Note: Descriptions are shown in the official language in which they were submitted.
~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
-2-
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-
--3--
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
--4--
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
--5--
~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-
--6--
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)
S03M
in which R is an alkyl or alkenyl group containing from
35-8 to 22 carbon atom~ and preferably from 12 to 18 car-
-7-
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,
--8--
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)
O CH3
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)
CH3
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)
CH3
in which R is a C7-C21 alkyl group and preferably a
C11-C17 alkyl group. These taurideQ are known compound~
- :
.
,
1280520
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
CH2 - C00
CH - COOe 0
R - NH + 3 M
CO (X)
C,H2 e
CIH ~ - C00
S03
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.
-12-
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.
-13-
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:
-14-
~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
-16-
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
IZ805Z0
-17-
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
-18-
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
-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
-21-
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
EXAMPLES 11- 2 6
The material to be floated was a scheelite
ore from Austria having the following chemical
composition, based on its princ~pal constituents:
WO3 0-4
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
-24-
- 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
-25-
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~
--26--
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 M5 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
-27-
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~ .
"
. . .
~,
1280520
--28--
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
