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Cellulose acetate is one of the most commercially used cellulose

derivative and it is a natural plastic. Its applications are implemented over a


range of product such as in cigarette filters, textiles, membrane separation and
frame material in eyewear. All thanks to its high performance thermoplastic
nature and other beneficial properties which are high mechanical strength,
compatibility with the human skin, transparency and good resistance against a
variety of chemicals. Cellulose acetates that are commonly used nowadays are
cellulose diacetate, having an average degree of substitution (DS) ranging from
2.2-2.7, and cellulose triacetate, with average DS above 2.8 (Heinze & Liebert,
2001). It is estimated that the global market for cellulose acetate to increase at
1% to 2% per year targeting 840,000 to 850,000 tonnes by 2015
(NPS,
2014). Thus, it is important for a continuous increase in the production of
cellulose acetate over the years to fulfil the worlds demand. In general, the
chemical reaction concerning with its production mainly involves acetylation of
the hydroxyl groups in the anhydroglucose units of cellulose followed by
hydrolysis, via several production routes. The raw materials involved are
cellulose (sourced from wood pulp or cotton), acetic anhydride, water and a
catalyst. Nevertheless, there are still several pre-treatments that need to be
applied to the cellulose for acetylation to occur effectively. This report aims to
discuss the possible production routes of cellulose acetate and its two production
processes, where the first outlines the commercial industrial manufacturing (The
Acetic Acid Proces), and the second, a promising approach to utilize a green
process for the future.
The synthesis of cellulose acetate first began in 1865 by Schutzenberger
in Germany by heating cellulose and acetic acid under pressure (Agreda, 1993).
With the aid of numerous studies, industrial manufacturing of cellulose was
established in the 1920s and catalysts are used to speed up the acetylation
process. There are 3 process conditions in which cellulose are produced; The
Acetic Acid, The Methylene Chloride and The Heterogenerous processes. The
Acetic Acid process first generates cellulose triacetate upon acetylation of the
raw materials. The catalyst used is sulfuric acid in which it enhances the
solubility of the cellulose triacetate in acetic acid. Several reaction conditions
such as temperature, catalyst level and cycle times can be varied for the
reaction however, it must be balanced. For example, having high catalyst level
(11-15% by weight) promotes higher solubility of the cellulose triacetate
however, it also promotes faster degradation of the material. Hence, a lower
temperature is must be used for the reaction mixture. The produced cellulose
triacetate is then hydrolised to a desired degree of substitution, normally to the
cellulose diacetate level. The Methylene Chloride Process on the other hand
utilizes methylene chloride instead of acetic acid in the recipe. This chemical
offers several advantages over acetic acid due to its nature as a better solvent
and its low boiling point allows reflux cooling to remove excess heat during the
acetylation stage. The Heterogeneous process uses the same chemicals from the
Acetic Acid Process except the acetic acid is substituted with a non solvent of
petroleum ether or toluene type.

Despite the different processes available, the Acetic Acid Process is


commercially used to manufacture cellulose acetate. The Methylene Chloride
Process requires high capital investment and has a low productivity, which is
uneconomical for industrial expansion. In addition, the flake quality produced by
the acetic acid process is of a higher quality. The heterogeneous process is only
used to produce cellulose triacetate flakes which are recovered in a fibrous state.
Since the commercial cellulose acetate has a DS of 2.2-2.7, the heterogeneous
process is seldom exploited. Thus, industrial manufacturing of cellulose acetate
nowadays is through the Acetic Acid Process. The following figure demonstrates
the process flowsheet:

The first unit of operation is shredding of the raw materials. As mentioned


earlier, the source of cellulose can be obtained from either cotton or wood pulp.
In commercial manufacturing, wood pulp is normally used due to its huge
availability and very high alpha-cellulose content (90% and over) which is of high
purity. There are 3 types of shredders commonly used; hammer mill, disc refiner
and pinpicker. The hammer mill operates by hammers rotating at high speeds
and pulverizes sheets of cellulose that passes through it. This shreds the
cellulose. The disc refiner consists of two circular plates adjacent to each other
with each having numerous teeth and blades on them. One of the plates is
stationary while the other rotates and a cellulose fluff is obtained. The
combination of hammer mill and disc refiner gives the optimum shredding. The

pinpicker produces light cellulose fluff. It consists of a rotating drum with sharp
pins protruding on the inner surface at close intervals. As the sheets of cellulose
are fed, they are being shredded continuously.
The pretreatment step, also known as swelling, is important to break the
hydrogen bond among the anhydroglucose units of cellulose subsequently
ensuring the hydroxyl group in cellulose is accessible for acetylation. Swelling
can be of vapor phase or slurry. In the vapor phase, a small amount of acetic acid
is added based on the weight of cellulose in a closed stainless steel vessel with
ambient temperature between 25 to 50C. They are left for 1 hour in the vessel
with minimum agitation. The uniform swelling of the cellulose occurs by both
condensation and vaporisation action of the acetic acid within the interstices of
fibres. If the cellulose contains 7% moisture and 35% glaical acetic acid, and
82/18 acetic acid and water is the best composition for swelling.
The slurry pretreatment involves a high liquid to cellulose ratio. The
cellulose is emerged in water or aqueous acetic acid and is vigorously agitated to
ensure uniform dispersion. The water is then exchanged with acetic acid through
a series of centrifuging or pressing the slurry. From time to time, the percentage
of acetic acid increases which in the end, results a dispersion with substantial
amount of acetic acid and only a small amount of water is present. It is important
for the water content to be low due to the high exothermic reaction at the
beginning of acetylation with acetic anhydride. The advantage of the slurry
pretreatment is that the wood pulp is not required to be shredded due to the
uniform dispersion. Normally, there is an activation step that follows. This
requires the addition of a catalyst, commonly sulfuric acid, to form an
intermediate which results in a faster acetylation.
The next stage, acetylation, occurs in a stainless steel acetylator equipped
with a cooling jacket and an agitator. The pretreated cellulose, acetic acid, acetic
anhydride and sulfuric are added into it. The acetic anhydride is added in excess
of 5%-15% weight to ensure complete reaction. The cooling jacket plays a vital
role during acetylation to control the temperature profile due to the high
exothermic reaction between acetic anhydride and water. Otherwise, significant
degradation will occur to the cellulose/cellulose acetate (Steinmeier, 2004). In
the case where high amount of catalyst is used, initial chilling of the reaction
mixture to the point of freezing crystals of acetic acid is necessary for heat sink.
The agitator is essential for a uniform dispersion of the reaction mixture during
acetylation. Acetylation initially occurs in the amorphous region of the cellulose.
The mechanism for acetylation may be described in two possible ways.
Nevertheless, both pathways utilizes the sulfuric acid to form as an intermediate.
The first chemical equation demonstrates the acetylation in terms of proton
activity:

R ( OH )n +n H 2 SO 4 + Ac 2 O R ( OS O2 OH ) +2 AcOH

OS O2 O

H +
R ( OSO2 OH ) + Ac 2 O R
H +

Ac 2 O
Alternatively, the cellulose acetic combines with sulfuric acid to form cellulose
sulfate:

R ( OH )n +n H 2 SO 4 + Ac 2 O R ( OS O2 OH ) +2 AcOH
R ( OSO2 OH ) + Ac 2 O R ( OS O2 OAc ) + AcOH
R ( OSO2 OAc ) + R ( OH ) n R ( OH )n1 OAc + R ( OS O 2 OH )
As acetylation proceeds, the viscosity of the reaction mixture increases and will
then form a uniform opaque viscous mixture. Later on, a clear mixture is
produced and the final product will have a viscous and clear characteristics. It is
crucial to take note that at the early stage, the acid dope appears to be grainy
and further acetylation needs to go beyond this grainy point until it appears to
be clear. This ensures the highly crystalline structure in the cellulose is
penetrated well by the reactants and acetylated. The acid dope will also attain
good filtration properties. Acetylation is stopped by the addition of water or
dilute acetic acid. This helps to destroy excess acetic anhydride and desulfate
residual sulfate linkages. Also, the water added into the reaction mixture ensures
that the latter is no more anhydrous because degradation of the produced
cellulose triacetate will occur much slower in an aqueous acetic system. The
stopping point helps to adjust the degree of polymerization which controls the
viscosity of the cellulose triacetate.