Flottec

Entrenamiento
Modulo Tres
 Temas a Tratar Modulo 3
• Repaso
– Objetivo de las Plantas Concentradoras
– Cómo se conforma la burbuja
– Reactivos Función de cada uno de ellos, Espumante, Colector, Depresor,
Activadores, Dispersantes, Modificadores
– Minerales mas comunes
– La burbuja
– Hidrodinámica en las Celdas de Flotación
• Químicas de los Colectores
• Químicas de los Espumantes
• Aire Retenido
 Desde la Roca al Metal

ROCA Extracción del Mineral

Mineral
Mineral de Valor
Mineral
Proceso de Flotación Separación
METAL
Metal
Obtención
PROCESAMIENTO DE MINERALES
Las dos Principales Etapas
 THE THOMPSON MILL
LIBERACION SEPARACION
Sand
Coarse Fill
Roughers Scavengers Sand
Ore Bins
Regrind Mill Plant

Tyrock Screen

Rghr Clnrs Scav Clnrs

7’ Std Cone
Crusher

Rod Cu /Ni Sep Scav Re-clnrs

Deck
Screen

7’ SH
Cone
Cyclones Smelter Slurry Pumped
Crusher Cu Clnrs
Fine Ore Nickel To Smelter For
Concentrate Thickening And
Bins
Filtration

Smelter Slurry Pumped

Ball Copper To Smelter For
Rod Mill Thickening And
Mill Concentrate
Filtration
La flotación empieza con una burbuja
 Uso de sensores hidrodinámicos para
optimización de plantas
Medición de Gas Hold up Medición de D32 Medición de Jg
 Zona de pulpa: Parámetros de Hidrodinámica
Proporción de gas(Jg), tamaño de la burbuja(Db)detención(εg),

Parámetro Definición Unidad

area Celda Prop. De aire
Jg cm/s
area

Volúmen de la burbuja
εg %
Volúmen de la celda
Burbujas
Db Diámetro de la burbuja mm
Proporción de aire
Sb – Flujo de burbujas en la superficie
• Bubble Viewer
 CURRENT STATUS
▪ Gas Hold Up Meter
Donde se están haciendo mediciones y
compartiendo experiencias
¿Qué pasa dentro de la celda?
Si se ve bien, hay mayores probabilidades de obtener Buenos resultados.
Si se ve mal no hay duda de que
obtendremos malos resultados.
Extensión de la superficie de la burbuja
 Efecto de hacer las burbujas más
pequeñas

• Incrementa el número de partículas contenidas

Asumiendo que toda la superficie está cubierta por partículas, luego el número
contenido de burbujas es:

0.1 mm partículas
Químicas de los
colectores.
Modulo Tres
 FLOTATION REAGENT TYPES

Colectores Son utilizados para hacer hidrofóbicos los minerales de valor seleccionados.
Rechazan el agua Se adhieren a la burbuja
Xantatos / DTP's / NCP Mercaptobenzotiazoles Aminas
Espumantes Los espumantes le dan estabilidad a la burbuja.
Alcoholes Glicoles Polipropilen Glicol
Depressants added to make selected minerals hydrophilic
water loving won't stick to air
Inorganics - NaHS, Polymeric - starch, guar, synthetic
Modifiers gives the slurry the right characteristics for better separation
pH, Eh, viscosity
Polyacrylates, Lime, Soda Ash
Activators added to modify mineral surfaces so that collectors will attach
copper sulfate
Processing Aids added to assist in the function of different processes
Filtration aids, Antiscalants, Defoamers
DOSS, PMA, Polyphosphates, polyacrylates, Silicone, polyglycols
Cómo trabajan los Colectores
 COLLECTOR
AMYL XANTHATE
Xanthate Amyl
the reactive part the hydrocarbon part

S
C
C O Combine

S
S

C O C

S
 REACTION WITH SULPHIDE

Hydrophilic group

Cu O
O Hydrophobic group
S

S + C O C

Fe S
 SULPHIDE AND AMYL XANTHATE
strong bond

Cu S

C O C
S
S
Fe

Result
• Hydrophilic site removed and replaced
by hydrophobic site (hydrocarbon)
• Reaction known as adsorption
• Mineral now floatable
Cómo trabaja el espumante
 CÓMO TRABAJAN LOS
ESPUMANTES
• Estructura

Estructura Actual Estructura Simplificada

Parte Hidrofóbica

= =

Parte Hidrofílica
 HOW DO FROTHERS WORK
• At the bubble surface

WATER

Properties of both parts

satisfied:
AIR • Hydrophilic OH group
remains in water

• Hydrophobic HC chain enters

air
 HOW DO FROTHERS WORK
• Consequence: as we have learned
water layer

water
molecule

H-bond
 HOW DO FROTHERS WORK
• Water layer prevents bubbles coming together (coalescing)

Mechanical Flotation Machine

water layer prevents
streamlines of water bubbles coalescing

impeller
air
blade

bubbles forming by shear

 WHAT SIZE OF BUBBLE IS
PRODUCED

1 cm

Water 10ppm MIBC

~ 0. 4 cm (4 mm) ~ 1 mm
 WHAT IS EFFECT OF MAKING
BUBBLE SMALLER

• Number of bubbles increases (for same volume of air)

Volume per bubble (mm3)

4 mm bubble 1 mm bubble

33.5 0.52

1 mm
Number of bubbles
4 mm bubble 1 mm bubble
4 mm
1 64
 WHAT IS EFFECT OF MAKING
BUBBLE SMALLER
• Increases number of particles carried
Assuming all surface is covered by particles then
number carried is

0.1 mm particles

1 bubble 64 bubbles

5,000 10,500
 Froth classes and results.

Figure 10 . Typical images from each of the four froth classes, with the number of images in each class indicated in
parentheses (top panel), as well as the corresponding relative froth grades of each class (bottom panel).
 CCC
20 20 25

FREQUENCY DISTRIBUTION
FREQUENCY DISTRIBUTION

FREQUENCY DISTRIBUTION
20
15 15

2 mm 15
10 10
10

5 5
5

0 0 0
0.1 1.0 10.0 0.1 1.0 10.0 0.1 1.0 10.0
Db (mm) Db (mm) D b (mm)

40

FREQUENCY DISTRIBUTION
30

20

10

0
5 0.1 1.0 10.0
D b (mm)
Jg = 0.5 - 1.2 cm/s 4
50

FREQUENCY DISTRIBUTION
D32 (mm)

3 40

2 30

20
1
10

0 0
0.1 1.0 10.0
0 5 10 15 20 25 30
FROTHER ADDITION (ppm) D b (mm)

Distribución de las burbujas, dosificación de espumante vs tamaño

 Flotation Machines and its results
monitoring.

Figure 2. Flotation machine (tank).

Grado vs Recuperación en
Flotación
 PERFORMANCE ADVANTAGES OF
PROPRIETARY REAGENTS

100%

Reactivos Selectivos
pH 8.5 - 10

Recup. % Cu Ventajas
Mejora Recuperación
Mejoras en Ley de Conc.
Ahorros en Depresores
Reducción en Penalizaciones

Xantato
pH 10 - 12

0 0.8% Ley de Concentrado, % Cu 35%

FEED GRADE THEORETICAL
MAX.
COST = Reduce Overall Reagent Cost (reducing lime, frothers, total consumption)
PRICE (NSR) = Copper + Penalty / Credit for Grade + Credit Other Valuables (Au/Ag) - penalty for penalty element (As, Hg, Sb)
 Sulfhydryl Collector Chemical Reactions
Base
Chemistry
Carbon Xanthates R = C2 to C5 Hydrocarbons

NaOH S
Reactants
CS2 + ROH R-O-C-S-Na+ + H2O

Carbon
Sulfur Disulfide Thionocarbamates R = C2 to C5 Hydrocarbons

S S
Alcohols Xanthates
catalyst
R-O-C-S-Na+ + R1-NH2 R-O-C-S-NH-R1 + NaHS
Cresylic
Acid Mono & Dialkyl Dithiocarbamates
R, R1 = C1 to C4 Hydrocarbons: R can also be H
Water
R1 R1 S
NaOH
NaOH
CS2 + R-NH2 R-NH-C-S-Na+ + H2O

NaMBT
Xanthogen Formates R = C2 to C5 Hydrocarbons

NH3
S O S O
R-O-C-S-Na+ + Cl-C-O-C2H5 R-O-C-S -C- O- C2H5 + NaCl + H20
Amines Di alkyl Mono & Alkyl
(N2 Based) Thionocarbamates Dithiocarbamates

Ethyl Chloro
Formate
Xanthogen Ethyl
Formate
Xanthate Esters
S S
Allyl Xanthate Allyl R-O-C-S-Na+ + Cl-CH2-CH=CH2 R-O-C-S -CH2-CH=CH2
Chloride Ester
+ NaCl + H20
 Sulfhydryl Collectors : C=S
Type -
Dialkyl Thionocarbamates -
Base
Chemistry
Carbon
Thionocarbamates
Reactants R Groups: C2 to C5 Hydrocarbons. S S
catalyst
R-O-C-S-Na+ + R1-NH2 R-O-C-S-NH-R1 + NaHS
Sulfur
COMMENTS
• This xanthate derivative is formed by reacting xanthate with methyl or ethyl amine.
Alcohols Xanthates
❑Many different types of manufacturing processes, each one making its own unique by-product which
needs to be disposed.
Cresylic
Acid ❑Reaction adds a second substituent group AND a N as an additional key donor atom to the functional
group
Water • Thionocarbamates are oily collectors (not soluble in water)
• Should be added neat
NaOH • The product is hydraulically stable
• Can be used in both acid and alkaline circuits from pH 4 – 10
NH3 • Thionocarbamates pKa is > 12.
❑Highly selective against iron sulfides. Selectivity decreases with increasing pH above 11.
❑Used extensively for copper and copper activated zinc flotation but not for lead flotation
NaMBT
❑The product is froth neutral
• Adsorption of thionocarbamates to mineral surfaces is believed to be via 4 member chelate
Dialkyl
• Thionocarbamates require some conditioning time for optimum performance.
Amines (N2
Based) Thionocarbamates

• May require other collectors to assist in recovery of middling particles.

• Thionocarbamates can have low levels of impurities that are considered carcinogenic or could
Ethyl Chloro
Formate
have depressing affects depending on the manufacturing process and the effluent generated
Allyl
Chloride
❑Purity of the thionocarbamates should be greater than 95%.
 Sulfhydryl Collectors: P=S Type
- Dialkyl & Diaryl Dithiophosphates -

RO S
Base
Phosphorous
Chemistry
P2S5 + ROH RO-P-SH + H2S

Reactants R = C2 to C5 or aryl compound (cresylic acid)

RO S RO S
Sulfur P2S5
RO-P-SH + (NaOH, NH3) RO-P-S- (Na+, NH4+) + H2O
COMMENTS
Alcohols
Dialkyl DTP
Acids
• Dialkyl or diaryl dithiophosphoric acids and their corresponding aqueous salts are liquids
❑ The acids are essentially 100% active while the salts are anywhere from 35 – 75% active. Acids are now rarely used due to the
potention H2S generation in water.
Dicresyl DTP
Cresylic Acid ❑ Aqueous DTP’s are water soluble up to as high as 70% depending on the R group and salt
Acids
• The dithiophosphates are much more stable than xanthates and have lower pKa of 1.8 for
Water alkyl and 2.2 for cresyl DTP’s.
❑ Used in the pH range of 5 – 11

Dialkyl Dicresyl • DTP’s are less powerful but more selective than xanthates, especially over pyrite and other
NaOH
DTP’s DTP’s iron sulfides because
❑ The diphosphogen dimer is not stable above pH 8
Ammonium Dialkyl Ammonium Dicresyl
NH3 ❑ This form of the collector is believed to be responsible for pyrite flotation
DTP’s DTP’s
• Dialkyl DTP’s strength increases with increasing carbon chain and selectivity decreases with
NaMBT increasing chain length
❑ These products have frothing action due to residual alcohols in final product
❑ They are used extensively for Cu, Zinc, Au, Ag and PGM flotation
Amines (N2
Based) ❑ The dialkyl DTP’s are always used in the aqueous salt form

• Diaryl DTP’s are available in both acid and salt form

Ethyl Chloro ❑ The acid form should never be diluted with water as this will release H2S gas
Formate ❑ The strength and selectivity of these products is dependent on the grade of cresylic acid used (90% cresol, 30% cresol/70% xylenol,
100% alkylates)
Allyl ❑ The higher the content of cresol, the more selective and less frothy the nature
Chloride ❑ They are used extensively for Pb, Ag and Au flotation
 Sulfhydryl Collectors : NaCN-S Type
- Functionalized Thionocarbamates -
Base
Chemistry
NaCN FTC’s have Alkoxycarbonyl Substituents added to Thionocarbamate molecule
These novel new collectors are based on replacing the R group attached to the N
in a thionocarbamate with a different type of substituent that actually adds more
Reactants
functionality and activity to the core functional group. That is why they are called
functionalized TC.
Sulfur NaSCN
The multiple step reactions for these types of products are complex :

Alkoxy 1) NaCN +S NaSCN

Alcohols
Thionocarbamates
2) NaSCN + R-OCOCl R-OCONCS + NaCl
O S
Cresylic Acid
3) R-OCONCS + R1OH R-O-C-NH-C-O-R1
R = C2 to C4 : R1 = C4 to C6 Alkoxy Carbonyl Alkyl Thionocarbamate
Water
COMMENTS
• Alkoxy groups add an electron withdrawing group to the collector molecule and
NaOH effectively lowers the pKa to 10.5 for thionocarbamates.
• These products are stronger collectors at lower pH than standard thionocarbamates but
still retain their selectivity against iron sulfides
NH3
• FTC’s are believed to adsorbed as 6 member chelates with surface Copper which is
much more stable than the 4 member chelates for thionocarbamates alone.
NaMBT
• Alkoxy carbonyl alkyl thionocarbamates are excellent collectors for Cu rich minerals
and coarse particles
• Benzoyl Thionocarbamates have shown to be excellent Moly collectors as well as
Amines (N2 possessing all the attributes of selectivity against iron.
Based)
• They are oily in nature and should be added neat with some conditioning. They are
frequently added with auxiliary collectors to lower the cost.
Ethyl Chloro
Formate
Isothiocyanates • Because they operate at lower pH levels, the froth generated can be dramatically
changed so the use of these products normally requires additional or stronger frothers.
Allyl • Care must be taken when using these products. They are stable but some impurities
Chloride could be produced through decomposition that could be harmful to health.
 Sulfhydryl Collectors : NaCN-S Type
- Alkoxy Carbonyl Thiourea -
Base Thiorureas have an amine substituents added to the Functionalized
NaCN
Chemistry Thionocarbamates molecule.
These products are made by replacing the O that is attached to the
Reactants
C=S in the alkoxy carbonyl alkyl thionocarbamate with a Nitrogen
group.
Sulfur NaSCN
The third reaction above becomes:
Alcohols
1) NaCN +S NaSCN
2) NaSCN + R-OCOCl R-OCONCS + NaCl
Cresylic Acid 3) R-OCONCS + R1NH2 O S

R-O-C-NH-C-NH-R1
Water Alkoxy Carbonyl Alkyl Thiourea

NaOH COMMENTS
• The Nitrogen added to the this molecule actually raises the pKa slightly to
NH3
11.0
• The thioureas are analogous to the functionalized thionocarbamates except
that they are preferred for silver and gold ores and for copper deficient
NaMBT minerals such as chalcopyrite
❑ They have also shown to be excellent PGM collectors
Amines (N2 Alkoxy Carbonyl ❑ Perform poorly on galena
Alkyl Thioureas
• These collectors can operate at higher pH’s than the thionocarbamates
Based)

because they are more stable and have a slightly higher pKa
Ethyl Chloro
Isothiocyanates ❑ They are very resistant to oxidation
Formate

Allyl
Chloride
 Sulfhydryl Collectors : NaCN-S Type
- Allyl-Alkyl Thionocarbamates -
Base Allyl substituent added to Thionocarbamates
Chemistry
These products are made by replacing the alkyl group attached
to the N in the thionocarbamate functional group with an allyl
Reactants group.
The difference is that in the second reaction, the ECF is replaced
Sulfur NaSCN with allyl chloride as follows:
1) NaSCN + Cl-CH2-CH=CH2 CH2=CH-CH2NCS + NaCl
Alcohols S
2) CH2=CH-CH2NCS + ROH CH2=CH-CH2NH-C-O-R
Cresylic Acid
COMMENTS
• The allyl group added as a substituent is extremely hydrophobic
Water ❑ Thes product has extremely rapid kinetics and functions at very low dosage
❑ It is often used in conjunction with DTP collectors to provide more flexibility in
producing a manageable froth
NaOH • They are oily in nature and should be added neat with some
conditioning
❑ They are frequently added with auxiliary collectors to lower the cost
NH3 • This product has shown excellent performance in copper and copper
activated zinc circuits
❑ Has been shown to complex with PGM minerals
NaMBT
❑ It is an extremely poor galena collector
• The Allyl group is extremely hydrophobic and has a tendency to
Amines (N2 destroy froth. it may not be as selective against iron sulfides as other
Based)
thionocarbamates due to high dosage sensitivity.
❑ When using this product, care must be taken not to overdose which can flatten
Ethyl Chloro
Formate the froth
• Only the allyl isobutly thionocarbamate is commercially available
Allyl Allyl –allyl
Allyl Isothiocyanate
Chloride Thionocarbamate
 Sulfhydryl Collectors - Others -

Sodium Mercaptobenzothiazole

S COMMENTS
S-Na+
• This product is stable in acid and alkaline conditions and comes in a liquid form
C • Strong bulk sulfide collector when used for the flotation of gold bearing pyrite in
acid to neutral pH
N
• Excellent collector for tarnished minerals in alkaline conditions.
• Used alone or in blends with DTP’s
• Behaves like xanthates in alkaline circuits but slightly more selective
Alkyl Mercaptans and Dialkyl sulfides
COMMENTS
•Mercaptans are very powerful sulfide collectors and can be used for bulk sulfide flotation and for native copper
in alkaline conditions. The pKa is >12.
❑ Odor can be an issue
•Ethyl octyl sulfide was developed by Dow in the 80’s as a powerful but selective sulfide and gold collector
❑ Its high cost and difficulty in operating has limited its usage

R-SH, where R is greater than 10 R – S – R1, where R is ethyl and R1 is octyl

 Xantato
• Como sabemos, el xantato es uno de los mejores colectores debido a que
con xantato somos capaces de flotar muchos tipos de sulfuros.
• Nosotros podemos flotar, Cu, Pb, Zn, Cd, Co, Mo, y otros, pero también Fe
que es el contaminante principal para muchos de los minerales.
• Después de flotar con xantato, inmediatamente tenemos que usar algún tipo
de depresor debido a que de lo contrario estaremos flotando no sólo
minerales con valor, sino también minerales sin valor.
• Es común encontrar que usando xantato como colector el volumen de masa
flotado será más alto que el volumen de masa flotado con un colector
selectivo.
• Xantato es igual a alta carga circulante, mientras que colector selectivo es
igual a baja carga circulante.
 Cianuro
• El cianuro deprime a los minerales a los cuales sus iones metálicos
forman complejos con él, por ejemplo Pirita, Calcopirita y Covelita.
La galena no se ve afectada ya que el plomo no forma complejos
con el cianuro.
• El cianuro deprime la pirita activada con iones cobre lo que no seria
posible solo con subir el Ph.
• Si se agregan iones cianuro en exceso, el contenido de cobre en su
fase acuosa se incrementa significativamente por disolución de
iones cobre.
• Mejora la cinética de la galena (PbS) en algunos minerales Pb-Zn.
 Efectos del cianuro en Fe y
CU
Fitted Line Plot Fitted Line Plot
Rec Fe % = 8.502 - 0.03853 NaCN Rec Cu % = 71.82 - 0.6485 NaCN
9.0 70
S 0.915730 S 6.44338
R-Sq 23.0% R-Sq 63.1%
8.5 R-Sq(adj) 15.3% R-Sq(adj) 59.4%
65

8.0
60

Rec Cu %
Rec Fe %

7.5
55

7.0
50
6.5

45
6.0

40
10 15 20 25 30 35 40 45 10 15 20 25 30 35 40 45
NaCN NaCN
 Efectos de la adición del Cianuro
de sodio en la flotación
Fitted Line Plot
Rec Pb % = 75.07 + 0.1427 NaCN
85
S 5.24725
R-Sq 11.1%
R-Sq(adj) 2.2%

80
Rec Pb %

75

70

65
10 15 20 25 30 35 40 45
NaCN
Análisis del ZnSO4

• Si subimos el
sulfato de Zn de 600
a 800 en promedio
tenderemos a perder
2 % de recuperación
de plata.
Análisis del ZnSO4

• Este efecto de 200 g/t mas

de sulfato de Zinc en la
recuperación de plata es
muy significativo pero
como vemos en la ley de
Zn en concentrado de
plomo no es perceptible o
estadísticamente
significativo por lo que
podemos decir que 600 y
800 g/t de sulfato de zinc
es igual en ley de zinc
pero si afecta en la plata
 Ley y Recuperación en
Flotación de Zn con y sin CAL
Interval Plot of %Rec Zn en Zinc vs PH Interval Plot of Conc. Zinc Zn vs PH
95% CI for the Mean 95% CI for the Mean
60 50

59

58
49
%Rec Zn en Zinc

57 48.5652

Conc. Zinc Zn
56.4516
56
54.8006 48
55

54 47.2853
47
53

52

51 46
10.5 7.6 10.5 7.6
PH PH
The pooled standard deviation was used to calculate the intervals. The pooled standard deviation was used to calculate the intervals.
Geologia

Minado

Chancado