Flocculants and Flocculation | Mick Bower : Kinsevere January 2015

Flocculants &
Flocculation for the
Copper Industry
DRC/Zambia January 2015
Great chemistry…….

…..but needs some care!

 Agenda:
Flocculation Basics

Flocculant Chemistry

Product Selection

Lab Testing

Example Responses

Calculations

Plant considerations
Thickening Processes
Cheap to run – motive force is gravity

Simple to operate – few moving parts.

Wide range of conditions :-

• Low pH acid leach circuits
• High pH Bayer process
• Seawater/saturated solutions
• High temperatures to 100C

Proven and reliable

4
 Particle Size
Colloids
1mm 100µm 10µm 1µm 0.1µm

1m
1m 3.5 years
1m 13 days
3 hours
1m Typical Water Contaminants
2 min
1m Settling velocity of spherical silica
Typical Tails Particles
1 sec (Sp.Gr.= 2.65) as computed from
Stokes Law.
 Colloidal Particles
The particles we must remove have Shells of cationic (positive)
a charge. This is usually negative charges can form around the
(anionic). particles.
+ + +
+
+ +
+ +
+ +
+ + +
+ The repulsion forces between
the particles are stronger than
the force of gravity.

As a result the particles stay in suspension.

 Colloidal Particles
+ - - Diffuse Layer
-
- - - + - -
- + - + + + - Rigid Layer
- +
-
- - + + - -
+ - + Particle + - -
+ +
- - + -
-
-
- - + + + - -
+ - - -
- + - - +
- - - -
Electrical Potential
Surrounding Particle ZETA Potential

Measures the degree of the charge keeping the particles in a stable suspension
CLASSIFICATION Presentation name, Author 26 June 2015 7
 Coagulation
+ +

+ +
+
+ + +
“Charge Patch”

+
+
+ +
+

+
+
+

+
+
+ mechanism
Negative Cationic Destabilized
Charge Coagulated
Coagulant  Purely electrical
Particles + Particles
+ + + + +
in nature
+ +
+
+ + + + + +
+
++
+ + + +  Weak
+ + + + + + +
+ +
+
+ + + + +
+
+
++ +
+ +
+ +
+
+ agglomerations
+ + + + + + +
+ + +
+ + +  Completely
+
+
Reversible
 Flocculation Mechanism
++
--- --- ++ +++
- - - - --- - -- - - + + ++ ---
--- - --
- - + + + + ++ - - +- +-++-+-- -
+
-
- - -
- - -- - - ++ +++++ - -+-+ - - ++-- -
- -- ++-- -- ++-- +-+ +-
+ ++++ + +
--- --- - -
-
- -
- -- -- - + ++ + +
+ + ++ ++
+ ++ ++ + +
+ ++ + +
- ------+
-+
-
+ + -
-- + -
+- +--+ +- -
++ -- - - -
- -- +- +-- -+- +
+- +- +-
++ +
--- - --- + ++ - + +
+
++
- --- - ++ +- +
- -- - - + + ++
- +
Negative-Charge HMW Cationic Flocculated
Particles Polymer Particles

Physical in nature - “Bridging”

CLASSIFICATION Presentation name, Author 26 June 2015 9
 Flocculation Vs Coagulation
Coagulation is the stage in the solids-liquids separation process whereby
the solids constituents in an aqueous suspension are de-stabilised.

Flocculation is the stage whereby the de-stabilised particles or particles

formed during the de-stabilisation are induced to collect into larger
aggregates and therefore separate from the fluid phase according to
Stokes’ Law.

D. A. Mortimer
Synthetic Polyelectrolytes – A Review
Polymer International 1990

CLASSIFICATION Presentation name, Author 26 June 2015 10

 Flocculation Vs Coagulation
Coagulation:
• Charge neutralisation
• Low solids systems
• Needs time to develop
• Needs mixing – insensitive to excessive
shear
• Reagent addition into turbulent region
• Once sheared aggregates will reform
Flocculation:
• Bridging
• High solids systems
• Very quick – few seconds
• Sensitive to excessive shear
• Reagent addition for minimum
turbulence
• Once sheared will not reform
CLASSIFICATION Presentation name, Author 26 June 2015| 11
Coagulation + Flocculation
Once de-stabilised the
aggregated particles are
flocculated using a small
amount of nonionic or
anionic flocculant.

Often referred to as
“coagulant aid”

Speeds up settling
process and reduces size
of equipment.
 Flocculation + Coagulation
Systems requiring both coagulation and
flocculation :-
Floc +
Anionic
Polyamine e.g. Coal Washeries
Floc

Often contain a fraction of fine clay, Floc

alone settles some but not all. Increasing
dose offers no improvement. Unsettled
material re-circulates and builds-up in
process causing problems.
Range 100 – 1000NTU+ remain

Treatment becomes addition of polyamine

coagulant followed by anionic flocculant.
Dosages 5 – 50 g/t coagulant.
Flocculants and
Coagulants
Flocculants
Flocculants are long chain water soluble
polymers

Chemistry is mainly acrylamide based

Anionic (negative) and cationic (positive)

charges are incorporated during the
polymerisation

Generally regarded as non-hazardous from a

chemical perspective

Biggest issue is that they are slippery when

wet
 Flocculant Characteristics
“Molecular Weight”
Length of the chain

“Cationic” “Anionic”

+ (positive) degree of charge (negative) -

 Product Forms
Emulsion Solution
Dry Powder

(Water-in-oil Very low solids

High solids
emulsion or
Free Flowing aqueous dispersion) High Viscosity
Cationics are Lower solids Easy to dilute
Hygroscopic

17
 Health & Safety
o Non-Toxic:-
o Potable water grades 200/500ppm residual Acrylamide
o Cationic types are toxic to fish – need to be careful.
o Non Flammable :-
o Dust has low explosion potential, minimum ignition energy >500mj
Main physical hazard :-

Slippery when wet.

Can be difficult to see on
wet surfaces

Control measures are

awareness and good
housekeeping

18
 Dissolution Characteristics
Dissolution time dependent on :-

• Product Charge
• Particle size
• Water quality
• Temperature
• Wetting out

How critical is it ?

Floc in overflow can have downstream effects:

• SX plants
• Flotation
• Filters

19
 Dissolution Characteristics

60 mins ~93.7%

120 mins ~99.9%

20
 Solution Viscosity
0.2% polycationic
12000
Solution viscosity depends on :-
B rookfield

10000
rpm
• Product type – both Charge and
0.3
Viscosity (#1 / UL) cps

0.6 MW
8000
1.5

6000
3 • Water quality – ionic content
6
12
4000
30
• Measurement method

2000
Difficult to use viscosity as
0 measure of polymer
0 100 200 300 400
concentration
[NaC l] ppm

21
 Solution Viscosity
Initial Dilution :-

0.1 – 0.5%, target 0.3% max

for HMW anionics used for
tails

Secondary dilution :-

To 0.01% or less – use as

much as possible or practical

Anionic polyacrylamide @ 0.4%

22
 Flocculants in the Mining Industry
“Molecular Weight”

BIOX CCD Kaolin waste

Kaolin Magnet
waste
Bayer red mud
Pre-leach gold
Mining Tails
Leach plant CCD

TiO2 processing

+ (positive) degree of charge (negative) -

Rheology Modifiers
Different chemistry – NaAMPS

Handling and make-down as normal

Cannot evaluate effect on underflow in

static cylinder testing – needs raked
cylinders

Generally fast settling rates but poorer

overflow clarities
Rheology Modifiers
Fast settling rate is significant:
• Higher capacity
• Finer grinds
• Changed ores
• Increased throughput

Drawback is high cost but products can be

useful where:
• Water recovery valuable
• Difficult/variable ore
• Capacity constrained
• Rake torque limited

No patents on the Chemistry or application

in thickeners
 Coagulants
Inorganic Types :-
High dose of low solids solution
Works at low concentrations
Can remove very small particles
Can alter pH of system
High sludge volume
Cost benefits
Re-stabilise particles less
Metals Removal
Organic Types :-
Low dose of high solids solution
Works over wider pH
Less impact on pH
Lower dosages
Lower sludge volume
Easy to dewater sludge
Easy to handle/dose
Overdose re-stabilises system
CLASSIFICATION Presentation name, Author 26 June 2015 26
 Organic Type Coagulants
CH3 Polyamines: (Epi)
I
+
– (– CH2 – CH – CH2 – N – ) – 20 – 50 % solutions
I I -
MW’s up to 250,000
OH CH3 Cl

CH2
Poly DADMAC: (DADM)
- ( - CH2-- CH CH -) -
I I
20 – 40% solutions
CH2 CH2
MW’s up to 400,000
+
N -
Cl
CH3 CH3

CLASSIFICATION Presentation name, Author 26 June 2015 27

 Application Specifics – Metals
• Flotation Tails – Copper/Gold Nickel/Lead/Zinc/Polymetallics
• Low medium anionics : Superfloc A100 – A130 and HMW variants

• Flotation Concentrates
• Generally use same as for tails
• Needs to watch out for excessive dosing and effect on filters
• Froth on thickeners is a big issue

• Gold Leach – pre/post leach thickening

• , Superfloc A100/A120 and HMW variants
• Superfloc N300 used in RSA with success, anionics elsewhere

• Copper/Nickel leach
• Superfloc N100 used widely
• Need to watch SX compatibility CLASSIFICATION Presentation name, Author 26 June 2015 28
 Application Specifics – Metals
• Copper/Nickel leach
• Superfloc N100 used widely, N300 can give better clarity
• Need to watch SX compatibility

• Iron ore Concentrate

• Low /medium anionics Superfloc A100 – A150

• Iron ore Tails

• Low /medium anionics Superfloc A100 – A150

• Bauxite
• Low /medium anionics Superfloc A100 – A130

CLASSIFICATION Presentation name, Author 26 June 2015 29

 Application Specifics – Non-metallic
• Mineral Sands
• Low – Medium anionics; Superfloc A100 – A137

• Diamonds/Kimberlite slimes
• Low – Medium anionics: Superfloc A100 – A130
• Many favour the standard over higher MW

• Fine Coal
• Low – Medium anionics: Superfloc A100 – A130
• May benefit from coagulant

• Coal Waste
• Low – Medium anionics: Superfloc A100 – A130
• May benefit from coagulant
CLASSIFICATION Presentation name, Author 26 June 2015 30
 Application Specifics – Non-metallic
• Kaolin
• Can be variable; Responds well with most anionics/nonionics
• HIMS waste needs cationic: Superfloc C494 – C498

• Sand and gravel/glass-sands waste

• Low – Medium anionics; Superfloc A100 – A137

CLASSIFICATION Presentation name, Author 26 June 2015 31

Product
Selection
Process
Product Selection
Depends on a lot of factors:
• Settling Rate:
• Clarity
• Cost
• Handling

Generally carried out empirically

Use other applications as guide
Not definite – several different products
may work

Responses can be different:

• optimisation on
rate/clarity/density/operability etc etc
Product Selection – Questions
Process and Slurry Type

pH and ionic content:

• Water chemistry
• Process variation

Solids Type:
• Mineralogy
• PSD: Fine or coarse
• Variations

Expectations and targets:

• Settling rate – rate of rise in thickener
• Overflow clarity requirement
Product Selection Process
Kemira multi-stage process :

Stage 1 – Get a rough test that you are

happy with:
• Inputs – Solids/dosage
• Outputs – Setting rate/clarity

Stage 2 – Refine product choice with

charge
• Modify test if needed

Stage 3 – Test effects of molecular weight

and confirm selection
Product Selection Bias
Results depend very much on conditions
used:

• Low solids/fast settling - favours higher

MW types

• Fine PSD and high solids favours lower

MW types

• However chosen product will still work!

• Some systems self coagulate at certain

pH’s

Conditions need to match operations –can

be difficult!
Flocculants and flocculation | Mick Bower | June 2013| 37
Laboratory Testing
Need to understand:

• Solids/dilution

• Addition mechanism

• Objectives

No specific right or
wrong way
 Flocculant Make-down

On On
Off Off

Dry PAMS Emulsion PAMS Solution PAMS

Target 0.1/0.2% Target 2.0% initial, 0.1/0.2% for use Target 1.0% or lower
30 minutes anioncs/cationics 10 minutes at 2% 1 minute mixing
120 minutes Nonionics. 2 minutes at 0.1/0.2%
Store for 2 days max Store at 2% for 2 days max. . Store at 1% for 2 days
 Flocculant Make-down
Dry PAM Procedure

1, Mark-up set of beaker/jars and weighing boats

2, Weigh out/measure water – which type?

3, Weigh out polymers for 0.1%

On
Off
4, Set –up beaker with strong vortex

Dry PAMS 5, Sprinkle polymer onto side of vortex

Target 0.1/0.2%
30 minutes anioncs/cationics
120 minutes Nonionics.
Store for 2 days max
over few a seconds
6, Continue stirring at high speed for 2 minutes
7, Keep moving until fully dissolved
 Flocculant Make-down Water
Anionics Nonionics Cationics

Avoid low pH Chemistry OK Need to avoid high pH to

prevent hydrolysis
OK at high pH but can Dissolution slow, and losing cationicity
get some hydrolysis Try to avoid
with time extremes of pH to Some buffering capacity
(ammonia smell) prevent hydrolysis built-in
(Adipic/Citric/Sulphamic)
Avoid high Ca/Mg
- can precipitate out . Avoid high Ca/Mg
Basic Cylinder Testing
Method

1, Decide dose and method for each

2, Split pulp carefully between cylinders
3, Working 1 cylinder at a time :-
- re-suspend solids
- add first dose
- mix
- add second dose
- mix
- start timing
- follow fall of interface
4 - Move onto next cylinder
5 – After fixed period measure NTU
 Basic Cylinder Testing
1st Dose 2nd Dose
Time fall
followed by followed by
of Interface
vigorous mixing gentle mixing
Plunger Vs. Inverting
Plunger:
• Safer
• More consistent mixing
• Allows more variation in mixing
• Allows stage dosage
• Incomplete mixing

Inverting the Cylinders:

• Gentle mixing – less shear
• Good with large PSD’s (150 – 200um)

Look at the trend rather than absolute!

Use both properly.
 Basic Cylinder Testing
Settling Rate (m/hr) = 0.068*(3600/Time) Units = m/hr (Sorry USA!)

1000 Induction – Unstable and difficult to time

900 900

~68mm 800 Free Settling – what we are trying to measure

Height In Cyliner
700
700
600
500
Hindered settling then compaction
400
300
200
100
18 seconds
0
0 20 40 60 80 100 120 140 160 180 200
Time (seconds)

45
Basic Cylinder Testing - Compaction
Do not use final compaction as a measure:-

Short term - depends on rate

1000 Long term – depends on dose
900 In reality – depends on raking
800

Height In Cyliner
700

600

500

400
“Compaction”??
300

200
100

0
0 20 40 60 80 100 120 140 160 180 200
Time (seconds)

46
 Supernatant Clarity
Clarity

Use syringe to pull sample from cylinder

10 – 30 minutes after floc.

Usually measured with P2100 Hach meter

Effective range 5 – 1000 NTU

Can dilute more turbid samples

Results expressed as NTU –

(conversion to mg/l possible)
Hach P2100 Turbidity Meter
 Lab testing Do’s and Don’ts
✔ Agree the objectives ✖ Make exact promises based on the results

✔ Understand the process ✖ Work without correct dilution

✔ Have and use a wide range of samples ✖ Rush the solution make-up

✔ Recognize the limitations. ✖ Work with results to 3 decimal places

✔ Split the pulp as well as possible ✖ Use old floc solutions, especially if dilute

✔ Make the solutions correctly, allow sufficient time for ✖Draw conclusions without processing the data
hydration

✔Work graphically ✖Draw conclusion from one set of data

✔ Be prepared to try different things

✔ Identify and account for “fliers”

✔ Understand the HSE implications

Flocculants and Flocculation | Mick Bower | May 2013

Example
Responses
Product Selection Responses - Screening
Basic screen response:

Low charge anionics

poor

Optimal settling at A110

Optimal clarity at A130

Note the clarity at

500NTU!!

“Responsive” Conditions
Product choice important
Product Selection Responses - Screening
Basic screen response:

Same charge range

favoured.

Optimal settling at A100

Optimal clarity at A137

Note the clarity at

<50NTU!!

“Less Responsive”
Product choice not
critical.

CLASSIFICATION Presentation name, Author 26 June 2015 51

Product Selection Responses - Screening
Basic screen response:

Higher MW products

Optimal clarity and

Settling rate together

Less response in clarity

than previous, more
response from settling
rate

CLASSIFICATION Presentation name, Author 26 June 2015 52

Product Selection Responses – Screening
Basic screen response:

Acidic conditions (10g/l

pH 1.8)

Clear preference for

nonionic types. Although
settling rate OK for low
charge the overflow
clarity was not

Going “broad” means it’s

easier to see trends.

CLASSIFICATION Presentation name, Author 26 June 2015 53

 Comparing Products
Dosage Comparisons
25
Product/Conditions A –
20 for 10m/hr settling rate
Settling rate (m/hr)

Product A

Product B
we need 44g/t dose
15
Target S/R for thickener
Product/Conditions B –
10 For 10 m/hr settling rate
We need 34 g/t dose
5
Very approximately we need
0 about 20% less of B to run the
0 10 20 30 40 50 60 70 thickener –
Dose (g/t)
providing settling rate is the driver
Comparing Products
Product Comparison:

For 5m/hr Settling rate-

Incumbent 8.2mls

A115HMW = 7.3mls

E-4832 = 6.3 mls

Runs at about 75% of the

incumbent dose.

(But settling rate has

gone from 5m/hr to
17m/hr)

CLASSIFICATION Presentation name, Author 26 June 2015 55

Comparing Products
Product Comparison:

A120HMW = 24g/t

A110HMW= 27g/t

A110 = 28g/t

A120 = 37g/t

Would normally expect to

see similar trend with
HMW vs Standard MW
Dosage Effects
Low solids system:

Superfloc A115HMW
(0.1% solution)

Quickly reach limit of

dosing, above 6 mls no
improvement in clarity
and only small difference
in settling rate

CLASSIFICATION Presentation name, Author 26 June 2015 57

Dosage Effects

CLASSIFICATION Presentation name, Author 26 June 2015 58

 Dosage Effects

Can see the structure created by the higher dose. Excessive floc created downstream
issues, pumping is harder and filtration a lot more difficult.

Higher dose does not mean higher underflow density

CLASSIFICATION Presentation name, Author 26 June 2015 59

Dosage Effects
Low solids system:

Superfloc N100
(0.1% solution)

Similar pattern,
Going from 80 to 160 g/t
does not improve the
results

Settling rate has

plateaued at less than
10m/hr.

If we needed faster what

to do?

CLASSIFICATION Presentation name, Author 26 June 2015 60

Dosage Effects
Differing behaviour:

Hydroxide precipitate is
dependant on solids –
changing floc dose has
little effect

Post leach behaves like a

lot on mining substrates
– good response from
dose

Different processes from

the same plant – are the
operators aware?
Increasing the dose on
the hydroxide is limited in
usefulness

CLASSIFICATION Presentation name, Author 26 June 2015 61

Dosage Effects
Differing behaviour:

Hydroxide precipitate is
dependant on solids –
changing floc dose has
little effect

Post leach behaves like a

lot on mining substrates
– good response from
dose

Different processes from

the same plant – are the
operators aware?
Increasing the dose on
the hydroxide is limited in
usefulness

CLASSIFICATION Presentation name, Author 26 June 2015 62

Dosage Effects
What is the “right” dose?

Difficult question and to a degree you

can trade equipment size for
flocculant dose.

Chile market traditionally uses very

large thickeners with low dosages (3 –
10 g/g)

African market has smaller equipment

running at higher rates but using much
higher dosages 10 – 25g/t)

Limit normally becomes something

else(rakes?)

CLASSIFICATION Presentation name, Author 26 June 2015 63

Solids Effects
High Rate Principle:

By dropping the solids

the settling rate
increases

This increase is
proportionally more than
the increase in the rate of
rise in the thickener

Net result is a gain in

settling capacity

3% ~ 2m/hr
1.5% ~6mhr

CLASSIFICATION Presentation name, Author 26 June 2015 64

Solids Effects

CLASSIFICATION Presentation name, Author 26 June 2015 65

Solids Effects
High Rate Principle:

The optimal solids levels

depends mainly on the
PSD:

The primary leach

residue is a typical tails
type material ~D80
100um. Optimal levels
would be 6 – 10%

The FAM material is very

fine. At 6 – 10% settling
is almost non-existent ,
even increasing the dose
has limited effect

CLASSIFICATION Presentation name, Author 26 June 2015 66

Dose and Solids Effects Combined
Finite limit to what
dosing can achieve

The material in question

was a fine copper
hydroxide precipitate

At 6.2% solids, no matter

how much you increase
the dose the settling rate
stayed below 2m/hr

Drop the solids by 50%

and the rate doubles.

Are the operators aware?

CLASSIFICATION Presentation name, Author 26 June 2015 67

Coagulation Example
Mode of addition

With coagulants you should

always experiment with the
addition order

CLASSIFICATION Presentation name, Author 26 June 2015 68

Be prepared for the unexpected

Not high precision science

Cannot measure/simulate plant

-particularly mixing/shear

We are looking for the trends

Where water
meets chemistry.
Flocculants and Flocculation | Mick Bower | May 2013

Flocculant
Calculations
 Density Calculations
Total volume:
926+74 = 1000 mls

Total Weight:
926 + 200 = 1126g
Top-up with
926 mls water Pulp Density:
1126/1000 = 1.126g/ml

Solids% (weight/weight):
= (200/1126) x100

Cylinder with 200g solids s.g. 2.7 = 17. 7% (not 20%)

Volume is 200/2.7 = 74mls
Remaining volume
= 1000 – 74 = 926mls
 Density Calculations
“50:50”
Dilution

Add
500 mls
water

Cylinder with 500mls pulp @ s.g 1.126 Now contains : 100g solids
Contains : 100g solids and 963 mls water
and 463 mls water Solids % = 100* 100/1063
17.7% solids 9.4% solids
Pulp Density Tables

From the Cytec Mining Chemicals Handbook

 Dosage Calculations
For “20 g/t ” dosage :

• Needs (20/1000000)*100g
= 0.002g floc on a real basis

• Floc solution strength – 0.1% (or 1.0g/l)

• Needs (0.002/0.001) =2.0 mls

Check :

• (2.0*0.001)/100*1000000 = 20
s.g. 1063 – 9.4% solids
Using pulp density tables Note - Low solids systems use “ppm” on total
Contains : 100g solids volume
and 963 mls water
 Worked Example
Cylinder s.g as measured 1.102

Pulp s.g. 2.7 in water (from customer)

For Cylinder with 162 g/ solids :-
Solids fraction = (2.7x(1.102-1.0))
(1.102x(2.7-1.0)) Target dose 20 g/t

= 0.1470 Real polymer req = 20/1000000x162

i.e. we have 14.1% solids (weight) or = 0.0032g

1102 x 0.1470
With solution at 0.1% = 0.0031/0.001
162 g solids in the 1l cylinder
= 3.2 mls floc solution

75