SCHOOL OF ENGINEERS OF PERU

REAGENT FLOTATION OF METAL AND NON-oxidized ore

VIDALÓN JOSE GALVEZ
LIMA, March 2004
Oxidized ore
Malachite ....... Azurite ........... .......... Cuprite Chrysocolla Tenorite ..
...... Cerussite ......... Anglesite ........ Smithsonite ... Willemite ........
Hemimorphite or Calamine CuCO3.Cu (OH) 2 2CuCO3.Cu (OH) 2 CuO Cu2O CuO.nSiO2.mH
2O PbCO3 ZnCO3 Zn2SiO4 2ZnO.SiO2.H2O PbSO4
Oxidized ore
Cassiterite ....... Chromite .......... Vanadinite ..... SnO2 FeCr2O4 (PbCl) Pb4
V3O12
NON-METAL MINERALS
Barite ...... Calcite BaSO4 ....... CaCO3 Dolomite .... (Ca, Mg) CO3 Fluorite ..
.... Scheelite CaF2 ... Phosphates CaWO4 .... Na5 (PO4) 3 (F, CO3)
SOLUBLE SALTS
Halite ......... Sylvite ......... Carnallite .... Langbeinite. Kainit ........
NaCl KCl epsomite KCl.MgCl2.6H2O 2MgSO4.K2SO4 MgSO4.KCl.3H2O MgSO4.7H2O
FLOTATION MECHANISMS
• The flotation process depends on complex phenomena that occur on the surface o
f mineral particles and air bubbles formed in water. • The flotation properties
of a mineral depends on its crystalline structure. • Factors that influence the
flotation:
- Presence of impurities in the ore, in solid solution or adsorbed on colloidal
minerals - Grade Release - Hard water affects the relationships between the mine
ral and reagents, and sometimes form insoluble compounds with the reagents.
CLASSIFICATION OF MINERALS AS FLOAT THEIR PROPERTIES
1. Sulphides (Cu, Pb, Zn, Ni, Hg, Sb) and native metals: They have low wettabili
ty. Float with xanthates. 2. Non-polar non-metallic minerals: graphite, sulfur,
coal, talc. Have low wettability. Collectors float with very weak and sometimes
with just sparkling. 3. Oxidized minerals (Cu, Pb, Zn): float with sulfurization
and xanthates, or fatty acids.
CLASSIFICATION OF MINERAL ...
4. Mineral Salts polar type Ca, Mg, Ba and Sr: Scheelite, powelita, apatite, pho
sphorite, fluorite, calcite, barite, magnesite, dolomite. They float with fatty
acids. 5. Oxides, silicates and alumino-silicate: silica, zircon, rutile, cassit
erite, ilmenite, feldspar, beryl, mica. Many float with anionic and cationic col
lectors, other cation-dependent activators. • 6. Soluble salts: sylvite, halite,
langbeinite keinita. Float with fatty acids or saturated brines cationic collec
tors.
FLOTATION REAGENTS
• They are the strongest variable and flexible interaction of the flotation proc
ess. • Major advances have been in the development of flotation reagents. • Theo
ry of hydrate layers: The effect of flotation reagents, is transferred through h
ydrated layers, leading to an active subject of mineral particles to bubbles.
CLASSIFICATION OF REAGENTS
According to the focus area
1. Reagents which are concentrated at the interface mineral-water, mainly in the
mineral surface: collectors and activators. 2. Reagents which are concentrated
in the air / water: sparkling and inorganic electrolytes. 3. Affecting the flota
tion reagents, remaining in the water: Activators, pH regulators and depressants
.
CLASSIFICATION OF REAGENTS According to its function
1. Collectors
• Organic acids:
- A. Na oleate oleic and - alkyl sulfate Na - alkyl phosphate Na
• Thio compounds: mercaptans, xanthates, dithiocarbonatos, dithiofosfatos, merca
pto-benzothiazol.
• Derived from Ammonia: Amines, salts
ammonium salts, pyridine, ethanol amines.
• Oils: kerosene, petroleum
Organic Acids
The most commonly used collectors of the first group contains the carboxylic gro
up, which is the anion of the fatty acids. Much less reagents are used with sulf
ate and sulfonate groups.
Carboxylic group:
Sulfate group:
O C OH
Sulfonate Group:
O O O O S O S OH OH
Fatty Acids
• They are good collectors commonly used for industrial minerals. • They are oft
en used as co-collectors for flotation of heavy minerals and feldspar, and apati
te in flotation. • Can be fed as fatty acids or as salts of Na in solution or aq
ueous dispersion. • They are also mixed with nonionic emulsifiers. There are sel
ective and are not used in mineral difficult to float, requiring more specific r
eagents.
RENT SODIUM SULFATE
Flotinor S-72 • Application is especially recommended for the flotation of barit
e as occurs with fluorite and calcite. • Can also be used in the flotation of ce
lestite, gypsum, kainit, anhydrite and anglesite. If necessary, you can use a fo
am.
ACID ESTERS OF MONO / diphosphorus
• Flotinor SM-15 is used in the flotation of heavy minerals with iron and titani
um and glass sand biotite. Can be used in combination with a fatty acid. • Other
uses: flotation of carbonates such as calcite,€dolomite and magnesite when the
stone is a silicate. Also in reverse flotation of phosphate in combination with
a collector eterpropilen alkyl silicate and fatty diamines. • Can be used other
phosphonic acid esters of various chain lonitudes and constitution or mixtures o
f these with others such as fatty acids, alkenyl succinic acid ester, an alkyl s
ulfo succinate succinamato and sulfo.
Cationic Collector
• They are derived from an ammonium ion complex.
N
+
The polar group is adsorbed on minerals has a positive charge. • They are used t
o float oxides, silicates and aluminosilicates. • Are less selective anionic rea
gents. Primary amine: secondary amine R-NH2 R2-NH tertiary Amina: Amina quaterna
ry-N R3: R4-N-Cl
dodecyl ammonium ion + + + + + + + + ion acetate
Hemimicelas of dodecyl ammonium ions on quartz
% Recovery
100 90 80 70 60 50 40 30 20 10
100 200 500
Na +
Fe3 +
1000
g / t Reagent
Effect of Na + and Fe3 + in the flotation of quartz with lauryl amine
CLASSIFICATION OF REAGENTS
2. Regulators:
• Electrolytes: Cal, NaOH, A. Sulfuric, Na bicarbonate, salts of Cu, Fe, Al, Pb,
Zn, Na2S, NaCN, Na silicate • No electrolyte: Dextrin, starch, tannins.
3. Sparkling:
Terpineol, phenol, cresol, pyridine, orthotoluidine
Oxidized ore flotation
A. Mineral surface oxidation
First Fleet sulphides and oxides after fatty acid • Flotation: Ac. Oleic not ver
y selective. It is applicable only few minerals that are relatively insoluble, b
ecause Ca and Mg ions activate the bargain, as well as pyrite and pyrrhotite. •
More selective is hydrolyzed palm oil (A. Palmitic with oleic and linoleic). • c
arbonate and silicate Na Na soften the water and disperse lamas. Should recycle
tailings water.
Mineral surface oxidation
• Flotation with sulfurization and thio collectors: It is more selective and eff
icient. There are difficulties when the mineral is clay and / or pyrite altered.
• Reagents: Na2S or NaHS, XmAK, palm oil and petroleum.
B. Oxidized ore flotation
• Vanadinite: sulphurize fleet without high doses of xanthates or other thio-cat
cher (1-2 kg / t) • Malachite and azurite: Sulfurization with Na2S or NaHS and x
anthates in dolomitic gangue minerals with Fe without sulfate added sulfurizante
ammonium together with the recovery and selectivity improvement • Chrysocolla a
nd other copper silicates are solid solutions of Cu in silicate in varying propo
rtions, and leaches Na2S • tenorite and Cuprite Cu: Not sulphurize under alkalin
e conditions. The fleet cuprite xanthates.
100
Cu% RECOVERY
80 60 40 20 200 400 600 800 1000 1200
pH: Amyl Alcohol 11: 97 mg / L Amil xanthate: 20 mg / L
mg / L Na2S.9H2O Effect of Na2S in the flotation of malachite
100
Cu% RECOVERY
A
B
pH: 11 Na2S: 432 mg / L Amil xanthate: 40 mg / LA: α-terpineol B: Amyl Alcohol
80 60 40 20
Sp rkling 10 20 30 40 mg / L
50
60
Effect of fo ming gents in the flot tion of M l chite
EFFECT OF SULFATE NIO AMO
1 00 95 90 85 80 75 70 65 60 55 50 0 5000 10000 15000 20000 25000
C u [N HS + (NH4) 2SO4]
C u [N HS]
HS N [g / t]
Oxidized ore flot tion
• Cerussite nd Anglesite: • Sulfuriz tion with N 2S or N HS nd x nth tes. Shou
ld be ground c refully, re fr gile nd e sily produce l m s. The cerussite is m
ore flo t ble. The sulfuriz tion becomes the surf ce l yer flo t ble sulphide wi
th x nth tes: PbCO3 + N 2S = PbS + N 2CO3 • N HS is more ctive th n N 2S. • The
re gent consumption is reduced with strong short-conditioning nd ventil tion i
n the cell nd dding N 2CO3.
Oxidized ore flot tion
• The sulfuriz tion nd flot tion of cerussite nd nglesite is expl ined by the
presence of Pb c tions uncompens ted ch rge on the surf ce of cle v ge. • Angle
site with difficulty nd w s sulphurize c n be flo ted with x nth tes. You c n
lso use f tty cids or lkyl sulfon tes where the ore is cidic nd in the bsen
ce of Fe oxides nd other insoluble sulph tes.
Oxidized ore flot tion
Smithsonite, Willemite nd Hemimorphite (C l mine) flo t ste ryl mine cet te
nd pine oil, nd / or 8-hydroxyquinoline (oxine), using s dispersing l m s: N 2
S, N 2CO3, N silic te. M ny times, pre desliming 5 or 10 microns, bec use cl
ys nd Fe oxides nd fine p rticles consume lot of collector. • N 2S is essent
i l bec use it blocks the solubiliz tion of Zn on the surf ce of the miner l. •
The concentr te is 30-40% Zn, but the ignition (c rbon te) to> 1000 ° C gives 65
-70% Zn.
Oxidized ore flot tion
Re gents in the flot tion of Oxidized Zn (g / t) REAGENTS
Amin (s lt) Amin oil emulsion Sp rkling N 2SiO3 N 2S
S. Giov nni
30 700 110 -2830
Morocco
700 40 2500 -500 -
% Zn Recovery
100 90 80 70 60 50 40 30 20 10 0.5 0.7 0 9 1.1 1.3 1.5
1
2
1.7 mol / t
Flot tion Smithsonite: 1: oct decyl mine 2: oct decyl methyl mine
Oxidized ore flot tion
• Oxides of Al, Sn, Mn nd Fe re concentr ted by gr vity processes, m gnetic n
d / or electrost tic. For fine-gr ined miner ls, the flot tion. • Chromite: To s
ep r te olivine nd serpentine h s been used gr vimetric methods. • C ssiterite:
Collectors studied: lkyl c rboxyl tes, lkyl sulf tes (sodium hex decyl sulf t
e), sulfosuccin m to cid, p-tolyl rsonic, phosphonic cid, s licylic ldehyde,
nd sulfuriz tion nd ctiv tion le d to flo t with x nth te
100
Sn% RECOVERY
90 80 70
HF IOF IHF TAs
IOF = iso octyl phosphonic cid = HF cid n-heptyl phosphonic cid IHF = TAs = i
so hexyl phosphonic cid p-tolyl rsonic
60
Collector 200 400 g / t
600
800
Flot tion of c ssiterite with different collectors
Oxidized ore flot tion
• Fe oxides: • M gnetite is concentr ted by m gnetic sep r tion. • The thin non-
m gnetic re tre ted by flot tion of qu rtz nd silic tes, or flo ting specul r
hem tite. • M jor collectors: c rboxylic cid nd petroleum sulfon tes, nd occ
sion lly, mine s lts of cid circuit. • For the remov l of c tionic re ctive si
lic te is used in circuit lk line. • fine concentr tes re pelleted nd sintere
d.
FLOTATION OF NON-METAL
FLOTATION OF NON-METAL
• Non-met llic Miner ls: They re used for industri l purposes nd not to remove
the met l they cont in. • Fluorite nd B rite: • flo t with f tty cids (oleic
nd linoleic A.) with c lcite depress nt: N 2CO3, N silic te, t nnic cid, queb
r cho. Quebr cho t nnin depresses c lcite (50 to 1000 g / t). • In flot tion of
fluorsp r to 75-85 ° C to depress silic nd c lcite.
Fluorite
8 phosphonic cid (IMPA-8): ide l for sep r ting fluorite collector of other min
er ls: Fluorite>> c lcite> fluor p tite
FLOTATION OF NON-METAL
• Scheelite: Fleet f tty cid (collector) nd N 2CO3 (pH regul tes), nd v rious
dispers nts nd depress nts of l m s. It combines with gr vity sep r tion. • Ph
osph te: The go l is to flo t c lcite nd dolomite (consumers cid) by oleic ci
d, depressing the rougher concentr te phosph tes by orthophosph te or fluorosili
c te ions. Other p tite depress nts: Cu nd lum sulph te N OH ctive c rbon te
s. Sp rkling: Ethyl Alcohol.
Flot tion of phosph te by b cteri
• In s mples of pure p tite nd phosph tes Florid g ngue dolomite flot tion re
se rch w s conducted using the b cteri Mycob cterium phlei nd B cillus licheni
formis JF-2, both s collector nd depress nts in flot tion with nionic colle
ctors. • The s mples h d good rele se but very l rge surf ce re so the re ge
nt consumption w s l rge, nd low selectivity. • The cell w lls of b cteri cont
in surf nt ntes both very ctive, which dr m tic lly reduces the surf ce tensio
n of the suspensions nd incre ses the cont ct ngle of miner ls which dsorb to
the queous solution.
Flot tion of phosph te by b cteri ...
• The results of the experiments show th t M.phlei m rkedly dsorbed on the surf
ces of dolomite nd p tite, nd show more ffinity for th t p tite dolomite,
nd B cillus licheniformis JF-2 h s even more ffinity M. phlei to join the dolo
mite. • Both b cteri ct s depress nts of dolomite in the flot tion of phosph
te, resulting concentr te with less th n 1% MgO in the flot tion of Florid phos
ph te.
FLOTATION OF SILICATES
• Miner ls of beryllium, lithium, tit nium, zirconium nd niobium silic tes exis
t s or ssoci ted with silic tes. • Use of nionic nd c tionic re gents nd fl
uoride ion s modifier.
SOLUBLE SALT FLOTATION
SOLUBLE SALT FLOTATION
• Sites cont ining mixtures of pot ssium chloride: H lite, sylvite nd c rn llit
e, nd / or sulph tes: L ngbeinbit , k init. • The recovery is done by fr ction
l cryst lliz tion. • In first s tur ted brine is sep r ted by cicloneo cl ys (re
sulting in high consumption of re gents nd incre sed viscosity of the solution)
, sylvite is flo ted with n- lkyl mine or sulfon te, or H lite with n- lkyl c r
boxyl te of he vy met ls nd non-oil pol r. • Sep r tion of Mg nd K sulf tes so
dium sulf te is less efficient.
TOXICITY
TOXICITY OF REAGENTS
Toxicity is the property of subst nce to c use dverse effects on n org nism.
It is rel ted to dose or exposure, nd v ries from one org nism to nother. Tox
icity of flot tion re gents nd ions is v ried:
- Very toxic: Collectors thiólicos, sulfon tes nd mines, cy nide - Moder te: S
p rkling lcoholics - No Toxic polypropylene glycol.
The toxicity of met ls in queous solution is ttributed to the concentr tion of
ions. E ch met l h s m ny compounds, c / u of which beh ves differently.
DESIGN OF REAGENTS
• Recent b sic rese rch on miner l-re gent inter ctions to identify the molecul
r recognition mech nisms nd predict the molecul r structure suit ble for the se
p r tion of one miner l from nother. Tools:
- - - - Synthesis nd ch r cteriz tion of miner l tests microflot tion dsorptio
n studies infr red extern l reflection techniques to determine the composition
nd structure of dsorbed l yers t the interf ce re ctive miner l-w ter - molecu
l r modeling of the inter ctions miner lre ctivo
DESIGN OF REAGENTS ...
• To qu ntify the rel tive ffinity of re gent in p rticul r, different miner
ls, c n be successfully used molecul r modeling comput tions of specific inter c
tions on miner l-re gent. • The correl tion between the order of the response to
miner l flot tion re gent b sed on theoretic l c lcul tions is very good comp r
ed to th t observed in experiments. • You must know th t the theoretic l c lcul
tions of the energy of the miner l-re gent inter ctions must be b sed on knowled
ge of the cryst l structure of miner ls nd molecules of re gent.
DESIGN OF REAGENTS ...
• It w s verified the effect of molecul r recognition with miner l fluorite, c
lcite nd fluor p tite. • It demonstr ted the cruci l role th t the cryst l str
ucture of the surf ce to determine the selectivity of given re gent. • The des
ign of re ctive molecules so th t their molecul r rchitecture is comp tible wit
h the surf ce of the miner l of interest nd confirming the rel tive ffinity /
strength of its inter ction with lo miner l surf ce using molecul r modeling te
chniques.
(B) © complexes optimized IMPA-8 ( ) Fluorite [111], (b) C lcite [110] nd © flu
or p tite [100]
(A)
Inter ction Energy (kc l / Mol)
915.4
-141.2
97.5
Fluorite
C lcite
Fluor p tite
Qu ntum chemic l c lcul tions IMPA IMPA = cid-8-bis methylene phosphonic Iminne
n
REFERENCES
• Dr. Pr dip, T t Rese rch Development nd Design Centre, Pune, Indi ; Prof.JMC
ses, L bor toire Environnement et miner l processing, INPL / ENSG V ndoeuvre-le
s-N ncy, Fr nce .- "Scientific Design of Flot tion Sep r tion Re gents b sed on
Molecul r Recognition t Miner l Surf ces. " December 1998 J. Lej "Surf ce Chem
istry of Froth Flot tion", University of British Columbi , Plenum Press, 1983. V
.I. Kl ssen / V.A. Mokrousov, "An Introduction to the Theory of Flot tion, Butte
rworths, 1963. Quiroz Roberto Lopez, "Flot tion At c mite" Proceedings of the Fi
rst L tin Americ n Congress of flot tion. Rese rch & Development GmbH Cl ri nt M
ining Chemic ls Division .-
• • • •
Th nk you very much