ISSN 1996-4196

Chemistry
&
Chemical
Editor-in-Chief
Michael Bratychak Technology

Volume 2 ? Number 2

LITTERIS ET ARTIBVS

Lviv Polytechnic
2008 National University
 CONTENTS
Chemistry

Oleksandr Pokutsa, Andriy Zaborovskiy, Daria Maksym,Roman Makitra, Jacques Muzart

and Andrzej Sobkowiak
The influence of the reaction medium on the cleavage
of hydrogen peroxide catalyzed with cobalt ions 71
Volodymyr Mizyuk, Volodymyr Shibanov, Lesya Kobrin, Galyna Marshalok and Georgiy Elagin
Peculiarities of NMR13C spectra of benzoi c acid and saturated alkylbenzoates.
I. Chemi cal shift of benzoyl fragment carbon atoms 77
Oleksandr Ivashchuk and Victor Reutskyy
Research of action mechanism of catalyti c solutions in the oxidization process of cyclohexane 85
Antonieta Middea, Marisa Bezerra de Mello Monte and Elizabete Fernandes Lucas
The influence of the solvent medium on the aggregation of asphaltene macromolecules
and determination of their molar mass 91
Oleh Suberlyak, Oleksandr Hrytsenko and Khrystyna Hishchak
Synthesis of new conducting materials on the basis of polymer hydrogels 99
Nafdey Renuka and Kelkar Deepali
Synthesis of polyaniline in presence of low magnetic field, its structure and electrical properties 105
Ragini Raj Singh, Amit Ron, Nick Fishelson, Irena Shur, Rina Socher, Dafna Benayahu
and Yosi Shacham-Diamand
Biological cell-based screening for specific membranal and cytoplasmatic
markers using dielectric spectroscopy 111
Yuliya Ioshchenko, Viktor Kablov and Gennady Zaikov
Biodegradation of oil products in polluted soil by using the mixture of the polymer complex
[chitosan–lactoserum protein]–active silt 123

Chemical Technology

Victor Yavorsky
New princi ples in the polymeric sulfur technology 129
Iryna Kosogina, Igor Astrelin, Natalya Klimenko and Andriy Kontsevoy
Regularities of low-waste technology of wastewater treatment by coagulation method 133
Andriy Baldis and Vasyl Shevchuk
Analysis and choice of optimal conditions for the burning of natural gas with heated air
in the reactor of carbon black obtaining 139
Sergey Nikulin and Viacheslav Misin
Technological and ecological aspects of the practical appli cation of quaternary ammonium salts
in production of syntheti c emulsion rubbers in Russia 147
Anatoliy Kubrak, Lesya Ladieva, Anatoliy Burban and Roman Dubik
Experimental method of contact membrane distillation process research 153

Current Events

Witold Brostow and Poonam Tandon

Report from 16th POLYCHAR World Forum on Advanced Materials,
World Unity Convention Centre, Lucknow, India, February 17–21, 2008 I
G. Zaikov, L. Zimina and L. Madyuskina
Modern achievements of the experimental methods in the field of investigation in the structure
and dynamics of polymers and polymer composite materials (XVI Enikolopov’s Readings) V
iii
 CHEMISTRY & CHEMICAL TECHNOLOGY

Vol. 2, No. 2, 2008 Chemical Technology

Victor Yavorsky

NEW PRINCIPLES IN THE POLYMERIC SULFUR TECHNOLOGY

Lviv Polytechnic National University, 12 Bandera str., 79013 Lviv, Ukraine
Yavorsky@polynet.lviv.ua
Received: February 11, 2008

Abstract. The new method of polymeric sulfur obtaining
based on the polymerization of atoms instead of molecules
has been proposed. It has been proven that using the new
method essentially increases polymerization degree (over
90 %).
Keywords: sulfur, homochain, cyclic octasulfur, atomic
sulfur, polymerization.
1. Introduction
The history of the human society and industry
development shows that the role and place of some
chemical elements in nature and men's life, as well as their
production and using often do not correspond to their
contents in the Earth's crust.
Sulfur is a striking example of all above mentioned.
Although its content in the Earth's crust is only 5⋅10-2 wt %,
it does not belong to the dispersed elements due to its
mainly concentrated state. Moreover, sulfur stands second
after oxygen as anion-forming element and binds a
considerable part of metals in sulfides and sulfates form.
However, the most important fact is that sulfur has the
range of features, which are not characteristic of the
majority of chemical elements and of p-elements of its
sub-group in particular. Owing to its specific and
remarkable features sulfur played a considerable role in
the development of humanity and its relations with nature.
that in sulfur (330000 against 263000 J/mol for sulfur).
Due to the above mentioned sulfur atoms are highly capable
of interacting between each other with the formation of
cyclic or chain molecules, followed by the formation of
great amount of different allotrope modifications with
geometrical isomerism. Therefore sulfur physical and
chemical properties substantially depend upon its allotrope
composition and production conditions [1].
It should be mentioned that sulfur homochains have
a zigzag form. This is due to the unpaired electrons of
mutually perpendicular p-orbitals of atom taking part in
their formation.
S S
S S
Crown shaped S 8 cyclic molecules (cyclic
octasulfur) are most stable (Fig. 1).
Cyclic octasulfur forms three crystalline allotropic
forms. Under normal conditions rhombic form (α-sulfur)
with melting temperature of 385.8 K is the most stable.
However, it remains stable only up to 368.5 K.
Within the temperature range of 368.5–385.8 K
α-sulphur is transformed into monocline modification
(β-sulfur) with further melting. When cooled the melt
transforms into -sulfur, which then gradually converts
into more stable rhombic form.

S S S S
2. Results and Discussion 0
105
The ability to form stable homochains is an essential
distinction of sulfur. Such an ability is due to higher energy of
two bonds in the S-S-S homochain (263000⋅2 =
S S S S
= 526000 J/mol) as compared with the S=S molecule
(210000⋅2 = 420000 J/mol). For oxygen, to the contrary, Fig. 1. Structure of S8 molecule
the bonds in the O=O molecule are stronger
(494000 J/mol) in comparison with two bonds in O-O-O Sulfur melt contains practically all allotropic forms,
homochain (420000 J/mol). Only in carbon the binding correlation between which is determined mainly by the
energy between atoms in chain structure is higher from temperature. Thus within the temperature range of 392.9–
130 Victor Yavorsky
428 K liquid sulfur contains octocyclic molecules, which
begin to collapse at the temperatures of 428–433 K,
converting into the open chains. Further heating results in
the chains length reduction (S6, S4, S2). At 433 K an
intensive process of the sulfur chains polymerization
takes place. The process is more intensified with the
temperature increase, but the length of the polymeric chains
reduces.
Sulfur has a clearly defined ability to sublimation. A
noticeable vapor pressure above solid sulfur is formed
already at 280 K. Such pressure above liquid sulfur sharply
increases and at 717.6 K sulfur begins to boil. The vapor
contains S8, S6, S4 and S2 molecules. S2 part increases
with the increase of the temperature and at 1873 K the
sulfur vapor contains only atoms. It is known [1] that the
less atoms the molecule of sulfur contains the more reactive
it is. It means that monoatomic sulfur, which is a biradical
with perpendicular unpaired p-electrons, is the most active.
It is these valence electrons that build polymeric molecules.
The technology of such specific type of sulfur as
polymeric sulfur is based on the tendency of chain
molecules of liquid sulfur to interact. Due to its
extraordinarily valuable specific properties application of
polymeric sulfur instead of ordinary (rhombic) sulfur
considerably improves the quality of wares and substantially
encourages technical progress in the sulfur-consuming
branches of industry. The main consumers of the polymeric
sulfur are rubber-technical industry, which produces the
bulk of rubber wares for different machines, mechanisms,
devices etc. and building industry, which applies sulfur
concretes, sulfur ceramics, sulfur bitumens, etc.
The traditional methods of polymeric sulfur
production consist in melt-quench of sulfur or its vapors
in the presence of stabilizers. In both cases such sulfur
molecules as S 8, S 6 and S 4 are polymerized; the
polymerization degree being not higher than 40–50 %.
According to the technical specifications (TS) the content
of the polymeric modification in the finished product must
exceed 90 wt %. Therefore, the rhombic sulfur needs to
be separated from the polymeric one. For this purpose the
grinded product is treated with the organic solvents
(products of oil processing, tetrachlorethylene, benzene
etc.) at high temperatures dissolving (extracting) the
rhombic sulfur. Then the solution is cooled to crystallize
the rhombic sulfur. Sulfur crystals with around 2 % of the
solvent are separated. The solvent is heated and re-
extracted.
The complexities of this process are the following:
– the rhombic sulfur solvents are toxic, explosive
and flammable;
– the presence of solvent residues in the rhombic
sulfur crystals limits the product application and make its
storage complicated;
– the rhombic sulfur can be cleaned from the organic
substances by heated air or overheated water steam [1].
In both cases either contaminated air or steam must be
cleaned. Thus the separation of the polymeric sulfur from
the obtained product is accompanied by the range of
accessory processes which are quite complicated in
technological and ecological aspects and thereby
deteriorating technical and economic indexes. Due to the
above reasons there is no industrial production of polymeric
sulfur on the territory of СIS and the world demand for
polymeric sulfur is considerably undersupplied .
Naturally the question arises what the major cause
of such low efficiency of the existent technological
principles of polymeric sulfur production is.
In an attempt to find an answer to the above question
a deep comprehensive analysis of sulfur physical and
chemical properties as well as technological bases of the
existent polymeric sulfur technologies have been conducted.
The results of such analysis along with our stored scientific
achievements in sulfur related problems allow us to
conclude that the main cause of polymeric sulfur
productions imperfection is that these productions are
based on the principles of polymerization of sulfur
molecules with different number of atoms in them. These
molecules are formed by sulfur thermal processing. At
definite temperatures they are polymerized, but during
quenching the system itself tends to form the most stable
structure – cyclic octasulfur. Stabilizers which "saturate"
free valence sulfur p-electrons retard this process but
obviously do not eliminate it fully. The polymerization
degree can be slightly increased by selecting active
stabilizers and by optimizing the heating and quenching
conditions but these measures do not remove the principal
cause of the low polymerization degree.
The cardinal solution of the problem is using
polymerization of atoms instead of molecules (atomic
polymerization). There are all reasons to suppose that under
certain conditions the atomic polymerization would proceed
with high speed and completeness allowing to obtain
polymeric sulfur rather than mixture of different sulfur
modifications as the final product. So far no arguments
against this conclusion have emerged.
With the aim to confirm our theoretical conclusions
we conducted investigations which proved the efficiency
of sulfur atoms polymerization. The polymerization degree
of above 90 % was reached [2]. The obtained positive
results confirmed the topicality of our scientific
investigations and brought up the question about obtaining
the atomic sulfur.
Atomic sulfur may actually be obtained by different
methods. Prima facie the thermal method is the simplest.
 New Principles in the Polymeric Sulfur Technology
The lump sulfur is melted, heated to boiling and then its
vapor is overheated to the temperatures of 1873 K, at which
sulfur exists only in the atomic state. Lump sulfur is a
commodity and relatively cheap product (up to 40 dollars
per 1 ton). Melting heat of rhombic sulfur is 49800 J/mol,
evaporation heat is 286900 J/mol, heat capacities of solid,
liquid and vaporous sulfur are also low. Hence, this process
involves low power inputs. However, there are serious
problems with the process equipment. Heat application
should be conducted through a wall. In order to provide
sufficient thermal transfer the temperature of the heat
carrier (apparently flue gases) has to be above 2000 K. It
is known that the coefficient of thermal transfer through a
wall is insignificant in the gas-gas system. Consequently
this process will need a large heating surface operating at
high temperatures. At the same time it should be stressed
that the sulfur vapors, especially atomic sulfur vapors,
penetrate into the crystal lattice of metals destroying it.
Thus high temperatures, low coefficient of thermal
transfer, complexity of constructive materials selection,
"sulfuric" corrosion are the main factors which render
practical realization of this method of atomic sulfur
obtaining impossible.
Obtaining atomic sulfur from hydrogen sulfide by
its atomization, which takes place at 1963 K and higher
temperatures, is one of the promising techniques. The heat
of hydrogen sulfide formation is minor (20150 J/mol
against 241840 J/mol for water). The hydrogen sulfide
resources are enormous. The basic source of H2S is natural
gas, where the hydrogen sulfide content increases with
the increase of the depth of the natural gas occurrence
[1]. The hydrogen sulfide is obtained as a by-product in
petroleum refining, by-product-coking and other industries.
To date the hydrogen sulfide has become the main raw
material for the sulfur obtaining (gas sulfur) and gas industry
has transformed into gas-chemical industry.
It should be stressed again that hydrogen sulfide is
a complex raw material containing two valuable elements –
Sulfur and Hydrogen. Taking into account a relatively low
hydrogen sulfide formation heat and importance of the
hydrogen energetics development, a conclusion about the
topicality of the problem of obtaining atomic sulfur and
hydrogen from hydrogen sulfide can be drawn.
Analyzing the atomic sulfur and hydrogen obtaining
process from the point of view of specific power inputs,
131
temperature range, equipment design, corrosive processes,
etc., it can be inferred that hydrogen sulfide thermal
dissociation has all drawbacks inherent in the process of
obtaining atomic sulfur from lump sulfur via the thermal
method. In addition to this the above process implies
intensive hydrogen corrosion. As a consequence practical
implementation of the thermal dissociation of hydrogen
sulfide is problematic. That is why there is an urgent need
in discovering effective and economically sound methods
of hydrogen sulfur atomization.
Acid decomposition of sulfur oxygen-containing
compounds, in which sulfur has intermediate oxidation
degree, is an encouraging method of atomic sulfur
obtaining. Thiosulfates, in which sulfur has the oxidation
degree of +2, are of the greatest interest. As it is known,
such oxidation degree is unstable, hence in an acid medium
disproportionation reaction proceeds with obtaining of
atomic sulfur and its oxide (IV). The results of our
experiments aimed at the development of effective
processes of obtaining atomic sulfur from hydrogen sulfide
and thiosulfates will be represented in our next publications.
3. Conclusions
The atomic polymerization is a brand new tendency
in polymeric sulfur obtaining. In future atomic sulfur may
be obtained via the acid decomposition of sodium thiosulfate
and the hydrogen sulfide plasmolysis.
References
1. Menkovskiy M. and Yavorsky V.: Tekhnologiya sery.
Khimiya, Moskwa 1985.
2. Yavorsky V. et al.: A.s. 1271006 SSSR.
НОВІ ПРИНЦИПИ В ТЕХНОЛОГІЇ
ПОЛІМЕРНОЇ СІРКИ
Анотація. Запропоновано принципово новий спосіб
одержання полімерної сірки, який ґрунтується на полімеризації
атомів, а не молекул, і дає змогу суттєво підвищити ступінь
полімеризації (понад 90 %).
Ключові слова: сірка, гомоланцюг, циклооктасірка,
атомарна сірка, полімеризація.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 2, 2008
Iryna Kosogina, Igor Astrelin, Natalya Klimenko and Andriy Kontsevoy
REGULARITIES OF LOW-WASTE TECHNOLOGY OF WASTEWATER
TREATMENT BY COAGULATION METHOD
National Technical University of Ukraine “KPI” 37, Peremohy Ave., 03056 Kiev, Ukraine
i.m.astrelin@xtf.ntu-kpi.kiev.ua; kosogina@gala.net
Received: April 01, 2008
Abstract. Mechanisms of wastewater purification from
surface-active substances and of sulphuric acid dissolution
of iron-containing sludge formed during the previous
process have been established. Kinetic regularities of
metal-containing sludge dissolution in sulphuric acid have
been investigated. Kinetic equation which adequately
presents the experimental data has been proposed;
constants of this kinetic equation have been calculated.
Keywords: sulphuric-acid dissolution, kinetics, quantum-
chemical calculation, mechanism.
1. Introduction
As imperfections of the existing technology of
valuable components of wastewater (WW) treatment
sludge regeneration cause accumulation of environmentally
hazardous sludge and increase its storage areas, studies
within the scope of the mentioned problems are of great
importance [1-3].
To increase completeness of WW treatment sludge
utilization at simultaneous decrease of the deleterious effect
of toxic sludge components on the environment as well
as to lower sludge amount in sludge traps and to re-use
the initial reagents during the recycling process, kinetics
of sulphuric acid dissolution of the textile industry WW
treatment sludge is investigated.
The purpose of this article consists in investigating
the kinetics of sulphuric acid dissolution of textile industry
WW treatment sludge in order to discover and substantiate
the process mechanism and technological parameters of
sludge acid dissolution. After sludge dissolution a product
is formed, which is used during the recycling process
thus promoting the decrease in the amount of the formed
industry waste products as well as profitability and
ecological compatibility of the production.
Chemical Technology
2. Experimental
2.1. Materials
Model of wastewater polluted by the following
surface-active substances (SAS): ludigol – m-nitrobenzene
sodium sulphate, Ñ6Í4NO2SO3Na; methaupon-sodium salt
N-methyl taurinate of fatty acid, RCON(R’)CH2SO3Na;
synthanol – mixture polyethylene glycol ethers of
synthetic primary alcohols of fraction Ñ 10 –Ñ 18 ,
Ñ10Í21Î(Ñ2Í4Î)10Í, and dye – ruby reactive dye 5 ÑÕ,
C19H11O3N6S2Cl2Na2.
2.2. Methods
As a subject of inquiry model solutions of
wastewater of Ukrainian textile factories containing totally
up to 15 mg/dm3 of SAS (ludigol, methaupon, synthanol)
and up to 6 mg/dm3 of ruby reactive dye 5 ÑÕ were used.
Coagulation treatment of the WW model solutions was
carried out by using coagulant FeSO4·7H2O at ðÍ 9-9.5
during 60 minutes.
Since there are no data on kinetics of acid dissolution
of iron-containing treatment sludge of the wastewater
polluted by dye and SAS in the literature, kinetic regularities
of this process were studied.
The process of sulphuric acid dissolution is
influenced by such factors as acid concentration,
stoichiometric acid excess, temperature regime, dissolution
process duration, and finally by the characteristics of the
sludge itself. Therefore the description of the kinetic
regularities of the process taking into account all the factors
is very complicated. Conditions of acid dissolution were
selected during the prior experiments in the way to facilitate
the achievement of the highest possible iron extraction
degree from sludge [4].
Kinetics of sludge dissolution was studied by the
integral method. Moist iron-containing sludge was placed
into an isothermal reactor with agitator, and the calculated
134 Iryna Kosogina et al.
amount of sulphuric acid with concentration 12 % was
added; sulphuric acid excess to stoichiometry ratio being
1.6. The dissolution time was 1–20 minutes. The content
of the regenerated iron in the solution was measured
photocolorimetricaly by a standard technique [5] at
wavelength λ=440 nm using 10 mm thick cuvette.
3. Results and Discussion
3.1. Mechanism of the process of organic
components removal from wastewater
by coagulation method
In order to determine the mechanism of sulphuric-
acid dissolution of iron-containing sludge it is necessary
1 2
Fig. 1. Photomicrographs of fragments of iron containing sludges of different phase composition: magnetite (1),
amorphous sludge (2) and lepidocrocite (marked by circles) (3). Magnification ×16
A basic compound capable of interacting with SAS
and dyes is aquacomplex of iron (III) hydroxide. A
drawback of magnetite and lepidocrocite formation is their
crystalline structure, which makes it impossible to
regenerate iron by acid method. However, magnetite is
magnetizable, therefore sludge separation and washing
processes are facilitated by applying magnetic field.
After iron (III) hydroxide aquacomplex formation,
SAS and dyes sorption at hydroxide flakes takes place.
As such SAS as ludigol and methaupon are salts of organic
acids there is a probability that the sorption process occurs
either due to elimination of labile sodium atom and partial
substitution of OH-group with acid anion or SAS acting
as a ligand owing to unshared electron pairs at nitrogen
and oxygen atoms within ludigol and methaupon molecules.
Sorption of dye proceeds only due to exchange reactions
in external sphere of aquacomplex. Synthanol is kept at
iron hydroxide flakes surface only owing to physical
to find a compound capable of forming a macromolecule
or a complex with SAS and dyes characteristic of textile
industry wastewater.
Qualitative and quantitative composition of sludge
depends on the conditions of the wastewater treatment
process. During WW coagulation treatment by iron (II)
sulphate aquacomplex of iron (II) hydroxide is formed
initially, which under dissolved oxygen action depending
on hydrolysis conditions can form amorphous
aquacomplex of iron (III) hydroxide, crystalline magnetite,
and/or lepidocrocite. The presence of crystalline structures
of magnetite and lepidocrocite against the background of
X-ray amorphous iron (ІІІ) hydroxide was confirmed both
visually (Fig. 1) and by X-ray analysis (Fig. 2).
3
adsorption by Van der Waals’ forces. After formation and
precipitation of iron-organic complex macromolecules,
sludge separation from supernatant by decantation was
carried out. Sulphuric-acid dissolution of iron-organic
sludge occurs with formation of iron (III) sulphate and
organic acids of corresponding SAS.
It is possible to represent the mechanism of WW
purification from SAS and dye by iron-containing
coagulant as follows:
1 stage – formation of aquacomplex of iron (II):
[Fe(H2O)6]SO4 + 2NaOH = [Fe(H2O)6](OH)2 + Na2SO4;
2 stage – formation of hydrolysates of iron (II):
a) 4[Fe(H2O)6](OH)2 + O2 + 2H2O = 4[Fe(H2O)6](OH)3;
b) 3Fe(H2O)6](OH)2 + 0.5O2 = FeO⋅Fe2O3 + 21H2O;
c) 4[Fe(H2O)6](OH)2 + O2 = 4FeO(OH) + 26H2O;
 Regularities of Low-Waste Technology of Wastewater Treatment by Coagulation Method 135

Fig. 2. Roentgenograms of iron containing sludges: magnetite (1) and lepidocrocite (2)

3 stage – interaction of iron (III) hydroxide with SAS and dye in WW:
with ludigol
a1) [Fe(H2O)6](OH)3 + C6H4NO2SO3Na = = [Fe(H2O)6](OH)2(C6H4NO2SO3) + NaOH;
a2) [Fe(H2O)6](OH)3 + 6C6H4 N && O SO Na =Na [Fe(C H N && O SO ) ] + 3NaOH + 6H O;
2 3 3 6 4 2 3 6 2

or in structural view:
O O O O
N N

[Fe(H2O)6]3+(OH-)2(
O
[Fe(H2O)6](OH)3+ O
) + NaOH
S O Na S O
O O

O .. O O .. O
N N

[Fe(H2O)6](OH)3 + 6( O
) Na3[Fe ( O
)6] + 3NaOH + 6H2O
S O Na S O
O O

with methaupon
b1) [Fe(H2O)6](OH)3 + C21H40ONSO3Na = [Fe(H2O)6](OH)2(C21H40ONSO3) + NaOH;
b2) [Fe(H2O)6](OH)3 + 6C21H40ÖNSO3Na =Na3[Fe(C21H40ÖNSO3)6] + 3NaOH + 6H2O;
&& SO Na = Fe(C H Ö N
b3) [Fe(H2O)6](OH)3 + 3C21H40Ö N && SO ) + 3NaOH;
3 21 40 3 3
136 Iryna Kosogina et al.

with ruby reactive dye 5 СХ

c) [Fe(H2O)6](OH)3 + C19H9N6Cl2(OH)(SO3Na)2 = [Fe(H2O)6]3+(C19H9N6Cl2(O–)(SO3–)2 + H2O + 2NaOH;
or in structural view:
Cl Cl
N N
OH HN N O HN N
N N
[Fe(H2O)6](OH)3 + N N Cl [Fe(H2O)6]3+ ( N N Cl ) + H O + 2NaOH
2
O S O O
S O S S
O O O
O O O O
O
Na
Na

4 stage – sludge dissolution in acid:

2[Fe(H2O)6](OH)2(C6H4NO2SO3) + 3H2SO4 = [Fe(H2O)6]2(SO4)3 + 2C6H4NO2SO3H + 4H2O;
2Na3[Fe(C6H4 N && O SO ) ] + 3H SO + 12H O = [Fe(H O) ] (SO ) + 6C H N && O SO Na + 6C H N && O SO H;
2 3 6 2 4 2 2 6 2 4 3 6 4 2 3 6 4 2 3
2[Fe(H2O)6](OH)2(C21H40ONSO3) + 3H2SO4 = [Fe(H2O)6]2(SO4)3 + 2C21H40ONSO3H + 4H2O;
2Na3[Fe(C21H40Ö N && SO ) ] + 3H SO + 12H O =
3 6 2 4 2
=[Fe(H2O)6]2(SO4)3 + 6C21H40ÖSO3Na + + 6C21H40Ö N && SO H;
3
&&
2Fe(C21H40Ö N SO3)3 + 3H2SO4 + 12H2O = [Fe(H2O)6]2(SO4)3 + 3C21H40Ö N && SO H;
3
3+ – –
2[Fe(H2O)6] (C19H9N6Cl2(O )(SO3 )2 + 3H2SO4 = [Fe(H2O)6]2(SO4)3 + 2C19H9N6Cl2(OH)(SO3H)2;
5 stage – recycling of regenerated coagulant:
[Fe(H2O)6]2(SO4)3 + 6NaOH = 2[Fe(H2O)6](OH)3 + 3Na2SO4.

3.2. Quantum-chemical calculation dissolution process duration effect on iron extraction rate
of thermodynamic characteristics into solution X = f (τ) by a quadric equation is carried out.
of the initial substances For mathematical description of the process, a part
of the experimental data was not taken into account because,
The literary sources provide no information after 15 minutes of sulphuric acid contact with sludge the
concerning the mechanism of SAS and dye interaction process decelerates and then almost reaches equilibrium
with coagulants, therefore quantum-chemical calculation condition (marked on the figure by the dotted line).
of thermodynamic characteristics of the initial substances For each of three curves, polynomial and reliability
was carried out to determine the thermodynamic possibility
R2 approximations are as follows:
of this process running according to the presented
mechanism (Table, Fig. 3). Quantum-chemical calculation for curve 1:
of structure and thermodynamic properties of SAS is Х = –0.0009τ2 + 0.0310τ + 0.4666 R2 = 0.9971
conducted using Hypercube Hyperchem Professional for curve 2:
v7.01 (trial) program. Х = –0.0009τ2 + 0.0307τ + 0.5208 R2 = 0.9997
for curve 3:
3.3. Kinetics of sulphuric-acid dissolution Х = –0.0005τ2 + 0.0223τ + 0.6279 R2 = 0.9993
of iron-containing sludge By derivation of the received polynomials at the fixed
time (τ) values, experimental values of sludge dissolution
Characteristic integral and differential curves of acid by acid rate wekc were calculated and expressed through
sludge dissolution are presented in Fig. 4. In order to the change of rate of iron extraction from sludge (X):
determine iron-containing sludge dissolution by sulphuric
dX
acid rate, approximation of the dependence of sludge wekc = . (1)
dτ

Thermodynamic characteristics of the basic wastewater contaminants

Binding energy, Heat of formation,
Pollutant Total energy, kJ/mol
kJ/mol kJ/mol
Ludigol 3870.0 198.8 527.9
Methaupon 7040.8 697.8 1458.1
Synthanol 7484.1 401.2 3775.9
Ruby reactive dye 5 СХ 10113.3 642.7 1034.0
 Regularities of Low-Waste Technology of Wastewater Treatment by Coagulation Method 137

S S

N
1 2

Cl

N
N

N N Cl
N
N

3 4
Common legend:
– C; – H; – O; – Na.

Fig. 3. Structures of the basic wastewater contaminants: SAS ludigol (1),

methaupon (2), synthanol (3) and ruby reactive dye 5 СХ (4)

Fig. 4. Isothermal kinetics of sludge acid decomposition at temperatures: 293 K (1),

298 K (2) and 303 K (3)
H2SO4 concentration and excess (from stoichiometry) 12 % and 1.6, respectively

Calculated process rate w p can be represented as Then the equation for description of acid sludge
dissolution kinetics should have the following view:
follows:
−E
wp = k ⋅ (1 − X )n , . w p = k0 e RT ⋅ (1 − X ) n (2)
where k is kinetic constant of the process, X – rate of After the transformations equation (2) takes the
iron from sludge extraction, n – order of reaction. following form:
−E E 1
k = k0 e RT , w p = ln k0 − ⋅ + n ln(1 − X ) (3)
R T
where k0 – preexponential factor, E – activation energy, Calculation of the unknowns of equation (3) was carried
J/(mol⋅К). out in Microsoft Office Exсel using function “LINEAR”.
138 Iryna Kosogina et al.
Kinetic parameters of equation (2) are as follows:
k0 = 12355; E = 30300 J/(mol⋅К); n = 0,96. Mean relative
difference between the experimentally measured and
calculated rates does not exceed ±12.5 %. Order n and
activation energy value Е indicate the probability of the
process of acid dissolution of iron-containing sludge
occurrence in internal diffusion range.
4. Conclusions
The mechanism of wastewater purification from
SAS and dyes by iron-containing coagulant has been
established. The main compound capable of reacting with
SAS and dye is aquacomplex of iron (III) hydroxide. The
process of sulphuric-acid dissolution of iron-containing
sludge takes place in external diffusion range, i.e.
dissolution rate depends on the rate of sulphuric acid
diffusion. As a result of dissolution, iron (III) sulphate is
formed, which is further used as a coagulant for typical
WW treatment. However, the regenerated coagulant
solution is polluted with the residues of SAS and their
derivatives, therefore, before using the obtained iron (III)
sulphate solution, it is necessary to treat the coagulant by
catalytic system Н2О2 – Fe2+ (Fe3+).
Acknowledgements
This work has been done under the financial support
of Ministry of Education and Science of Ukraine (grant
No. 0107U002381) and Department of Science and
Innovation of NTUU “KPI” (grant No. 4/9 for young
researchers).
References
[1] Adamenko O., Cheljadin L., Cheljadin V. and Skrobach M.:
Ekotechnologii i Resursozberezhenie, 2007, 6, 68.
[2] Sidko R., Kerzhener B. and Shevchenko M.: Khimia i
Technologia vody, 1986, 8, 50.
[3] Dontsova M., Romodanova V. and Kulskiy L.: Stroitelstvo
i Arhitektura, 1978, 2, 117.
[4] Kosogina I., Astrelin I. and Klimenko N.: Ekotechnologii i
Resursozberezhenie, 2007, 6, 53.
[5] Lurje J.: Analiticheskaya khimiya promyshlennyh
stochnyh vod. Khimiya, Moskva 1984.
ЗАКОНОМІРНОСТІ МАЛОВІДХОДНОЇ
ТЕХНОЛОГІЇ ОЧИЩЕННЯ СТІЧНИХ ВОД
КОАГУЛЯЦІЙНИМ МЕТОДОМ
Анотація. Встановлено механізм процесу очищення
стічних вод від поверхнево активних речовин та сульфатно-
кислотного розчинення, утвореного в результаті очищення
ферумвмісного осаду. Досліджено кінетичні закономірності
розчинення металовмісного осаду сульфатною кислотою.
Запропоновано кінетичне рівняння, яке адекватно описує
експериментальні дані; розраховані константи кінетичного
рівняння.
Ключові слова: сульфатно-кислотне розчинення,
кінетика, квантово-хімічний розрахунок, механізм.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 2, 2008
Andriy Baldis1 and Vasyl Shevchuk2
ANALYSIS AND CHOICE OF OPTIMAL CONDITIONS
FOR THE BURNING OF NATURAL GAS WITH HEATED AIR
IN THE REACTOR OF CARBON BLACK OBTAINING
JSC “Kremenchuk carbon black plant”, 4 Svishtovska str., Kremenchuk, Ukraine
1
2
Lviv Polytechnic National University, 12 Bandera str., 79013 Lviv, Ukraine
Received: March 25, 2008
Abstract. The mixing and burning of natural gas with
heated air in the reactor of carbon black obtaining have
been analyzed. Commercial test results for the device of
partially premixed components with single-flow burner
have been considered. Construction peculiarities and
operational conditions of single- and multi-flow burners
have been examined.
Key words: burner, reactor, carbon black, natural gas,
flame stability.
1. Introduction
The world output of carbon black exceeds 7 million
tons per year [1]. Ukraine has high capacities of carbon
black production in Kremenchuk and Stahanovsk. The
development of new and advanced processes with
simultaneous improvement of performance characteristics
is of great importance.
At present carbon black is obtained by thermal
conversion of hydrocarbon raw material in high-temperature
flow of natural gas and air combustion products at majority
of plants in the world, as well as at Ukrainian plants. The
main parts of the reactor of carbon black obtaining are: a
device for burning of natural gas with air, a mixing chamber
for combustion products with hydrocarbon raw material,
a reaction chamber, a chamber for reaction products cooling
(quenching) till 1073 K using spray water. For the rational
heat usage and reduction of natural gas specific
consumption, air is preheated by gas-carbon mixture passing
from the reactor after quenching zone.
The burning device consists of a burner, through
which natural gas and air are supplied, and combustion
chamber, where burning of natural gas with air takes place.
The burner or its separate parts are made of steel. In order
to achieve the stable and continuous operation of the
reactor and maximum possible yield of carbon black the
burning process must be organized in such a way that
completeness of natural gas combustion, equal distribution
of combustion products concentrations along cross-
Chemical Technology
section before their mixing with hydrocarbon raw material,
stable burning without flame-out or flashback and flame
origin in the burner due to the self-ignition are ensured.
Moreover, it is necessary to prevent the destruction of
the burner metal parts occurring due to their burning or
melting. A single burning device should guarantee a
sufficiently high productivity ( ∼1000–2000 nm3/h for
natural gas and 10000–20000 nm3/h for air).
For the above-mentioned tasks solution it is advisable
to choose the most acceptable burner type and to determine
the device optimum geometrics as well as gas flow rates
while burning of natural gas with heated air takes place.
Different types of burners are widely used. They are
classified by mixing method of gas flows, gas and air
pressures before their feed to the burner, number of gas
flows feeding to the burning zone, fuel gas calorific values
etc. [2-4]. The choice of a burner type mainly depends
upon gas flow parameters (pressure, temperature).
Usually at the plants of carbon black natural gas is
supplied with overpressure not less than 3·105 Pa and air
is supplied with overpressure (0.4–0.5)·10 5 Pa and
preheated to 673–1073 K. Single- and multi-flow burners
with preliminary mixing of the components and multi-
flow diffusive burners without preliminary mixing are used
[5-7]. Advantages and advisability of the mentioned
burners used in the reactors of carbon black obtaining are
open to discussion. Below we analyze conditions of natural
gas with preheated air burning using burners of above-
mentioned types.
2. Results and Discussion
2.1. Device with single-flow burner
of preliminary mixed components
for burning of natural gas with heated air
The principal scheme of the device is represented
in Fig. 1.
The mixing and combustion chambers are lined with
refractory and called as tunnels or tunnel burners [3, 8].
140 Andriy Baldis et al.
The device with single-flow burner of preliminary
mixing is relatively simple in constructing and meets the
mentioned demands under proper conditions of mixing
and burning of natural gas with heated air. The burners
with preliminary full or partial mixing may be used in the
device. Chemically homogeneous mixture is obtained from
the full mixing burner and kinetic burning takes place in
the chamber. The burner with preliminary partial mixing
ensures distribution of components small volumes along
flow section and partial mixing at molecular level takes
place with the formation of combustion mixture volumes;
further mixing of the components and burning take place
simultaneously in the combustion chamber, i.e. diffusive-
kinetic burning takes place. Under other equal conditions
(temperature, pressure, flow rates, diameter of burner
outlet) the mixing chamber length is several times less
and combustion chamber is longer of the burners with
partial mixing compared with those with full mixing. At
high heating temperatures of air in the mixing chamber
the temperature of natural gas with air mixture may be
Fig. 1. Device with single-flow burner of preliminary mixed components for burning of natural gas with heated air: feed
chamber (1), mixing chamber (2) and combustion chamber (3). Flows: natural gas (I), air (II), combustion gases (III)
The penetration depth of jet fed to the continuous
flow at the angle of 90° may be determined using Eq.(1):
Wj γj
h = ks d, (1)
Wf γf
where h – penetration depth of jet into the continuous
flow; Wj– jet linear velocity at the outlet; Wf – flow linear
velocity; γ j – density of gas fed by jet; γ f – density of
gas flow; d–diameter of a hole, throughout which the gas
is fed by jet; k3–proportionality coefficient depending upon
the distance between holes.
higher than self-ignition temperature. To prevent preignition
of the mixture it is necessary that its residence time in the
mixing chamber should be minimum possible. Therefore,
it is advisable to use single-flow burner with partial
preliminary mixing for natural gas combustion in the
reactor of carbon black obtaining.
2.1.1. The choice of gas flow feed method
to the burner
Different methods of gas flow feed (accompanying
flows, counter-current flows, flow feed at an angle) to
the burner are described in the literature [2, 3]. Since
natural gas and air are fed to the reactor of carbon black
obtaining under pressure, it is recommended to feed natural
gas into the heated air coming to the mixing chamber
throughout the holes of little diameters by jets. Such jet
method of mixing allows to distribute small volumes of
natural gas along cross-section of air flow for a very short
periodof time(∼10–3 s). The main regularities of jet method
of mixing are listed in [3, 4].
The jet develops in the continuous flow. The
diameter of developed jet D at the distance of penetration
depth is 0.75h.
Different variants of holes arrangement are used:
in the walls of pipe, through which air is fed, in the walls
of pipe placed along air flow axis etc. At Omsk carbon
black plant in a single-flow burner natural gas is fed by a
pipe through the holes situated in the walls of gas collector
made in a form of beams which are joined to the pipe [7].
At Kremenchuk carbon black plant natural gas is fed into
the air flow through the holes situated in the walls of gas
collector made in the form of the ring with beams [9].
 Analysis and Choice of Optimal Conditions for the Burning of Natural Gas...
Such a design of feed chamber ensures equal distribution
of natural gas small volumes along cross-section of the
air flow in the mixing chamber of large diameter with
corresponding large consumption of natural gas and air.
2.1.2. The choice of gas flow rate from the burner
While burning of preliminary prepared mixture (gas
and air) in the described device (tunnel) stable burning
(stable position of flame basis in the combustion chamber)
is possible within definite limits of gas flow rates. If
mentioned rate is less than a lower limit flashback takes
place in the mixing chamber. If the rate is higher than the
upper limit, flameout from the combustion zone takes
place. The rate lower limit is called as flashback rate Wfb
and the rate upper limit – flameout rate Wfo.
In accordance with theoretical and experimental
results [10, 11] under turbulent conditions of gas flow in
cylindrical pipe the flashback rate of methane-oxygen and
methane-air mixtures may be determined from equation
(2):
W fb = 1.78 Re 0.1 U n , (2)
where Un – normal rate of flame spread; Re – Reynolds
number of gas flow in the cylindrical pipe.
Reynolds number does not exceed value of 106 in
the mixing chamber. Pro tanto Wfb does not exceed Un in
more than 7 times. Under the conditions of carbon black
obtaining the temperature of natural gas and air mixture
which is fed to the combustion chamber does not exceed
1073 K. At mentioned temperature [8] the maximum value
of Un is 4 m/s (for the mixture with excess air coefficient
α ≈ 1). In accordance with Eq. (2) the flashback rate
does not exceed 30 m/s.
The flameout rate depends upon physico-chemical
properties of initial burning mixture (normal rate of flame
spread, heat conductivity, heat capacity, flame
temperature), gas dynamic characteristic of the flow in
the combustion chamber, the chosen method of burning
stabilization. In mentioned device the burning stability is
achieved by circulation of high-temperature flows of
combustion products to the gas flow of initial mixture at
the burner outlet. Using such method of burning
stabilization in tunnel burners while burning of cold
methane-air mixture with α = 1.1 –1.5 the flameout rate is
180–170 m/s, correspondingly [3]. It is mentioned in [3,
8] that under other equal conditions the flameout rate is
proportional to the normal rate of flame spread to the
degree nearly one. The normal rate of flame spread
increases in 5 times with the increase of initial temperature
of methane-air mixture from 293 to 673 K [8]. Hence,
the flameout rate is more than 300 m/s while combustion
141
of natural gas with air preheated to 673 K and higher
temperatures. Thus, in described device a stable
combustion is ensured within a wide range of flow rates
from 30 to 300 m/s.
The gas flow rate at the burner outlet and
correspondingly in the burner mixing chamber is admitted
within a range of 60–200 m/s in the commercial reactors
of carbon black obtaining to support the stable process
without flashback and flameout. The higher gas flow rates
are limited by permissible loss of pressure in the burner
mixing chamber.
2.1.3. Determination of main geometric dimensions
of the mixing chamber and combustion chamber
Burner mixing chamber. The diameter of a burner
mixing chamber is determined by the assigned flow rate of
combustible mixture and gas flow rate at the burner outlet.
In order to achieve necessary productivity in the commercial
reactor of carbon black obtaining at above-mentioned flow
rates the diameter of a burner mixing chamber is within
0.2–0.3 m. The mixing chamber length may be comparable
with the chamber diameter (0.7–1.0 of the diameter). At
the jet feed of natural gas into air stream and mentioned
length of mixing chamber the equal distribution of natural
gas small volumes along cross-section of gas flow which
leaves the burner outlet is achieved.
Combustion chamber. It is necessary to ensure
flame stability and natural gas completeness of combustion
in the combustion chamber. As mentioned above the stable
burning (without flameout) is achieved by circulation of
combustion products to the gas flow of initial mixture at
the burner outlet. The circulation intensity and efficiency
of burning stability depend upon ratio between diameters
of combustion and mixing chambers. To prevent the
flameout at high flow rate at the burner outlet it is necessary
that the mentioned ratio would be within 2–4 [3, 8].
The combustion chamber length must be no less
than turbulent flare length, at which completeness of
natural gas combustion is achieved. A lot of experimental
and theoretical investigations are devoted to the turbulent
combustion of gas flows. The analysis and review of such
works are presented in monographs [3, 8]. In general the
dependence of turbulent flare length upon main factors
may be described as follows:
L f = К f d nW mU n− р , (3)
where Lf – turbulent flare length, m; d – diameter of burner
hole, m; W –rate of gas flow at the burner outlet, m/s;
Un – normal rate of flame spread, m/s; Kf – proportionality
coefficient (its dimensionality m1–n–m+p ⋅sm–p coordinates
values of flare length in meters with other values).
The effect of temperature and combustion mixture
composition on the flare length is evaluated using Un. Values
142 Andriy Baldis et al.
n, m, p and K f in Eq. (3) depend upon gas dynamic
characteristic of turbulent flow (diameter, linear velocity,
Reynolds number).
In accordance with experimental data presented in
[12-14] for the kinetic burning of natural gas-air or natural
gas-oxygen mixtures in developed turbulent flow of
different diameters and rates in the tunnel the above-
mentioned values are following: n = 0.8–0.9, m = 0.2–
0.3, p = 0.45–0.5 and Kf = 1.1–1.2.
For the diffusion-kinetic burning the turbulent flare
length also depends upon mentioned factors but values of
exponents and Kf may differ from those of kinetic burning.
Under similar conditions (burner diameter, temperature,
gas and air flow rates) the length of turbulent diffusion-
kinetic flare is larger than that of kinetic flare. The
quantitative dependence of the length of turbulent
diffusion-kinetic flare upon main factors is described in
literature insufficiently. Therefore such length of the
combustion chamber is needed that completeness of
combustion would be guaranteed. The length is calculated
mainly on the basis of experimental data. Based on the
analysis of operating conditions of the reactor of carbon
black obtaining using devices with single-flow burner of
components partial mixing the general length of the
combustion chamber is 6-8 times larger than the diameter
of a burner hole.
It should be noted that turbulent flare length is
proportional to the diameter of a burner hole to the degree
nearly one and insignificantly depends upon gas flow linear
velocity for the kinetic burning as well as for the diffusion-
kinetic one. Insufficient effect of linear velocity increase
on the change of turbulent flare length is caused by the
fact that increase of linear velocity increases the turbulent
diffusion coefficient, turbulent rate of flame spread and
decreases time of burning completion in the turbulent flow.
Therefore devices with assigned geometrical dimensions
of the mixing and combustion chambers, the completeness
of combustion changes slightly with the change of linear
velocity and combustion mixture flow rate within wide
interval (in 1.5–2 times).
2.1.4. Analysis of self-ignition conditions of heated
mixture of natural gas and air in the burner
mixing chamber
Natural gas containing mixture of ethane and
propane (10–12 vol %) together with some amount of
C4-C 5 hydrocarbons as well as methane is used for
production of carbon black in Ukraine. A heated mixture
of gaseous alkanes with air is formed in the burner mixing
chamber. The excess air coefficient α in the mixture may
be within 1.0–1.5.
Self-ignition of the gas-air mixture may occur in
the case, when mixture residence time in the mixing
chamber is equal or greater than induction period for
assigned temperature, pressure and conditions of mass-
and heat transfer. It is necessary to take into account that
ideal displacement regime of gas flow movement is not
fully reached and residence time of individual elementary
volumes of combustible mixture, in which self-ignition is
possible, may be greater than average residence time of
the gas mixture in the chamber. To prevent self-ignition
of combustible mixture the average residence time of gas
flow in the mixing chamber would be nearly 5 times less
than self-ignition induction period for assigned temperature.
As it was shown above, the gas flow rate in the
mixing chamber of the industrial burner is within
60–200 m/s and the mixing chamber length is 0.2–0.3 m.
The maximum average residence time of combustible
mixture in the burner mixing chamber is 0.005 s. To
prevent premature flame origin in the mixing zone self-
ignition induction period would be more than 0.025 s.
Accordingly to literature data [15, 16] self-ignition
induction period of mixtures of C1-C3 alkanes with air or oxygen
at 853–873 K and atmospheric pressure is nearly one second.
It is obvious that self-ignition of natural gas-air mixture in the
burner mixing chamber is impossible at mentioned temperatures.
At higher temperatures (> 973 K) experimental values of self-
ignition induction period of gaseous alkanes mixtures with air
or oxygen are absent in literature. The self-ignition induction
period decreases with the temperature increase and may be
calculated from Eq. (4):
E
τ = Ae RT , (4)
where τ – self-ignition induction period of the mixture
with assigned composition at temperature T, s; T – mixture
temperature, K; E – effective activation energy, J/mol;
R – absolute gas constant = 8.314 J/mol⋅K; A – constant, s.
In [15] there are experimental values of self-ignition
induction period of mixtures of C 1–C 4 with oxygen
determined within 673–873 K at atmospheric pressure.
Effective activation energies are calculated on the basis
of obtained data. At constant temperature self-ignition
induction periods change slightly with the change of excess
air coefficient α within 1.0–1.5. The effective activation
energy E is ∼250 kJ/mol for the methane-oxygen mixtures
and E = 160 kJ/mol for the mixtures containing ethane and
propane (to 10 vol % calculated for methane) in addition
to methane. Under other similar conditions (temperature,
pressure and excess air coefficient α) self-ignition induction
periods of the mixtures of combustible gas with air or
oxygen slightly differ from each other [16].
Results obtained in [15] with valid approximation
allow to determine the maximum temperature of natural
gas-air mixture at which self-ignition in the burner mixing
chamber does not occur. For the mixtures of natural gas
with oxygen or air which contain the mentioned amount
 Analysis and Choice of Optimal Conditions for the Burning of Natural Gas... 143

of ethane and propane in addition to methane the calculated
values of self-ignition induction period are: 0.06 s – at
973 K, 0.03 s – at 993 K and 0.016 s – at 1013 K. To
prevent self-ignition the temperature of natural gas-air
mixture should be less than 993 K.
At the carbon black plants only air is mainly heated.
Natural gas is fed into a reactor with the temperatures of
293–303 K. In order to achieve mixture temperature of
993 K the air should be heated to 1073 K. Thus, in
accordance with adjusted results self-ignition of natural
gas-air mixture will not occur in the burner mixing
chamber at air heating to 1073 K.
2.1.5. Test of device with single-flow burner
of components partial premixing
for the combustion of natural gas with heated air
in the commercial reactor of highly active carbon
black obtaining
Reactors with mentioned device have been widely
used at Kremenchuk carbon black plant for two years.
Jet mixing is used in the reactor burner. Natural
gas is fed into air continuous flow through the holes with
different diameters situated in the tube walls of metal gas
collector made as a ring with beams. In accordance with
above-mentioned dependences of the jet penetration depth
into a continuous flow and diameter of developed jet upon
main factors the holes optimum dimension and distance
between them were calculated. Equal distribution of natural
gas small volumes along cross-section of air flow is
achieved at these values.
Scheme of the reactor with described device is
presented in Fig. 2.
The ratio between geometrical dimensions of the
burner mixing chamber and combustion chamber agrees
with the above-mentioned dependencies. At the same time
it is necessary to pay attention to some constructive
peculiarities of the combustion chamber. In the reactors
of highly active carbon black obtaining a diameter of the
mixing chamber of combustion products with
hydrocarbon raw material must be considerably less than
that of the combustion chamber after the burner. In
connection with this fact the outlet part of combustion
chamber looks like truncated cone finished by the cylinder.
The cylinder diameter is the same as that of the mixing
chamber of hydrocarbon raw material with combustion
products. The diameter of inlet part is less than the diameter
of central part of combustion chamber, it may additionally
turbulize the flare in the burning zone.
The device for natural gas combustion was tested
under reactor hot bank regime. Under such regime only
burning process was supported, the hydrocarbon raw
material was not fed to the reactor. Before the reactor
outlet combustion products were cooled in the quenching
zone by spray water. The composition of natural gas fed
to the reactor was following (vol %): CH4 – 86.3, C2H6 –
7.3, C3H8 – 3.0, C4H10 – 0.9, C5H12 – 0.1, N2 – 1.3 and CO2
– 1.1. Operating performance: natural gas consumption –

Fig. 2. Scheme of the reactor of carbon black obtaining with device for the burning of natural gas with air: metal gas
collector (1), mixing chamber of natural gas with air (2), combustion chamber (3), mixing chamber of combustion gases with
raw material (4), reaction chamber (5), quenching chamber (6).
Flows: natural gas (I), air (II), raw material (III), water (IV), mixture of reaction gases with carbon black (V).
Indexes: d – diameter of the burner mixing chamber (hole), D1 – diameter of the inlet cylindrical part of combustion
chamber, D2 – diameter of the central cylindrical part of combustion chamber, D3 – diameter of the outlet cylindrical part of
combustion chamber, Lmc –length of the burner mixing chamber, Lcc –combustion chamber length.
144 Andriy Baldis et al.

980 nm3/g, air consumption – 12400 nm3/g, water
consumption for the quenching of combustion pro-
ducts – 4200 l/g, natural gas temperature – 293 K, air
temperature – 723 K, temperature of lining wall in
narrowed part of combustion chamber (measured by
pyrometer)– 2053 K, temperature of combustion products
after quenching – 1103 K, reactor pressure – 0.027 MPa.
At mentioned consumptions of gas flows and
composition of natural gas the excess air coefficient is
1.2. Calculated adiabatic temperature of combustion
products is 2353 K. The gas flow rate at the burner outlet
is more than 100 m/s.
To determine the completeness of natural gas
combustion and equal distribution of components
concentration along the cross-section of combustion
products in the end of burning zone samples of combustion
products were taken by special sampling device cooled
by water. Samples were taken through the holes of raw
jets in the narrowed part of combustion chamber at
different distances from chamber walls. The composition
of combustion products (residue gas) was determined by
chromatography and presented in Table. The analysis
sensitivity was 0.01 vol %.
One can see from the Table that methane is absent
in combustion products and amount of incomplete
combustion products (CO and H2) is miserable. 0.2 vol %
of H2 presented in Sample 3, taken from the middle of the
chamber, is perhaps connected with water vapors
dissociation at high temperatures of gas flow in this place.
A difference of CO2 and O2 concentrations in various
samples does not exceed 1.5 vol %. The excess air
coefficient α is within limits 1.14–1.21. At chosen
geometrical dimensions of device for the combustion and
assigned consumptions of gas flows the complete
combustion of natural gas and equal distribution of
components concentration along cross-section of
combustion products flow before their mixing with
hydrocarbon raw material are ensured.
The experience of reactor long-term commercial
operation shows that stable combustion without flashback,
flameout and flame vibration (buzzing) is achieved using
above-mentioned device for the combustion of natural gas
with heated air. The burning of metal gas collector is
prevented because direct contact between its surface and
high-temperature flow of combustion products is absent.
Described device ensures long-term, persistent and stable
operation of the reactor of carbon black obtaining.
2.2. Multi-flow burners with partial
premixing of combustible gas with air
Similarly to the single-flow burners it is possible to
ensure completeness of combustible gas combustion and
stable combustion for the multi-flow burners by choice
of the optimum geometrical dimensions, consumptions
and gas flow rates. The increase of flow amount will allow
to achieve high productivity of the device at relatively short
combustion chamber.
Nevertheless it is a problem of multi-flow burners
to achieve equal distribution of natural gas and air
consumption by separate flows. Moreover, the
completeness of combustion may be achieved only at
larger excess air coefficient compared with that of a single-
flow burner. Multi-flow burners are more complicated in
manufacture. So, it is more advisable to use single-flow
burners with partial premixing of the components.
2.3. Device with the burner without
components partial premixing for the
combustion of natural gas with air
The mixing and combustion of combustible gas with
air take place simultaneously in the combustion chamber
using the burners of such type, i.e. diffusion burning takes
place. The flame spread rate in turbulent gas flow is defined
by turbulent diffusion rate. In accordance with literature
data [3, 8] the length of diffusion turbulent flare is
proportional to the diameter of single gas flow fed to the
combustion chamber in degree more than one (1.2–1.5).
It is also proportional to the linear velocity of gas flow in

Composition of combustion products (residue gas) in the samples taken

at the outlet of combustion chamber

Sample Composition of combustion products (residue gas), vol %

number CO2 O2 CO H2 CH4 N2
1 9.8 4.1 0 0 0 86.0
2 10.2 3.4 0 0 0 86.4
3 10.6 2.7 0 0.2 0 86.5
4 10.1 3.6 0 0 0 86.3
5 9.9 4.0 0 0 0 86.1
Note: Samples 1 and 5 were taken near chamber walls on the opposite sides. Sample 3 was taken from the middle of the chamber.
Samples 2 and 4 were taken at the distance of 1/4 D3 from chamber walls on the opposite sides.
 Analysis and Choice of Optimal Conditions for the Burning of Natural Gas...
degree less than one and essentially depends upon flow
gas dynamic characteristics at the combustion chamber
inlet. The normal rate of flame spread has a minor effect
on the length of diffusion flare.
For the same diameters and rates of single gas
flows fed to the combustion chamber the length of
diffusion turbulent flare is sufficiently greater (in several
times) than the length of kinetic or diffusion-kinetic flare.
To achieve the high productivity of the device for the
combustion of combustible gas with air using relatively
short combustion chamber (the length is 1–3 m) multi-
flow burners without components premixing are used.
The burners may be of tube type (combustible gas is fed
by tubes and air is fed into tube space), may be constructed
as concentrically placed cylindrical tubes (gas and air
flows are fed separately into gaps between tubes) or can
be of some other type. It is recommended to swirl the
flow for the combustion intensification.
The increase of holes amount through which gas
flows are fed (tubes, gaps) may ensure the necessary
productivity of commercial device for the gas combustion.
Using the burners of diffusion type it is also possible to
ensure the stable combustion without flameout at high
(100 m/s and higher) gas flow rates at the burner outlet
[2, 3]. Instable combustion as a result of flashback or
self-ignition is impossible because the zone of flows
premixing is absent. Therefore, using the burners of
diffusion type there are no limits for the heating
temperatures of flows which are fed into the burning zone.
However, as it was mentioned above, it is a problem to
achieve equal distribution of gas and air consumption in
multi-flow burners. Pro tanto, it is a problem to achieve
the completeness of gas combustion and equal distribution
of components concentration along flow cross-section at
the outlet of the combustion chamber.
Moreover, outlet of the burner of diffusion type
directly contacts with high-temperature combustion
products resulting in possible burning or melting of the metal
burner. To prevent the burner destruction it is recommended
to choose gas flow rates at which flame becomes stable at
the small distance from the burner outlet.
Multi-flow burners of diffusion types are also
complicated in manufacture compared with single-flow
burners with premixing.
3. Conclusions
On the basis of carried out investigations optimum
geometrical dimensions of the device with single-flow
burner of partial premixing of initial components have been
determined. Gas flow rates have also been determined, at
which the flame stability and completeness of combustion
of natural gas with heated air are ensured in the reactor of
carbon black obtaining. It is advisable to use single-flow
145
burners with components partial premixing and the air
heating to 1073 K. At higher temperatures multi-flow
burners without premixing are used.
References
[1] Gulmirasyan T.: Khimiya i tekhnologiya topliv i masel, 2002,
2, 44.
[2] Arseev A.: Szhiganie prirodnogo gaza. Metalurgizdat,
Moskva 1963.
[3] Speisher V.: Szhiganie gaza na electrostanciyah i v
promyshlennosti. Gosenergoizdat, Moskva 1967.
[4] Ivanov Yu.: Gazogorelochnye ustroistva. Nedra, Moskva
1972.
[5] Zuev V. and Mihailov V.: Proizvodstvo sazhi. Khimiya,
Moskva 1970.
[6] Orlov V.: Proizvodstvo i ispolzovanie tekhnicheskogo
ugleroda dlya rezin. “Alexander Rutman” izd-vo, Yaroslavl 2002.
[7] Ivanovskiy V. Tekhnicheskiy uglerod. Procesy i aparaty.
Tekhuglerod, Omsk 2004.
[8] Khitrin L.: Physika goreniya i vzryva. Izd-vo
Moskovskogo universiteta, Moskva 1957.
[9] Baldis A.: Patent Ukrainy No.80734, 2007.
[10] Khitrin L., Moin F., Smirnov B. and Shevchuk V.: 10th
Symposium (International) on Combustion. Pittsburg,
Pensilvania, 1965, 1285.
[11] Moin F. and Shevchuk V.: Physika goreniya i vzryva,
1968, 2,209.
[12] Romanuk I., Zeliznyi A. and Shevchuk V.: Gazovaya
promyshlennost, 1964, 10, 34.
[13] Romanuk I., Zeliznyi A. and Shevchuk V.: Khimicheskaya
promyshlennost, 1964, 12, 11.
[14] Shevchuk V. and Romanuk I.: I Vsesouznyj symposium
po macroscopicheskoi kinetike i khimicheskoi gazodinamike.
Alma-Ata, 1984, 123.
[15] Churik G., Shevchuk V., Romanuk I. and Schemelev G.:
Gazovaya promyshlennost, 1973, 1, 42.
[16] Iost V.: Vzryvy i gorenie v gazah. Inostrannaya literatura,
Moskva 1952.
АНАЛІЗ І ВИБІР ОПТИМАЛЬНИХ УМОВ
СПАЛЮВАННЯ ПРИРОДНОГО ГАЗУ
З НАГРІТИМ ПОВІТРЯМ В РЕАКТОРІ
ОДЕРЖАННЯ ТЕХНІЧНОГО ВУГЛЕЦЮ
Анотація. Проведений аналіз процесів змішування і
горіння потоків природного газу з нагрітим повітрям в
пристрої реактора одержання технічного вуглецю. Наведені
результати промислових випробувань пристрою з однопоточним
пальником попереднього часткового змішування компонентів.
Розглянуті конструкційні особливості і умови експлуатації
однопоточних і багатопоточних пальників для спалювання
природного газу з нагрітим повітрям в реакторах одержання
технічного вуглецю.
Ключові слова: пальник, реактор, технічний вуглець,
природний газ, стабільність полум‘я.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 2, 2008
Sergey Nikulin and Viacheslav Misin
TECHNOLOGICAL AND ECOLOGICAL ASPECTS OF THE PRACTICAL
APPLICATION OF QUATERNARY AMMONIUM SALTS
IN PRODUCTION OF SYNTHETIC EMULSION RUBBERS IN RUSSIA
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences
4, Kosygina str., 119334 Moscow, Russia
misin@sky.chph.ras.ru
Received: November 26, 2007
Abstract. In the review physical and chemical aspects
and technological parameters of the rubbers production
processes from industrial latex with application of ammo-
nium halogenides, tetraalkylammonium salts, poly-(N,N-
dimethyl-2-oxypropyleneammonium) chloride, poly-N,N-
dimethyl-N,N-diallylammonium chloride, and his
copolymer with SO2 are considered. A significant ecological
effect of polymeric flocculants application is shown.
Key words: quaternary ammonium salts, rubber, latex,
flocculants, ecology.
1. Introduction
Coagulation of the rubber emulsion is one of the
main stages during production of synthetic emulsion
rubbers. A routine and quite efficient way of emulsion
rubbers extraction from latexes is the application of inorganic
salts (first of all NaCl) under acidification of the coagulating
system with a mineral acid [1]. It is known that for
coagulation of 1 ton of the industrial emulsion of different
rubbers (butadiene-styrene, butadiene-nitrile, polybutadiene
ones or others) a required quantity of NaCl is from 250 to
1500 kg. Mineral salts in the process of wastewater
treatment at waste disposal plants are not decomposed and
entrapped but drained to the natural wells. This results in
pollution of the environment, soil, and drinking water
salinization. For example, if production capacity of emulsion
butadiene-styrene rubbers is of 100000 tons per year waste
discharge of salts in the form of aqueous solution attains
30000 tons per year just from the extraction workshops.
Thus, at emulsion rubbers production the annual waste
discharge from the extraction workshops to the natural
wells is of hundred thousand tons of NaCl and other salts,
causing an irreversible ecological damage.
The most efficient way of perfection of the rubbers
from latexes extraction technology is the elaboration of
brand new coagulating agents providing a decrease of salt
components consumption or their complete elimination
Chemical Technology
from the technological process. Such coagulating agents
can be water-soluble ammonium salts, particularly
quaternary ammonium salts (QAS).
However, only in Russia a full-scale investigation
work in the field has been made including:
• the study of physical-chemical processes of
latexes coagulation for industrial rubbers production with
the use of cationic polyelectrolytes;
• the study of rubbers properties, their mixtures,
and vulcanizates;
• applied investigations of possible application of
cationic polyelectrolytes in industry.
Previously, flocculation mechanisms of polystyrene
latexes [2-4] and some rubbers [4-7] with the use of QAS
were investigated. However, the works aimed at solving
the chemical and technological problems of the industrial
production of synthetic emulsion rubbers were made later
in Russia.
This article presents the results of the investigations
conducted by the authors concerning the application of
different QAS as coagulating and flocculating agents of
the industrial latexes used in the production of synthetic
rubbers. The works that are directly aimed at the
elaboration of the new approaches to the technology of
extraction of synthetic rubbers from butadiene-styrene
latexes are considered in most details.
According to the abbreviations accepted in Russia
emulsion rubbers are denoted as follows:
• SKS-30 – butadiene-styrene rubber (styrene
content is 30 %);
• SKMS-25 – butadiene-(α-methyl) styrene rubber
(styrene content is 25 %);
• EPB – emulsion polybutadiene;
• SKN-26 SM – butadiene-nitrile rubber
(acrylonitrile content is 26 %);
• Letters A, R, K, P, M, O, C after the numbers
denote: A – a rubber of low-temperature polymerization,
R – regulated, K – colophony emulsifier, P – waxed
emulsifier, M – oil-filled, O – oxide-filled, and C – carbon-
filled (technical carbon).
148 Sergey Nikulin et al.

2. Results and Discussion Me 4 NCl, Et 4NCl, Et 4NBr and n-Bu 4NI a complete
coagulation of latex can be achieved for the consumption
2.1. Low-molecular ammonium salts standards of 60–150 kg/ton of rubber. These values are
2–5 times less than the consumption standard for the
In [8] a reduction of coagulating activity of industrial coagulating agent – NaCl.
ammonium halogenides was observed in a series of In general, coagulating ability of all the low-
NH4F > NH4Cl > NH4Br > NH4J for the discharge intensity molecular salts was not very high.
of these salts equal to 20, 25, 50 and 100 kg/ton of rubber
(pH = 2.5–3.0; temperature is 333 K). Efficiency of
SKS-30 ARK and ARKPN rubber extraction from latexes 2.2. Mixtures of the routine coagulating
in the presence of NH4Cl under the influence of different agents with poly-N,N-dimethyl-N,N-
parameters was studied in details in [9]. The analysis of diallylammonium chloride
the rubber properties as well as compounded rubbers and
vulcanizing agents on their basis demonstrated that these By the example of SKS-30 ARKP (ARK, AKO,
properties do not change in fact under the change of the ARKM) and butadiene-(α-methyl) styrene latexes SKMS-
commonly applied coagulating agent NaCl by NH4Cl (see 30 ARKP (ARK, ARKM) of industrial rubbers [12-15] it
Table 1). was shown that addition of PDMDAACl to the routine
Using SKS-30 ARKP and SKS-30 ARK latexes as coagulating agents (NaCl, leather glue, protein hydrolyzate)
an example it was shown [10, 11] that with the use of created the following advantages:
Table 1
Properties of SKS-30 ARKPN rubbers extracted with the use of NaCl and NH4Cl
as well as rubber compounds and rubber resins
Coagulating agents
Quality performance
NaCl Ammonium chloride
Mooney viscosity 45 46
Conditional toughness under stretching, MPa 25.0/26.9 27.5/26.9
Relative extension under fracture, % 690/670 675/650
Relative residual deformation after fracture, % 16/18 14/16
Rebound elasticity, % 42/40 41/39
Content of antioxidant (Agidol-2), % 1.0/1.0 1.2/1.0
Mass fraction of organic acids, % 4.92 6.06
Mass fraction of saponaceous organic acids, % 0.16 0.05
Loss of mass under drying, % 0.17 0.12
Mass fraction of the bound styrene, % 22.5 22.5

• a long-term preservation of protein coagulating
agents in aqueous solutions at 293–295 K without their
decomposition and appearance of unpleasant smells;
• a part of each of the coagulating agents in a
composition of 2- or 3-component mixture was
considerably less than in case of their individual usage,
resulting in 1.5–2.0 time reduction in a leather glue
consumption;
• application of NaCl- PDMDAACl mixtures enabled
a 5–10 times NaCl consumption reduction to the values
of 20–50 kg/ton of rubber;
• complete coagulation was attained in a wider range
of pH values pH = 2.5–4.5 making it possible to reduce
consumption of H2SO4 from 15–18 to 8–12 kg/ton of
rubber;
• consumption rate of PDMDAACl was 0.4–1.2
kg/ton of rubber;
• the extracted rubbers satisfied the Standard of
the USSR (GOST) and technical specifications (TU)
requirements for the corresponding grade marks of
rubbers;
• the properties of the vulcanizates did not yield to
the properties of the check samples.
All of the oil-filled rubbers and their vulcanizates
satisfied the requirements of the Russian national standards
for the corresponding grade marks of rubbers [13, 14].
The role of PDMDAACl was decisive in the experiments;
increasing the dosage of PDMDAACl to more than 2 kg/
ton of rubber demonstrated the possibility of complete
elimination of NaCl from application.
2.3. Poly-N,N-dimethyl-N, N-
diallylammonium chloride
Since according to [12-15] individual PDMDAACl
is an efficient flocculating agent for the industrial emulsions
of rubbers a large amount of investigations concerning
the influence of different parameters (latex and coagulating
 Technological and Ecological Aspects of the Practical Application of Quaternary Ammonium... 149

agent concentrations, polyelectrolyte consumption and its products of its interaction with the components of
molecular mass, temperature of the process) on the emulsion system.
process of extraction and on the properties of different The investigation of the flocculation of the emulsive
rubber grade marks – SKS and SKMS was performed. polybutadiene (EPB) [21] showed that the consumption
The rubbers extracted with the use of NaCl were used as rate value for PDMDAACl was 8.0 kg/ton of rubber. At
the reference samples [15-20]. 333–353 K the rate value was reduced to 5.0 kg/ton of
The mass of the extracted coagulum was shown rubber. The change of concentration of the operation
to increase with the increase of PDMDAACl amount added PDMDAACl solution from 2.0 to 45.0 % did not have
to the latex [17, 18]. Flocculation completeness was any effect on its consumption rate value. For H2SO 4
achieved for the consumption rate of PDMDAACl ≈ consumption rate value 11–15 kg/ton of rubber a complete
≈ 4 kg/ton of rubber and application rate of H2SO4 ≈ latex flocculation takes place. However the amount of
≈ 15 kg/ton of rubber. Here the application rate of cationic coagulum was regularly reduced from 96–98 % to
polyelectrolyte required for attaining of a complete 94–96 % under decrease of H2SO4 consumption rate value
SKS-30 ARK latex coagulation depends on the temperature: from 10 to 9 kg/ton of rubber. Thus it can be concluded
an optimal coagulation temperature was 333 K. The the process of flocculation is less sensitive to the dosage
application of higher temperatures did not result in a of H2SO4 than under the use of NaCl as a coagulating
considerable increase of a coagulum yield. For the agent. Rubbers, rubber compounds, and vulcanizates of
temperatures of 293 and 353 K flocculation curves did EPB extracted with the use of PDMDAACl and NaCl were
not in fact depend on the value of PDMDAACl molecular equivalent by the main quality parameters. Just as in case
mass (172000, 62000 and 16000). The concentration of of butadiene-styrene rubbers EPB rubber compounds were
the initial aqueous solution of cationic polyelectrolyte did vulcanized a little more rapidly (Table 3) [21].
not have any considerable effect on its consumption rate Similar regularities were found for latex flocculation
necessary for complete extraction of rubber from latex. process of butadiene-nitrile rubber SKN-26 SM with the
The extracted rubbers very slightly differed from use of PDMDAACl [16] as well as for its two fractions
the check samples by their chemical composition and with mean-viscous molecular masses of 11.5⋅104, 2.3⋅104,
satisfied the requirements of the Russian standards. The 17.4⋅104, respectively.
main quality coefficients of vulcanizates on the basis of
the experimental and check samples were equivalent (see 2.4. PDMDAACl copolymer with sulphur
Table 2). However, rubber compounds on the basis of dioxide
SKS-20 ARK rubber extracted with the use of PDMDAACl
were vulcanized more rapidly. According to [17-19] the Flocculation activity of alternative low-molecular
role of vulcanization activators could belong to polymer copolymer of N,N-dimethyl-N,N-diallylammonium
QAS remained in the rubber after its flocculation and/or chloride with sulphur oxide (PDMDAACl-OS) was studied
Table 2
Properties of SKS-30 ARK rubbers extracted with the use of PDMDAACl and NaCl as well as rubber
compounds and vulcanizates based on these rubbers
Flocculating agent
Quality performance
PDMDAACl NaCl
Mass content, %
free organic acids 6.3-6.8 5.8
bound organic acids absent 0.15
antioxidant VTS-150 1.3 1.3
ashes 0.12 0.18
bound styrene 22.5 22.5
Mooney viscosity 54 52
Loss of mass at 378 K, % 0.13 0.19
Duration of vulcanization, min 60 80
Elastic recovery, mm 3.0 3.0
Strain under 300 % extension , MPa 9.4 8.3
Toughness under extension, MPA 27.8 28.8
Relative extension under fracture, % 580 630
Relative residual deformation after fracture, % 14 10
Rebound elasticity, % 40 42
150 Sergey Nikulin et al.

Table 3
Properties of rubbers extracted with the use of NaCl and flocculating agent PDMDAACl as well as rubber
compounds and vulcanizates based on oil-filled EPB
Flocculating agent
Quality performance
PDMDAACl NaCl
Mass content, %
free organic acids 6.0 5.6
bound organic acids absent 0.10
antioxidant VTS-150 0.25 0.25
ashes 0.12 0.18
oils of PN-6K 0 15
Loss of mass at 378 K, % 0.15 0.20
Mooney viscosity 40 40
Strain under 300 % extension, MPa 12.0 10.3
Toughness under extension, MPa 17.7 18.6
Relative extension under fracture, % 430 480
Relative residual deformation after fracture, % 6 10
Plasticity 0.37 0.37

for the industrial latex samples of SKS-30 ARK and EPB
[23]. The completeness of the flocculation for SKS-30
ARK latex was attained at the flocculating agent supply
rate of 18–20 kg/ton of rubber, while for EPB latex it was
14–15 kg/ton of rubber. The introduction of the increased
amount of sulphuric acid as the acidifying agent under
the optimal discharge rate of PDMDAACl-OS did not have
a considerable effect on the amount of the obtained
coagulum. However, the influence of H2SO4 dosage was
more significant under reduced discharge rate of the
flocculating agent. For example, discharge rate of
PDMDAACl-OS was almost twice reduced up to
9.0 kg/ton of rubber for the discharge rate of sulphuric
acid equal to 8.0 kg/ton of rubber. The rubber compounds
on the basis of SKS-30 ARK rubber resin extracted from
the latex with the flocculating agent of PDMDAACl-OS
were vulcanized more rapidly than the check sample due
to the presence of the flocculating agent or the products
of its interaction with the components of the emulsion
system. The physico-mechanical quality indexes of the
vulcanizates on the basis of SKS-30 ARK rubber
correspond to the requirements of the Russian standards.
Similar regularities were observed under the
flocculation of EPB latex. For the discharge rate of
PDMDAACl-OS 10.8 kg/ton of rubber completeness of
the flocculation for EPB latex was attained under the
discharge rate of H2SO4 6.0 kg/ton of rubber. Thus, the
use of PDMDAACl-OS as a flocculating agent would
require its high-precision dosage.
2.5. Poly-(N,N-dimethyl-2-
oxypropyleneammonium) chloride
Dependence of the flocculation process for
SKS-30 ARK latex on the concentration of the dispersed
phase in the presence of poly-(N,N-dimethyl-2-oxypropy-
leneammonium) chloride (PDMOPACl) was investigated
in [24]. The formula of this salt is:
CH 3
+
[ N CH 2 CH CH 2 ]n
Cl-
CH 3 OH
A maximum (optimal point) of flocculation was
found just as in case of latexes extracted with the use of
PDMDAACl. According to [24] this maximum was
associated with two factors (neutralization and bridge)
that can influence the flocculation mechanism. The value
of the concentration of the dispersed phase in the range
of 50, 100, 150 g/l was insignificant in the discharge rate
value of the flocculating agent.
The change of the temperature did not have any
considerable effect on the process of rubber extraction
from latex. Nevertheless, a slight increase of mass of the
forming coagulum was observed with the increase of
the temperature from 293 to 353 K at the initial stage of
the extraction process (for low discharge rate of
PDMOPACl). Decrease of PDMOPACl discharge rate
from 4 to 3 kg/ton of rubber allowed attaining complete
flocculation of SKS-30 ARK la tex only at high
temperatures of 353–368 K and discharge rate of
acidifying agent of up to 30 kg/ton of rubber. If the
discharge rate of PDMOPACl was reduced to 2 kg/ton
of rubber complete extraction of the rubber would not
be achieved even at these temperatures.
The discharge rate of the acidifying agent
demonstrated a greater influence on the flocculation
process than the temperature and concentration of the
dispersed phase in the investigated intervals. For example,
 Technological and Ecological Aspects of the Practical Application of Quaternary Ammonium... 151

under discharge rate of PDMOPACl ~ 4 kg/ton of rubber
mass of the formed coagulum was regularly increased
with the increase of the introduced H2SO4. Coagulum mass
attained ~ 100% for the discharge rate of sulphuric acid
15 kg/ton of rubber that proved to be the optimal
technological parameters of the process.
Rubber compounds and vulcanizates did not
surrender the check sample (Table 4) [24].
2.6. Implementation of the new
technology in the industry of Russia
The performed investigations demonstrated high
efficiency of the utilization of QASs as flocculating agents.
Due to its unique set of properties the most perspective
one proved to be PDMDAACl. By elaborating the
technological conditions for the process of rubber
extraction from latex in the laboratory the following was
achieved:
• PDMDAACl was proven to be a high-efficient
flocculating agent for rubber latexes;
• optimal technological parameters of the
flocculating process for latex were elaborated;
• application of cationic polyelectrolyte PDMDAACl
has no negative effect on the properties of the obtained
rubbers, rubber compounds, and vulcanizates based of
these compounds.

Table 4
Properties of rubber compounds and vulcanizates on the basis of SKS-30 ARK rubber extracted with the
use of NaCl and PDMOPACl flocculating agents and rubber resins

Quality performance NaCl PDMOPACl

Mooney viscosity 53.0 42.5

Carrer placticity, arb. un 0.30 0.28
Recovery, mm 1.86 1.84
Optimum of vulcanization at 416 K, min 80 60
Conditional strain under 300 % stretching, MPa 8.4 14.0
Conditional toughness under stretching, MPa 27.0 27.6
Relative extension under fracture, % 600 540
Relative residual deformation, % 16 15
Rebound elasticity, %
at 293 K 37 32
at 373 K 50 46
Shore hardness, arb. un. 59 65
Shopper-Schlobach abrasion, 10-3 cm3/m 1.80 1.31
Resistance to the growth of cuts up to 12 mm with a puncture, thousands of cycles 39200 115200
Conditional toughness under stretching after ageing (373 K, 72 h) 18.0 20.0
Relative extension after ageing (373 K, 72 h) 242 257

During the period of 1992–1994 the implementation
of the obtained laboratory results was performed at the
synthetic rubber plant, namely:
• operating modes of the industrial flocculation for
SKS-30 latex were completely elaborated;
• more than 372 tons of SKS-30 rubber was
produced;
• application of PDMDAACl did not require
considerable changes in the technology of rubber extraction
from latexes, no capital investments were needed either;
• the factory treatment works operated in normal
mode;
• the produced rubber satisfied the Russian
standards.
Thus, transition to the new technology of all the
manufacturers of emulsion rubbers of only SKS marks in
Russia (the production volume is about 240000 tons) can
significantly reduce the annual ecological damage by:
• ceasing the discharge of 100000–135000 tons of
sodium chloride a year
• decreasing the amount of industrial waste
discharge by 8–10 % (240000 m3 per year).
3. Conclusions
As a result of the performed investigations the
fundamental of a new exclusive ecologically reasonable
industrial technology of latex flocculation for the emulsion
rubbers with the use of cationic polyelectrolyte poly-N,N-
dimethyl-N,N-diallylammonium chloride was elaborated.
This technology was practically implemented in the Russian
industry.
152 Sergey Nikulin et al.
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ТЕХНОЛОГІЧНІ ТА ЕКОЛОГІЧНІ АСПЕКТИ
ПРАКТИЧНОГО ЗАСТОСУВАННЯ ЧЕТВЕРТИННИХ
СОЛЕЙ АМОНІЮ У ВИРОБНИЦТВІ
СИНТЕТИЧНИХ ЕМУЛЬСОВАНИХ КАУЧУКІВ
В РОСІЇ
Анотація. Розглянуто фізичні та хімічні аспекти і
технологічні параметри виробництва каучуків з промислового
латексу із застосуванням галогенідів амонію, тетраалкіламо-
нієвих солей, полі(N,N-диметил-2-оксипропіленамоній)хлориду,
полі-N,N-диметил-N,N-діаліламоній хлориду та його кополімеру
з SO 2. Показано важливий екологічний вплив полімерних
флокулянтів.
Ключові слова: четвертинні солі амонію, каучук,
латекс, флокулянт, екологія.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No. 2, 2008
Anatoliy Kubrak1, Lesya Ladieva1, Anatoliy Burban2 and Roman Dubik1
EXPERIMENTAL METHOD OF CONTACT MEMBRANE DISTILLATION
PROCESS RESEARCH
1
National technical university of Ukraine NTUU “KPI”,
37 Peremohy prosp., 03056 Kiev, Ukraine, làdiåvà_lr@èsers.ïtè-êði.êiåv.ua
2
National University of “Kyiv-Mohyla Academy” 2 G. Skovorody st., 04070 Kiev,Ukraine
burban@ukrma.kiev.ua
Received: March 19, 2008
Abstract. A laboratory setup for the research of contact
membrane distillations (CMD) process is described; a non-
standard algorithm of defining dynamic characteristics of
a channel, which are directly inaccessible for
measurement, by its transitive characteristics that can be
represented as a chain of consistently connected elements,
as well as separate elements of this chain, is offered.
Keywords: contact membrane distillation, desalination,
experimental researches, identification of dynamic
characteristics.
1. Introduction
Experimental research method of the process of
contact membrane distillations is investigated with the
purpose of creating a mathematical dynamics model of
this process.
Membrane distillation (MD) is of interest, imprimis,
as a water purification and desalination as well as
technological solutions concentration method. In comparison
with baromembrane processes (reverse osmosis, ultra- and
microfiltration) MD has advantages as it allows to
concentrate the solutions of numerous non-volatile organic
and inorganic substances close to their solubility limit. The
driving force of the MD process is the solvent’s vapors
partial pressures difference at both sides of the membrane
created due to the temperatures differences of the initial
solution on the outlet side of the membrane and the permeate
or distillate on its inlet side. The membrane is porous and
hydrophobic and plays a role of a selective barrier which is
permeable to vapor only.
The membrane distillation process is insufficiently
investigated, and the reliable formulas for obtaining specific
productivity and other characteristics of the membranes
exist only for the limited number of elementary tasks at
certain assumptions.
Using such dependences frequently causes
substantial divergences with the real data. Moreover,
Chemical Technology
membrane productivity decreases with the exploitation time
due to the change of the hydrophobic-hydrophilic balance
and salt formation on the membrane surface.
For the purpose of the process control a mathematic
model of contact membrane distillations (CMD) dynamics,
which takes into account channel-length and time change
of the membrane permeability, was developed [1].
To check the conformity of the mathematical model
to the process and adjust the indexes of the model
experimental investigations of the dynamic modes of
operation were conducted [2].
2. Experimental
Experimental investigations were carried out on the
laboratory plant graphically represented in Fig. 1. The
laboratory plant has the characteristic of the real processes
running in the industrial machines. The device consists of
two circuits: hot solution and cold distillate. The liquids
are supplied into the membrane module 1 with the help of
a peristaltic pump 2 from collecting vessels 3 and 4,
100 ml each. A membrane module of flat-chamber type
with the membrane area of 0.0063 m2 and channel length
of 0.5 m is used. The experiments were carried out using
MFFK-5 membrane.
The necessary temperature of the solution was
maintained with the help of a heater 5 from whose piped
opening using a peristaltic pump the solution was supplied
to the membrane module. From the membrane module
the solution got to the collecting vessel 3, from where it
got to piped space of the heater 5. Through the tube space
5 the heat carrier, heated with the help of thermostat 6,
was pumped. Such design allowed carrying out the
experiment at the solution concentration close to
crystallization, which could lead to the thermostat damage.
From the collecting vessel 4 distillate was supplied to
the membrane module 1 and then to the piped space of
trumpet space of the coiled refrigerator 7 and poured into
154 Anatoliy Kubrak et al.
Fig. 1. The scheme of the laboratory setup for CMD process research 1 – membrane module; 2 – peristaltic pump;
3 – collecting vessel for solution; 4 – collecting vessel for distillate; 5 – heater; 6 – thermostat; 7 – refrigerator;
8 – measuring vessel; 9, 10 – mercury thermometer; 11-18 – thermocouples; 19 – thermo converter
the collecting vessel 4. Such solution enabled maintaining
constant temperature of water in a cold circuit. Vessel 4 was
also equipped with an overflow pipe. The surplus of water
which appeared in the cold circuit due to its penetration
through the membrane from the solution of the hot circuit,
overflowed through this pipe into the measuring vessel 8.
The temperature mode of the membrane module was
defined with the help of system chromium-copal
thermocouples 11-12 which were mounted on the inlet and
outlet pipes of solution and distillate and two thermocouples
per the membrane module and channels of a solution and
distillate channels. As a secondary device digital multichannel
thermal converter TSP-100 19 was applied.
The productivity of the device by the speed of
solution and distillate streams was established with the
help of the peristaltic pump which allowed changing speeds
in the range of: 1.25–5 ml/s.
The productivity of the membrane module by
permeate was established by fixing the time during which
the volume of water which got to the measuring vessel
reached the value of 100 ml.
It is necessary to note that it is impossible to read the
transitive characteristic for the channel “temperature of the
solution at the inlet point of the membrane module –
temperature of the solution in a control point on the membrane
module length axis” since prior to being supplied to the
membrane module the solution is heated in the coiled heater.
To obtain the transitive characteristics of the
membrane module for the channel “temperature of the
solution at the inlet point of the membrane module –
temperature of the solution in a control point on the
membrane module length axis” transitive characteristics
for the channels: «heater capacity in the thermostat –
temperature of the solution at the inlet point of the
membrane module» and «heater capacity – temperature
of the solution in a control point on the membrane module
length axis» were taken (Figs. 4, 5).
To establish the transfer function of the channel
“temperature of the solution at the inlet point of the
membrane module – temperature of the solution in a control
point on the membrane module length axis” a non-standard
approximating structure shaped as a closed contour
presented in Fig. 2 is used. Such a structure allows to
unite both the smoothing and the identification processes
within one algorithm.
For experimental data smoothing a closed system
like below was used:
Fig. 2. Approximating structure scheme
Fig. 3. Normed approximating structure
As the object transfer factor kobj in the presence of
the transitive characteristic is determined as the height of
the transitive characteristic, the normed (reduced to the
transfer factor) approximating structure was determined.
The transfer factor of the normed structure is equal
to one; the resulting transfer function looks like:
k
(Tp + 1) p =
n
k
W ( p) = .
( + ) +
n
k Tp 1 p k
1+ (1)
(Tp + 1) p
n
 Experimental Method of Contact Membrane Distillation Process Research 155

Structure (1), having only three factors ( k , T , n ) As the result we have the system of three equations
that are subject to definition, can have any exponent (6) - (8) with three unknowns: k, T, n . From (6) we will
( n + 1) under the condition that n ≥ 1 ; by selecting k determine k:
structure (1) can be made both oscillating and aperiodic. 1
By means of elementary transformations structure k=−
(1) can be transformed to: e1 . (9)

Let us put (9) in (7):

1
W ( p) = n +1 e2 − e12
1 + ∑ as p .
s (2) −e1 ( −e1 − nT ) = e2 ⇒ nT = . (10)
s =1
e1
First let us consider k , T , n definition algorithm. For Since

2 ( e3 − e13 − 2e1v )
this purpose Symoju identification method will be used.
Let us develop (1) as Maclaurin series in p. For this purpose v
v = e2 − e ; R = ; w =
2
1 .
we will present (1) as: e1 v
k then from (8) we will obtain:
W ( p) =
n ( n − 1) 2 3 (3)  R 
k + p + nTp 2 + T p + ... n = round 
2 . (11)
 R− w
After division of numerator by denominator we will As (10) is R we can determine:
obtain:
R
T= . (12)
1 11  n
W ( p) = 1 − p +  − nT  p 2 +
k kk  Formulas (9), (11), (12) solve the problem.
Certainly, due to rounding in (11) equation (8) is satisfied
1  nT n ( n − 1) 2 1  3 (4) approximately. If п is specified due to some additional
+ 2 − T − 2  p + ...
k k 2 k  reasons then the problem of inaccurate satisfaction of the
condition (8) is eliminated.
Here p factor was somewhat simplified. Obtaining Maclaurin series for the channel “heater
The factors of the Maclaurin series the transfer factor capacity in the thermostat – temperature of the solution at
is developed can be determined from the corresponding
the inlet point of the membrane module”:
transitive characteristic using the formulas below

es = ( −1) Fs , 1 ≤ s ≤ Ne,
s

t
де Fs = ∫ ( Fs − Fs −1 )dt ,
0 (5)
Fs = lim Fs ( t ) , F0 ( t ) = hn ( t ) .
t →∞


− 1 = e1 , (6)
 k
 1 1
 
  − nT  = e2 , (7)
k  k 
 1  nT n ( n − 1) 1
 2 − T 2 − 2  = e3 . (8)
 k  k 2 k  Fig. 4. The transitive characteristic and visualization
of experimental data for the channel “heater capacity
in the thermostat – temperature of the solution
Having determined hn ( t ) of the necessary amount at the inlet point of the membrane module”
of ( Ne = 3) factors es , comparing the factors of series
Obtaining approximation parameters and transfer
(4) with the corresponding we will obtain: function factors:
156 Anatoliy Kubrak et al.
Obtaining Maclaurin series for the channel
“temperature of the solution at the inlet point of the
membrane module – temperature of the solution in a control
point on the membrane module length axis”:
Fig. 5. The transitive characteristic and visualization of
experimental data on the channel “temperature of the
solution at the inlet point of the membrane module –
temperature of the solution in a control point on the
membrane module length axis”
Obtaining approximation parameters and transfer
function factors:
Let us divide transfer function W2(p) by W1(p), and
in the resulting transfer function reduce close zeros and
poles, and bring it to normed. The final result is:
0,00135
W ( p) =
p + 0,6923p 3 + 0,1872p 2 +
4
+0,0236p + 0,001328
Transitive characteristic of approximated structure
is presented in Fig. 6.
4. Conclusions
The transitive characteristic obtained by this
algorithm (Fig. 6) coincides with the information on the
transitive characteristics for this channel and can be used
for the development of the mathematical model of the
CMD process.
Fig. 6. Transitive characteristic
of approximated structure
References
[1] Ladieva L. and Zhulinskiy O.: ААEKS, 2004, 14, 46.
[2] Ladieva L., Zhulinskiy O., Bryk M and Burban A.:
Avtomatizaciya vyrobnychyh procesiv, 2004, 19, 34.
ЕКСПЕРИМЕНТАЛЬНИЙ МЕТОД ДОСЛІДЖЕННЯ
ПРОЦЕСУ КОНТАКТНОЇ МЕМБРАННОЇ
ДИСТИЛЯЦІЇ
Анотація. Описується лабораторний стенд для дослідження
процесу контактної мембранної дистиляції (КМД);
пропонується нестандартний алгоритм визначення дина-
мічних характеристик каналу, безпосередньо недоступного для
вимірювання за перехідними характеристиками каналів, які
представляють ланцюжок послідовно з’єднаних елементів та
окремих елементів цього ланцюжка.
Ключові слова: контактна мембранна дистиляція, знесолення,
експериментальні дослідження, ідентифікація динамічних
характеристик.
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No 2, 2008
Witold Brostow1 and Poonam Tandon2
REPORT FROM 16TH POLYCHAR WORLD FORUM ON ADVANCED
MATERIALS, WORLD UNITY CONVENTION CENTRE, LUCKNOW,
INDIA, FEBRUARY 17–21, 2008
1
Laboratory of Advanced Polymers & Optimized Materials (LAPOM), Department of Materials
Science and Engineering, University of North Texas, Denton, TX 76203 – 5310, USA; http://
www.unt.edu/LAPOM/; brostow@unt.edu, tcd0033@unt.edu
2
Department of Physics, University of Lucknow, Lucknow 226 007,India
As in past years, the POLYCHAR Forum was
preceded by the popular (16 th) Course on Polymer
Characterization. This time the Course was held on
February 14 at the Indian Institute of Techology ((IIT),
New Delhi. In the following we list the contents of the
Course, some of the presentations made at the Forum,
the award winners, new members of the POLYCHAR
Scientific Committee and the dates for POLYCHAR 17 in
2009.
The Course on Polymer Characterization has been
integral part of POLYCHAR from the very beginning. It
has been organized by VEENA CHOUDHARY this year.
The Course provides basic information on important
characterization techniques. Students, newcomers to
materials science and others take advantage of it. Well
established researchers also find the Course useful - to
get updated information on recent developments outside
their own field. The areas covered were: Basic Theory,
Instrumentation and Application of Vibration Spectroscopy
in Polymer Science (H.W. Siesler, Essen); Liquid
Chromatography of Synthetic Copolymers (Dusan Berek,
Bratislava); Dynamic Mechanical Properties of Polymers
(Michael Hess, Siegen and Kwangju); Light-, Neutron-,
and X-Ray Scattering by Polymer Systems (Jean-Michel
Guenet, Strasbourg); Glass Transition in Glassy Polymers
and other Disordered Materials (Jean-Marc Saiter, Rouen);
Electron Microscopy of Polymers (Goerg Michler, Halle);
Polymer Tribology (Witold Brostow, Denton, TX); and
Hyper Differential Scanning Calorimetry (Prem Chand
Jain, Mumbai). The instructors were available for
questions and discussions during the Course and during
the entire Forum. The Course is a ‘distinguished education
project’ of the International Union of Pure & Applied
Chemistry (IUPAC). Support by Polymer Division of
IUPAC enabled to cover the expenses for all hand-outs
and to waive the fees for a fair number of students.
POLYCHAR 16 was organized by the outgoing Vice
Chancellor of the University of Lucknow RAM P. SINGH
and coordinated by POONAM TANDON. Poonam Tandon
I
Current Events
seemed to be everywhere at once – as were her
collaborators led by ALKA MISHRA. The new Vice
Chancellor AJAIB S. BRAR and JAGDISH GHANDI,
Chairman of World Unity Convention Centre, provided
full support for organization of POLYCHAR 16. We, as
participants, would like to thank them all for good
organization.
As in past years, POLYCHAR puts emphasis on
the quality of research presented – in contrast to
maximizing the number of participants. This allows in
recent years to avoid parallel sessions, and there have been
none this year. The areas covered include Nanomaterials
and Smart Materials; Natural and Biodegradable
Materials and Recycling; Materials Synthesis; Polymers
for Energy; Rheology, Solutions and Processing;
Mechanical Properties and Performance; Characterization
and Structure-Property Relationships; Biomaterials and
Tissue Engineering; Dielectric and Electrical Properties;
Surfaces, Interfaces and Tribology; Predictive Methods.
Symptomatically, the number of papers on ‘green’ science
was higher than at POLYCHAR 15 last year in Búzios,
Rio de Janeiro.
There was a total of 292 registered participants
from 35 countries (Austria, Bangladesh, Belgium, Brazil,
China, Colombia, Croatia, Czech Republic, Egypt, Fiji,
UK, France, Germany, India, Iran, Israel, Japan, Korea,
Kuwait, Mauritius, Malaysia, Mexico, Nepal, Netherlands,
New Zealand, Poland, Portugal, Russia, Sri Lanka,
Slovakia, South Africa, Ukraine, USA, Uzbekistan, and
Venezuela) who have contributed 48 oral presentations
and 170 posters. Many contributions were presented by
students (a number of oral presentations and the majority
of posters). This reflects the philosophy of POLYCHAR
to provide international forum for encourage young
scientists and advanced students to present their scientific
work and give them the opportunity to meet with
colleagues and well-known scientists to discuss their
results, exchange experiences, and make new contacts,
in particular international ones. Many industrial contacts
 Witold Brostow et al.
and international cooperations with exchange of students
and scientists have resulted from this and earlier
POLYCHAR meetings.
Once again, it is virtually impossible to make a
selection from the multitude of excellent oral or poster
presentations from universities, research institutes, and
industry without overlooking important contributions. A
few representative contributions (pars pro toto, but see
also prizes below) are:
ABDEL-AZIM A. ABDEL-AZIM, Egyptian
Petroleum Research Institute, Cairo: Polymeric Additives
for Removal of Petroleum Sludge from Crude Oil Storage
Tanks
HANS-JUERGEN P. ADLER, Andrij Pich, Dirk
Kuckling and Veena Choudhary, Technical University of
Dresden and Indian Institute of Technology New Delhi:
Stimuli-sensitive Nano- , Micro- and Macrogels
HANS-WERNER BEWERSDORFF, Lausitz
University of Applied Sciences, Senftenberg: Drag
Reduction by Additives: Fundamentals and Applications
AJAIB S. BRAR, University of Lucknow: NMR
Studies of Acrylated Copolymers
MICHAEL BRATYCHAK, Lviv Polytechnic National
University: Functional Petroleum Resins Based on
By-products of Hydrocarbon Pyrolysis to Ethylene
WITOLD BROSTOW, University of North Texas:
Prediction of Long Term Service Performance and
Reliability of Polymer-Based Materials (PBMs) from Short
Term Tests
YOSHIKI CHUJO, Kyoto University: New Pi-
conjugated Organoboron Polymers
VERA CIMROVA, D. Výprachtický, P. Pavlaèková,
I. Kmínek and H.-H. Hörhold, Institute of Macromolecular
Chemistry of the Academy of Sciences of the Czech
Republic, Prague: Photophysical and Electrochemical
Properties of Advanced Polymeric Materials for
Optoelectronics
PIOTR CZUB, Cracow University of echnology:
Characterization of Epoxy Resins Compositions with
Modified Natural Oils
ULMAS GAFUROV, Institute of Nuclear Physics,
Tashkent: Molecular Structure, Local Loads Distribution
and Elastic Modulus Connection in a Deformed Oriented
Crystalline Polymer
ANUP K. GHOSH, Indian Institute of Techology,
New Delhi: Process Rheology and Characterization of
Polypropylene-based Nanocomposites
VIRENDRA K. GUPTA, Reliance Industries,
Mumbai: Polymer Research and Technology
HALEY E. HAGG LOBLAND, Witold Brostow,
Miriam Estevez, J. Rogelio Rodriguez and Susana Vargas,
University of North Texas, Denton, and National
Autonomous University of Mexico, Queretaro: Synthesis
II
and Characterization of Novel Porous Hydroxyapatite-
Based Dental Obturation Materials
ALEX M. VAN HERK, Eindhoven University of
Technology: The Origin of Molecular Mass Distributions
in Free Radical Polymerization Seen from a Kinetic
Standpoint
MICHAEL HESS, Stefan Wunderlich and Byoung-
Wook Jo, Siegen University and Chosun University,
Kwangju: Fluorescence Studies af the Interaction of Serum
Albumin with Polymer-modified Drugs
BYOUNG-WOOK JO, Chosun University,
Kwangju: Processable Polybenzoxazole Precursors with
Flame Retardancy
DYLAN D.B. JUNG, D. Bhattacharyya and A.J.
Easteal, University of Auckland: Rotational Moulding of
Flax and Glass Fibre Composites
ALAMGIR KARIM, B.C. Berry, A.W. Bosse, R.L.
Jones, J.F. Douglas, R.M. Briber and H.-C. Kim, National
Institute of Standards and Technology, Gaithersburg, MD,
and IBM Almaden Research Center, San Jose, CA: Guided
Self-assembly of Block Copolymer Thin Films
YUSUKE KAWAKAMI, Japan Advanced Institute
of Science and Technology, Ishikawa: Formation and
Inter-conversion of Polyhedral Oligomeric Silsesquioxanes
JAGJIT KHURMA, University of the South Pacific,
Suva: Miscibility and Molecular Interactions in Polymer
Blends Containing Chitosan
ELIZABETE F. LUCAS, Federal University of Rio
de Janeiro: Polymeric Additives for Petroleum Industry
PETER E. MALLON, University of Stellenbosch,
Matieland: Inorganic-Organic Hybrid Copolymer
Nanofibers
GONZALO MARTINEZ-BARRERA, Enrique
Vigueras-Santiago and Witold Brostow, Autonomous
University of the State of Mexico, Toluca, and University
of North Texas, Denton:
Mechanical Properties of Gamma Irradiated
Concrete
AKIRA MATSUMOTO, Kansai University, Osaka:
Molecular Design of Advanced Vinyl-Type Network
Polymers
MASARU MATSUO, Nara Women’s University:
Gelation/Crystallization Mechanism of Polymer + Carbon
Nanotubes Systems in terms of Thermodynamic and
Morphological Aspects
GOERG H. MICHLER, Martin Luther University,
Halle: Mechanical Properties of Nanostructured Polymers
SARAH E. MORGAN and R. Misra, University of
Southern Mississippi, Hattiesburg: Surface Modification
via Polyhedral Oligomeric Silsesquioxane Nanostructured
Chemicals
SUBRAMANIAM RADHAKRISHNAN, National
Chemical Laboratory, Pune: Conducting Polymer Hybrid
 Report from 16th Polychar World Forum on Advanced Materials, World Unity Convention Centre...
Composites as Smart Materials for Sensive and Protective
Coatings
JEAN-MARC SAITER, University of Rouen:
Influence of the Crystallization on the Average Volume of
the Cooperative Rearrangement Region in the Amorphous
Poly(l-lactic acid)
IRENE SCHNOELL-BITAI, Frank Hinkelmann and
Oscar F. Olaj, University of Vienna: Determinatation of
the Radical Reactivity Ratios in Restricted Penultimate
Copolymerization Systems by a New Linearization
Procedure
RAM P. SINGH, University of Lucknow: High
Technology Materials Based on Modified Polysaccharides
JOHN TEXTER, Eastern Michigan University,
Ypsilanti: Advanced Porous Materials from Ionic Liquid-
based Copolymers
CHUNYE XU, S. Kim and C. Ma, University of
Washington, Seattle: Electrochromic Polymer Windows
and Lenses
The POLYCHAR Prize Committee chaired by Goerg
Michler, Martin Luther University, Halle, has awarded the
following Prizes:
Paul J. Flory Research Prize: JIASONG HE,
Institute of Chemistry, Chinese Academy of Sciences,
Beijing, for a large ensemble of his contributions including
his lecture on Rheological Hybrid Effect and its Conditions
in Filled Polymer Melts
International Materials Science Prize: RAMESHVAR
ADHIKARI, Tribhuvan University, Katmandu, for his
contributions to cooperation between European materials
scientists and their colleagues in Nepal and for his
presentation on Etching of Polycarbonate by DC Glow
Discharge
Bruce Hartmann Award for a Young Scientist (not
older than 32 years): ARCHANA BHAW-LUXIMON,
University of Mauritius, Reduit, and Station Biologique,
Roscoff, for her presentation on Oligoagarose-Grafted
PCL or PDMAEMA Polymers: Synthesis and
Characterization
Juergen Springer Award for a Young Scientist (not
older than 32 years): ROHIDAS AROTE, Seoul National
University, for his presentation on Novel Biodegradable
and Branched Poly(ester amine)s Based on Glycerol
Dimethacrylate and Low Molecular Weight
Polyethyleneimine as a Gene Carrier
Carl Klason Award for the Best Student Paper: Victor
H. Orozco, University of Antioquia, Medellin, for his
presentation on Preparation and Characterization of
Poly(lactic acid)-g-Maleic Anhydride Starch Copolymers
(advisor: Betty L. Lopez)
IUPAC Student Poster Prizes went ex aquo to:
POOJA CHHABRA, Indian Institute of Technology
New Delhi, for her poster on Effects of Structure on
III
Thermal Behaviour of Polyimides (advisor: Veena
Choudhary)
R. DHANYA, Cochin University of Science and
Technology, for a poster on Photophysical and
Electrochemical Investigations on Photocoducting Poly(6-
tertiarybutyl-3,4-dihydro-2H-1,3-benzoxazine) (advisor:
Rani Joseph)
DEWYANI PATIL, North Maharashtra University,
Jalgaon, for a poster on Organic/Inorganic Hybrid of
Poly(o-anisidine) and SnO2: Study of Humidity Sensing
Properties (advisor: Patil Pradip)
Diplomas of Distinction for Student Presentations:
LOPAKSHI BARBORA, Indian Institute of
Technology Guwahati, for her presentation on Composite
Polymer Electrolyte Membranes for Direct Ethanol Fuel
Cell (advisor: A. Verma)
DUSTIN ENGLAND, Eastern Michigan University,
Ypsilanti, for his poster on Reversibly Porating Materials
and Coatings (advisor: John Texter)
JACOB SAMUEL, Kuwait University, Safat, for his
presentation on Microporous Network Polymers Based
on Cobalt-phthalocyanines (advisor: Saad Makhseed)
DOMAGOJ VRSALJKO, University of Zagreb, for
his presentation on Effect of Filler Surface Modification
on Properties of Filled Polyurethane + Poly(vinyl acetate)
Blends (advisor: Vera Kovacevic)
Special Prof. Brar’s 60 th Birthday Celebration
Awards were given to IUPAC Poster Prize winners and to
Domagoj Vrsaljko.
During the Forum there was a meeting of the
POLYCHAR Scientific Committee. Several new Members
have been elected - who have all since agreed to serve:
RAMESHVAR ADHIKARI, Tribhuvan University,
Katmandu
AJAIB S. BRAR, University of Lucknow
JIASONG HE, Institute of Chemistry, Chinese
Academy of Sciences, Beijing
ALEX M. VAN HERK, Eindhoven University of
Technology
MD. MOZAFFOR HOSSAIN, Rajshahi University
ALEJANDRO J. MÜLLER, Simon Bolivar
University, Caracas
IRENE SCHNOELL-BITAI, University of Vienna
POONAM TANDON, University of Lucknow
JOHN TEXTER, Eastern Michigan University,
Ypsilanti
At this time 53 countries are represented on the
POLYCHAR Scientific Committee.
 Witold Brostow et al.
POLYCHAR 17 will be held at the University of
Rouen, April 20 – 24, 2009. Again there will be first a one
day Course on Polymer Characterization. The Forum
format will be similar to that this year and in the past
years. The European Organizing Committee consists of:
Jean-Marc SAITER, University of Rouen, Chair,
Gisèle BOITEUX, University of Lyon
Jean-François FELLER, University of Lorient
José Luis GOMEZ RIBELLES, University of
Valencia
IV
Jean-Michel GUENET, University of Strasbourg
Colette LACABANNE, University of Toulouse
Françoise LAUPRETRE, University of Paris Est
Jean-Marc LEFEBVRE, University of Lille
Helmut MUENSTEDT, University of Erlangen
Jean-Jacques PIREAUX, University of Namur
Correspondence should go to: allison.saiter@univ-
rouen.fr, marie-sylvie.kaelin@univ-rouen.fr, jean-
marc.saiter@univ-rouen.fr
 CHEMISTRY & CHEMICAL TECHNOLOGY
Vol. 2, No 2, 2008
G. Zaikov, L. Zimina and L. Madyuskina
MODERN ACHIEVEMENTS OF THE EXPERIMENTAL METHODS
IN THE FIELD OF INVESTIGATION IN THE STRUCTURE AND
DYNAMICS OF POLYMERS AND POLYMER COMPOSITE MATERIALS
(XVI ENIKOLOPOV’S READINGS)
N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences
4 Kosygin str., 119334 Moscow, Russia
The conference with the title “Modern achievements
of the experimental methods in the field of investigation in
the structure and dynamics of polymers and polymer
composite materials” was held on March 13, 2008 at N.S.
Enikolopov Institute of Synthetic Polymer Materials
(ISPM) Russian Academy of Sciences – RAS (Moscow).
The late academician Enikolopov was the founder of ISPM
and the first director of this Institute.
This conference was organized by Division of
Chemistry and Material Science (CHMS) of RAS, ISPM,
Scientific Council “Highmolecular Compounds” of CHMS,
N.N.Semenov Institute of Chemical Physics (ICP) RAS
(Moscow), Institute of Problems of Chemical Physics
(Chernogolovka, Noginsk district, Moscow area) and
Moscow Physical-Technical Institute (Dolgoprudnyi town,
Khimki district, Moscow area).
About 150 scientists from 25 research centers of
RAS, Ministry of High Education of Russian Federation
and some companies took part in the conference. The
program of the conference included seven plenary lectures
which were divided between two sessions.
The first report was presented by O.M. Sarkisov
(ICP) and was devoted to new directions of chemical
investigations in application of phemtoseconds technologies.
The method of investigation of structure
information in polymer systems (blends and composites)
were discussed in the lecture of A.E. Chalykh, V.K.
Gerasimov, A.V. Shpagin (A.N. Frumkin Institute of
Physical Chemistry and Electrochemistry, Moscow).
V
Current Events
The group of scientists from ISPM (S.L. Bazhenov,
A.S. Kechek’yan) and Chemical faculty of M.V. Lomo-
nosov Moscow State University (A.L. Volynskii, N.F. Ba-
keev, N.V. Bol’shakovsa, S.V. Moiseeva, D.A. Panchuk
and L.M. Yarysheva) presented information about the new
approach for estimation of mechanical properties of solid
materials (nanomethric layers).
The report of A.I. Buzin (ISPM) and N.A. Erina
(VEECO Co., New York, USA) was devoted to the
application of scanning force microscopy methods for
investigation of structure of polymers and composite
materials.
Application of widediapasone dielectric
spectroscopy for control of heterogenety in distribution
of carbon nanopipe and nanoparticles of alumosilicates in
polymer matrix was presented in the report of
I.A. Chmutin, N.G. Ryvkina, I.L. Dubnikova (ICP) and
S.P. Kuznetsov (P.N. Lebedev Physical Institute of
Academy of Sciences).
The director of ISPM A.N. Ozerin delivered the
last lecture of the conference. He spoke about forms and
structures of nanoparticles that can be obtained on the
basis of lowangle X-ray analysis.
The XVI Enikolopov’s readings show that the ideas
of N.S. Enikolopov are implemented in the researches of
his pupils and scientists of his Institute as well as in
different research centers all over the world.
The next XVII Enikolopov’s readings will be held
in March 2009 in ISPM (Moscow).
 INSTRUCTIONS TO AUTHORS
Manuscripts of the articles should be addressed
to the Editor-in-Chief
Prof. Michael Bratychak
Lviv Polytechnic National University
12, Bandera str, 79013 Lviv
and via e-mail: mbratych@polynet.lviv.ua
General
The content of the manuscripts must correspond to the
scope of the journal and be written in English. The Journal is
currently accepting articles in such fields as:
• analytical chemistry;
• general and inorganic chemistry;
• organic chemistry;
• physical chemistry;
• chemistry of high molecular compounds;
• materials science and engineering
• chemical kinetics and catalysis;
• technology of inorganic substances;
• technology of organic synthesis products;
• chemical technology of processing of combustible
minerals;
• processes and apparatus of chemical and food
productions;
• biotechnology;
• ecology.
Authors are fully responsible for the content of their
published materials.
Note for Ukrainian authors. Inclusion of an expert
conclusion (the original) and Ukrainian version of manuscript (2
copies) of the article is obligatory.
After the review of the manuscript and acceptance by the
Editor, page proofs are sent to the authors for correction. The
corrected proofs should be returned to the Editorial Board not later
than 5 days upon review receipt. Otherwise the Editorial Board can
decline the article or postpone its publication.
Preparation of the article
Manuscripts have to be submitted in Microsoft Word 97
or Word 2000 text editor, preferably by e-mail, or 2 copies by
regular mail. Papers should be typed on A4 (210×297 mm) paper
with the following margins: 18 mm on the left, 25 mm on the right,
20 mm on top, 27 mm below. Font – Times New Roman, size 10.5,
1.1 space interval. All pages must be numbered, starting from the
title page. Figures and tables given in a text also should be sent by
separate files (see ii. 10, 11).
Composition of the article
1. A manuscript should contain the following: title page, abstract,
keywords (up to 10), introduction, experimental part, results
and their discussions, conclusions, acknowledgements,
references, tables and figures. In general, SI units should be
used. Abbreviations and uncommon symbols should be explained
at the first mention.
VI
2. The title page should be typed in capital letters (size 14) and
should contain:
• complete name of the author and coauthors
• affiliation and i e-mail, address and name of the author
to whom the correspondence is to be sent
• title of the article
3. An abstract should contain not more than 50 words. It should
shortly present the results of the work and demonstrate its
novelty.
4. Key words should represent content of the whole article and be
characteristic of the terminology used within the particular field
of study.
5. An introduction should be brief and clear and needs to include
relevant references.
6. All materials and methods by which the results were obtained
should be described in the experimental or basic theory part.
Subheadings may be used.
7. Results should be presented with clarity and precision. The
Discussion should interpret the findings in view of the results.
Also here subheadings may be used.
8. Conclusions should emphasize the main achievements of this
work, underline their significance and give examples of their
possible application.
9. Acknowledgements of people, grants, funds, etc should be brief.
10. References must be numbered consequently in the text, in
square brackets. Book titles are given, but titles of articles are
not. Names of authors and journal titles in the Ukrainian or
Russian languages must be typed in Latin letters.
Example:
[1] Kovalskiy D.: Neorganichna khimiya. Naukova dumka, Kyiv
1990.
[2] Novakivskiy V. and Malynovskiy D.: Dopovidi Nats.Akad.
Nauk Ukrainy, 2007, 66, 198.
11. Illustrations (figures, graphics, and pictures) must be given in
a text and by separate graphic files as separate objects, suitable
for corrections or changes, by sizes which correspond to the
parameters of the page. Figures are signed and numbered (if
they are more than one) under the figure, in the center (size 9.5).
Pictures and photocopies must be of high quality, suitable for
copying.
12. Tables should be in the text and be prepared by separate files in
Excel or MS Word. Basic size of the table is 10; size of the
table titles is 10.5. A title is placed in the center of tables, and
numbered consequently throughout the right edge of the table.
13. Formulas are placed in the middle of the text and numbered in
parenthesis on the right.
 National Academy of Sciences of Ukraine
Ministry of Education and Science of Ukraine
Ministry of Health Care of Ukraine
Institute of Organic Chemistry of NAS of Ukraine
Lviv Polytechnic National University
Danylo Halytsky Lviv National Medical University

National Scientific-Technical Conference

with International Participation

ACTUAL PROBLEMS OF SYNTHESIS

AND CREATION OF NEW BIOLOGICALLY ACTIVE COMPOUNDS
AND PHARMACEUTICAL PREPARATIONS

October 15-18, 2008

Lviv, Ukraine

Conference is dedicated to 85 years of Department of Technology

of Biologically Active Compounds, Pharmacy, and Biotechnology
of Lviv Polytechnic National University

Sections:
1. Synthesis of new biologically active compounds.
2. Problems of drugs creation.
3. Technologies of biologically active additives and
pharmaceutical preparations.
4. Biotechnology of biologically active compounds
and drugs production.
5. Polymeric materials of the medical, biotechnological,
and ecological application.
6. Round table for the directors of pharmaceutical
and biotechnological firms and enterprises.

Address for correspondence:

Lviv Polytechnic National University
Department of Technology of Biologically Active
Compounds, Pharmacy and Biotechnology,
Organizing Committee
12, S. Bandera str., 79013, Lviv, Ukraine
E-mail: vnovikov@polynet.lviv.ua,
vladnovikov@list.ru, dr_r_lesyk@org.lviv.net
Site: http://www.lp.edu.ua/index.php?id=2292

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