 1: collector - 0.0042 kg / ton MIBC - 0.015 kg / ton - conditioning - 1 minute - flotation - collection enrichment 1 minute.

30 Step 2: collector - 0.0021 kg / ton MIBC - 0.005 kg / ton - conditioning - 0.5 minutes - flotation - collection enrichment 1.5 minutes 35 30 799 51

Step 3: collector - 0.0016 kg / ton MIBC - 0.005 kg / ton - conditioning -, 0.5 minutes - flotation - collection enrichment 2 minutes 5 Step 4: collector - 0.0033 kg / ton MIBC - 0.005 kg / ton - conditioning - 0.5 minutes - flotation - assembly enrichment 2.5 minutes

10 Table V

Copper / molybdenum ore from western Canada

Cu Mo Cu Mo Fe yield yield concentration- Size- Dosage R_7 R_7 orally and kg / ton. . u 15 ___1_min min__ A 0.0112 0.776 0.725 0.056 0.00181 0.254 B 0.0112 0.688 0.682 0.063 0.00233 0.108 B 0.0067 0.659 0.759 0.099 0.00402 0.137 B 0.01121 0.648 0.747 0.080 0.00314 0.127 20 ' A - potassium amyl xanthate (not an example according to the invention)

O

25 B - C6H13S (CH2

B

The slurry was not treated with lime and the pH was adjusted to 8.2.

Table V shows that significantly higher concentrations of copper and molybdenum are achieved compared to standard collector A. Copper had a minimum increase of more than 10% and a maximum increase of 77%. For molybdenum, the minimum increase in concentration was about 30% and the maximum optimized increase di was about 122%. Such improvements require a significantly lower load on the mining smelter.

3i 79951

The iron content of the product when using one of the collectors B according to the invention again shows a substantial reduction of about 50% compared to the standard collector A, which indicates that considerably 5 less undesirable pyrites accumulate. very advantageous in the further processing of mining operations because it reduces sulfur emissions.

Example 6 - Flotation of nickel-10 cobalt ore from Western Australia

A series of 750 g batches of nickel / cobalt ore is prepared as a slurry (30% solids). The flotation cell is of the Agitaiif and 500 mark and is equipped with an automatic scraper that rotates at 15 to 60 rpm to remove foam. According to the standard run, 0.2 kg / ton CuSO 4 is first added, conditioned for 7 minutes, 0.1 kg / ton collector is added, conditioned for 3 minutes, 0.14 kg / ton guar gum, talc depressant, and 0.16 kg / ton tons of collector, and a blowing agent 20 (e.g., triethoxybutane) is added to form a moderate foam layer. Concentration of the concentrate is started for 5 minutes (called pre-concentrate). Then 0.16 kg / tonne of collector +0.07 kg / tonne of guar gum is added to the remaining cell contents together with any of the required blowing agents and the concentrate collection is started for 9 minutes (called intermediate product) while the remaining contents of the cell are called flotation bases. The pre-concentrate is then transferred to a smaller cell. 0.08 kg / ton of collector +0.14 kg / ton of 30 guar gum but no blowing agent is added to the cell, the concentration of the concentrate is started for 3 minutes (called post-enrichment) while the contents of the cell are called post-foaming . Samples are filtered, dried and examined using X-ray analysis mediation. Recoveries 35 are calculated using standard metallurgical methods. The results of this experiment are summarized in Table VI. The compounds used in Examples 1-5 in Table VI are listed below: Collector 1 * - Sodium ethyl xanthate 2 - C6H13S (CH2) 2NH2 0 10 3 - c6h13s (ch2) 2n-c-c2h5

B

4- (C4H8) 2 "N2H2CH2 ^ 2 ^ 2

O H

5 - C7H15C-N- (CH2) 2NH2 * Not according to the invention 33 79951 I O '· σ> co ro <n • H φ _ ** * "" - σ> cm o <o

to O Ή CM (N

df> d> 0

»-P

O

p I 5 oio c ^^ omao 3 c-H'djj ”'·’ · ’·” ·· <U, c I: ιβ ^ O) 00 f- co <- φ H Ιβ (O It H °

-P aö n! 3 C O

h b> + »a (0 c p 3

CO o lo O <ro o -E

• ητ3 +) "'" * · “·“ p

p r I: uj n σι lh r · »ro G

h (0 tn ρ ή S

• g (0 3 a> x h Λ> P O. nj E O p h «tn id -d

E φ O * CM CO iH O

• H I -P 13

P -h tn cm ro tn cm S

-i-l, V (0 i> 0 t ~~ vO vO tD (3 -h 3 m ϋ o: rö -P ** Λ b) P (0

O H

^ -P

H \ | S

> -P -PQJiJirPiHiPrO · rj γη λ <p -p p

o φ tn o m t-ι h σ o x S

xx φ c pptNro x tn

a; x «-P p P

3 -h a> fr

h c E

0 -H: rq to 3 i tn: m

H p ίο σ> o ao ro ro Φ -H

(0 -H Ό P w -P

ro AixJitto ^ or- ^ tN C 3 tn dpptotnpcNP <h a) g «ms® e _

tö o b> 4J ft · ρ C

p p to S

tn p x p to o I 3 3 • p C "oi ro p t ·" o <o <E rj

rH <ϋΌ <ϋ S

(0 QIrC & iC'CntO'O'r-t C ^ tO P to tn p: 0 p p> H to 3: iö C φ p to> p p cg

tn P h X

Pi tn Q

<C -H * 3 i-pp ^ oo ^ po a) p • H »H * HQ)«. r- »^ 4 ω ^^ Ρ ^ ΜίΛ ^ Γ'ΐΡ zj

.5 rί rj <2 νΡΓ ^ Γ'ΐΛΐη · ρ S

: t0 Λί: t0 (0 (1) p · η b ^ g

Z * S

I - o 9 * I-H CM ro ^ LT)

Oto

Mn 34 7 9 9 51

The results presented in Table VI represent a full-scale simulation of a continuous industrial flotation method. The information in the column entitled "flotation stems" is the most significant because it 5 shows the actual metal loss, i. the lower the value in the flotation column, the lower the metal loss. The superiority of the collectors of the invention used in the experiment over the industry standard in this category is obvious. At a minimum, the flotation bases showed an 8% decrease in the recovery of 10 nickel, at most the decrease in the flotation bases surprisingly showed a decrease of 81%. For the robot, similar improvements were made, with the exception of the collector 3.

Example 7 - Flotation of 15 Pb / Zn / Cu / Ag ore from Central Canada

Prepare uniform ore samples of 1000 g. For each flotation run, a sample is added to a rod grinder together with 500 cm "* of tap water and 7.5 ml of SC 2 solution. (75 microns) After grinding, the contents are transferred to a cell equipped with an automatic scraper to remove foam, which is attached to a standard Denver foam-25 dosing mechanism.

This is followed by a 2-stage flotation treatment. In stage I, copper / lead / silver pre-enrichment, and in stage II, zinc pre-enrichment. To start the flotation of step I, 1.5 g / kg ^ 200 ^ is added and the pH is adjusted to 8.5, after which the collector (s) are added. The slurry is then conditioned for 5 minutes with air and stirred. This is followed by a conditioning time of 2 minutes, during which the slurry is only stirred. MIBC blowing agent (standard dose 0.015 ml / kg) is then added.

35 The concentrate is collected for a flotation period of 5 minutes and the product is marked as copper / lead pre-concentrate.

35

In stage II flotation, 0.3 kg / ton of C11SO4 is added to the cell density of stage I. The pH is then adjusted to 9.5 by adding lime. It is then conditioned for 5 minutes with stirring only. The pH of the broth is then checked again and adjusted back to 9.5 with lime. At this time, the collector (s) are added, followed by a conditioning time of 5 minutes, at which point the slurry is only stirred. MIBC foaming agent (standard dose 0.020 ml / kg /) is then added. Concentrate 10 is collected for 5 minutes and labeled as zinc pre-concentrate.

The enrichment samples are dried, weighed and suitable samples are prepared for the experiment using X-ray methods. Using the experimental results, tal-15 yields and concentrations are calculated using standard mass equilibration formulas.

36 79951 en B. ^ ^ tn i ή inhi ro i ro '01 «* I - C -H ° ° N ^ 1 Φ co ro ro lo t" o in ro 1 Ή 00 rH 00 oä - oooo rtn 2 <n!> L§ S ! S '! 13 cT' cT 1 and -n

Oh 00 in o ^ m ro m γη>

• Γ "rH Γ- H

• H 05 * - - · - -

E O O O O

Γ — i nj m E .Bo en 1 g in i cn i

t? '.S Ή I Ή I

<Q - I - I

\ ϋ O O

53 3 -H

U U Oj vO ^ ro m in m rH m [71 e I σι o mo> N 05-- - - ο Λ o o o o * ϋ ¢ 1 53 <3 kO O * “[rH 5 S ® 1 rvj I -y

3 Id -¾ ° t! "'3 -H

B S <]. ° ° ° W -3 2

2 Si 3 δ S 2 «I

M i ® H. ®. H -P -H

5 o o O o "%"

(Ö C

6, -H m m e S

5 Λ, + -> m r- o m m ^ r-ι. B 2 7 £ \ O O CN H O O CN 7j Ln.5

• h eng °°, 00 oo o iJ B

S S3- °° O'o o-Q- o * s 8 3

0) -P C E

«C«

I (0 -rH (0 C

o Q «Q ^ U 5Γ1" C

M -H + J (0 25 C C

0 Ifl H +) ID (N ¢) -H

«N ^ (OE '-' Cm

> 1 (0 (0 cn -H M

Λ Λ ΦΐηίπυΉΑί oio £ 7 „^ H ε o« - ®

XI I Ό \> C 3 4-1 ΛΙ V) T3 C

-rl · Η £ 1 p N 53 N -rl 0 0 ro 0: r0 (Ö in (0 UT U U Ij-HCrH + Jg

> 0 (0 D + J. | J0K: nJ

> -P (O-H-HiOCl-P

C T3 -P U 0

•B

I I I I in w

* I

h cn <oquqo5- «37 79951

Table VII depicts the efficiency of optimized industry standard collectors compared to the collector of the invention in recovering precious metals. In Experiment 1, a combination of standard collectors A and B was used in step I, while in phase II a combination of standard collectors A and C was used. In step I of Experiment 2, a mixture of standard collector B and collector D according to the invention was used in approximately equal amounts. In step II of experiment 2, a collector D according to the invention was used.

10 The aim of this experiment was to maintain the recovery of silver and copper in phase I and to increase the recovery of zinc in phase II. The results show that collector D approximately maintained the recovery level of silver and copper, with an improvement in concentration. What was most significant was that in Phase II of Experiment 2, both zinc recovery (R-5) and concentration were improved by 3% and 6%, respectively, compared to the standard collectors in Experiment 1.

Claims (9)

38,79951 Patented Applications A collector for recovering metal sulphides or sulphidated metal oxides from ore by foaming, characterized in that it is a compound of the formula R 1 -X * R> -nNfR 2) a (H) b H 0 I II wherein R is -CH 2 -, -C-, -C- or a combination thereof, OH n is an integer from 1 to 6 or - (R) ^ is -fCH 2 Cs, where m is an integer from 0 to 6, R 1 and R 2 independently represent a C 1-4 hydrocarbyl group which may be substituted by one or more hydroxy, amino, phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano, halogen, ether, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbylimino, and R 2 may further be a divalent group bonded by a double bond directly to a nitrogen atom, X is -S-, -O-, -N-R 3 0 OR3 0 1. ii II -C-S-, -C-N- or -CO-R3 is H or a .22 hydrocarbyl group which may be substituted; a is an integer 0, 1 or 2; b is an integer 0, 1 or 2; provided that the sum of a and b is 2, except when R2 is a divalent group bonded by a double bond directly to a nitrogen atom, in which case a = ljab = 0, or when (R) n is (CH2) mCs , in which case a + b = 0, and has the condition that when X is s sr s The carbonyl group of -C-S, -C-N- or -CO- is attached to R1. 39 79951 A collector according to claim 1, characterized in that the compound has the formula R 1 -X 2 CH-WR 2) - 2. a R h (H) b 5 wherein R 1 is a C x 22 hydrocarbyl group which may be substituted by one or more hydroxy -, amino, phosphonyl or alkoxy; R 2 is C 1-6 alkyl, C 1-6 alkylcarbonyl, C 1-6 alkyl group substituted with amino, hydroxy or phosphonyl, or C x. A 6-alkylcarbonyl group substituted with an amino, hydroxy or phosphonyl group; and X, a, b and n have the same meaning as in claim 1. Collector according to Claim 2, characterized in that R 1 is C 2-4 hydrocarbyl; R 2 is C 1-6 alkyl or C 1-6 alkylcarbonyl; R 3 is hydrogen or C 2-4 hydrocarbyl; a is an integer 0 or 1; b is a size 20 female number 1 or 2; and n is an integer from 1 to 4. A collector according to claim 3, characterized in that R 1 is C 4 x x -hydrocarbyl; R 2 is C 1-4 alkyl or C 1-4 alkylcarbonyl; R 3 is hydrogen or C 4-14 hydrocarbyl; n is an integer 2 or 3; and X is 25 -S-, -N-R3 or -O-. Collector according to Claim 4, characterized in that X is -S- or -N-R 3. Collector according to Claim 4, characterized in that X is -S- · Collector according to Claim 1 or 2, characterized in that the compound is selected from: omega- (hydrocarbylthio) -alkylamines; omega- (tetrahydro-karbyylitio) -alkylamide; S- (omega-aminoalkyl) carbon-vetytionaatit; N- (hydrocarbyl) alpha-omega-alkanediamine; (Omega-aminoalkyl) hydrocarbon amides; omega- (hydrocarbecarboxyloxy) alkylamines; omega-aminoalkyylihydrokarbo-tops; and mixtures thereof. A process for recovering metal sulphides or sulphidated metal oxides from ore by foaming the ore as an aqueous slurry in the presence of a collector under conditions such that the minerals are recovered in the foam, characterized in that a compound according to any one of claims 1 to 7 is used as collector. Method according to Claim 8, characterized in that the collector is added in an amount of 5 to 250 g per tonne. 41 79951