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CHAPTER - II

ACTIVATED CARBON
TECHNOLOGY
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1. INTRODUCTION

Activated carbon possess unique properties when compared to other

class of organic substance. It contains considerable quantity of adsorbed

oxygen and hydrogen. The activated carbon is a complex organic polymer

and not an amorphous form of the element carbon. From other organic

polymers it differs in having an exceptionally large surface area and is a

good conductor of electricity. It is thus essential to understand both physical

and chemical characteristics of activated carbon with respect to gold

adsorption.

2. MEANING OF ACTIVATED CARBON

The term activated carbon, represents the family of highly porous

carbonaceous material. It can neither be characterised by a structural formula

or by chemical analysis. In normal practice the activated carbon is produced

by charring coconut shell or peach pips at around 700°C to 800°C in the

presence of steam. Thus prepared, charcoal possesses a porous skeletal

structure with a high surface area (> 1000 m2/gr) and the pore size varies

from 10 to 20 A°. The pore spaces are classified based on their size as :

a) Macro pores 500 to 20,000 A°


b) Meso pores or 100 to 500 A°
Transitional pores
c) Micro pores 8 to 100 A°
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The internal surface area of activated carbon serves as transport

arteries to the molecules being adsorbed. This mainly depends on the nature

of the carbonaceous raw material employed and the manufacturing process,

like grinding, agglomeration of the raw material and activation process.

The macro pores contribute very little to the total internal surface

area of the product. The transitional pores account for about 5% and the micro

pores for about 95% of the internal surface area. The micro pores are largely

the product of the activation process.

Commercially the activated carbons are availale as powder, granular


chips in various sizes, shapes and also as moulded products, commonly in

0.8 to 6 mm diameter and 3 to 10 mm in length.

The XRD studies have shown that the structure of thermally


activated carbon is similar to that of graphite (Boehm 1970). However, exact

chemical structures of the activated carbon are not known with certainity.

Basic surface groups have also been identified and it appears that the nature
of the surface groups depend upon conditions during and after manufacture.

3. GOLD ADSORFITVE PROPERTIES OF ACTIVATED CARBON

The reduction mechanism for aurocyanide adsorption onto carbon


was explained by Feldmann (1914) and Edmands (1917). Later Julian and

Smart (1921) have explained about the gold adsorption. Kuzminykh and
Tyurin (1968) have proposed that under acidic conditions the neutral molecule
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H Au(CN)2 is concentrated on the surface of the carbon by a capillary

condensation mechanism. Under neutral or alkaline conditions the Au (CN)2,

anion is retained on the carbon, together with an equivalent amount of an

alkali cation, such as K+ or Na+. This is held on the carbon electrostatically.

Davidson (1979) opines that the degree of gold adsorption is strongly

dependent on the nature and concentration of the cations (namely Na+ and

Ca+) in the adsorption medium.

Dixon et al„ (1976), Cho (1978 and 1979), Dixon and Pitt (1979) have

explained the kinetics and thermodynamics of the adsorption of gold and

silver cyanide on activated carbon. The adsorption rates for both gold and

silver cyanide are controlled by the rate of pore diffusion in the temperature

range 25° to 55°C and the activation energy of 8 to 13 KJ per mole. It is also

noticed that the size of the grains affect the initial rate of adsorption. Higher

rates for the smaller size fractions are observed. It has no effect on the

equilibrium amount of gold adsorbed. The equilibrium gold loading is strongly

dependent on the pH value of the adsorption medium. The amount of gold

adsorbed in the pH range 4 to 7 being about twice that adsorbed in the pH

range 8 to 11. The mechanism that involves the adsorption of gold as a metal

dicyanoaurate, Mn+ [Au(CN)2]6 is advanced. In support of this hypothesis, it

is claimed that, when the cation of the complex M"+, is a diavalent alkaline

earth metal, the complex is bound more firmly to the carbon than when Mn+ is

a monovalent alkaline metal. It is found that the strength of the Mn+[Au(CN)2]n

adsorbate followed the sequence Ca2+ > Mg2* > H+ > Li+ > Na+ > K+.
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Bemadin (1914), Feldmann (1914) and Tsuchida, et. al., (1984) have

described about adsorptive properties of activated carbon. Accordingly

adsorption of metal values onto activated carbon in typical cyanide circuit

takes place via an easily reversible ion pair mechanism. The adsorption of the

ion paired metal complex is likely to follow a homologous series, depending

on the solubility of the adsorbed gold. According to the theories explained by

Plaskin (1958) and Cho (1979) about the behaviour of loaded carbon, thus

claim that, the activated carbon behaves like an oxygen electrode and

molecular oxygen reacts with the surface of the carbon to form a surface

functional group CX° or CX°2 which reacts with water according to equation

CX° + H20 * Cx2"+ 2 OH' This reaction suggest that higher gold adsorption

capacity observed in acidic solutions, as low pH values. The equilibrium would

be shifted towards the right and more positively charged adsorption sites

would be produced that would attract an equivalent number of Au(CN)2~~

anion with regard to the adsorption of silver cyanide as the loading of silver

on the carbon was increased the zeta potential of the carbon surface

becomes more negative. This led to decide that the adsorbate is an anion.

Ag(CN)~ The deleterious effect of gold cyanide is about 3 times more than

silver cyanide. This is attributed to the larger ionic radius of gold i.e. 13.7 nm

compared to the smaller ionic radius of silver 12.6 nm.

The mechanisms of gold adsorption from aurocyanide solution onto

carbon is summerised as follows.

a) Reduction of Au(CN)~to gold metal.


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b) Adsorption of Ca[ Au(CN)J2 ion pairs.

c) The initial adsorption of ion pairs followed by a partial reduction

step to Au(CN)x or cluster type-species.

d) The initial adsorption of ion pairs followed by an oxidation step in

which Au(CN)“is degraded to Au(CN).

Actually it could be said that the specific nature of the functional

groups on the carbon surface are involved in the adsorption process is only

speculative.

4. PARAMETERS AFFECTING CARBON LOADING

There are numerous factors that control the loading on to activated

carbon. According to Baily (Stanely, 1987) following parameters affect carbon

loading.

a) Ionic strength of the adsorption medium.

b) Cyanide concentration and temperature.

c) pH of the adsorption medium.

d) Other process solution/pulp constituents.

e) Oxygen availability.

f) Carbon activity.
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g) Physical effects.

h) Operational considerations.

a) Ionic strength of the adsorption medium

Davidson (1974), Cho (1979), McDougall et al. (1980) have

described the adsorption of gold and silver in the presence of added salts,

particularly Ca2+. Tsuchida et al. (1984) have described the adsorption of gold

in the presence of various monovalent and divalent cations and

indicated that the adsoprtion of these counter cations appeared to be

pH dependent.

b) Cyanide concentration and temperature

From the thermodynamic considerations the gold adsorption onto

carbon is adversely affected by the presence of free cyanide in the adsorption

media and this effect is more pronounced with increase in temperature. From

the kinetic considerations, the increase in temperature would increase the

initial rate of gold adsorption. When the gold loading is in equilibrium a

decrease in adsorption rates will result.

c) pH of the adsorption medium

Increase in the pH of the medium increases the gold adsorption

rates; A marginal decrease in gold adsorption capacity in the region

of 6-12 pH, whereas the gold capacity increases strongly at lower

pH levels.
d) Other process solution/pulp constituents

The activated carbon is most selective to gold adsorption. The metal

selection for adsorption is a complex displacement sequence. Gold is followed

by silver, but there is no well defined sequence of metal displacement may be

formulated. The adsorption is very sensitive to processing parameters like

pH and free cyanide concentration, temperature and relative concentration

of gold, silver and other base metals in a particular plant solution or pulp. In

general the selectivity of carbon for gold adsorption will increase with increase

in pH and free cyanide concentration.

e) Oxygen availability

Oxygen plays a dominant role in gold adsorption, cyanide oxidation

and in calcium carbonate deposition. In addition to this adsorbed oxygen also

influence the character of the surface active groups involved in gold

adsorption. The gold adsorption is adversely affected on treating solutions

devoid of oxygen (Davidson et ah1982 and Tsuehid&ef ah 1984). The actual

role played by oxygen dissolved in the adsorption medium and oxygen

adsorbed on the carbon surface are particularly difficult to define

quantitatively.

f) Carbon activity

The carbon activity and the rate at which the carbon adsorb gold

from the pulp or solution, controls the whole process of activated carbon
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technology. The lower activity results in low adsorption of gold in the first

stage. The thermal regeneration of the activated carbon, is required to maintain

the quality of the carbon. During adsorption of gold from cyanided pulp or

solution, unwanted organic and inorganic adsorption can accumulate within

the porous structure of the activated carbon. The consequent pore loss results

in the fall off of carbon activities experienced in practice. One of the two main

classes of adsorbates (organic and inorganic), which are poisoning the carbon

are the organic chemicals like, flotation chemicals, lubricants, oils etc in the

process stream, which are selectively removed from carbon during thermal

regeneration.

The following table shows the effect of flotation reagents on gold

adsorption rate. (Unpublished test results from Bharat Gold Mines, Kolar Gold

Fields, Karnataka).

Solvent Solids concentration Rate constant, K. for different


% m/m % m/m flotation reagents/h'1
K. Ethyl K. Methyl K.Amyl Pine MIBC
Xanthate Xanthate Xanthate oil

0.000 00 1850 1850 1850 1850 1850


0.005 00 1.250 1.110 — — —

0.020 00 0.950 1.02 — — —

0.050 00 0.400 300 — — —

0.050 50 700 650


0.500 00 — —
300 650 700
1.000 00 — —
200 350 250
2.000 00 — —
170 170 300
2.000 50 — —
400 560 550
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Possible mechanism of 'carbon poisoning' affects rate of loading but

not the loading capacity, due to the formation of a film of the solvent onto the
superfacial surface of the carbon granule (which creates a barrier to mass

transfer) without sufficient penetration of the solvent into the pores of the
granule. It is also significant that the influence of the organic solvent or circuit

organics as the rate of carbon loading is substantially reduced, in typical gold

process pulps. Indicating that the organic solvents adsorption by the solids,
there by reducing the effective concentration in solution on the carbon. The

effect of carbon fouling is not serious, provided highly active carbon is present

in the last adsorption stage or column. The gold escape adsorption in early
stages is forced downstream will be adsorbed readily by more active carbon.

$o to the possible extent it is advisable to avoid unnecessary contamination or

uses of such reagents.

g) Physical effects

All operating plants where gold loading onto the carbon should

not be allowed to approach equilibrium. At any stage it nears equilibrium,


the rate of adsorption decreases and any factor that influences the loading
capacity has a bearing on overall plant performance. The factors of activated
carbon usually influence the plant performance are carbon grain size, mixing
rate of pulp and pulp densities, fineness of grind and retention time of pulp

with carbon i.e. flow rate.


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h) Operational considerations

Efficient recovery is possible when balance between the amount of

carbon in the circuit and the amount of gold fed to the circuit is maintained.

For normal operating plant best results can be obtained by holding uniform

or even distribution of carbon in all the stages. Interstage transfer of carbon

within 5 or 6 stage operation is important. Frequent small transfers upsets the

adsorption kinetics and the carbon distribution per stage. The common

acceptable method of plant operation is sequential up-bank transfer. The rate

of mixing of carbon has a significant effect on the carbon activity. But a coarse

grind and/or low pulp density, the attrition loss is more due to constant contact

of carbon with impellers. The impeller blades reduce the mixing rate and also

reduces the attrition losses and increases setting rates of carbon and pulp.

The improper handling of carbon during the elution and thermal

regeneration cause for concern for the carbon loss. The pulp with high

pulp-density, say > 1. P.D. behaves as dense-media and reduce the carbon

settling rate and increase the adsorption rates, as all the carbon surface is

exposed to pulp equally.

5. CARBON UTILIZATION PROCESSES

The recovery of gold, utilizing activated carbon technology from

cyanided pulp/or cyanided-filtered mother liquor (Head liquor) is possible

under four conditions. Each of these conditions demand significantly different

process designs. These processes are as follows;


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a. Carbon-in-solution (C—I-S)

b. Carbon-in-pulp (C-I-P)

c. Carbon-in-leach (C-I-L)

d. Carbon-in-leach by oxygen (C-I-L-O)

a. Carbon-in-solution (C—I-S)

Activated carbon is packed in circular carbon columns, where in

filtered gold solution (sodium-aruo-cyanide solutions) is passed. Gold is

adsorbed onto carbon from the sodium aurocyanide solution. The barren

solution is leaving the columns is recirculated in the processes. The gold loaded

carbon is processed by continuous elution and electrowinning, the gold loaded

cathode smelting to produce gold bullion. Then the carbon is recirculated in

the process after thermal reactivation and acid treatment.

b. Carbon-in-pulp (C-I-P)

The activated carbon is directly mixed with the cyanide leached

gold ore pulp. The cyanided gold ore pulp is made to pass through the

activated carbon contactor, where in activated carbon is held in between the

thin stainless steel (usually 16 to 19#) mesh. The pulp and tide activated carbon

are kept under suspension by mechanical agitation compressed air, and by

density of the pulp. The compressed air is also used to keep the inter

compartmental screens clean, to avoid blocking of the mesh openings. The


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gold content from the leached gold ore pulp is adsorbed onto the activated

carbon and the barren pulp leaves the system. The gold loaded carbon is taken
for continuous elution and electrowinning for gold bullion recovery. The

carbon after elution is thermally reactivated and acid washed and recirculated

in the process.

c) Carbon-in-leach (C-I-L)

The activated carbon is added to the ore pulp in the mixing tanks

during cyanidation. The leached gold is directly adsorbed by the activated

carbon, as soon as it gets leached from the ore and before it forms the
complicated complexes. The carbon-in-leach (C-I-L) circuits usually

operates in association with linear screens or Kambalda screens. The gold


loaded carbon is taken out for elution and electrowinning to recover gold

bullion. Then the carbon recirculated later after thermal regeneration and acid

treatment.

d) Carbon-in-leach by oxygen (C-I-L-O)

This process is similar to C-I-L process except oxygen is used with


compressed air during cyanidation to aid gold dissolution by cyanide solution.

6. CARBON ADSORPTION SYSTEMS, (C-I-S)

These are numerous carbon adsorption systems developed in recent


past. The following ones are the popular ones.
.(T-v

>» V
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a) Gravity cascade system

b) Closed tank system

c) Deep fluidised beds

d) Moving packed bed columns

e) NIMCIX columns.

Each of these systems have advantages and disadvantages. The

employed system must give high metallurgical efficiency. This could be

achieved by proper correct contact of the carbon and solution. Channelling

and dead spaces and bypassing must be avoided and back mixing of either
phase is not advisable. Activated carbon level must be maintained. Attrition

during adsorption and carbon transfer should be minimum. The operation

must be viable and require the minimum of supervision. Finally capital and

working costs should be low.

7. DESIGN CONSIDERATIONS, (C-I-S)

The system design depends on the number of stages and the


inventory of carbon. This in turn depends on many factors like;

a) the gold concentration in the feed,

b) kinetics of gold adsorption,

c) the solution flow rate,

d) the carbon flow rate,


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e) carbon size, (the diameter of a fixed bed column),

f) affects of the loading of calcium carbonate within carbon along with

gold, and

g) the absorption of other base metals viz; Cu, Zn, and Ni and

also Ag and Pb.

8. MANUFACTURE OF ACTIVATED CARBON

Activation of the carbon is an important step in the manufacture of


activated carbon. Manufacture of activated carbon is carbonising the raw

material and then converting it into a fine crystalline form of carbon that is
permeated by the greatest possible number of randomly distributed pores of

various shapes and sizes. These pores give rise to the extended internal surface
area. In the manufacture of activated carbon, it is devisable to develop the

maximum accessible surface area that is commensurate with economic


viabilities and product application. The surface area of pulverised charcoal,

which is essentially external surface area, is only 2 to 4 m2/gm as against

typically 1000 m2/ gm for a granular activated carbon product. This is

measured by the nitrogen BET, (Brunauer, Emmett and Teller) method.

Activated carbon can be manufactured from any carbonaceous raw


material, and numerous patents have been granted for processes using such

diverse starting materials such as various ranks of coal (peat, lignite,


bituminous coal and anthracite), coconut shells, peach pips, apricot stones,
waste tyres, wood, saw dust, petroleum heavy oil, cellulose, rice husks, com
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cobs, bones eta. The manufacturing processes involves the removal of volatile

matter from the raw material. The economic relationship between the price,

availability and quality of the raw material on the one hand, and its volatile

content on the other hand. One of the advantages of bituminous coal and

anthracite coal is their relatively low volatile content (as shown in Table below)

and hence, their high yield and product.

Fixed Carbon Content of raw materials commonly employed


in the manufacture of activated carbon (after Holden 1982)

Material Approximate Carbon Content %

Soft wood 40

Hard wood 40

Coconut shell 40
T trmi’fp
60

Brituminous coal 75

Anthracite on

The suitable raw material at low cost like coconut shell and rice

husks have very high volatile content and give low yields of activated carbon.

The chemical nature of the activated carbon, the surface oxides,

active surface area, the pores, pores structure, sizes of pores, are largely

determined so the activation processs and the raw material employed for the

manufacture. The activated carbon is manufactured by two main methods

viz; - a) Wet Chemical Process : b) Physical or thermal gas process


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a) Wet Chemical process (Chemical activation)

The wet chemical process is generally employed to convert

uncarbonised cellulose material like wood into active carbon. The most popular

activating agent is phosphoric acid, zinc chloride, sulphuric acid, sodium

carbonate, sodium or calcium hydroxide, chloride salts of magnesium, calcium,

ferric iron and aluminium. These chemicals have in common their strength as

dehydrating agents.

The process using saw dust, rice husks, wood chips as the starting

material involves mixing often raw material and the dehydrating agents into

paste. The paste is dried and carbonised in special rotary kilns, between

temperature 300° to 650°C. On calcination the oxidising agents dehydrate the

raw material, resulting in changing and automatisation of the carbon skeleton,

with the concomitant creation of a porous structure and extended surface

area. This method yields a powder product. If a granular or grain sizes,

required with granular raw material the same procedure is repeated after

carbonisation. The activating agents are recovered and recycled for economic

reasons. All the commonly used chemical activators impose constraints on

the overall activation process and the equipments employed or on the quality

of the product. Mixtures of sulphuric acid and wood, cannot be heated above

200°C. This product, after leaching out sulphuric acid has the adsorptive

properties, only when wet. With phosphoric activation, require temperature

between 375 to 500°C and the reagent is readily leached out by use of water
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but the corrosion of equipments is the major problem. With zinc chloride

activation occurs at 550 to 650°C, the resulting activated carbon retains little

amount of zinc salts which creates further processing problem. So the activated

carbon produced with phosphoric acid and zinc chloride can be dried up

without any, loss of adsorptive capacity. The product activity can be controlled

by the addition of the calculated amount of activating agent and the raw

material viz., with phosphoric acid activation the proportion is between

1:0.5 and 1:4. The activation rate is measured by the number of pores

created, the pores created are increased by the amount of activating

agents, time of residence of material in kiln and the temperature of

activation.

b. Physical process (Thermal activation)

The first step under this method is carbonization, which is the

formation of char from the source material. Carbonisation is the process of

heating the source material, as lumps or grains, or powder (powder in

agglomerates form, or moulded form) in an inert atmosphere to a temperature

between 650° to 700°C, so that dehydration and devolatization of the carbon

atoms can occur in a controlled conditions. The purpose of carbonisation is to

reduce the volatile content (of the source material a fixed carbon content of 85

to 90% or higher percentage is desirable) to convert it to a suitable form for

activation. Rearrangement of the carbon atoms into graphitic like structures

also occurs during carbonisation.


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The process by which the carbonised product develops an extended

surface area and a porous structure of molecular dimensions is referred

to as activation. This step is generally conducted at temperature between 800°

and 1100°C in the presence of a suitable oxidising agents such as steam, air,

carbondioxide, or any mixture of the gases. The active oxygen is the

activating agent burns away the more reactive components of the

carbon skeleton like carbon monoxide or carbon dioxide, depending on the

oxidising agent employed. Although the burning out of the carbon

skeleton to create new pores is believed to occur at different rates

on different parts of the exposed surface, the detailed mechanism of this

process is not clearly understood.

The art of the manufacture lies in conducting the activation process

in such a way that combustion of the carbonised raw material occurs internally

and not from the exterior of the granules. The term bum-off is used to denote

the degree of activation, which is the loss of char (in percentage by mass) that

is allowed to occur. The bum off and the yield of activation can be related as

below.

A = 100 - Y - G

A = Activation, Y = yield of activation, G = Gases or volatiles

A typical flow sheet for manufacture of activated carbon is in the

next page:
37

Raw material

Carbonisation

V
Optional
Crushing/Screening to
the required fineness

Activation

i
Cooling

Screening

*F I'

U/F O/F
Fine carbon Granular carbon
(Bagging) (Bagging)

The most significant difference between the thermally activated


carbon to chemically activated carbon, is related to pore size distribution and
semi conductor properties. Chemically activated carbon are characterised by
a macroporous pore size distribution and these products therefore generally
have a high molasses number and comparatively low nitrogen BET and iodine
numbers. Such activated carbons are used mainly in applications, that require
38

the removal of large molecules from solution like decolourisation of sugar

syrups. The absence of semi-conductor properties relates to the fact that the

temperature generally employed in the manufacture is too low for the

formation of the graphitic zones, which is presumably responsible for the

semi-conductor redox properties of thermally activated products. (McDougall,

and Hancock, 1981). Again, the properties of thermally activated carbon

measured by a graphite-rod technique has been found to be typically above

0.14 V/Vs. the saturated calomel electrode at a pH value of 6. These carbon

can therefore function as reducing agents, and many of the intriguing

properties of thermally activated carbon, particulars their redox and catalytic

properties are believed to be related to their semiconductor properties. The

chemically activated carbons have a poor affinites for the sodium

dicyanoaurate anion. This property is useful in gold extraction, from a cyanide

solution.

The important unit operations that constitute the whole operation

are carbonisation and activation.

Carbonisation : Coconut shell is considered as the source raw material,

since the coconut shell results in hard granules. Carbonisation is

essentially a devolatization, which produces a char with a significantly higher

content of fixed carbon (between 70 and 85 percent) than is present in raw

coconut shells.
39

Activation : Before activation, the carbonised material is crushed, sized,

and freed from extraneous materials such as sand or large chunks of

it may be fed directly to the activation stage. Activation is usually

conducted in a directly fired rotary kiln, where the product is activated

at between 850°C to 1000°C in the presence of steam, air, flue gas,

or mixtures of these, for known time. The formation of higher porous

product is generally associated with the degree of burn off or loss in

mass of the char.

In the activation of carbonaceous materials, there are variable

like; a) The type of source material or quality of the char, b) The composition

of the activation atmosphere and flow rate of activating gases, c) The

temperature of activation and d) Duration of burn-off period. The

inter-relationship between the various activation parameters is complex

(Me Dougall, 1991).

The process flow-sheet using coal as the raw material is presented

next page.

Since the coconut based activated carbon are most suitable for gold

adsorption in solutions of aurocyanide and also coconut shell is available

abundantly in India in almost all southern states. The coconut industries have

grown up, as major exporters of activated carbon to South Africa, United States,
«

Canada, Japan, Australia, etc.


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Coal
I
Crushing and Sizing

t------------- Deashing
Grinding

£------------ Oxidation
'r
Binder/Blending with Binder

Sizing

( ------------- Oxidation
4/
Carbonisation
i'
Activation

( -------------Sizing
v
Granular activated carbon bin.
(Bagging)

9. LABORATORY TESTING METHODS FOR ACTIVATED CARBON

The activated carbon used in any gold ore processing plants are

selected on the basis of its qualities, and sorption rate (activities)

hardness, grain size required (different carbon grain sizes are required for

C-I-S, C-I-P, C-I-L and C-I-L-O, operations), its source of origin, either
natural (like coconut shell) or synthetic, bulk densities, abrasion
resistence etc. There are experimental difficulties in attempting to simulate
the plant environment in the laboratories in order to measure the

above properties.
41

The following table gives the details of tests recommended for fresh

or new virgin carbons, thermally regenerated process carbons and for other

plant carbons.

Tests Virgin or Regenerated Other plant


fresh carbons carbons carbon

Adsorption activity Required Required Required

Adsorption rate Reauired


X
Reauired
X Not reauired
X

Adsorption Required Not required Not required


coefficient (k-valuc)

Loading factor Required Required Not required

Elution Not required Not required For loaded carbons


only

Iodine or Benzene Required Required Not requried


number

Moisture content Required Required Not required

Volatile matter Required Reauired


X Requried

Ash content Required Required Required

Size distribution Required Required Required

Bulk densities Required Required Not required

Abrasion resistance Required Required Not required

Flake content Required Required No required


42

The laboratories testing schedules for virgin or fresh carbons to be

utilised in the process is given below:

Sample

Nlt
Divide

Moisture Size distribution

5re condition

Split
J L
Crushed Unsized fractions
powder

Sized fraction
1 I

v 7
K value Activities Adsorption rate
Iodine Number Loading
Elution
Volatiles
Ash
Bulk densities
Abrasion resistance

Testing procedures adopted

Testing of activated carbon is required to select a suitable carbon

for particular gold recovery process. Following properties are tested in the

present study before employing the activated carbon for recovery of gold;
43

1) Adsorption activity test

2) Adsorption rate

3) Adsorption equilibrium (k value)

4) Gold loading

5) Elution

6) Iodine number

7) Moisture, volatile and ash content

8) Size distribution

9) Flake content

10) Abrasion resistance.

These tests are required for testing both plant process carbons as

well as for selection of the fresh activated carbon for the process i.e. the vigrin

carbon. These tests are performed for indigenously manufactured carbons.

1) Adsorption activity test

Washed and screened fraction of activated carbon in three sizes

(-6+12, -12+18 and -18 mesh) are considered for this test. Three types of carbon

are used viz. Amar, Industrial and RRL carbons.

One liter of head liquor with gold value of 4 gms/ton of solution is

mixed with 50 gms of pre attrited and pre treated carbons of the fractions are

bottle rolled for 30 minutes. The liquor is analysed after 30 minutes and results

are tabulated in the next page.


44

Fractions Liquor analysis Percent of Activity %


size Adsorption

Amar carbons
-6+12 3.70 92.50 92.50
-12+18 3.80 95.00 95.00
-18 3.95 98.75 98.75

Industrial carbons
-6+12 3.75 93.75 93.75
-12+18 3.85 96.25 96.25
-18 3.97 99.25 99.25

RRL carbons
-6+12 3.80 95.00 95.00
-12+18 3.87 96.75 96.75
-18 3.98 99.50 99.50

Au content in head liquor is 4 gms/ton. All gold values are in gms/ton.

These fractions are used in C-I-S and C-I-P process. After using in

the process plants, these carbons are subjected to elution, electrowinning, acid

treatment, water wash, thermal reactivation at 650°C under steam. Later these

carbons are screened, quenched in hot dil-hydrochloric acid and water washed.

Further, these subjected to activity tests, as explained above. The results

obtained from activity tests for each fractions of these carbons are similar to

those of the activities of fresh virgin carbon.

2. Adsorption rate

The procedure for adsorption rate is same as for activity testing

except that, the carbons are not screened before testing, but only washed over

one mm screen to remove fines. There is positive relation between adsorption


45

rate in test results and in plant results. Thus the reduction in adsoprtion rate

constant means adeterioration in plant performance. So immediate corrections

in the necessary parameters is required.

3. Adsorption equilibrium (k-value)

The k-value is mainly of significance as an indication of the total

capacity of the carbon and its ability to adsorb gold on the final stages of the

C-I-P circuit. The gold on the eluted carbon returned to the circuit is noramlly

of the order of 60 to 100 gms/ ton of carbon. Carbons with a low K value will

have a low capacity and will not achieve these barrens-unless extremely well

eluted and regenerated. Use of such carbons will result in increased soluble

gold losses. There are two isotherms of gold adsorption.

a) Freundlich isotherm [Au]_ = Kf [A-l]a

(Some carbons do not fit in this isotherm)

b) Langmuir isotherm
[Au]c - KJAu]s
[Aul = --------------------------
[1 + Kl (Au)s]
(All carbons fit in this isotherm)

4) Gold loading

The main purpose of this test is to provide loaded carbon for the

elution test. 5 gms of pre conditioned carbon is bottle rolled with head liquor
46

(gold value 100 gms/ton), for 24 hrs. The head liquor and carbon are both

analysed for gold and are as below.

> Feed head liquor : 100 gms/ton

> Liquor analysis after bottle rolled for 24 hours : 0.001 gms/ton

> Gold adsorbed by carbon : 99.99%

5) Elution testing

100 grams of gold loaded carbon is refluxed with 500 ml cyanide

solution (0.1% NaCN and 1% NaOH at 90°C) for one hour. The solution

samples are withdrawn at the interval of 15 minutes for eluted gold analysis.

The results are given below.

Time Gold loaded Solution


Carbon analvsis
j
Analvsis
j

15 2.50 gms/kg 0.0010


30 2.00 " 0.0020
45 1.50 " 0.0030
60 1.45 " 0.0031

Au in feed carbon 3 gms/kg.

The above table indicates that the pattern and the total time required

for elution operation.

6) Iodine Number

10 grams of powdered carbon is bottle rolled with 100 ml of standard

iodine solution for one hour. The residual iodine in solution is measured. The
47

results are within a predefined range and the specific surface area of the carbon

is compared with the standard tables. In the plant scale this test is of little use,

but it is useful for thermally reactivated carbon before the carbon is recirculated

in the process.

7) Moisture, volatile and Ash content

10 gms of carbon is heated as shown below for the respective

properties.

Test Temperature Time

Moisture 110°C Twenty four hours

Volatile 950°C Seven minutes

Ash 750°C Twenty four hours

The moisture includes low boiling point organics and some adsorbed

inorganics, such as cyanide and carbonates may decompose at the temperature

used for the volatile and ash determinations. These tests are useful for mass

balance calculations and monitoring unit operations like acid treatment and

thermal regeneration.

8) Size distributions

500 gms of the thermally reactivated or fresh virgin carbon are

screened using standard sieves, before they are considered for any specific

purposes. The size distribution is given in the next page.


48

Mesh size Wt. in Cumulative Weight Processes


gms weight in gms per cent in gms

+2 - - -

-2+6 4 4 0.8 C-I-L-O

-6+10 115 119 23

-10+14 200 319 40 C-I-P &

-14+20 150 469 30 C-I-S

-20+25 25 494 5

-25 6 500 1.2 Rejected

9. Flake content

The flake content is measured by passing the carbon over the shape

sorter. The undersize of the shape sorter is collected and expressed as a

percentage of the total mass. The flakes content normally indicative of the

quality of the virgin carbon. Normally flakes pass through a slotted screen,

which sorts according to the minimum particle dimensions. The flake content

measurement is required for virgin carbon and is not necessary for plant or

process carbons. Usually 1 to 1.5% flake content is present in the Indian

manufactured carbon. The flake contents in carbon from different suppliers

are given in the next page.


49

Name of Flake
carbon supplier content in %

Amar 1.50

Gujarat 1.65

Industrial 0.80

Goa 1.00

RRL, Hyderabad 0.50

10) Apparent bulk density

A known mass of carbon is poured into a measuring cylinder. The

carbon volume is noted. The density is calculated. Most granular activated

carbons have a density of approximately 0.4 to 0.5 gms/ml. Extruded carbons

may deviate significantly from this value due to the different degree of packing

caused by the different particle shape. Process carbon are only carbons for

which this parameter is measured. The bulk density calculations has a direct

impact on carbon concentration measurements in C-I-P plants.

11) Abrasion resistance factor (ARF)

About 50 gms of preconditioned carbon is stirred with 200 ml water

for 30 minutes at 100 RPM. The carbon is recovered by screening, washing

and then by drying. The abrasion resistance factor is the mass percent of the

carbon recovered.
50

The test is to stimulate the wear pattern in actual C-I-P plant. The

carbon should show a comparatively low ARF. This would steadily rise to a

surface as the weaker particles are broken down and lost. If the carbon is not

made up with regular additions of new carbon, then the ARF would fall as

the carbon structure weakens due to continued recycling. This would indicate

a need to replace the carbon.

10. ELUTION AND ELECTROWINNING

Elution is stripping of gold form the gold loaded carbons and

simultaneous electrowinning of gold. All the gold loaded carbons from the

adsorption circuits from C-I-S, C-I-P, C-I-L, C-I-L-O etc are pumped to elution

and electrowinning circuit. Gross and Scott (1972) have studied a wide range

of inorganic compounds for eluting the gold cyanide complex adsorbed onto

carbon. Further they have stressed that KCN and Na2S04 are the best solvent

powders for the adsorbed gold. Zadra (1950) has shown that the caustic

cyanide solution at +93°C could be most effective. This solution is made to

pass through a bed of gold loaded carbon. The hot caustic cyanide (1 % NaOH,

0.1% NaCN, +93°C) solution desorb or strip the gold from the gold loaded

activated carbon. The solution carrying desorbed gold is fed to the circular or

rectangular electrowinning cell. The electrolytic cell is with stainless steel

anode and stainless steel cathode wrapped with steel wool. (Grade 2, ISI).

The gold from the solution gets deposited on the cathodes. Depending upon

the quality of loading and amount of gold loading onto the cathodes. They
51

are removed and the new cathodes are introduced to the electrowinning cell.

Since the elution and electrowinning are in close circuit and continuous and

simultaneous, cycle of operation is continuous till the gold content in carbon

come down to lowest level say 60 to 80 gms/ton of carbon. This whole

operation of one cycle may take from 48 to 68 hours and even some time 72

hours. This depends on the stripping efficiency of the solution and the gold

loading on the carbon. The gold loaded cathode are removed and acid treated

with hydro chloric acid or by nitric acid to dissolve the steel wool. The resulting

precipitate is dried at 100°C/ fluxed and smelted to produce gold bullion.

The above stripping takes normally very high operating time for

every cycle (48 to 72 hrs) which led to the development of a pressure stripping

method. This method reduces the stripping time and improve overall operating

performance of the stripping process. In this process high pressure (350 kpa

or 50 psi) and temperature 160°C are used. This process reduces the total

stripping time by 72 to 6 hrs and also reduces reagent consumption, carbon

inventory and size of stripping section. However, tire use of high pressure and

temperature needs extensive cooling of solutions before pressure reduction.

This involves high capital cost on the installation and lot of instrumentation.

MINTEK, S. Africa has introduced alcohol stripping. This has brought down

the stripping time 12 to 18 hours by enhancing stripping rate. The hazards

connected to the process and highly evaporative nature of alcohol, requires

more precautions and highly sophisticated controls. Due to this reason this

method is not practicable under the circumstances.


52

Davidson (1974) has developed a stripping process which involves

pre conditioning the loaded carbon with half a bed volume of 5% NaOH and

1% NaCN for 30 minutes to 1 hour and then stripping the carbon with 5 bed

volumes of hot (110°C) water at a flow rate of three bed volume/hour. The

high operating temperature imposes an operating pressure of 50 to 100 kpa.

The high operating temperature imposes an operating pressure of 50 to 100

kpa. The total cycle time including acid pre washing is nine hours.

A simplified flowsheet of the elution circuit is shown below :

Flow sheet of elution

/fr-> Stock solution Stripping solution


and heating tank ------------------ > (1% NaOH and 0.1% NaCN
+ 93°C)
NaCN T
+ ie Loaded carbon chamber
NaOH usually one ton capacity
'l'
Eluted, gold loaded stripping
solution
k— Pump 4- Solution <-
I
Electrolytic cell — 6 volts and
100 Amps.
' *

Gold loaded cathode

Acic treatment
Calcination
Fluxis

Carbon after one cycle i-------- Golcf Bullion


of stripping
4
Washed with water
HC1 acid treated
Waterwashed
Thermal regeneration & screened
T—> Quenching in mild acid
and water washed recirculated
to adsorption circuit.
53

11. GOLD RECOVERY FROM GOLD LOADED CATHODE

The gold loaded cathodes from the electrowinning cells are treated

by two methods viz. (a) Calcining and smelting cathodes (b) Acid treating

and smelting cathodes.

a) Calcining and smelting cathodes

Gold loaded cathodes are rinsed in clean water and loosely

packed into stainless steel calcining trays and oxygen is passed. Nitre

or manganese dioxide is added to assist oxidising process. Calcination

is performed between 600°C and 800°C for 12 to 16 hours. Calcined

cathodes are smelted in a oil fired pit furnace or electrically fired or heated

furnaces.

b) Acid treating and smelting cathodes

Cathodes are rinsed with water to remove the cyanide, then

acid treated in a mechanically agitated tank, with either 10 to 20% HC1

or 10% H2S04. The steel wool is digested for 1 to 2 hours. Heating the

acid to 60° to 80°C accelerates the reaction. After acid treatment the

solids are allowed to settle. The solution is decanted and filtered and

dried and smelted by using the following flux combination to produce gold

bullion of better quality than the earlier process.


54

Calcined cathodes 100 parts

Borax 60 to 80 parts

Sand (silica) 10 to 40 parts

Sodium carbonate 5 to 35 parts

Nitre 5 to 35 parts

12. THERMAL REGENERATION OF ELUTED CARBON

During the process period that the carbon is in contact with pulp, it

is progressively poisoned and its activity is reduced. It is essential that the

carbon added to the circuit is as active as possible to counter act this loss, due

to deactivation or fouling. This can be achieved by restoring the activity of

the carbon before it is recirculated. About 5% of the fresh carbon is added

with regenerated carbon for each cycle. Therefore the activity of the carbon in

the circuit is very dependent on the efficiency of the regeneration system.

If a carbon has been loaded with a heterogeneous mixture of

adsorbates, as would be present in a gold plant process stream. Only partial

restoration of activity is usually achieved using chemical regeneration

techniques. Thermal regeneration techniques are effective in restoring the

activity of carbon loaded with organic adsorbates. The thermal regeneration

could be carried out in various furnace system viz; rotary kiln, fluidised bed

furnaces, multiple hearth furnace, electrical resistance furnace, conveyor or

shaking hearth furnace, vertical kilns and infrared furnace. Normally,

horizontal kiln is under practice.


55

The object of regeneration is to remove selectively adsorbates that

have accumulated during the adsorption operation, then recovering the

original porous structure and activity with as little damage as possible to the

activated carbon itself. Thermal regeneration involves three types of reaction

corresponding to three types of adsorbates as the spent carbon (VanVliet, 1985).

Type I - Thermal desorption of volatile organic compounds initially adsorbed

on the activated carbon, but not irreversibly bound to active surface sites.

Type II - Thermal decomposition (cracking) of organic compounds not

efficiently volatile for thermal desorption and/or which are tenaciously bound

to surface sites.

Type III - Pyrolysis of the remaining compounds with the concomitant

deposition of a carbonaceous residual compounds involved in this type of

reaction are critical to regeneration considerations.

Since the carbonaceous residues has to be removed selectively, in

practice this is achieved by the use of endothermic steam or carbondioxide

oxidation at comparatively high temperature. Within this temperature domain

energy losses increase significantly, equipment specifications become more

stringent and costly and activated carbon losses invariably occur, concurrent

with the oxidation of pyrolysed adsorbate residuals.

In reality, many organic adsorbates will display combinations of

type I, II and III behaviours.


56

The following steps usually occur during thermal regeneration of a

spent carbon.

a) Drying including loss of highly volatile adsorbates - below 200°C.

b) Vaporisation of volatile adsorbates and decomposition of unstable

adsorbates to form volatile fragments (about 200-500°C).

c) Pyrolysis of non volatile adsorbates, with the deposition of a

carbonaceous residue on the activated carbon surface (about 500-

700°C).

d) Selective oxidation of the pyrolysed residue (above 700°C) using

steam or carbondioxide.

The first three steps, viz; drying, vaporisation and pyrolysis,

normally proceed with few complications. The pyrolysis step, however, should

not be conducted above temperature 850°C.