Fibre Chemistry, Vol. 40, No.

6, 2008

EXTRACTION PROCESSES IN EXTRACTION OF THE

BIOPOLYMER CHITIN FROM CRAB SHELLS

V. F. Abdullin, S. E. Artemenko, UDC 66.01.547.995

G. P. Ovchinnnikova, and O. S. Arzamastsev

The kinetic characteristics of demineralization and deproteinization of chitin-containing raw material were
investigated. It was found that increasing the concentration of extractant and the temperature significantly
increases the intensity and rate of these processes. It was noted that these processes take place more
efficiently and quickly in diffusers, which allows recommending apparatus of this type for conducting
extraction processes in separating chitin from chitin-containing raw material.

Chitin is a linear aminopolysaccharide consisting of N-acetyl-2-amino-2-deoxy-D-glucopyranose units. It is a

natural polymer separated from crab shells and is used as raw material for production of a large number of derivatives, of
which chitosan is the best known. Chitosan is formed when the acetyl group is removed from position C2 in chitin as a result
of treating it in severe conditions with an alkali solution, which allows substituting the acetyl groups in chitin by amino
groups.
Due to the broad spectrum of useful properties, chitin and chitosan are increasingly widely used. The areas of their
application are varied and include the textile industry (in sizing and antishrinkage or water-repellent treatment of fabrics),
paper and photographic industry (for preparation of high-quality and special kinds of paper and for improving the properties
of photo materials), nuclear industry (for localization of radioactivity and concentration of radioactive wastes), medicine (as
suture materials, wound- and burn-healing dressings, in ointments and drugs, as an enterosorbent), agriculture (for fertilizer
production, protection of seeds and crops), the food industry as a preservative, juice and wine clarifier, dietetic fibre, emulsifier,
and unique results as a food additive and enterosorbent), perfumery and cosmetics (incorporated in moisturizing creams,
lotions, gels, hair sprays, shampoos), water purification (acts as a sorbent and flocculant). The indisputable advantages of
chitosan include its total safety for humans and the environment: it is environmentally clean and totally decomposes in
natural conditions [1].
The crab shell is constructed from three fundamental elements — chitin, which plays the role of the skeleton, the
mineral part, which gives the shell the necessary strength, and proteins, which make it a living tissue. Crab-shell chitin
forms a fibrous structure and is bound with proteins, in the form of a chitin-protein complex. The mineral and protein
constituents must thus be separated to remove chitin from shell-containing raw material.
Based on the above, separation of chitin consists of stages of demineralization and deproteinization, which are
extraction processes. The essence consists of extracting the components from the solid substance with a liquid. In the given
case, the solid substance is the crab shell.
For extraction of chitin, a liquid solvent (solution of hydrochloric acid in demineralization and sodium hydroxide in
deproteinization) goes inside the porous body, the shell, and dissolves the extrinsic component (in demineralization, the
mineral constituent, and in deproteinization, proteins and lipids) by saturating near the dissolution surface. The dissolved
substance diffuses along the pores filled with the solution and pass from the mouths of the pores into the basic mass of the
liquid solvent.
Demineralization and deproteinization processes are traditionally conducted in periodic extractors (with or without
a stirrer) where the chitin-containing raw material is flooded with the extractant for a certain time. A drawback of this

Saratov State Technical University. Translated from Khimicheskie Volokna, No. 6, pp. 21-24, November-December,
2008.

0015-0541/08/4006-0513 © 2008 Springer Science+Business Media, Inc. 513

 Fig. 1. Diagram of the diffuser: 1) housing; 2) false
bottom (grating); 3) hinged bottom; 4) connecting
pipe for removing used extractant; 5) connecting
pipe for adding fresh extractant.

2
1
2 1

3 3
4
4

τ, min τ, min

Fig. 2. Fig. 3.
Fig. 2. Kinetic characteristics of demineralization of shell with
hydrochloric acid solutions of different concentration (in %): 1) 2;
2) 4; 3) 6; 4) 8.
Fig. 3. Kinetic characteristics of deproteinization of shell with sodium
hydroxide solutions of different concentration (in %): 1) 2; 2) 4; 3) 6; 4) 8.
method is the unavoidable decrease in the driving force of the processes (difference in concentration) and as a consequence,
their rates. In addition, the relatively high bath ratio [1:(5-8)] significantly reduces the output of this equipment.
A continuous extractor — diffuser — consisting of a cylindrical body, a false bottom (grating), and a hinged bottom
— was selected for comparison for evaluating the efficiency of different types of extraction equipment (Fig. 1).
The diffusers are serially connected in a battery which ensures their continuous operation. The solvent is pumped
in by a pump from bottom to top successively through all of the units in the battery where extraction is taking place at a given
time. The battery of diffusers operates according to the counterflow principle, i.e., fresh solvent reacts with material which
is already spent to a significant degree [2-5].
The conditions and implementation of the extraction processes determine both the properties and degree of purity
of the target product and its cost. Selecting and optimizing the main implementation of the chitin separation processes are
extremely important.
Extraction kinetically obeys the laws of mass exchange, convective and molecular diffusion, and the laws transfer
of the extracted substance from the solid to the liquid phase. The difference in its chemical potentials in the phases is the
driving force of transfer of the target component. In practice, to simplify the correlation between the rate of the process and
the composition of the material streams, the driving force of extraction is expressed by a concentration gradient of the
extracted substance in the corresponding phases which varies in time.
The efficiency of demineralization and deproteinization are essentially a function of the hydrodynamic characteristics
of the medium, determined by the type of equipment used, and also the concentration of the reagents, temperature, and
duration of the processes. The chitin separation conditions must be maximally mild to prevent its degradation.
Kamchatka king crab shells were used as the raw material for obtaining chitin. Since extraction of mineral and
protein impurities from the shell is determined by the rate of their dissolution in the extractants, a method consisting of

514
 2 1

3
4

τ, min

Fig. 4. Kinetic characteristics of demineralization of shell

with 6% hydrochloric acid solution at different
temperatures (in °C): 1) 20; 2) 40; 3)60; 4) 80.

1
2
1
3
2
4 3

τ, min τ, min
Fig. 5. Fig. 6.
Fig. 5. Kinetic characteristics of deproteinization of shell with 6% sodium hydroxide
solution at different temperatures (in°C): 1) 20; 2) 40; 3) 60; 4) 80.
Fig. 6. Kinetic characteristics of demineralization of shell with 6% hydrochloric acid solution
at 80°C in extractors of different types: 1) periodic extractor with no stirrer; 2) periodic
extractor with stirrer; 3) diffuser.

periodic sampling of treated material in the given conditions and determination of the fraction of undissolved compounds in
it was selected for determining the kinetic characteristics of the demineralization and deproteinization processes. The
duration of total dissolution of impurities was found at the end of the experiments. A graph of the dependence in coordinates
of γ(τ) — τ, where γ is the relative fraction of dissolved substance and τ is the duration of the process, was plotted with the
results obtained.
Shell samples of the same weight ground to a 2-3 mm fraction size were weighed for determining the kinetic
characteristics of demineralization and a series of experiments was conducted in extractors of different types (periodic
extractor with and without stirrer and diffuser) by varying the concentration of acid and the temperature. Cp hydrochloric
acid of 36.2% concentration (GOST 3118-77) was used for preparing the solutions.
Several samples of demineralized raw material of the same weight were prepared for determining the kinetic
characteristics of deproteinization, and a series of experiments was then conducted in extractors of the same type with
different concentrations of sodium hydroxide and temperatures. Analytically pure sodium hydroxide was used for preparation
of the solutions (GOST 4328-77).
The relative fraction of dissolved substance was found with the ratio X/X0, where X is the amount of dissolved substance
(degree of demineralization or deproteinization) and X0 is the initial content of mineral or protein impurities in the shell.
The degree of demineralization (deproteinization) was calculated with the equation

X = 100(M1 – M2)/M1,

where X is the degree of demineralization (deproteinization), %; M1, M2 is the weight of the shell before and after
demineralization (deproteinization), g.
The demineralization parameters were optimized in three stages.
1. At a different concentration of hydrochloric acid (2, 4, 6, and 8%), the fraction of the dissolved mineral part in
the raw material was determined at fixed times. Graphs of the fraction of dissolved mineral part as a function of the duration

515
 1
2
3

τ, min

Fig. 7. Kinetic characteristics of deproteinization of shell with

6% sodium hydroxide solution at 80°C in extractors of different
types: 1) periodic extractor with no stirrer; 2) period extractor
with stirrer; 3) diffuser.

of the process were then plotted and the optimum concentration of hydrochloric acid was determined with the kinetic curves
obtained. All of the experiments were conducted at a temperature of 20-25°C in static conditions without stirring.
2. At different process temperatures (20, 40, 60, 80°C), the fraction of dissolved mineral part in the raw material at
the concentration of hydrochloric acid selected in the first stage was determined at fixed times. The optimum process
temperature was determined with the kinetic curves obtained. All of the experiments were conducted without stirring.
3. Using the optimum values of the concentration of hydrochloric acid and process temperature determined in the
first two stages, the same experiments were conducted in different extractors and the optimum type of extractor was determined
with the graphs obtained.
The optimum deproteinization process parameters were selected similarly using solutions of sodium hydroxide as
the extractant.
The kinetic curves of demineralization and deproteinization for selecting the optimum concentration of extractants
are shown in Figs. 2 and 3. The data on selection of the optimum process temperatures are shown in Figs. 4 and 5. In turn,
Figs. 6 and 7 demonstrate the character of occurrence of the processes in the different types of equipment.
The data obtained as a result of the tests indicate that these processes take place more intensively with an increase
in the temperature and concentration of the extractants. It was shown that these processes take place more efficiently and in
less time in diffusers, which allows recommending equipment of this type for conducting demineralization and deproteinization
in separating chitin from chitin-containing raw material. The u*se of such equipment is also expedient from the point of
view of increasing output. The degree of filling of these units in comparison to the equipment traditionally used in obtaining
chitin and chitosan with periodic extractors of the same size is 50-60% higher, which significantly increases product take off
per equipment unit. Connecting the diffusers into a battery allows maximally efficient use of the extractant solutions and
obtaining a larger amount of chitin in less time [6].

REFERENCES

1. K. G. Skryabin, G. A. Vikhoreva, and V. P. Varlamov (eds.), Chitin and Chitosan. Production, Properties, and Use
[in Russian], Nauka, Moscow (2002).
2. I. P. Mukhlenov (ed.), General Chemical Engineering [in Russian], Vol. 1, Vysshaya Shkola, Moscow (1984).
3. D. A. Kasatkin (ed.), Processes and Equipment in Chemical Engineering [in Russian], Vysshaya Shkola, Moscow
(1973).
4. I. P. Mukhlenov et al., Principles of Chemical Engineering [in Russian], Vysshaya Shkola, Moscow (1991).
5. A. M. Kutepov, T. I. Bondareva, and M. G. Berengarten, General Chemical Engineering [in Russian], Vysshaya
Shkola, Moscow (1985).
6. V. F. Abdullin, S. E. Artemenko, and G. P. Ovchinnikova, Method of Obtaining Chitosan. RF Patent No. 2277543,
Int. Cl.7 C 08 B 37/08 No. 2005119540/04, Submitted 06.23.2005, Published Byull., No. 16 (06.10.2006).

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