CHAPTER NO.

DECOLOURISATION OF RAW SUGAR MELT OR CLARIFIED

MELT BY POWDERED ACTIVATED CARBON

5.0 CLARIFICATION PROCESSES FOLLOWED IN THE WORLD SUGAR

REFINERIES.

In recent years, it has been necessary for sugar factories to produce

high quality raw sugar for export or use raw sugar for production of
good quality refined or semi refined white sugar for direct consumption.

It is almost universal for sugar refineries to use either Carbonation or

Phosphatation process to clarify the melt liquor. These processes have
helped in removing finely divided particles of Insoluble matter and
Colloids and also eliminated significant amount of colour and other non
sucrose impurities which otherwise have given higher and expensive
load on decolurising methods.

Further the clarified melt liquor is to be decolourised by Powdered

activated carbon or by Granulated activated carbon or by Ion Exchange
methods before sending it for crystallization.

5.1 DESCRIPTION OF CARBONATION AND PHOSPHATATION PROCESS

IN NUTSHELL.

A.S. Vawda4, Savola Sugars Middle east in his paper entitled as. “A
comparative evaluation of Carbonatation and Phosphatation” which
gives differentiation between the two processes. Carbonation is
supposed to be the most effective technical and commercial solution
in sugar refining. Considering the increased / decreased prices of
Chemicals such as Phosphoric acid, Lime, Fuel etc and improved quality
of raw sugar, one can decide for process by considering the economics.

Jamal Al Ghurair, Antonino Longakit and Shekhar Pachpute39 in their

paper entitled as, “Modification of the Carbonatation Process in the Al-
Khaleej sugar, L.L.C.” studied the modification of Carbonatation station in

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the refinery and also by determining the slurry resistance created in
carbonated liquor filtration by using laboratory filtration apparatus.

The calculations of Slurry resistance created by carbonated liquor of

different raw sugar types was studied and compared with the Specific
resistance of filter from the operation instructions of PUTSCH77 -
Filtration Coefficient measuring Instrument.

In some cases, carbonation would be suitable because of use of

cheaper and freely available chemicals while in other cases,
phosphatation would be more appropriate because of local conditions.

Leo Briones46 in his paper on, “Comparison of Carbonation and

Phosphatation Process of clarification for sugar solutions” highlights of
technical review for decision making over either of clarification process
for new sugar refineries with respect to local conditions.

Carbonation process of raw sugar refining is considered to be cheap

and robust process. The Process consists of adding slurry of Calcium
Hydroxide in water to the raw melt solution of about 60°Bx. The Carbon
dioxide gas is bubbled into the sugar solution in Carbonators or
Saturators under controlled conditions of pH and temperature. The C02
gassing is followed in two stages with major parts of gassing is carried out
in first saturator.

The impurities and coloring matters are adsorbed by Calcium carbonate

precipitate formed due to reaction between calcium hydroxide and
Carbon dioxide gas. The final pH of the carbonated liquor remains as 8.2
to 8.3. The precipitated liquor is separated into Clear liquor and Calcium
carbonate by Pressure filtration and desweetening of Calcium Carbonate
is further continued. The significant portion of Calcium Carbonate cake is
required to act as filter aid and its growth is important as colour removal.

One of the major objectives of carbonatation is the removal of impurities

present in raw sugar entering in the refinery. These impurities have
profound effect on filtration of liquor and if remain in solution will
adversely affect sugar crystallization and refined sugar quality also.

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Phosphataion / Floatation process consist of precipitating insoluble
Calcium Phosphate in hot raw melt liquor of 60°Bx by adding Phosphoric
acid followed by Calcium hydroxide either as a slurry with water ( Milk of
lime) or dissolved in sugar melt as lime sucrate to give final pH in the
range of 7.10 to 7.20.

The process produces Calcium phosphate floe which is filtered with

difficulty hence micronized air floatation is commonly used to separate
precipitated solids from the liquor in frothing clarifiers.

During flocculation and in the course of rising through the liquor, the
floccules collects most of the suspended impurities in the solution.
Impurities such as gums, waxes, fine particles are swept from the
liquor and appear at the surface as scum.

The scum which is removed by skimming device is complete separation

of precipitate and impurities without using settling or filtration.

In phosphatation process, application of colour precipitants as Cationic

flocculent is used which precipitates anionic high molecular weight colour
and other impurities and subsequently removed in floatation scum.

Table No. 37: COMPARATIVE BETWEEN CARBONATION AND

PHOSPHATATION PROCESS

Sr. No. Parameters Carbonation Phosfloatation

1 Colour Removal % 40 to 50 30 to 40
2 Insoluble solids 95 to 99 50 to 70
Removal %
3 Ash Removal % Negligible 0 to 20
4 Sucrose Inversion % Nil 0.005 to 0.010
original liquor
5 Turbidity 90 to 95 % 90 to 92 %
6 Dextran Removal Not effective Not effective

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5.2 CHOICE OF OPTIMUM DECOLOURISATION SCHEME IN REFINERY :

Bardwell et al7 showed that colour formation in the refinery can be

high up to 60 to 90% of incoming liquor and it is directly related to

Temperature, Retention time and aeration of liquor in the refineries.
Dr. Chung Chi Chou20, in his paper entitled as , “Process development

projects for the new Millenium" explained about decolourisation methods

and its limitations. Granular Activated Carbon (GAC) system is excellent in
decolonization, but lack buffered capacities resulting in higher sucrose
loss through the system. Comparing to ion exchange resin decolorization
system, GAC process is more capital intensive. Both systems do not
remove ash which is an essential step with high ash raw sugar. The
disposal of dark brine, regenerated from ion exchange process pose
environmental problem, particularly in the future.
Nick Jackson68, Brimac, in his paper entitled as .“Decolourisation of liquor

by char “gives the expected removal of colour by looking at the

formation and structure of colour. It looks at the physical and chemical
properties which enable char to remove the colour. Finally, the methods
for evaluation of the individual aspects are addressed, with a view to
establishing guide lines for the evaluation of new char.
Francis Gula and Dominique Paillat28, Applexion, France reported in

their article presented in International Sugar Journal April 2005, Page 235
-240 entitled as, “Decolourisation of Refinery liquors : A technical and
economical comparison between the different systems using activated
carbon or Ion exchange resins” that purpose of efficient decolourisation
process is to remove the colorants formed during manufacturing
process by understanding their behavior. The sugar colorants are a
very complex mixture of organic compounds from various origins. They
can be categorized as Natural colorants resulting from cane and those
developed during juice processing. The Classification of colorants
is given as follows.

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 Table No. 38: CLASSIFICATION OF COLORANTS IN CANE JUICE
PROCESSING:

Natural Colorants Colorants developed during Juice

processing.

Flavonoids Melanins Chlorophylls Melanoidins Caramel HADPs

Xanthophyils (Maillard (Glucose (Hexose
Carotene Reaction &Fructose Alkaline
Products) degradation degradation
in acidic Products)
media)

Van der waals forces are main attractive forces between chemical
groups in contact. Van der waals force bonding is the main adsorption
mechanism taking place on the surface of activated carbon.
Luis S.M. Bento et. al51 /53. Symposium for S.l.T. paper No. 716, “Sugar

Colour in Refineries.” and ISJ Vol.105 / 2003 on “Technological colour

control of sugar Products” discussed about Color in cane sugar, raw or
refined is made up of many different compounds. These compounds can
be classified in several ways by origin, whether they come from the
sugarcane plant or are generated in processing from non-colored
compounds: by degree of color or by chemical structure and properties.
This classification was based on the work of the late Dr. Peter Smith, of
CSR Ltd., on colorants in sugarcane juice. The four types of colorant
were" Plant pigments (Phenolics, flavones, anthocyanins ) Maillard
reaction products (browning reaction - amines and sugars ) Caramels -
(thermal degradation of sugars) and Alkaline degradation products (ADF).
Mary An Godshall, Vercellotti John R and Triche Ron58 in the article

Comparison of Cane and Beet sugar macromolecules processing,

published in International sugar journal Vol.104, 2002 page No. 228 -233
have given with the basic studies made that transfer of colour from
Syrup to crystal is much higher in cane sugar processing than in
beet sugar processing. Beet sugar having 20-30 ID colour obtained
from syrup of 2000-3000 IU while same colour is possible from Syrup of

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200 1U in cane processing.. The paper further highlights on studies of
colorant and polysaccharides in beet and cane sugar. The results
indicates that beet and cane colorants are fundamentally different. Beet
colorant tends to produce colors from alkaline degradation of invert and
melanoidin formation. While cane colorant enters the process in the cane
juice as plant pigments associated with polysaccharides.
Michel Mabillot63, concluded in his paper , “Granular activated carbon
decolourisation”-The diversity of sugars which have been processed since
the installation of the GAG unit has shown the great adaptability of
granular activated carbon to the different varieties of colouring substances
of raw cane sugar. Sub-contracting of the reactivation work has given us
entire satisfaction.
G. M. Hubbard and G.B. Dalglish30, in the paper -“Decolourisation of
carbonated liquor using the ISEP ® principle of continuous ion exchange"
mentioned about Advanced Separation Technologies have developed
and patented a system that is able to separate and recover specific
materials from liquid streams in a continuous ion exchange process. The
ISEP Continuous Contactor is claimed to have the flexibility to achieve
substantial reductions in resin usage and regeneration chemical
requirements in carbonated liquor decolourisation process.
S.B. Davis83, in his paper- “ Color Removal with Ozone in Cane sugar
Processing” shown that there is good potential for ozone as a colour
removal agent in the sugar refining industry and that very high colour
removals can be achieved. However, further work still needs to be done to
understand the chemical reactions that take place, the specific
compounds that are oxidised and the resulting products formed.
M Moodley, SB Davis and M Adendorff55 in their paper entitled as, Full
scale decolourisation trials with ozone at the Male lane refinery” have
given observations of using Ozone as decolourising agent. Ozone has
been shown to be a powerful chemical for the destruction of colour bodies
and colour precursors in sugar solutions and it has a great potential for

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use in refineries. The advantage of ozone is that it destroys some of the
bacteria, yeasts and moulds in the melt. The possible disadvantage that it
was thought to hold of destroying sugars appears not to be valid, given
proper control of pH, which is usual in refineries in any case.
Peter Rein76, in his book, “Cane sugar Engineering hand book” has
given details about Identification of colorants, Colour formation in raw
sugar mill, colour formation in refinery and colour inclusion in sugar
crystals. He has also given the details about comparative in different
decolourisation processes, which are summarized as given below.
Table No. 39: COMPARATIVE OF DIFFERENT DECOLOURISING
PROCESSES.
Particulars Bone Char Granular Ion Powder
Carbon Exchange Carbon
Capital cost Very high High Medium Low
Regeneration Separate Sep. Loading Same equip. Regeneration
Loading and with high temp for loading / is not
Reg. vessels. Kiln. regeneration suitable
Operating Cost High Medium Low Very high
Cycle time 4-5 days 3-6 week 24 hrs. Maximum
two passes/
Cycle
Usage 50-150 5-8 0.08-0.150 0.60 - 3.00
(Kgs / T melt) lits / ton melt
Effective Medium High Medium to Very high
decolourisation high
Colorant / Ash Colour & some No ash Mostly color No ash
Removal ash removal Removal removal. Removal
Plant Flexibility Low Highly Moderate Highly
Ash inhibits Ash not affect High ash Ash not
decolourisation decolourisation inhibits dec. affect decol.
Environment Flue gas & Minor flue gas Major Minor solid
-Effluent dust effluent waste

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5.3 POWDERED ACTIVATED CARBON IN DECOLOURISATION :

V. E. Baikow101, in the book, “Manufacturing of Refined and Raw

sugar” - Alternative decolourising Method, page No. 356 to 361
discussed about Powdered activated carbon, Advantages of Powdered
carbon, Treatment with PAC, injection of carbon slurry in to solution to
be treated, pH adjustments etc.
M. Asadi67, in the book, “ Beet sugar Handbook” have described the
process of decolourisation by activated carbon mentioning that, it not only
removes colour but also colloids, unpleasant odour, Odour causing
substances and foam causing substances- saponins. PAC application
can remove colour up to 50 % but it is mostly depend upon Particle size,
and surface area.
Lennitech110, Adsorption/Active carbon in web site,” www.Lennitech.com”
highlighted the description of adsorption process, exhaustion during
usage of carbon and factors that influence • the performance of active
carbon in air etc.

Jacobi Carbons37, are producers of premium activity adsorbent,

.manufactured using chemical activation ( H3PO4) of selected grade of
wood. This material has a predominantly macro porous structure for
efficient diffusion and effective adsorption of high molecular weight
organic substance in liquid phase decolourisation applications. The
chemical activation process produces an adsorbent with a surface pH
designed to maximize decolourisation performance. Strict control of the
particle size is used to optimize adsorption kinetics and assist with
efficient filtration.
NORIT69, Activated carbon website,"www.Norit-americas.com", explained
the details of activated carbon basics i.e. adsorption, Carbon types and
surface area. Adsorptive tests, Influencing performance of Particle size
distribution, Molasses number and decolourisation efficiency etc.
Robert J. Potwara and Larry R. Ingle and Dennis O. Rester80 1 81
entitled paper as “Powdered Activated Carbon - A new generation of
sugar refining” mentioned about manufacturing of PAC by grinding

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 with wide range of particle sizes and it affects filtration characteristics of
liquor. But New generation “RAC” reduces cost of filtration and improve
sugar quality by using layer filtration technology.
Activated carbon, also called activated charcoal or activated coal, is
carbon material mostly derived from charcoal. For all three variations of
the name, "activated" is sometimes substituted by "active". It has an
exceptionally high surface area. Due to a high degree of micro porosity,
just one gram of activated carbon has a surface area of approximately 500
m2 as determined typically by nitrogen gas adsorption.
Sufficient activation for useful applications may come solely from the high
surface area, though further chemical treatment often enhances the
adsorbing properties of the material.

5.3.1 PROPERTIES :

A gram of activated carbon can have a surface area in excess of 500 m2,
with 1500 m2 being readily achievable. For comparison, a tennis court is
about 260 m2. Carbon aero gels while more expensive, have even higher
surface areas and are used in special applications.

Under an electron microscope, the structure of activated carbon looks a

httte like ribbons of paper that have been crumpled together, intermingled
wtth wood chips. There are a great number of nooks and crannies and
many areas where flat surfaces of graphite-like material run parallel to
each other separated by only a few nanometers or so. These micro pores
provide superb conditions for adsorption to occur, since adsorbing
material can interact with many surfaces simultaneously. Tests of
adsorption behavior are usually done with nitrogen gas at 77°K under high
vacuum but in everyday terms activated carbon is perfectly capable of
producing the equivalent by adsorption from its environment, liquid water
from steam at 100 °C and a pressure of 1/10,000 of an atmosphere.

Physically, activated carbon binds materials by Van der Waals force

or London dispersion force.

Activated carbon does not bind well to certain chemicals, including

alcohols, glycols, ammonia, strong acids and bases, metals and most
morganic such as lithium, sodium, iron, lead, arsenic, fluorine and boric
acid. Activated carbon does absorb iodine very well and in fact the iodine

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 number (mg/g) (ASTM D28 Standard Method test) is used as an indication
of total surface area.

Activated carbon can be used as a substrate for the application of various

chemicals to improve the adsorptive capacity for some inorganic (and
problematic organic) compounds such as hydrogen sulfide (H2S),
ammonia (NH3), formaldehyde (HCOH), radioisotopes iodine-131 (131l)
and mercury (Hg). This property is known as chemisorption.

5.3.2 CLASSIFICATION:

Activated carbons are complex products which are difficult to classify on

the basis of their behavior, surface characteristics and preparation
methods. However, some broad classification is made for general purpose
based on their physical characteristics.

Powdered activated carbon (PAC)

Traditionally, active carbons are made in particular form as powders or

fine granules less than 1.0 mm in size with an average diameter between
0.15 and 0.25 mm. Thus they present a large surface to volume ratio with
a small diffusion distance. PAC is made up of crushed or ground carbon
particles, 95-100% of which will pass through a designated mesh sieve or
sieve. Granular activated carbon is defined as the activated carbon being
retained on a 50-mesh sieve (0.297 mm) and PAC material as finer
material, while ASTM classifies particle sizes corresponding to an 80-
mesh sieve (0.177 mm) and smaller as PAC. PAC is not commonly used
in a dedicated vessel, owing to the high head loss that would occur. PAC
is generally added directly to other process units, such as raw water
intakes, rapid mix basins, clarifiers, and gravity filters.

Granulated activated carbon (GAC)

Granulated activated carbon has a relatively larger particle size compared

to powdered activated carbon and consequently, presents a smaller
external surface. Diffusion of the adsorbate is thus an important factor.
These carbons are therefore preferred for all adsorption of gases and
vapours as their rate of diffusion are faster. Granulated carbons are used
for water treatment, deodorization and separation of components of flow
system. GAC can be either in the granular form or extruded. GAC is

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 designated by sizes such as 8x20, 20x40, or 8x30 for liquid phase
applications and 4x6, 4x8 or 4x10 for vapour phase applications. A 20x40
carbon is made of particles that will pass through a U.S. Standard Mesh
Size No. 20 sieve (0.84 mm) (generally specified as 85% passing) but be
retained on a U.S. Standard Mesh Size No. 40 sieve (0.42 mm) (generally
specified as 95% retained). AWWA (1992) B604 uses the 50-mesh sieve
(0.297 mm) as the minimum GAC size. The most popular aqueous phase
carbons are the 12x40 and 8x30 sizes because they have a good balance
of size, surface area, and head loss characteristics.

5.3.3 PROPERTIES OF ACTIVATED CARBON:

Iodine Number

Many carbons preferentially adsorb small molecules. Iodine number is the

most fundamental parameter used to characterize activated carbon
performance. It is a measure of activity level (higher number indicates
higher degree of activation), often reported in mg/g (typical range 500-
1200 mg/g). It is a measure of the micropore content of the activated
carbon (0 to 20 A, or up to 2 nm) by adsorption of iodine from solution. It is
equivalent to surface area of activated carbon between 900 m2/g and 1100
m2/g. It is the standard measure for liquid phase applications.

Molasses Number

Some carbons are more adept at adsorbing large molecules. Molasses

number or molasses efficiency is a measure of the macropore content of
the activated carbon (greater than 20 A, or larger than 2 nm) by adsorption
of molasses from solution. A high molasses number indicates a high
adsorption of big molecules (range 95-600). Molasses efficiency is
reported as a percentage (range 40%-185%) and parallels molasses
number (600 = 185%, 425 = 85%). The European molasses number
(range 525-110) is inversely related to the North American molasses
number.

Tannin

Tannins are a mixture of large and medium size molecules. Carbons with
a combination of macropores and mesopores adsorb tannins. The ability
of a carbon to adsorb tannins is reported in parts per million concentration
(range 200 ppm-362 ppm).

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Methylene blue
Some carbons have a mesopore structure which adsorbs medium size
molecules, such as the dye Methylene Blue. Methylene Blue adsorption is
reported in g/100g (range 11-28 g/100g).

Apparent density
Higher density provides greater volume activity and normally indicates
better quality activated carbon.

Hardness/abrasion number

It is a measure of the activated carbon’s resistance to attrition. It is

important indicator of activated carbon to maintain its physical integrity
and withstand frictional forces imposed by backwashing, etc. There are
large differences in the hardness of activated carbons, depending on the
raw material and activity level.

Ash content

It reduces the overall activity of activated carbon. It reduces the efficiency

of reactivation. The metals (Fe203) can leach out of activated carbon
resulting in discoloration. Acid/water soluble ash content is more
significant than total ash content.

Carbon tetrachloride activity

Measurement of the porosity of an activated carbon by the adsorption of

saturated carbon tetrachloride vapour.

Particle size distribution

The finer the particle size of an activated carbon, the better the access to
the surface area and the faster the rate of adsorption kinetics. In vapour
phase systems, this needs to be considered against pressure drop, which
will affect energy cost. Careful consideration of particle size distribution
can provide significant operating benefits.

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5.4 PRINCIPLE AND THEORY OF ADSORPTION

Adsorption6, weikipedia, The free encyclopedia explains in detail about

adsorption is a process that occurs when a gas or liquid solute
accumulates on the surface of a solid or more rarely a liquid (adsorbent),
forming a molecular or atomic film (the adsorbate). It is different from
absorption in which a substance diffuses into a liquid or solid to form a
solution. The term sorption encompasses both processes while desorption
is the reverse process.

Adsorption is operative in most natural physical, biological and chemical

systems and is widely used in industrial applications such as activated
charcoal, synthetic resins and water purification. Adsorption, ion exchange
and chromatography are sorption processes in which certain adsorptive
are selectively transferred from the fluid phase to the surface of insoluble,
rigid particles suspended in a vessel or packed in a column.

Similar to surface tension, adsorption is a consequence of surface energy.

In a bulk material, all the bonding requirements (be they ionic, covalent or
metallic) of the constituent atoms of the material are filled. But atoms on
the (clean) surface experience a bond deficiency because they are not
wholly surrounded by other atoms. Thus it is energetically favorable for
them to bond with whatever happens to be available. The exact nature of
the bonding depends on the details of the species involved but the
adsorbed material is generally classified as exhibiting physisorption or
chemisorption.

LK. A Edye44, Queensland Australia and G. Kahn44, Carbochem USA in

the paper entitled as, “Activated Carbon in Sugar and Soft drinks
manufacture.” described the use of activated carbon in sugar refining
industry with brief explanation on adsorption property. The paper
further deals with the acid floe problem occurring in soft drink

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industry. The rectification of acid floe problem was noticed in sugar
produced. In the Carbonation refinery, sugar has no acid floes while
phosphatation refinery sugar noticed acid floe due to pH and
temperature of the process.

Luis Bento54, in his paper, “Activated carbon adsorption of sugar

colorants and chemical regeneration” discuss regarding Colour in Sugar
solutions consists of complex mixture with cane juice or formed
during the' process. The activated carbon having the fine pore
structure and high surface area results in high adsorption capacity
for sugar colorants. The studies made evaluates major sugar
colorants such as HADP, melanoidins and caramels.

Francis GULA, Dominique PAILLAT28 on, “Decolourisation of

Refinery Liquors” reviews the latest developments and focusing on the
technical and cost/performance aspects of activated carbon and ion
exchange processes. Nowadays the environmental constrains are
increasing and the energy cost is quite volatile, therefore it is essential to
consider these aspects before selecting a decolourisation process. Further
the paper deals with the comparison of decolourisation effect of IER
(Ion Exchange resin) and Activated Carbon.

Benhur Rodolfo Pabon, et al8. on, “Improving the Efficiency of Carbon /

Diatomaceous Earth Filtration in Sugar Refining using the Carbo-UA

Process” discussed on the utilization of Powder carbon (PAC) and
diatomaceous earth (DE) is a well established purification method in
sugar refining. Carbo-UA has sought methods of optimizing and improving
the overall process efficiency of Sugar Refineries currently using PAC/DE
filtration. Authors have defined several parameters as success criteria for
improving the PAC/DE filtration process.

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 Dr. Chung Chi. Chou21, Domino Sugar Corp. and Jasovsky, Graver
chemical Co. Advantages of Ecosorb' Precoats “ discussed about the
Adsorption Isotherms of adsorbing materials. The initial plant data
indicates that the liquid sugar operations at Domino Sugar's Baltimore
and Brooklyn locations can be operated with less solid waste and more
economically utilizing Ecosorb +S-405 than with their typical powdered
carbon and DE processes.
5.4.1 ADSORPTION ISOTHERMS:

Adsorption is usually described through isotherms that is functions which

connect the amount of adsorbate on the adsorbent with its pressure
(if gas) or concentration (if liquid).

Freundlich isotherm :

The first isotherm is due to Freundlich and Kiister (1894) and it is a

x T _i
— = kPn
purely empirical formula valid for gaseous adsorbates: m , where
x is the adsorbed quantity, m is the mass of adsorbent, P is the pressure
of adsorbate and k and n are empirical constants for each adsorbent-
adsorbate pair at each temperature. The function has an asymptotic
maximum. As the temperature increases, the adsorbed quantity rises
more slowly and more pressure is required to achieve the maximum.

Langmuir isotherm

In 1916, Irving Langmuir published a new isotherm for gases adsorbed on

solids, which retained his name. It is an empirical isotherm derived from a
proposed kinetic mechanism. It is based on four hypotheses:

1. The surface of the adsorbent is uniform,i.e.all adsorption sites are equal.

2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.

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4. At the maximum adsorption, only a monolayer is formed: molecules of
adsorbate do not deposit on other already adsorbed but molecules
of adsorbate only deposit on the free surface of the adsorbent.

These four points are seldom true: there are always imperfections on the
surface, adsorbed molecules are not necessarily inert the mechanism is
clearly not the same for the very first molecules as for the last to adsorb.
The fourth condition is the most troublesome, as often more molecules
can adsorb on the monolayer, but this problem is solved by the BET
isotherm.

Langmuir suggests that adsorption takes place through this mechanism:

A{g)+ S — AS, where A is a gas molecule and S is an adsorption site.

The direct and inverse rate constants are k and k-i. If we define surface
coverage, 0, as the fraction of the adsorption sites occupied in the
equilibrium we have,

k
K= KP
e=
k-i (1 - 9)P or 1 + KP

For very low pressures 9 ~ KP and for high pressures 0~ 1

0 is difficult to measure experimentally; usually, the adsorbate is a gas and

the adsorbed quantity is given at standard temperature and pressure
(STP) volume per gram of adsorbent. Therefore, if we call vmon the STP
volume of adsorbate required to form a monolayer on the adsorbent (per

0= —
gram of adsorbent too), vmon and we obtain an expression for a
straight line:
'
i I

+
II

Kv man. •
^

Vimon

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Through its slope and y-intercept, we can obtain vmon and K, which are
constants for each adsorbent / adsorbate pair at a given temperature. vmon
is related to the number of adsorption sites through the ideal gas law. If we
assume that the number of sites is just the whole area of the solid divided
into the cross section of the adsorbate molecules, we can easily calculate
the surface area of the adsorbent. Surface area of adsorbents depends on
their structure, the more pores they have, the greater the area, which has
a big influence on reactions on surfaces. If more than one gas adsorbs on
the surface, we call QE the fraction of empty sites and we have,

Frumkin isotherm

Frumkin isotherm is an extension of Langmuir isotherm. It states that

adsorbed molecules do interact and affect further adsorption by either
repulsion or attraction of molecules.

5 GFrumkin ~ 6 Giangmu/r ~ 2gfF,

BET isotherm

Often molecules do form multilayer, that is, some are adsorbed on already
adsorbed molecules and the Langmuir isotherm is not valid. In 1938
Stephan Brunauer, Paul Emmett and Edward Teller developed an
isotherm that takes into account that possibility. The proposed mechanism
is now,

A(g) + S — AS A(g) + AS A2S

A(g) + A2S ^ A3S and so on

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5

Langmuir isotherm (red) and BET isotherm (green)

The derivation of the formula is more complicated than Langmuir's and it

is given as,

x = 1 J(c- 1)

x is the pressure divided into the vapour pressure for the adsorbate at that
temperature, v is the STP volume of adsorbed adsorbate, vmon is the STP
volume of the amount of adsorbate required to form a monolayer and c is
the equilibrium constant K we used in Langmuir isotherm multiplied by the

vapour pressure of the adsorbate. The biggest step in BET isotherm is to

consider that the successive equilibrium for all the layers except for the
first are equal to the liquefaction of the adsorbate.

Langmuir isotherm is usually better for chemisorption and BET isotherm

works better for physisorption.

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 Adsorption enthalpy:

Adsorption is an exothermic process because energy is liberated,

therefore enthalpy is always negative. Adsorption constants are
equilibrium constants, therefore they obey van’t Hoff's equation:

alnK
SI 1-
CD

As can be seen in the formula, the variation of K must be isosteric, that is,
at constant coverage. If we start from BET isotherm and assume that the
entropy change is the same for liquefaction and adsorption we obtain
AHads = AHiiq - RT\nc, that is to say, adsorption is more exothermic than
liquefaction.

5.4.2 ADSORBENTS ( CHARACTERISTICS AND GENERAL REQUIREMENTS )

The adsorbents are used usually in the form of spherical pellets, rods,
moldings or monoliths with hydrodynamic diameter between 0.50 and 10
mm. They must have high abrasion resistance, high thermal stability and
small micro pore diameter, which results in higher exposed surface area
and hence high capacity of adsorption. The adsorbents must also have a
distinct macro pore structure which enables fast transport of the gaseous
vapours.

Different types of industrial adsorbents generally fall into three classes:

• Oxygen-containing compounds - Are hydrophilic and polar including

materials such as silica gel and zeolites.
• Carbon-based compounds - Are hydrophobic and non-polar including
materials such as activated carbon.
• Polymer-based compounds - Are polar or non-polar functional groups in a
porous polymer matrix.

Page 133 of 181

Silica gel

Silica gel is a chemically inert, nontoxic, polar and dimensionally stable

(< 400 °C) amorphous form of Si02. It is prepared by the reaction between
sodium silicate and sulphuric acid, which is followed by a series of after-
treatment processes such as aging, pickling, etc. These after treatment
methods results in various pore size distributions on its surface. Silica is
also used for drying of process air (e.g. oxygen, natural gas etc) and

adsorption of higher (polar) hydrocarbons from natural gas.

Zeolites
Zeolites are natural or synthetic aluminum silicates which form a regular
crystal lattice and release water at high temperature. Zeolites are polar in
nature and generally used to filtrate water.

They are manufactured by hydrothermal synthesis of sodium

aluminosilicate in an autoclave followed by ion exchange with certain
cations (Na+, Li+, Ca++, K+). The channel diameter of zeolite cages
usually ranges from 2 to 9 A { 200 to 900 pm). This process is followed by

drying of microcrystal, which are palletized with a binder, to form

macropores and thermally activated at a temperature of 6500°C.

Zeolites are applied in drying of process air (only traces), C02 removal
from natural gas, CO removal from reforming gas and air separation.

Non-polar zeolites are synthesized by dealumination of polar zeolites. This

is done by treating the zeolite with steam at elevated temperatures,
greater than 500°C (1000°F). This high temperature heat treatment breaks
the aluminum-oxygen bonds and the aluminum atom is expelled from the
zeolite framework. Non-polar zeolites are mostly used in non-polar
organics removal.

Page 134 of 181

Activated carbon:

They are highly porous, amorphous solids consisting of micro crystallites

with a graphite lattice. They are non-polar and cheap. One of their main
drawoacks is that they are combustible.

Activated carbon nitrogen isotherm showing a marked micro porous type

behavior. Activated carbon can be manufactured from carbonaceous
material, including coal (bituminous, sub bituminous, and lignite), peat,
wood, or nutshells (i.e. coconut). The manufacturing process consists of
two phases carbonization and activation. The carbonization process
includes drying and then heating to separate by-products, including tars
and other hydrocarbons, from the raw material as well as to drive off any
gases generated. The carbonization process is completed by heating the
material at 400-600°C in an oxygen-deficient atmosphere that cannot
support combustion.

The carbonized particles are “activated" by exposing them to an oxidizing

agent usually steam or carbon dioxide at high temperature. This agent

Page 135 of 181

 burns off the pore blocking structures created during the carbonization
phase and so they develop a porous, three-dimensional graphite lattice
structure. The size of the pores developed during activation is a function of
the time that they treated in this stage. Longer exposure times result in
larger pore sizes.

The most popular aqueous phase carbons are bituminous based because
of their hardness, abrasion resistance, pore size distribution and low cost
but their effectiveness needs to be tested in each application to determine
the optimal product.

Activated carbon is used for adsorption of organic substances and non­

polar adsorptive and it is also usually used for waste gas (and waste
water) treatment. It is the most widely used adsorbent. Its usefulness
derives mainly from its large micropore and mesopore volumes and the
resulting high surface area.

5.4.3 STUDIES ON REACTIVATION AND PRODUCTION OF POWDERED

ACTIVATED CARBON.
James C.P. Chen60, Cane Sugar handbook, Page no. 590 gives idea of
reactivation of Powder activated carbon. The regeneration of Powder
carbon were tried by scientist Zagrodzki and Kubiak.

They use horizontal furnace of 12 mt long by 300 mm diameter. It has

screw conveyer which helps in conveying and drying of the spent
carbon to lowest practically possible moisture content. Then it is heated
to 500-560°C temperature in furnace- and finally cooled down to
temperature 90°C.The conveyer speed is maintained between 2-5 rpm.
The heating was arranged by means of electricity and steam at 4 atm.
Pressure. The received carbon shows the same decolurisation
efficiency as fresh carbon.
Calgon Carbon10, on web enquiry dated 11/01/2009, it was replied that
Powder Activated carbon is not re-activable. Many test have been
made in the past however and because of very small sizes of

Page 136 of 181

 Particles the powder carbon tends to burn in the furnace. Hence the
entire process is not technically and economically feasible.

L.A. Edye and G. Kahn30, Queensland University Brisbane, Australia, in

their Paper on, “ Activated carbons in Sugar and Soft drink manufacture”
discussed about the history, use, manufacture and feedstock sources of
activated carbons. The current production and markets of carbons are
reported the use of activated carbon in the sugar refining industry is
described and the theory of adsorption is briefly mentioned. The acid
beverage floe problem in soft drink manufacture is reviewed and it is
proposed that activated carbon filtration processes could provide a
practical solution for the acid beverage floe problem.

5.4.4 PRODUCTION OF ACTIVATED CARBON FROM SUGARCANE BAGASSE:

Sixto A. Valencia et. Al92 reported in their paper that Char and
activated carbon were produced from sugarcane by employing two
stage thermal activation process.

The activated carbon is produced in Pyrolyzer by Carbonization of

bagasse at 300°C and then activation at three temperatures i.e. 600°C,
700°C and 800°C. The product was analyzed for Yield, Moisture,
Volatile combustible matter, Ash, Fixed carbon content, Iodine number,
Bulk density, Pore size (through electro micrograph.)

However, it was noticed that the yield of activated carbon shows

decreasing trend as the activation temperature increased from 600°C
to 800°C. The yield reduced from 65.85% to 52.20%.

Further, it was noticed that with rise in activation temperature, there was
corresponding increase in pore size up to 42 micron. The VCM content
reduced from 12 % to 8.74% while Ash content increased from 9% to
10.25%. The increased ash content may be due to unprotected
withdrawal of samples from Pyrolyzer in hot condition and it combust with
Oxygen in the air.

Page 137 of 181

 The iodine number which indicates the adsorptive capacity of carbon
increases with increase in activation temperature and the value of
Iodine number is 777 at highest activation temperature of 800°C.

Khadija Qureshi et al43, in their paper on Physical and Chemical

analysis of Activated carbon prepared from Sugarcane bagasse and use
for sugar decolourisation, published in International journal of chemical
and Bimolecular engineering gives the details of physical and chemical
properties of activated carbon and adsorption characteristics.

5.4.5 ADSORPTION THEORY OF SUGAR LIQUORS AND CONSUMPTION OF

ACTIVATED CARBON:

Sugar liquor colorants are mixture of different components with

different adsorptive potentials hence during adsorption process large
number of individual colorants and their adsorptions is taking place.

The distinguishing character for each individual colorant is simply

difficult but overall impact under certain conditions of adsorbing
material, process conditions and its contact time are prime important
• in the study of decolourisation which was considered in studies.

The standard consumption of use of activated carbon in the sugar

refineries for decolurisation is in the range of 3 kg / Ton raw sugar
(Minimum) to 4 Kg /Ton raw sugar ( Maximum).

The studies explained further regarding decolourisation of raw melt

liquor shows that highest usage of Powder activated carbon was made
only up to 1.66 Kg/ Ton of raw sugar, which directly reflects with
reduction of about 50 % than standard consumption figure. This will help
in reducing the cost of production of white sugar / refined sugar.

Page 138 of 181

5.5 STUDIES CONDUCTED FOR DECOLOURISATION OF RAW MELT
LIQUOR USING POWDERED ACTIVATED CARBON. - PART -1
Carbo UA International11, Paper on, “Increasing Plant Utilization,
Process Efficiency, Flexibility and Product Quality with High-Performance
Adsorbent Solutions” gives the details of Powder carbon decolourisation
effects. Carbo-UA products utilize extremely high-activity powdered
adsorbents optimized for decolourising and filtration of sugar solutions.
These products are designed to obtain long cycle lengths to reduce
downtime and associated operating costs (sluicing, sweet water
evaporation, ion-exchange chemical regenerants, GAC regeneration),

George Jasovsky and Bruce wells32'33, Graver Technologies in their

Paper on, “Performance of Adsorption / Filtration Media for Polishing
Sugar liquors” - discussed about their product ECOSORB with PAG.
ECOSORB when used in conjunction with PAG can economically upgrade
lower grade sugars to refined quality and also provides cost savings.

George Jasovsky and Bruce wells31, Graver Technologies in their

Paper on, “ Advantages of Ecosorb Precoats in polishing sugar syrups”
discussed about Ecosorb precoats with Powder activated carbon provide
the essential elements of an ideal adsorption process. Fine particles
provide rapid kinetics and high purity.

The studies made with different samples of powdered activated carbon

considering the concept of adsorbing nature and their effect on
decolourisation of sugar liquor with respect to the conditions of liquor
such as temperature, pH, concentration and dosing rate of carbon slurry.

The name of different brands available with powdered activated carbon

from manufacturing company source and used in the experiment are
as follows.

1. PAG - C9 2, PAG - M5

2. PAG - P7 4. Mixture of C9 + M5 + P7

Page 139 of 181

 Table No. 40: SPECIFICATIONS OF POWDERED ACTIVATED CARBON

Parameter Unit PAC C9 PAC M5 PAC P7

Iodine No. Mg / gm N.A 800 900

Surface area M2/ gm N.A. 750 1150

Molasses No. Mg / gm N.A, 216 140-160

Methylene Blue Gm /100g N.A. 12 N.A.

Total Pore Vol. Cm3 / gm N.A. 2.1 N.A.

App, Density Kg/m3 N.A. 380 380 - 400

Moisture % % N.A. 8 10

Water soluble % N.A. 1 N.A,

Matter

Ash Content % N.A. 7 4-6

pH N.A. 6-7 6-7

Filtering speed Secs N.A, 60 55

Particle size Above 75 micron N.A. 20 15

Below 75 micron N.A. 80 85

5.5.1 Method and Dosing of PAC used and sample preparation

The raw sugar sample is mixed with pure water { D.M. plant water) to
make brix of 60 + 2. The temperature of the sugar solution - melt is
kept between 75 to 80°C. The powdered activated carbon slurry is
made having concentration of 5 % in pure water keeping temperature
of slurry between 70 to 75°C. Different volumes of powdered activated
carbon slurry such as 2.5 cc, 3.5 cc, 5 cc, 7 cc, 10 cc are added to 500
gms of raw sugar solution.
The 500 gms of melt solution of 60°Bx contains 300.24 gms of raw
sugar having moisture content as 0.08 %. Similarly 5 gms PAC
dissolved in 100 ml / cc water will give corresponding gms of PAC in
each CC of slurry added to melt solution.

The laboratory filters were precoated similar to Pressure filters in the

plant with CELITE-Hyflosupercel, Diatomaceous filter aid. The retention
time of 30 mins as a soaking time for powder carbon in water was

Page 140 of 181

 kept which was later continued in plant operation also. After mixing
the carbon slurry in raw melt liquor, a retention time of 15 minutes to
half an hour was maintained in all the experiments.

The testing is conducted in three media such as Neutral, Acidic and

Alkaline. The solution is made acidic or alkaline with 0.10 N HCI and 0.10
N NaOH solutions respectively. Each table contains average data for
three different readings taken under same conditions..

Following Calculation table gives the idea of dosing rate of 5% RAC

slurry in raw sugar melt.

Table No. 41: DC SING RATE OF PAC SLURRY I N RAW MELT

Amount of RAC Equivalent Amount of raw PAC dosing

slurry (cc) added gms of PAC sugar (gms) in rate Kg / ton
to each 500 cc in melt liquor 500 cc melt. raw sugar
melt liquor

2.50 0.125 300 0.416

3.50 0.175 300 0.582

5.00 . 0.250 300 0.832

7.00 0.350 300 1.165

10.00 0.500 300 1.664

5.5.2 POWDER ACTIVATED CARBON TRIALS WITH DIFFERENT PH

CONDITIONS OF RAW MELT LIQUOR.

5.5.2.1 TRIALS WITH POWDERED ACTIVATED CARBON PAC-C9.

Table No. 42: ALKALINE CON DITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank ( Raw melt) 8.64 60.12 450 0.00

Raw melt + 2.5 cc PAC 8.49 61.89 414 8.00

Raw melt + 3.5 cc PAC 8.32 60.74 410 8.89

Raw melt + 5.0 cc PAC 8.35 60.49 386 14.22

Page 141 of 181

 Table No. 43: ACIDIC CO NDITIONS.

Sample preparation pH % Brlx Colour in % Colour

IU. removal

Blank ( Raw melt) 6.16 60.61 346 0.00

Raw melt + 2.5 cc PAC 6.39 61.20 307 11.27

Raw melt + 3.5 cc PAC 6.40 60.31 301 13.00

297 | 14.16
Raw melt + 5.0 cc PAC 6.45 62,10

Table No. 44 : NE UTRAL CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank ( Raw melt) 7.11 61.37 327 0,00

Raw melt + 2.5 cc PAC 7.19 59.36 303 7.34

Raw melt + 3.5 cc PAC 7.14 59.20 284 13.15

Raw melt + 5.0 cc PAC 7.16 58.46 278 14.98

Table No. 45 : NEUTRAL CONDITION WITH DOSAGE OF DRY PAC.

The trials of PAC - C9 were conducted by adding dry powder of

activated carbon on weight basis to 500 cc of raw sugar melt liquor
such as 100 mgs, 300 mgs, 500 mgs, 700 mgs respectively.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 7.12 61.37 402 0.00

Raw melt + 100mg PAC 7.23 59.36 315 21.64

Raw melt + 300mg PAC 7.33 59.20 312 22.38

Raw melt + 500mg PAC 7,01 58.46 282 29.85

Raw melt + 700mg PAC 7.15 58.25 274 31.84

Page 142 of 181

Graph No. 5.5.2.1 - GRAPHICAL PRESENTATION ON EFFECT OF

PAC-C9 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR.

EFFECT OF pH VALUE ON COLOUR REMOVAL BY USING RAC -C9
<£>

g§S §S §S § oo
pH V A LU E S IN D IFFE R E N T M ED IU M
p> o> cn oo

5.00
0.00 8.00 8.89 11.27 11.31 13.00 13.15 14.16 14.22 14.98
PERCENT COLOUR REMOVAL

CONCLUSION :

From all the tables referred above, it is justified that RAC C-9 is not
showing the desired decolourisation effect for the cane raw sugar melt
under any conditions i.e. Alkaline, Acidic or Neutral.

In all the cases, the decolourisation effect is limited up to 15 %

maximum, which is not a good indicative figure for decolourisation of
clarified melt considering the cost of activated carbon and dosage
rate in sugar liquor considered.

However in Neutral medium with higher dosage amount of C-9 and

direct addition of powder is helping to have better removal of colour
up to 32 % maximum in laboratory stage but it is practically difficult
during plant stage as direct additions creates proper mixing problems,
creation of small pockets of unreacted carbon bubbles and environmental
issues.

Hence suitability of C-9 PAC usage is limited in raw sugar melt

decolourisation for both processes of sugar refineries.

Page 143 of 181

S.5.2.2 Table No.46

TRIALS WITH POWDERED ACTIVATED CARBON PAC-M5.

ALKALINE CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 9.21 60.87 467 0.00

Raw melt + 5 cc PAC 8.93 61.71 387 17.13

Raw melt + 7 cc PAC 8.74 59.00 330 29.34

Raw melt + 10 cc PAC 8.80 60.02 316 32.33

Table No.47

TRIALS WITH POWDERED ACTIVATED CARBON PAC - M5.

ACIDIC CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 6.40 60.00 450 0.00

Raw melt + 5 cc PAC 6.15 55.89 280 37.77

Raw melt + 7 cc PAC 6.25 59.87 240 46.66

Raw melt + 10 cc PAC 6.30 61.89 210 53.33

Table No.48

TRIALS WITH POWDERED ACTIVATED CARBON PAC-M5.

NEUTRA L CONDIT ONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 7.14 63.26 327 0.00

Raw melt + 5 cc PAC 6.95 63.39 278 14.98

Raw melt + 7 cc PAC 7.03 62.72 203 37.92

Raw melt + 10 cc PAC 7.10 60.86 140 57.18

Page 144 of 181

Graph No. S.5.2.2 - GRAPHICAL PRESENTATION ON EFFECT OF

PAC-M5 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR.

EFFECT OF pH VALUE ON COLOUR REMOVAL BY USING PAC-M5

10.00
«£i
D IF F E R E N T M E D IU M
«0
o

f J.4-----».8u_
oo Ino «oo0
TO

□ pH In Alkaline
OO

Medium
b»
o

IT

7.10
a
'4

6.95 7.03 ■ pH in teldlc

Medium
pH V A L U E S IN

=s=

6=25 6-30-
8

I I i
□ pH in Neutral
q u8i
(d

Medium
i
«

0.00 14,98 17.13 29.34 32.33 37.77 37.92 46.66 53.33 57.18
PERCENT COLOUR REMOVAL

CONCLUSION : From all the tables referred above, it is justified that

M-5 PAG has higher adsorptive properties in Acidic and Neutral
medium ranging pH values between 6.40 to 7.10 for the cane raw
sugar melt.
In Alkaline conditions , the decolourisation effect is limited up to 32 %
maximum considering the highest dosage rate in all cases i.e. addition
of 10 cc of carbon slurry in raw melt.

However in Neutral medium with higher dosage amount of M-5 is

lucrative / beneficial as one can avoid further inversion of melt due
to acidic medium.
Hence any raw sugar refinery working with Phosfloatation process
will have Clarified and filtered liquor of pH 6.90 to 7.00 and Powder
activated carbon M-5 is most suitable for further decolourisation
effect.

Page 145 of 181

5.S.2.3 Table No.49

TRIALS WITH POWDERED ACTIVATED CARBON PAC - P7.

ALKALINE CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 8.87 60.63 458 0.00

Raw melt + 2.5 cc PAC 8,80 60.02 358 21.83

Raw melt + 3.5 cc PAC 8.74 60,67 238 48.03

Raw melt + 5.0 cc PAC 8.64 60.43 228 50.22

Table No.50

TRIALS WITH POWDERED ACTIVATED CARBON PAC - P7.

NEUTRAL CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 7.17 62.40 395 0.00

Raw melt + 2.5 cc PAC 7.07 61.93 337 14.68

Raw melt + 3.5 cc PAC 6.98 61.24 268 32.15

Raw melt + 5.0 cc PAC 7.03 60.17 227 42.53

Table No.51

TRIALS WITH POWDERED ACTIVATED CARBON PAC - P7.

Table No. 51 : ACIDIC CONDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 6.11 63.19 376 0.00

Raw melt + 2.5 cc PAC 6.10 63.42 333 11.43

Raw melt + 3.5 cc PAC 6.08 62.12 316 15.95

Raw melt + 5.0 cc PAC 6.03 61.36 292 22.34

Page 146 of 181

Graph No. S.5.2.3 - GRAPHICAL PRESENTATION ON EFFECT OF

PAC-P7 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR.

CONCLUSION :

From all the tables referred above, it is justified that RAC P-7 has
higher adsorptive properties in Alkaline and Neutral medium than acidic
conditions. The pH values in alkaline medium ranging between 8.50 to
8.60 gives better reduction in colour removal of raw melt even with
lower dosage rate also.

In Neutral conditions of the liquor, the decolourisation effect is also up

to 42 % maximum, with highest dosage rate of activated carbon but
ac die medium is not suitable for decolourisation effect.

Hence any raw sugar refinery working with Carbonation process will
have carbonated filter liquor of pH 8.30 to 8.50., so the powder
activated carbon P-7 is most suitable for decolourisation in refineries
following carbonation process of clarification for raw melt. However it
can be useful in Phosfloataion refinery also as the final pH of the
clarified liquor remains in the range of 6.90 to 7.00.

Page 147 of 181

S.5.2.4 TRIALS WITH POWDERED ACTIVATED CARBON MIXTURE
OF M5 + P7 + C9.

The trials are taken by changing the dosages of PAC carbon in melt.
Powdered activated carbon was added in dry form to raw melt.

Table No. 52 : ALKALINE COND TIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 9.05 64.42 418 0.00

Raw melt + 100 mg PAC 8.93 60.63 397 5.00

Raw melt + 300 mg PAC 8,72 61.26 327 21.77

Raw melt + 500 mg PAC 8.76 64.06 288 31.10

Raw melt + 700 mg PAC 8.63 64.56 248 40,66

Table No. 53 : NEUTRAL CO EDITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 7.16 65.83 453 0.00

Raw melt + 100 mg PAC 7.20 66.56 390 17.84

Raw melt + 300 mg PAC 7.10 66.50 207 41.35

Raw melt + 500 mg PAC 7.10 66.49 191 45.89

Raw melt + 700 mg PAC 7.08 64.70 131 62.32

Table No. 54 : ACIDIC CON DITIONS.

Sample preparation pH % Brix Colour in % Colour

IU. removal

Blank (raw melt) 6.16 61,06 344 0,00

Raw melt + 100 mg PAC 6.18 60.20 261 24.13

Raw melt + 300 mg PAC 6.31 59.87 224 34.88

Raw melt + 500 mg PAC 6.34 61.70 209 39,24

Raw melt + 700 mg PAC 6.46 62.95 176 48.84

Page 148 of 181

 Graph No. S.5.2.4 - GRAPHICAL PRESENTATION ON EFFECT OF

MIXTURE OF PAC - P7 + M5 + C9 IN DIFFERENT pH CONDITIONS ON

RAW MELT LIQUOR.
EEFECT OF pH VALUE ON COLOUR REMOVAL BY USING MIX. OF PAC'S (C-9+M-5+P-7)
ph VALUES IN DIFFERENT MEDIUM

I pH in Alkaline
Medium

I pH in Acidic
Medium

□ pH in Neutral
Medium

CONCLUSION ; From all the tables and the graph of effect of pH

value on colour removal as above, it is justified that the mixture of
RAC’s C9 + M5 + P7 has higher adsorptive properties in neutral medium
than acidic and alkaline conditions. The pH values in Neutral medium
ranging between 7.00 to 7.20 gives higher reduction in colour removal
of aoout 62 % than in any of the previous cases with individual
usage of powder activated carbon.

In Acidic conditions of the liquor, the decolourisation effect is also up

to 48 % maximum, with maximum dosage of activated carbon.

The difference in above case than others is that usage of direct

addition of RAC to liquor instead of slurry, which is not suitable in
normal working conditions due to variations in additions and proper
mixing of RAC in reaction tanks and environmental issues.

Hence any raw sugar refinery working with Carbonation /

Phosfloataion process will have usage of the three mixtures together
to get the desired effect. However the carbonated and filtered liquor
from Carbonation refinery may have to reduce the pH by using
partial Sulphitation ( S02 gas) to bring down pH up to 7.00 to 7.20.

Page 149 of 181

5.6 STUDIES CONDUCTED FOR DECOLOURISATION OF RAW MELT
LIQUOR USING POWDERED ACTIVATED CARBON. - PART - II

In continuation, the studies have been made with different samples of

powdered activated carbon with different brands and their effect on
decolourisation of sugar liquor with respect to the conditions of liquor
such as temperature, pH, concentration and dosing rate of carbon slurry.

5.6.1 The name of different brands available with Powdered activated carbon
from manufacturing company source and used in the experiment are
as follows.

1. PAG- 1 CN3

2. PAG - 2 PN5

Table No. 55: SPECIFICATIONS OF POWDERED ACTIVATED CARBON .

Parameter Unit PAC -1 CN3 PAC- 2 PN5

Iodine No. Mg/gm 850 600

Surface area M2/gm 1000 700

Molasses No. Mg/am 250 550

Methylene Blue Gm/100g 20 min. 7 min.

App. Density Ka/m3 430-470 600

Moisture % % 10-15 max. 3-10 max.

Ash Content % 5 11

pH 5.50-8.00 6.00 - 7.20

Filtering speed mins 7 23

Particle size micron 35 to 100 30 to 140

METHOD AND DOSING OF PAC USED WITH SAMPLE PREPARATION ;

The raw sugar sample is mixed with pure water ( D.M. plant water) to
make brix of 60 + 2. The temperature of the sugar solution (melt
liquor) is kept between 75 to 80°C. The powdered activated carbon
slurry is made having concentration of 5 % in pure water ( D. M. plant
water) keeping temperature of slurry between 70 to 75°C.

Page 150 of 181

Different volumes of PAG slurry such as 2.5 cc, 3.5 cc, 5 cc, 7 cc, 10 cc
are added to 100 cc of raw sugar solution.

In this experiment, the retention time of PAG solution is considered as

a basis. In first trials the retention time of two hours without heating was
maintained and in second trial, retention of PAG solution after making
the solution is about 3 to 4 hrs. This time is considered as a soaking
time followed by slow agitation for 30 to 40 minutes.

After agitation is complete, the solution is again kept soaking for one
to two hrs before use. The procedure of PAG usage was studied and
discussed with some experts for implementation and used in practice.

It has been noticed that the usage of PAG slurry prepared and used
by above mentioned method is giving satisfactory results in plant
operation.

The testing is conducted in three media such as Neutral, Acidic and

Alkaline.

The solution is made acidic or alkaline with 0.10 N HCI and 0.10 N NaOH
solutions respectively. Following calculation table shows the Dosing
rate of 5% PAG slurry in raw sugar melt.

Table No. 56 : DOSING RATE OF PAC SLURRY IN RAW MELT

Amount of PAC Equivalent Amount of raw PAC dosing

slurry (cc) added gms of PAC sugar (gms) in rate Kg / ton
to each 500 cc in melt liquor 100 cc melt. raw sugar
melt liquor

2.50 0.125 60.05 0.416

3.50 0.175 60.05 0.582

5.00 0.250 60.05 0.832

7.00 0.350 60.05 1.165

10.00 0.500 60.05 1.664

The following tables contains data which is the average of three

trials conducted on different dates by maintaining same conditions.

Page 151 of 181

5.6.1.1 Table No. 57

TRIALS WITH POWDERED ACTIVATED CARBON PAC -1 CN3.

EFFECT OF PAC -1 CN3 IN DIFFERENT pH CONDITIONS.

5 % PAC SOLUTION WITH RETENTION TINIE - 2 HRS ( NO HEATING) IN

ALKALINE CONDIT ONS.

Sample Blank Raw melt + Raw melt + Raw melt +

preparation 2.5 cc PAC 3.5 cc PAC 5 cc PAC

(raw melt)

pH 8.09 8.26 8.06 8.08

Brix 62.75 62.21 62.13 61.00

Colour 518 478 410 337

% Colour 0.00 7.72 20.85 34.94

removal

5% PAC SOLUTION WITH RETENTION T IME - 2 HRS ( NO HEATING)

IN A(3IDIC CONDITKDNS.

pH 6.15 6.07 6.02 6.01

Brix 65.19 64.24 63.51 62.72

Colour 442 392 385 379

% Colour 0.00 11.31 12.90 14.25

removal

5 % PAC SOLUTION WITH FDETENTION TIME - 2 HRS ( NO HEATING) IN

NEU1CRAL CONDITIONS.

pH 7.15 7.09 7.11 7.03

Brix 62.71 61.57 61.93 61.33

Colour 492 405 377 318

% Colour 0.00 17.68 23.22 35.36

removal

Page 152 of 181

Graph No. 5.6.1.1 : GRAPHICAL PRESENTATION ON EFFECT OF
PAC -1 CN3 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR

EFFECT OF pH VALUE ON COLOUR REMOVAL BY USING RAC -1 CN3

pll VALUE IN D irTE R E N T MEDIUM

PERCENT COLOUR REMOVAL

CONCLUSION : From all the tables and the graph of effect of pH

value on colour removal as above, it is justified that RAC -1 CN3 has
higner adsorptive properties in neutral and alkaline medium than acidic
conditions. The pH values in Neutral medium ranging between 7.00 to
7.15 gives higher reduction in colour removal of about 35%.

In Acidic conditions of the liquor with pH of 6.00, the decolourisation

effect is also up to 14 %, with maximum dosage of activated carbon.
Hence acidic conditions of liquor are not suitable for getting
maximum decolourisation effect.

Based on above, PAC -1 CN-3 is more suitable for decolurisation of

Catenated and filtered liquor in sugar refinery following Carbonation
process and partially also for Phofloatation process.

Page 153 of 181

5.6.1.2 TRIALS WITH POWDERED ACTIVATED CARBON PAC-1 CN3.

IN DIFFERENT MEDIUM BY KEEPING MORE RETENTION TO PAC

SOLUTION AND HEATING IT WITH AGITATION.

Table No. 58 : EFFECT OF PAC -1 CN3 IN DIFFERENT pH CONDITIONS.

5% PAC SOLUTION WITH RETENTION TIME OF 5 HRS { HEATING &

AGITATION) N ALKALINE CONDITIONS.

Sample Blank Raw melt + Raw melt + Raw melt +5

preparation (raw melt) 2.5 cc PAC 3.5 cc PAC cc PAC

pH 8.16 7.69 7.66 7.52

Brix 63.05 62.03 62.24 61.54

Colour 675 474 299 288

% Colour 0.00 29.71 55.68 57.25

removal

5% PAC SOLUTION WITH RETENTION TIIHIE OF 5 HRS ( HEATING &

AGITATION ) IN ACIDIC CCINDITIONS.

pH 6.16 6.17 6.11 6.07

Brix 61.41 60.36 60.72 61.09

Colour 504 339 293 195

% Colour 0.00 32.67 42.52 61.34

removal

5 % PAC SOLUTION WITH RETENTION TIME OF 5 HRS ( HEATING &

AGITATION) IN NEUTRAL CONDITIONS.

pH 7.05 6.95 6.92 6.93

Brix 62.55 60.07 60.05 60.71

Colour 510 460 390 265

% Colour 0.00 9.70 23.57 47.90

removal

Page 154 of 181

 Graph No. 5.6.1.2 : GRAPHICAL PRESENTATION ON EFFECT OF
PAC -1 CN3 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR
WITH MORE RETENTION, HEATING AND AGITATION.
EFFECT OF pH VALUE OF COLOUR REMOVAL BY USING PAC-1 CN 3 +
RETENTION + HEATING
10.00

9.50
pH VALUES IN DIFFERENT MEDIUM

9.00
I pH in Alkaline
8.50
8.16 medium

8.00 7. 69 7. 66
7.52 I pH in Acidic
7.50 Medium
705 6.95 6.92 6.93
7.00 O pH in Neutral
Medium
6.50
( .1 6-17 6.11

6.00

5.50

5,00
0.00
—

9.70 23.57
—

29.71
ID
32.67 42.52 47.90
PERCENT COLOUR REMOVAL
—

55.68
-a\
57.25 61.34

CONCLUSION :

Frcm all the tables and the graph of effect of pH value on colour
removal by using same PAC -1 CN-3 sample, it is observed that
PAC -1 CN-3 has higher adsorptive properties in all three mediums i.e.
Acidic, Neutral and Alkaline.
In this experiment, the retention of PAC sample for soaking time of
four ( 4 ) hrs is kept along with heating of PAC solution to the
required temperature of 75 to 80°C. After soaking time is over, the PAC
slurry was agitated for half an hour and kept standing again for half
an hour. The sample retention of about 5 hrs helped in better results
and understanding the effectiveness of same PAC CN-3 sample in all
mediums.
Hence it can be considered as universal adsorbent and can be used
in both sugar refineries i.e. refinery with Carbonation as well as with
Phosfloatation process of melt liquor clarification.

Page 155 of 181

5.6.1.3 TRIALS WITH POWDERED ACTIVATED CARBON WITH PAG - 2

PN5 SAMPLE IN DIFFERENT MEDIUM.

Table No. 59 : EFFECT OF PAC- 2 PN5 IN DIFFERENT pH CONDITIONS.

5 % PAC SOLUTION WITH RETENTION T IME - 2 HRS ( NO HEATING)

IN ALKALINE CONDI TIONS.

Sample Blank Raw melt + Raw melt + Raw melt +

preparation (raw melt) 2.5 cc PAC 3.5 cc PAC 5 cc PAC

pH 8.48 8.12 8.03 7.95

Brix 59.27 61.28 62.01 61.16
Colour 518 480 471 466
% Colour 0.00 7.33 9.07 10.04
removal

5 % PAC SOLUTION WITH RETENTION Tl ME - 2 HRS ( NO HEATING)

IN ACIDIC CONDITKDNS.
pH 6.15 6.04 6.12 6.11
Brix 60.83 63.52 63.07 62.80
Colour 483 353 3339 289
% Colour 0.00 26.91 29.81 40.16
removal

5 % PAC SOLUTION WITH RETENTION Tl ME - 2 HRS ( NO HEATING)

IN NElJTRAL CONDIT IONS.

pH 7.17 6.93 7.02 7.06

Brix 63.59 62.82 63.47 62,73
Colour 472 467 453 422
% Colour 0,00 1.06 4.02 10.59
removal

Page 156 of 181

Graph No. 5.6.1.3 : GRAPHICAL PRESENTATION ON EFFECT OF
PAC-2PN5 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR.

EFFECT OF pH VALUE ON COLOUR REMOVAL BY USING RAC - 2 PN5

10.00

9.50
pH VALUE IN D IFFE R E N T M EDIUM

9.00 I pH in Alkaline
8.48 Medium
8.50
8.12 8 03
7.95
8.00
I pH in Acidic
7.50 - 7717------------
7.02 7.06 Medium
n 6.93
7.00

6.50 - 715 6.04 6.12 6.11 D pH in Neutral

6.00 J-

D Q I
Medium

5.50

5.00
0.00 1.06 4.02 7.33 9.07 10.04 10.59 26.91 29.81 40.16

PERCENT COLOUR REMOVAL

CONCLUSION :

From all the tables and the graph of effect of pH value on colour
removal as above, it is justified that the RAC - 2 PN 5 has higher
adsorptive properties and decolourisation effect in acidic medium only
with pH values ranging between 6.05 to 6.15.

Further with our normal procedure of keeping the solution for two
hours and analyzing the same in Alkaline and Neutral medium gives
lower reduction in colour removal of about 10%.

Considering the effect of decolourisation in acidic medium, the NORIT

PN - 5 may be used in Phosflotation method, where the pH of clarified
liquors is slightly acidic i.e. 6.80 to 6.95.

But at pH level of 6.05, there will be invert gain, hence it has limitations
to use in Decolourisation of Clarified liquor from Phosfloatation process.

Page 157 of 181

5.6.1.4 TRIALS WITH POWDERED ACTIVATED CARBON PAC-2 PN5

IN DIFFERENT MEDIUM BY KEEPING MORE RETENTION TO PAC

SOLUTION AND HEATING IT WITH AGITATION.

Table No. 60 : EFFECT OF PAC-2 PN5 IN DIFFERENT pH CONDITIONS.

5% PAC SOLUTION WITH RETENTION Tl ME OF 5 HRS ( HEATING &

AGITATION) IN ALKALINE CONDITIONS.

Sample Blank Raw melt + Raw melt + Raw melt +

preparation (raw melt) 2.5 cc PAC 3.5 cc PAC 5 cc PAC

pH 8.26 7.68 7.51 7.45

Brix 64.59 63.33 63.13 64.80

Colour 679 480 437 390

% Colour 0.00 29.30 35.64 42.56

removal

5% PAC SOLUTION WITH RETENTION™/IE OF 5 HRS ( HEATING &

AGITATION ) IN ACIDIC CCINDITIONS.

pH 6.50 6.35 6.12 6.10

Brix 62.77 63.71 63.16 62.44

Colour 530 509 452 ‘ 394

% Colour 0.00 3.96 14.72 25.66

removal

5 % PAC SOLUTION WITH RETENTION TIME OF 5 HRS ( HEATING &

AGITATION) IN NEUTRAL CONDITIONS.

pH 7.07 6.93 6.91 6.97

Brix 61.88 - 63.41 63.16 62.72

Colour 518 415 343 330

% Colour 0.00 19.88 33.78 36.30

removal

Page 158 of 181

 Graph No. 5.6.1.4 : GRAPHICAL PRESENTATION ON EFFECT OF
PAC -2 PN5 IN DIFFERENT pH CONDITIONS ON RAW MELT LIQUOR
WITH MORE RETENTION, HEATING AND AGITATION.

EFFECT OF pH VALUE ON COLOUR VALUE BY USING PAC- 2 PN5 WITH

HEATING AND RETENTION
10.00

9.50
pH VALUES IN DIFFERENT MEDIUM

9.00
P pH in Alkaline
8.50 8.26
Medium
8.00 7.68
7.51 7.45 ■ pH in Acidic
7.50
Medium
6.93 | | 6.91 6.97
7.00
1.5) □ pH in Neutral
6.50 6.35
e .1 2 6tt0 Medium
6.00

5.50

5.00
0.00 3.96 14.72 19.88 25.66
I
29.30 33.78 35.64 36.30 42.56

PERCENT COLOUR REMOVAL

CONCLUSION :

From all the tables and the graph of effect of pH value on colour
removal by using same PAC - 2 PN5 sample, it is observed that it
has higher adsorptive properties in two mediums i.e. Neutral and
Alkaline while in acidic medium it has decolourisation effect up to 25 %.

In this experiment, the retention of PAC sample for soaking time of

four (4) hrs is kept along with heating of PAC solution to the
required temperature of 75 to 80°C with constant stirring. After soaking
time is over, the PAC slurry was agitated for half an hour and kept
soaking again for half an hour. The sample retention of about 5 hrs
helped in better results and understanding the effectiveness of same
PAC - 2 PN5 sample in all mediums.

Hence it can be considered as adsorbent with option to PAC -1CN3

and can be used satisfactorily in refineries following Carbonation and
decolourisation using Powdered activated carbon. It’s usage in
Phosfloatation process are limited due to low pH value.

Page 159 of 181

 Table No. 61

.7 COMPARATIVE CHART FOR USAGE OF DIFFERENT POWDERED

ACTIVATED CARBON IN DIFFERENT PH CONDITIONS OF RAW MELT
LIQUOR.

Sr. Powdered Activated Clarified Melt decolonisation effect

No. Carbon type in Refinery Process Following

Carbonation Phosfloatation

1 PAC - C9 Limited usage Limited usage

2 PAC - M5 Limited usage Satisfactory

3 PAC - P7 Most satisfactory Satisfactory

4 PAC - mixture •Satisfactory Most Satisfactory

( C9 + M5 + P7)

5 PAC -1 CN -3 Satisfactory Satisfactory

( with 2 hrs retention )

6 PAC - 2 PN -5 Limited usage Limited usage

(With 2 hrs retention )

7 PAC -1 CN -3 Most Satisfactory Most Satisfactory

(With heating. Agitation

and 5 hrs retention)

8 PAC - 2 PN -5 Satisfactory Satisfactory

(With heating, Agitation

and 5 hrs retention)

Page 160 of 181