CA1280520C

CA1280520C - Method of separating non-sulfidic minerals by flotation

Info

Publication number: CA1280520C
Application number: CA000508843A
Authority: CA
Inventors: Wolfgang Von Rybinski; Rita Koester
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1985-05-11
Filing date: 1986-05-12
Publication date: 1991-02-19
Anticipated expiration: 2008-02-19

Abstract

ABSTRACT OF THE DISCLOSURE
A process for separating non-sulfidic minerals from an ore by flotation in which the ore is contacted with a mixture of (a) at least one adduct of ethylene oxide and pro-pylene oxide with a C8-C22 fatty alcohol and (b) at least one anionic, cationic or ampholytic surfactant.

Description

~805~0 PATENT
Case D 7301 METHOD OF SEPARATING NON-SULFIDIC
MINERALS BY FLOTATION
BACKGROUND OF THE INVENTION
1. Field of the Invention This invsntion relates to the use of mixtures of non-ionic ethylene oxide/propylene oxide adduots and anionic or cationic surfactants which are known ~_ se as collectors for flotation processes, as aids in the flotation of non-sulridic ores.

2. Statement of Related Art __ _ ___ Flotation is a separation technique commonly used in the dressing of mineral raw materials for ~eparating valuable minerals from those with no value. Non-sulfidic minerals are, for example, apatite, fluorite, scheelite and other salt-containing minerals, cassi-terite and other metal oxides, such as oxides of tita-nium and zirconium, and also certain silicates and alumosilicates. For flotation, the ore is sub~ected to preliminary size-reduction, dry-ground or preferably wet-ground, and suspended in water. Collectors are nor-mally added to the non-sulfidic ores, frequently in con~unction with frothers and, optionally, other auxi-_ 1 _ ~8Q5~(~
liary reagentq such aq regulators, depreq~ora (deactivatorq) and~or activator~, in order to facili-tate ~eparation of the valuable mineral~ from the unwanted gangue conqtituents of the ore in the ~ub-sequent flotation proce~q. These reagent~ are normally allowed to act on the finely ground ore for a certain time (conditioning) before air is blown into the su~pen~ion (flotation) to produce a foam at itq ~urface. The collector act~ as a hydrophobicizing agent on the qurface of the mineralq, cau~ing the mineralq to adhere to the gaq bubbles formed during the aeration step. The mineral constituents are selectively hydrophobicized ~o that the unwanted constituents of the ore do not adhere to the gas bubbles. The mineral-containing foam is qtripped off and further processed.
The object of flotation i~ to recover the valuable mineral in the ores in a~ high a yield as posqible while at the same time obtaining a high enrichment level.
Anionic and cationic surfactants are uqed as collectors in known flotation procesqes for non -sulfidic ores. Known anionic collectorq are, for example, saturated and unsaturated fatty acids, par-ticularly tall oil fatty acids and oleic acid, alkyl sulfates, particularly alkyl sulfates derived from fatty alcoholq or fatty alcohol mixtures, alkyl aryl sulfonateq, alkyl sulfosuccinates, alkyl sulfosuc-cinamates and alkyl lactylates. Known cationic collec-tor~ are, for example, primary aliphatic amines, particularly the fatty amines derived from the fatty acids of vegetable and animal fats or oils, and also alkyl-substituted and hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition qalts of these amineq .
By virtue of their surfactant character, many collectors for non-~ulfidic mineral~ themselve~ develop a foam sultable for flotation. However, it may also be nece~ary to develop or suitably modify the foam by special frothers. Known flotation frothers are C4-C10 alcohol~, polypropylene glycols, polyethylene glycol or polypropylene glycol ethers, terpene alcohols (pine oils) and cresyl acids. If necessary, modifying reagent~, suQh as for ex?mple pH regulator~, activators for the mineral to be recovered in the foam or deactivator~
for the unwanted mineral~ in the foam, or dispersants, are added to the flotation ~u~pension~ tpulps).
In contrast to anionic and cationic surfactants, nonionic surfactants are not often used as collectors in flotation. In Tran~. Inst. Met. Min. Sect. C., 84 (1975), pp. 34-39, A. Doren, D. Vargas and J. Goldfarb report on flotation tests on quartz, cassiterite and chrysocolla which were carried out with an adduct of 9 to 10 moles of ethylene oxide with octyl phenol aq collector. Combination3 of ionic and nonionic surfac-tants are also occa~ionally de~cribed as collectors in the relevant literature. Thu~, A. Doren, A. van Lierde and J.A. de Cuyper report in Dev. Min. Proc. 2 (1979), pp. 86-109 on flotation tests carried out on cassi-terite with a combination of an adduct of 9 to 10 moles Or ethylene oxide with octyl phenol and an octadecyl sulfosuccinate. In A.M. Gaudin Memorial Volume edited by M.C. Fuerstenau, AIME, New York, 1976, Vol. I, pp.
597-620, V.M. Lovell describes flotation tests carried out on apatite with a combination of tall oil fatty acid and nonyl phenyl tetraglycol ether.
Cationic, anionic and ampholytic collectors are used for the flotation of non-sulfidic ores. In many cases, collectors such as the~e used in economically rea~onable quantities do not lead to sati9factory reco-very of the valuable minerals. In order to make flota-8C~5~0 tion processes more economical, it i9 desireable to find improved collectors with which it is po~sible to obtain either greater yieldq of valuable minerals for the ~ame quantitieq of collector or the same yields of valuable minerals for reduced quantities of collector.
DESCRIPTION 0~ THE INVENTION
Accordingly, it is an ob~ect of the present inven-tion to improve ~own collectors (primary collector~) for the flotation of non-~ulfidic ores by suitable additives (co-collectors) to such an extent that the recovery of valuable minerals in the flotation proce~s can be significantly increased for substantially the same collector selectivity, this effect also being used to obtain the same yields of valuable minerals for reduced amountq of collector and co-collector as com-pared with the prior art.
It has now been found that adducts of ethylene oxide and propylene oxide with Ca-C22 fatty alcohols represent extremely effective additives aq co-collectors to anionic, cationic or ampholytic surfac-tants of the type known as collectors for the flotation of non-sulfidic ores.
Other than in the operating examples, or where otherwise indicatd, all numbers expre~sing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term nabout" .
~he pre~ent invention relates to a flotation pro-cess for qeparating non-sulfidic minerals from an ore wherein the ore is contacted with a mixture of (a) at least one adduct of ethylene oxide and propy-lene oxide with a Cg-C22 fatty alcohol and (b) at lea~t one anionic, cationic or ampholytic ~ur-factant.
Component (a) consists in particular Or adducts of 86~5ZO
m mole~ ethylene oxide and n moles propylene oxide with Cg-C22 fatty alcohols, m and n each being a number of from 1 to 15, the sum of m and n being from 2 to 25 and the ratio of m to n being from 1:5 to 2:1. These ethy-lene oxide/propylene oxide adducts are known substances which may be synthesized by known processes. In general, they are obtained by addition of the intended quantities of ethy~lene oxide and propylene oxide with the fatty alcoholq used as starting material in the presence of known alkaline alkoxylation catalysts. The addition of the alkylene oxide3 may be carried out either by reacting a ccrre~ponding mixture of ethylene oxide and propylene oxide with the fatty alcohol starting material or by addition of first one alkylene oxide and the* the other. Products obtained by addition of ethylene oxide and subsequent reaction with propy-lene oxide are preferably used as component (a) in the mixtures used in accordance with the invention.
The fatty alcohol component o~ the ethylene oxide/propylene oxide adducts defined under (a) may consist Or straight-chain and branched, saturated and unsaturated compounds of this category containing from 8 to 22 carbon atoms, for example of n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n-hexadecanol, isotridecanol and i~ooctadecanol. The fatty alcohols may lndividually form the basis Or the ethylene oxide/propylene oxide adducts. In general, howerer, products based on fatty alcohol mixtures are u~ed as component (a), these fatty alcohol mixtures being derived from the fatty acid com-ponent Or fats and Qils Or animal or vegetable origin.
It is known that fatty alcohol mixtures such as these may be obtained from the native fats and oils, inter alia by transesterirication of the triglycerides with methanol and subsequent catalytic hydrogenation Or the ~L~805~0 fatty acid methyl e9ter. It i9 po~slble to uqe both the fatty alcohol mixture~ accumulating during production and also suitable fractions having a limited chain-length range as a basis for the addition of ethylene oxide and propylene oxide. In addition to the fatty alcohol mixtures obtained from natural fats and oil-q, synthetic fatty alcohol mixtures, as for example the known Ziegler and~xo fatty alcoholq are suitable ~tar-ting materialq ~or the production of the ethylene oxide/propylene oxide adducts defined under (a).
Adducts of ethylene oxide and propylene oxide with C12-C18 fatty alcohols are preferably used aq com-ponent ~a).
The polyalkylene glycol component of the above adducts preferably contains on a statistical average from 1 to 10 moles ethylene glycol units and from 1 to 15 moles propylene glycol units per mole fatty alcohol.
The molar quantities are coordinated with one another in such a way that from 2 to 25 moles of alkylene gly-col units are present per mole of fatty alcohol and that the molar ratio Or ethylene glycol to propylene glycol units is in the range of from 1:5 to 2:1.
Preferred products are those which contain from 2 to 6 ethylene glycol units and from 4 to 12 propylene glycol units per mole of fatty alcohol and in which the molar ratio of ethylene glycol units to propylene glycol units is in the range of from 1:1 to 1:2.
Anionic, cationic and ampholytic surfactants of the type known per se as collectorq for the flotation of non-sulfidic ores can be used as component (b).
If anionic surfactants are to be used as component (b) in accordance with the invention, they are pre-ferably selected from fatty acidq, alkyl sulfate~, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl qulfonates, petroleum sulfo-1~80S~0 nates, alkyl qulfonate~, petroleum ~ulfonateY and acyl lactylates Suitable fatty acids include the straight-chain fatty acid~ containing from 12 to 18 carbon atoms and 5more especially from 16 to 18 carbon atoms obtained from vegetable or animal fats and oils, for example by lipolysis and, optionally, fractionation and/or separ-tion by the hydr~ophilization process. Oleic acid and tall oil fatty acid are preferred.
10Suitable alkyl ~ulfates include the sulfuric acid semiesters of Cg-C22 fatty alcohols and preferably of C12-C18 fatty alcohols which may be linear or branched.
The foregoing di~cussions of the fatty alcohol com-ponent of the ethylene oxide/propylene oxide adducts 15tcomponent (a~) also apply to the fatty alcohol com-ponent of the ~ulfuric acid semiesters.
Suitable alkyl sulfo~uccinates include Qulfosuc-cinic acid ~emiesters of Cg-C22 fatty alcohol~ and pre-ferably of C12-C18 fatty alcohols. These alkyl 20sulfoAuccinates may be obtained, for example, by reaction of corresponding fatty alcohols or fatty alco-hol mixture~ with maleic acid anhydride and subsequent addition of alkali metal sulfite or alkali metal hydro-gen sulfite. The foregoing discussions of the fatty 25alcohol component of the ethylene oxide/propylene oxide adducts (component (a)) also apply to the fatty alcohol component of the sulfosuccinic acid esters.
The alkyl ~ulfosuccinamates which can be employed as component (b) correspond to the following formula R O
R - N - C - CH - CH2 - COOM (I) in which R is an alkyl or alkenyl group containing from 35-8 to 22 carbon atom~ and preferably from 12 to 18 car-12~305Z0 bon atoms, R' represent~ hydrogen or a C1-C3 alkyl group and M i~ a hydrogen ion, an alkali metal oation, e.g. sodium, potassium, lithium etc., or an ammonium ion, preferably a sodium or ammonium ion. The alkyl sulfosuccinamates corresponding to formula I are known substances obtained, for example, by reaction of corresponding primary or secondary amineq with maleic acid anhydride an~d~qubsequent addition of alkali metal sulfite or alkali metal hydrogen sulfite. Examples of primary amines suitable for use in the preparation of the alkyl sulfosuccinamates are n-octyl amine, n-decyl amine, n-dodecyl amine, n-tetradecyl amine, n-hexadecyl amine, n-octadecyl amine, n-eicosyl amine, n-docosyl amine, n-hexadecenyl amine and n-octadecenyl amine. The above amines can individually form the ba~is of the alkyl sulfosuccinamateq. However, amine mixtureq of which the alkyl groups are derived from the fatty acid component of fat~ and oils of animal or vegetable ori-Bin are normally u~ed for preparing the alkyl sulfosuc-cinamateq. It is known that amine mixtures quch aq these may be obtained from the fatty acids of native fats and oils obtained by lipolysis via the corre~pon-ding nitriles by reduction with qodium and alcohols or by catalytic hydrogenation. Secondary amines suitable for uqe in the preparation of the alkyl sulfosuc-oinamates corresponding to formula I include the N-methyl and N-ethyl derivativeq of the primary amineq disclosed above.
Alkyl benzene sulfonates suitable for use as com-ponent (b) correspond to the following formula R - C6H4 - S03M (II) in which R is a stralght-chain or branched alkyl group oontaining from 4 to 16 and preferably from 8 to 12 carbon atoms and M iq an alkali metal cation, e.g.
~odium, potaqsium, lithium etc., or ammonium ion, 1'~805Z0 preferably a ~odium ion.
Alkyl ~ulfonates ~uitable for u~e a~ component (b) corre~pond to the following formula R - S03M (III) in which R i~ a ~traight-chain or branched alkyl group preferably containing from 8 to 22 carbon atom~, and more preferably, from 12 to 18 carbon atom~, and M iQ an alkali metal cation, e.g. ~odium, potas~ium, lithium etc., or an ammonium ion, preferably a sodium ion.
The petroleum sulfonate~ ~uitable for use as com-ponent (b) are obtained from lubricating oil fractions, generally by ulfonation with sulfur trioxide or oleum.
Those compoundQ in which most of the hydrocarbon radi-cal~ contain from 8 to 22 carbon atoms are particularly suitable.
The acyl lactylate~ suitable for u~e as component (b) corre~pond to the following formula R - C - O - CH - COOX (IV) in which R is an aliphatic, cycloaliphatio or alicyclic radical containing from 7 to 23 carbon atom~ and X is a salt-forming cation, e.g. an alkali metal cation or an ammonium ion. R is preferably an aliphatic, linear or branched chain hydrocarbon radical which may be saturated, mono- or poly-un~aturated, e.g. olefinically un~aturated, and optionally ~ub~tituted by one or more hydroxyl group~. The u~e of the acyl lactylate~
corre~ponding to formula IV a~ collectors in the flota-tion of non-~ulfidic ore~ is described in German Patent Application P 32 38 060.7 (German Offenlegungsschrift No. 32 38 060).
If cationic ~urfactants are to be used as com-ponent (b) in accordance with the invention, they are preferably ~elected from primary aliphàtic amine3, from alkylene diamineq ~ub~tituted by a-branched alkyl _g_ ~280520 group~ or from hydroxyalkyl-~ub~tituted alkylene diami-nes and from water-~oluble acid addition ~altq of theqe amineq.
Suitable primary aliphatic amines are preferably the Cg-C22 fatty amine~ derived from the fatty acidq of native fat~ and oils which were discussed earlier in connection with the alkyl ~ulfoquccinama~e~ also suitable for uqe~às component (b). Mixture~ of fatty amine~ are generally used, ~uch aq for example tallow amines or hydrotallow amines of the type obtainable from tallow fatty acids or from hydrogenated tallow fatty acids via the corresponding nitriles and hydroge-nation thereof.
The alkyl-sub~tituted alkylene diamines suitable for use as component (b) correspond to the following formula R - CH - R' HN - (CH2)n~NH2 (V) in which R and R' represent saturated or unsaturated, straight-chain or branched alkyl groups, which together contain from 7 to 22 carbon atoms, and n is an integer of from 2 to 4. The production of theqe compounds and their use in flotation is described in East German Patent No. 64,275.
The hydroxyalkyl-qubAtituted alkylene diamines ~uitable for use as component (b) corre~pond to the following formula R1 _ CH - CH - R2 Hl NH - (cH2)n - NH2 (VI) in which R1 and R2 represent hydrogen and/or unbranched C1-C18 alkyl groups, the sum of the carbon atoms in Rl and R2 being from 9 to 10, and n is an integer of from 2 to 4. The production of the compounds corresponding to . formula VI and their use in floation is described in German Offenlegung~chrift 25 47 987.

_ 10--lZ80520 The amine compound~ di~cu~ed above may be used either a~ such or in the form of their water-soluble acid addition salt~. The salt~ are obtained by neutra-lization which may be carried out both with equimolar quantities and al~o with an excesQ or Aubmolar quantity of acid. Suitable acidQ are, for example, sulfuric acid, phoQphoric acid, hydrochloric acid, acetic acid and formic acid. ~
The ampholytic 3urfactant~ which can be used aQ
component (b) in accordance with the invention are com-pound~ which contain at lea~t one anion-active and one cation-active group in the molecule, the anion-active groups preferably being sulfonic acid or carboxyl groupq and the cation-acti~e groupQ being amino group~, preferably 3econdary or tertiary amino groupQ.
Particularly suitable ampholytic ~urfactant~ are ~ar-coside~, taurideQ, N-Qub~tituted amino-propionic acidQ
and N-(1,2-dicarboxyethyl)-N-alkyl ~ulfoQuccinamates.
The sarco~ide~ suitable for u~e as component (b) correspond to the following formula R - C0 - NH - CH2 - C00 (VII) in which R is a C7-C21 alkyl group and preferably a C11-C17 alkyl group. TheQe sarcoside~ are known com-poundQ which may by obtained by known methods. For their use in flotation, see H. Schubert, Aufbereitung fester mineralischer Rohstoffe, 2nd Edition, Leipzig 1977, pp. 310-311, and the literature cited therein.
The tauride~ suitable for use a~ component (b) corre~pond to the following formula 6~ ~
R - C0 - ~H - CH2 - CH2 - S03 (VIII) in which R is a C7-C21 alkyl group and preferably a C11-C17 alkyl group. These taurideQ are known compound~

- :

.
, which may be obtained by known methods. The use of taurides in flotation i~ known, see H. Schubert referred to above.
N-~ubstituted aminopropionic acids ~uitable for use a~ component (b) correspond to the following for-mula R - (NH - CH2 - CH2)n - NH2 - CH2CH2 - C00 (IX) in which n i~ 0 qr a number of from 1 to 4 and R is an alkyl or acyl group containing from 8 to 22 and pre-ferably from 12 to 18 carbon atom~. The N-sub~tituted aminopropionic acids mentioned are also known compounds obtainable by known method~. For their use as collec-tor~ in flotation, see the above reference H. Schubert and Int. J. Min. Proc. 9 (1982), pp. 353-384, more especially p. 3O0.
The N-(1,2-dicarboxyethyl)-N-alkyl sulfosuc-cinamate~ suitable for use as component (b) in the collector mixtures according to the invention correspond to the following formula CH - COOe 0 R - NH + 3 M
CO (X) C,H2 e CIH ~ - C00 in which R i~ an alkyl group containing from ô to 22 carbon atoms and, preferably, from 12 to 18 carbon atom~, and M i~ a hydrogen ion, an alkali metal cation, e.g. sodium, pota~sium, lithium, etc., or an ammonium ion, preferably a ~odium ion. The N-(1,2-dicarboxyethyl)-N-alkyl ~ulfosuccinamates are known compound~ whioh may be obtained by known method~.
The use Or these compounds as collectors in flotation iq alQo known; ~ee H. Schubert, supra.

1280~;20 The ratio by weight of components (a) to (b) in the mixtures of surfactant3 used in accordance with the invention i~ in the range of from 1:19 to 3:1 and, pre-ferably, in the range of from 1:4 to 1:1.
The quantities in which the collector mixtureq employed in accordance with the invention are used are determined by the type of ores to be floated and by their content of~ valuable mineral~. Accordingly, the particular quantities neces~ary may vary within wide limits. In general, the collector mixtures according to the invention are used in quantities of from 20 to 2000 g per metric ton of crude ore.
The collector activity of the ~urfactant mixtures used in accordance with the invention iq virtually unaffected by the hardness of the water used for pre-paring the pulps.
In practice, the mixtures of primary collectorq and co-collectors used in accordance with the invention are used instead of the known anionic, cationic and/or ampholytic collectors in the known flotation processes for non-sulfidic ores~ Accordingly, the particular reagent~ commonly used, such for example as frothers, regulators, activators, deactivator3 and the like, are added to the aqueous quspensions of the ground ores in addition to the collector mixture~. Flotation is carried out under the same conditions as state-of-the_ art pro¢esses. In this connection, reference is made to the following literature references on ore preparation technology: H. Schubert, Aufbereitung fester minera-lischer Roh~toffe, Leipzig 1967; B. Wills, Mineral Processing Technology Plant De~ign, New York, 1978;
D.B. Purchas (ed.), Solid/Liquid Separation Equipment Scale-up, Croydon 1977; E.S. Perry, C.J. van Os8, E.
Grushka (ed.), Separation and Purification Methods, New York 1973 - 1978.

lZ805Z0 The collector mixture~ in accordance with the invention may be u~ed, for example, in the flotation of apatite, ~cheelite and wolframite ore~, in the ~epara-tion of fluorite from quartz, in the ~eparation of quartz or alkali ~ilicate~ from hematite, magnetite and chromite by inver~e flotation, in the ~eparation of ca~siterite from quartz and ~ilioates and in the ~eparation of oxidès of iron and titanium from quartz for the purification of vitreou~ ~andQ.
The pre~ent invention also relate-~ to a proce~
for the separation of non-sulfidic mineral~ from an ore by flotation, in which ground ore i3 mixed with water to form an ore ~u3pen~ion, air i~ introduced into the resulting ~uspen~ion in the pre~ence of the surfactant mixtures of the pre~ent invention a~ collector, and the froth formed is ~tripped together with the mineral therein.
The following Example~ are intended to demonqtrate the ~uperiority of the collector mixture~ used in accordance with the invention. The te~t~ were carried out under laboratory condition3, in ~ome ca~e~ with increased collector concentrations considerably higher than necessary in practice. Accordingly, the potential application~ and in-u~e condition~ are not limited to the separation exerci3eq and te~t condition~ de~cribed in the Example~. All percentage9 are percentage~ by weight, unle~s otherwi3e indicated. The quantitie~
indicated for reaBents are all ba~ed on active 3ub~tance.
3o EXAMPLES 1 to 8 __ The material to be floated con~i~ted of an apatite ore from the South African Phalaborawa Complex which contain~ the following mineral9 as it~ principal con~tituents:

~Z805~0 39~ magnetite 11~ carbonate~
9~ olivine 14~ phlogopite 18~ apatite The P205-content of the ore was 6.4~. The flotation batch had the following particle size distribution:

lZ80520 18% <25 ym 34% 25-loO ,um 43% 100-200 ~m S% >200 ~
s The following compounds or mixtures were used as collectors (pbw - parts by weight) Collector A
2 00 pbw technical oleic acld (saturated 1% C12 3% cl4; 0 5~ Cls; 5% C16; 1~ c17; 2% C18;
monounsaturated 6% C16; 70% C18; di-unsaturated 10% C18; tri-unsaturated o 5% C12; acid number 199-204;
saponiflcation number 200-205, lodine number 86-96) 1 00 pbw adduct o~ 2 moles ethylene oxlde and 4 mole~ propylene oxld- vlth 1 mol- technlcal lauryl alcohol (0-3% C10; 48-58 C12 19 24% C14; 9-12% C16 10-13% C18 acld number 0; hydroxyl numb-r 265-2~S
saponl~lcatlon nu~ber 1 2; lodln- number 0 5) Collector B ~comparison) Technlcal olelc acld tcompos~tion and characterlstlc~ as ~or collector A) Collector C
2 00 pbw sodlu~/amnonlum salt (molar ratlo Na~ NH~ - 1 1) ot a nonoalkyl "i sul~o~ucclnate Or whlch the alkyl group ls derlved from a technlcal oleylcetyl alcohol (2% C12; 3-8% C14; 27-36% C16 58-68% C18;
0-2% C20 acld nu~ber 0 5 hydroxyl nu~ber 210-225; saponi~lcatlon number 2; lodlne number 48-55) I

l o pbw adduct o~ 2 ~ole~ ethylene oxide and 4 moles propyleno oxide wlth 1 mole technical lauryl alcohol (see collector A) Collector ~
2 00 pbw sodium/ammonium salt o~ a monoalkyl sulfosucclnate ~see collector C) 1 00 pbw adduct o~ 2 mole~ ethylene oxlde and 4 moles propylene oxide wlth 1 mole isotrldecanol Collector E ~comparlson) Sodlu~/am~onlu~ salt ot a monoalkyl sul~o-succlnate (se- collector C) Collector F fcomp~rlson) 2 00 pbw sodium/ammonlu~ salt ot a nonoalkyl sul~o-5ucclnate ~see collector C) 1 00 pbw adduct ot S moles propylene oxlde with 1 mol- 2-ethyl hexanol Collector G
2 00 pbw acetat- o~ N-(2-hydroxy-Cll-Cl~-alkyl)-ethylene dlanln- obtalned by reactlon Or a 1,2-epoxy-Cll-C14-alkan- (chaln length dl~trlbutlon 22% Cll 30% C12 26% C13 22% C14) wlth thylen- dlamln- and sub~-qyent neutrallzatlon wlth glaclal acetlc acld 1 00 pbw adduct o~ 2 moles ethylen- oxlde and 4 moles propylene oxlde wlth 1 ~ole technical lauryl alcohol (see collector A) Collector H
30 2 00 pbw acetate o~ an N-(2-hydroxy-Cll-C14-alkyl)-ethylen- dlamln- (~ee collector G) 1 00 pbw adduct o~ 2 nole- ethylen- oxide and 4 mole- propylen- oxlde wlth 1 nole lsotrldecanol .
.

,, ~ 80 S2 0 The flotation tests were carried out in a laboratory flotation cell (Denver Equipment Model D-l, capacity 1.2 liters) at 20-C. In Examples 1 to 6, tapwater having a hardness of ~8-dH (dH = German hardness) was used for prepar~ng the pulps. In Examples 4 and 6, th~pulps were prepared with hard water ~945 ppm Ca2+ and 1700 pp~ Mg2+). After the ore had been suspended in the flotation cell, the magnetite was removed with a hand magnet, washed and the wash water returned to the cell. The pulp density was 500 g/l. Waterglass was used as depressor ln guantities o~ looO and 2000 g/t. The pH-value of the pulps was ad~usted to 11 in each case. Flotation was carried out at a rotational speed of the mixer o~ 1500 r.p.m. The rlotation tlme was 6 minutes. After rougher ~lotation, the concentrate was purified twice, collectors being introduced for the first purifying flotation in Examples 3 and 7.
In Table I below, the particular collsctors and the quantities in which they are used are shown in column 2. The quantity of waterglass used as depressor ls shown in column 3. In column 4, "Magn."
stands for magnetic separation, "R.F." for rougher flotation, "P.F." for purifying ~lotation and "conc. n for concentrato. Column 5 show~ the total recovery o~ the particular flotation step, based on total ore, column 6 shows the P205 content of the waste in the particular process step and column 7 shows the proportlon of P205 recovered ln each process step out of tho total of P205 formed ln tho oro.

1;~80520 T A B L E
RecoverY of apatite (S. Africa) . . l Example Collector Depresso Flot. Recovery P205 P25-Recovery (glt) (g/t) Stage (~) (~) (~) 1 A 1000 Magn. 25.8 0.6 2 600 R.F.32.2 2.7 14 P.F.10.7 3.1 5 Conc.31.1 16.1 79 2 B* 2000 Magn.30.6 2.7 13 1000 R.F.45.3 4.2 30 P.F.7.5 5.1 6 Conc.16.6 19.9 51 3 C 2000 Magn.25.8 1.7 7 600 R.F.35.3 0.4 2 1st P.F.10.0 3.1 5 +50 2nd P.F.5.5 4.3 4 Conc.23.4 22.5 82 4 D 2000 Magn30.4 2.6 12 750 R.F.32.2 0.4 2 +50 1st P.F.9.9 3.8 6 2nd P.F.5.9 4.5 4 Conc.21.6 22.4 76 E 1000 Magn26.7 1.7 7 550 R.F.57.8 7.4 67 1st P.F.11.5 10.5 19 2nd P.F.2.7 11.7 5 Conc.1.3 10.4 2 .

6* F 2000 Magn30.2 2.6 12 600 R.F.27.1 3.9 16 1st P.F.21.6 9.1 31 2nd P.F.5.6 6.5 7 Conc.15.5 14.2 34 , _ .
*) Comparison tests r 1280~;20 T A B L E I (continued) Example Collector Depresso~ Flot. Recovery P205 P25-Recovery (B/t) (glt~ Stage (~) (~ (~) 7 G 2000Magn. 31.6 2.3 11 600 R.F. 28.8 0.2 +50 1st P.F. 8.1 1.4 2 2nd P.F. 4.5 3.3 2 Conc. 27.0 19.8 84 H 2000Magn. 31.0 15 600 R.F. 32.6 0.3 1st P.F. 5.4 1.4 nd P.F. 3.2 3.2 2 Conc. 27.8 18.7 81 ,- , .
*) Comparison tests lZ80520 EXAMPLES 2 and 10 The ore to be floated consisted o~ an apatite ore from arazil contalning ca. 20% apatite, ca. 35%
magnetite, limonite and hematite and ca. 16% calcite.
s The P2O5-content of the ore was ca. 22%. The ~lotation batch had thè ~ollowlng partlcle 9~ ze distribution:
21% <25 38% 40 - lOo 35% 100 - 250 6% >250 ~
The ~ollowlng collector~ were used:
Collector L
1.00 pbw sodlum salt o~ a 8ul ~osucclnamate derlved ~rom tallowamlne 1.00 pbw adduct o~ 2 moles ethylene oxlde and 4 moles propylen- oxlde vlth 1 ~ole technical lauryl alcohol (~e- collector A) Collector M tcomparlson~
sodlu~ ~alt o~ a oulro-ucclnanat- derlved rrom tallowanln-The rlotatlon te~t- wer~ carried out under the same conditlon~ as ln Example- 1 to 8 wlth the ~ollowlng modl~lcatlons: ~tarch wa- used as depressor. The pH-value o~ the pulp9 was 10.5. The pulps were prepared uslng tap-vater having a hardness o~ 18- dH. The lron oxldes were renoved by magnetlc separatlon be~ore ~lotatlon ot the apatlte.
The result~ obtalned are ~hown ln Table II
below ~n whlch the re~ult- o~ the 1st and 2nd puri~ylng ~lotatlon are co~blned, but to whlch the explanatlons o~ Table I otherwlse apply accordlngly.

l~ao5zo T A B L E II
Flotation of apatite (Brazil) Example Collector Depressor Flot. Recovery P205 P25~Recovery (glt) (g/t) Stage(~) (~) (Z) ._ 9 I 600 R.F.29.5 2.0 3 420 P.F.9.1 2.7 1 Conc.61.4 34.6 96 10* J 600 R.F.60.3 11.7 32 440 P.F.7.6 28.1 10 Conc.32.1 39.6 58 _~

*) Comparison test ~805Z0 The material to be floated was a scheelite ore from Austria having the following chemical composition, based on its princ~pal constituents:

CaO6~8~%
SiO259.5%
Fe237 %
Al 231 2 . 1 %
MgO 5.7~
The ~lotatlon batch had the following par~icle size distribution:
2~ <25 43% 25-100 y~
29% 100-200 ,u~
All the collector mixture~ used contalned as component (b) used in accordance with the invention a sodium/ammon~um salt (molar ratio ~a~:NH4 - 1:1) of a monoal~ylsulfosuccinate of whlch the alkyl group is derlved from a technical oleyl-cetyl alcohol (2t C12;
3 8% C14; 27-36% C18; 0-2% C20: acid number 0.5:
hydroxylnumber 210-225: saponification number 2:
iodine number 48-55) referred to as collector A' in the following Table).
The ~ollowing adducts of ethylene oxide and propylene oxlde with a technical lauryl alcohol (0-3%
C10; 48 58% C12: 19-24% C14; 9-12% C16: 10-13% C18;
acid number 0: hydroxyl number 265-275;
saponlficatlon number 1.2; iodine number 0.5) were uged as component (a) in accordance with the invention:
- an adduct of 2 moles ethylene oxide and 4 moles propylene oxide with 1 mole fatty alcohol (co-collector A" in Table III below) ~80520 - an adduct of 2.5 moles ethylene oxlde and 6 moles propylene oxide with 1 ~ole tatty alcohol (co-collector B") - an adduct o~ 4 mole~ ethylene oxlde and 5 moles s propylene oxide wlth 1 mole ~atty alcohol ~co-collector C")~
The comparison compositlon used in Example 22 contained as component (a) an adduct of s moles ethylene oxide with 1 mole nonylphenol (co-collector D").
The tlotatlon tests were carrled out in a modl~led Halllmond tube (mlcrotlotation cell) accordlng to B. Doblas, Collold ~ Polyner Scl. ~
(1981), pp. 775-776 at a temperature ot 23-C. Each tsst wa~ carrled out wlth 2 g ore. Dl~tllled water was used to prepare the pulp. Collector and co-collector were added to the pulp- ln such quantltles that a total collector quantlty ot 500 g~l was present. The condltlonlng tlne was lS nlnutes in each test. Durlng tlotatlon, an alr strean was passed through the pulp at a rate ot ~ ln. In every test, the ~lotatlon tl~e wa- 2 ~lnute-.
The resultJ obtaln-d are s-t out ln Tabl- III
below. ColumnQ 2 and 3 show th- collector- and co-collectors used and column ~ their ratlo- by welght. Column 5 shows the total recovery, based on the total quantlty o~ ore, and colu~n 6 the recovery ot metal, based on the total quantlty ot WO3 ln the ore. The WO3, CaO and SlO2 cont-nt~ ot the concentrates are shown ln colu~n- 7, 8 and 9, respectlvely.

: ,.

. . .

' , ., ~7~80SZ0 o ~ _ ~ _ ~q .
~ r ~ o ~ ~ I a v~ ~ ~ ~ 4 o ~ _ 6 ~ ~ ~ ~:t, I~ _~

_ 6 ~-J a . ................. ~
_ ~ O ~ ~ ~ _ æ
. . . ~J g _ _ _ ~ _ ~ ~ ~ 0 ~ ~ O W O ~ `O .. ~ ~ O ~ ~
_ ~ ~ ~ ~ ~ W _ ~
--a -~ ~ ~ ~ ~ ~ .... ~ _ ~o ~ a~ ~ o - ~ ~ ~
. .
, O l- _ _ O _ _ O I .~, , W~ .
~ ~ J ~ W w ~o ll l_ ~ _~
~_ ~ ~ o ~ ~ o ~ ~ o, ~ _ g ~ a~ - ~ w ~ ~ w o -- ~ U~ U~
O O Cl~, ~ _ ~O ~ O ~ u~
. . . . , 1~ . . . . . . .
- ~ o - V~ o O ~_ "
_ .. I . .

1~8052~

EXAMP~ES 27-3~
The material to be floated consisted of a kaolinite ore from the Oberpfalz containing 55.1%
clay and 44.g% feldspar. The ~lotation batch had ~he followin~ particle size distribution:
64% c25 um 22% 25-40 um 14% >40 um The ~ollowing substances or mlxtures of sub6tances were used as collectors:
Collector K
3.00 pbw commercial sodium alkylbenzenesul~onate of which the alkyl group~ contaln 12-16 carbon atoms, predominantly 12 carbon atoms, 1.00 pbw adduct o~ 2 moles ethylena oxide and 4 moles propylene oxlde with 1 mole commerclal lauryl alcohol ~seo collector A) Collector L
2.00 pbw commerclal alkylbenzene sul~onata (seo collector I) 1.00 pbw adduct o~ 2 moles ethylene oxide and 4 moles propylene oxlde with 1 mole commer-clal lauryl alcohol (see collector A) Collector M 5 1.00 pbw commerclal al~ylbenzenesul~onate ~see collector I) 1.00 pbw adduct o~ 2 moles ethylene oxlde and 4 moles propylene oxlde wlth 1 mole commerclal lauryl alcohol (see collector A) Collector N
2.00 pbw N-B-hydroxy-C12-C14-alkylethyl-enedlamlne ~ormata prepared by reactlon o~
a linear ~-C12-Cl~-epoxy-alkane with lZ80S20 ethylenediamine and ~ubseqyent neutralization with ~ormlc acid 1.00 pbw adduct o~ 2 mole~ ethylene oxide and 4 moleq propylene oxlde wlth 1 mole co~mercial lauryl alcohol (see collector A) Collector O ~comparlsonl commercial alkylbenzene~ulfonate (see collector I) The tlotatlon test~ were carrled out in a Humbold-Wedag laboratory ~lotation ~achine (XHD
Industrieanlagen AG, Humbold-Wedag, Cologne; se~ ;~
Sei~en-FettQ-Wachse 105 (1979~, p. 248) u~lng a 1 llter ~lotatlon cell. Tapwater havlng a hardness o~
18- dH wa~ used tor preparlng the pulps. The pulp ~5 density was 250 g/l. Alumlnlu~ sulrate in a quantity o~ 500 g/t wa~ u~ed a~ actlvator. The pH-value wa~
ad~u~ted to 3 wlth sul~urlc acld. Th- conditionlnq tlme was 10 mlnute~. Flotatlon wa~ carrled out tor 15 minutes at 23-C at a rotatlonal epoed ot the rotor O~ 1200 r.p.m. Tho collector wa~ added to th- pulps ln 3 or 4 portlon- a8 ~hown ln Tabl- IV belov.
The result~ obtalned are shovn ln Table IV to which the explanatlons ot Table I apply accordingly.

1.
3~ .

"

. . .

~, T A B L E I V
Flotation of kaolinite Example Collector Flot.Recovery ClayMetal Recovery type/quantity Stage (~) (~) (2) 23 K 400 Conc.l 31.4 80.9 46 200 Conc.2 16.7 74.5 23 200 Conc.3 10.3 73. 8 14 100 Conc.4 3.1 64.8 4 900 62.9 75.4 87 Waste 37.1 20.7 13 24 L 400 Conc.l 2 7.5 86.8 43 200 Conc.2 15.4 85.2 24 200 Conc.3 10.6 75.9 15 100 Conc.4 4.2 70.4 5 900 57.7 83.~l 87 Waste 42.3 21.1 13 .

25 M 400 Conc.l 22.7 84.9 35 200 Conc.2 15.4 82.1 23 200 Conc.3 10.9 71.9 14 100 Conc.4 4.8 67.1 6 900 53.8 79.9 78 Waste 46.2 22.5 22 26 N 400 Conc.l 33.4 84.9 51 200 Conc.2 20.0 77.7 28 200 Conc.3 11.5 55.0 11 800 64.9 77.4 90 Waste 35.1 12.3 10 1.~:

~X80520 ~ g T ~ B r, E r v (continued) Example Col lector Flot.Recovery Clay ffetal rec~very type/qu~ntl ty s tage _ ~q~) _ (~) ~) . (~) . _ 27~ O4 0 0 Conc . 1 4 4 . 5 7 8 . 9 6 3 200 Conc.213 .0 t0.2 17 200 Conc . 3 8 . 06 3 . 3 9 100 Conc.42.5 54 .7 3 900 6~ . 0 75 . 592 _ wa s te3 2 . 0 16 . 9 .

Compa r l son te s t

Claims

1. A process for separating non sulfidic minerals from an ore by flotation which comprises the steps of A. contacting the ore with a mineral collector-active quantity of a mixture of (a) at least one reaction adduct of ethylene oxide and propylene oxide with a C8-C22 fatty alcohol; and (b) at least one anionic, cationic or ampholytic surfactant, in the presence of water; and B. aerating the aqueous mixture from step A. to produce a foam containing the non-sulfidic mineral; and C. separating the foam from the aqueous mixture.

2. The process of Claim 1, wherein component (a) comprises an adduct Or m moles ethylene oxide and n moles propylene oxide with C8-C22 fatty alcohols, m and n each being a number of from 1 to 15, the sum of m plus n being from 2 to 25 and the ratio of m to n being from about 1:5 to about 2:1.

3. The process of Claim 1, wherein component (a) comprises an adduct of ethylene oxide and propylene oxide with C12-C18 fatty alcohols.

4. The process of Claim 1, wherein component (b) is at least one anionic surfactant selected from the group consisting of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkylben-zenesulfonates, alkyl sulfonates, petroleum sulfona-tes and acyl lactylates.

5. The process of Claim 1, wherein component (b) is at least one cationic surfactant selected from the group consisting of primary aliphatic amines, alky-lene diamines substituted by .alpha.-branched alkyl groups, hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of the above amines.

6. The process of Claim 1, wherein component (b) is at least one ampholytic surfactant selected from the group consisting of sarcosides, taurides, N-substituted aminopropionic acids and N-(1,2-dicarboxyethyl)-N-alkylsulfosuccinamates.

7. The process of Claim 1, wherein the ratio by weight of component (a) to component (b) in the mixture of components (a) and (b) is from about 1:19 to about 3:1.

8. The process of Claim 1, wherein the ratio by weight of component (a) to component (b) in the mixture of components (a) and (b) is from about 1:4 to about 1:1.

9. The process of Claim 1, wherein the mixture is used in a quantity of from about 20 to about 2000 g per ton of crude ore.

10. A process for the separation of non-sulfidic minerals from a ground ore by flotation comprising the steps of A. mixing the ground ore with water to form an ore suspension;
B. introducing into the suspension a mineral collector-active quantity of a mixture of (a) at least one reaction adduct of ethylene oxide and propylene oxide with a C8-C22 fatty alcohol and (b) at least one anionic, cationic or ampholytic surfactant;
C. aerating the suspension to produce a foam containing the non-sulfidic mineral; and D. separating the foam from the suspension.

11. The process of Claim 10, wherein in step B. compo-nent (b) is at least one anionic surfactant selected from the group consisting of fatty acids, alkyl sulfates, alkyl sulfosuccinates, alkyl sulfosuc-cinamates, alkylbenzenesulfonates, alkyl sulfona-tes, petroleum sulfonates and acyl lactylates.

12. The process of Claim 10, wherein in step B. compo-nent (b) is at least one cationic surfactant selected from the group consisting of primary aliphatic ami-nes, alkylene diamines substituted by .alpha.-branched alkyl groups, hydroxyalkyl-substituted alkylene diamines and water-soluble acid addition salts of these amines.

13. The process of Claim 10, wherein in step B. component (b) is at least one ampholytic surfactant selected from the group consisting of sarcosides, taurides, N-substituted aminopropionic acids and N-(1,2-dicarboxyethyl)-N-alkylsulrosuccinamates.

14. The process of Claim 10, wherein in step B. the ratio by weight of component (a) to component (b) in the mixture of components (a) and (b) is from about 1:19 to about 3:1.

15. The process of Claim 10, wherein in step B. the ratio by weight of component (a) to component (b) in the mixture of components (a) and (b) is from about 1:4 to about 1:1.

16. The process of Claim 10, wherein in step B. the mixture 13 used in a quantity of from about 20 to about 2000 g per ton of crude ore.