Volume 04 Issue 09-2024
26
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
ABSTRACT
A process for obtaining naphthalene, indene and phthalic anhydride based on distillation of liquid and solid fractions
of heavy pyrolysis products has been implemented. The quantitative and qualitative composition of resin samples and
the products of processing their fractions have been determined. Superplasticizers-additives for cement have also
been created, their strength, average density of cement particles, the effect of the amount of superplasticizers and
the duration of their action on the properties of the material have been studied.
KEYWORDS
Pyrolysis heavy distillate, naphthalene, indene, phthalic anhydride, superplasticizer.
INTRODUCTION
The purpose of pyrolysis processes, which are
extremely common in modern petrochemistry, is to
Research Article
PRODUCTION OF SUPERPLASTICIZERS BASED ON PYROLYSIS
PRODUCTS OF HEAVY RESINS
Submission Date:
Sep 16, 2024,
Accepted Date:
Sep 21, 2024,
Published Date:
Sep 26, 2024
Crossref doi:
https://doi.org/10.37547/ajast/Volume04Issue09-05
Ziyadullaeva Kamola Xaitboevna
Associate professor at University of Geological Sciences of the Republic of Uzbekistan, Uzbekistan
Ziyadullaev Anvar Egamberdievich
Associate Professor at Tashkent Chemical-Technological Institute of the Republic of Uzbekistan, Uzbekistan
Eshpulatov Mukhammadi
Master's student at Tashkent Chemical-Technological Institute of the Republic of Uzbekistan, Uzbekistan
Journal
Website:
https://theusajournals.
com/index.php/ajast
Copyright:
Original
content from this work
may be used under the
terms of the creative
commons
attributes
4.0 licence.
Volume 04 Issue 09-2024
27
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
obtain lower olefins, primarily ethylene, which is a
valuable raw material for the synthesis of the most
important petrochemical products [1-3].
The pyrolysis process produces ethylene, propylene,
butylene, butadiene, as well as a significant amount of
benzene, aromatic hydrocarbons such as toluene,
xylene, indene, naphthalene and anthracene. Ethylene
obtained by pyrolysis is used to produce ethylene
oxide, ethyl alcohol, polymers, styrene, plastics and
other products. The main areas of application of liquid
pyrolysis products include the production of benzene
and other aromatic hydrocarbons, oils from polymer
resins, diesel fuel, coal and high-quality coke [4-5]. To
improve the quality of the cement composition, it is
important to use highly effective plasticizing additives.
In the construction industry, superplasticizers are used
to regulate the processes of structure formation and
rheological properties of concentrated suspensions.
These are chemical additives that allow changing the
mobility of raw materials and the properties of finished
products. One of the urgent tasks today is the search
for new effective additives that will allow changing the
interfacial properties and rheological characteristics of
dispersions [8-12].
METHODS
For the first time, catalysts of the VBS-33, VBS-44, VBS-
55, VBS-66 types were created for the separation of
naphthalene and indene fractions from secondary
products of gas chemistry at different temperatures
and for the production of plasticizers. The methods of
UV
spectroscopy,
Raman
spectroscopy,
gas
chromatography, mass spectrometry and differential
thermal analysis (DTA) were used in the work. Heavy
pyrolysis oils from gas processing plants, naphthalene,
indene and their homologues, plasticizers for concrete
and cement, phthalic anhydride, naphthalene were
studied.
RESULTS
The main direction of economic development of the
Republic is the development of natural resources, their
use,
large-scale
modernization
of
industrial
production, technical and technological renewal, the
introduction of modern scientific achievements and
progressive innovative technologies in production, the
creation of competitive import-substituting products
with stable demand in the world market. Pyrolysis
distillates and pyrolysis oils, such as naphthalene and
aromatic hydrocarbons, are currently the main
secondary raw materials for the production of valuable
chemical products needed for industry. Processing of
heavy fractions of liquid pyrolysis products and the
introduction of these products into practice in the
future are considered relevant, which allows producing
expensive and necessary products based on modern
technologies. Due to the lack of acceptable
technologies for processing pyrolysis waste for the
production
of
indene,
naphthalene
and
its
homologues, phthalic anhydride is not produced in the
country. Therefore, research aimed at developing
technologies for processing waste from gas chemical
complexes is an urgent task and requires its own
solution.
Pyrolysis distillates and pyrolysis oil, as well as heavy
fractions of liquid pyrolysis products, are secondary
raw materials with great potential for the production
of naphthalene, aromatic hydrocarbons, indene,
phthalic anhydride and other valuable chemical
products.
Currently, modern technologies allow us to produce
expensive and necessary products. Due to the lack of
acceptable technologies for processing pyrolysis
waste for the production of indene, naphthalene and
its homologues, phthalic anhydride is not produced in
our country. Therefore, research aimed at developing
Volume 04 Issue 09-2024
28
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
an integrated technology for processing waste from
gas chemical complexes operating in the republic is an
urgent task and requires a solution.
The process of thermal pyrolysis of hydrocarbon raw
materials is the main method for obtaining low-
molecular unsaturated hydrocarbons-olefins (alkenes)
- ethylene and propylene. The main areas of application
of liquid pyrolysis products include the production of
benzene
and
other
aromatic
hydrocarbons,
naphthalene, petroleum polymers, gasoline, raw
materials for the production of high-quality coke, etc.
Currently, due to the decline in oil production in the
petrochemical industry, the problem of expanding the
raw material base for the production of aromatic
hydrocarbons and their various derivatives is becoming
more urgent. Heavy pyrolysis products such as indene
and naphthalene, as well as their homologues, are of
great interest as potential raw materials for the
production of petrochemical products.
Secondary gas chemical products were separated into
naphthalene and indene fractions at different
temperatures. Based on the obtained products,
catalysts of various compositions were created (VBC-
33, VBC-44, VBC-55, VBC-66) [6].
In Uzbekistan, ethane, propane-butane fractions and
gas condensates are priority raw materials for thermal
pyrolysis of hydrocarbons. During the study, heavy
fractions of liquid and solid pyrolysis products,
secondary gas chemical products and the chemical
composition of pyrolysis distillate were studied.
Analysis of the results showed that the secondary
products isolated from heavy pyrolysis are a liquid with
a pungent odor, in the form of a dark brown fat-like
liquid, and the composition of the resulting raw
materials for pyrolysis is unstable. In order to use liquid
pyrolysis products as secondary raw materials and
develop a technology for their processing, work was
carried out to study the chemical composition of the
pyrocondensate produced at the Ustyurt Gas Chemical
Complex.
Table 1. Chemical composition of pyrolysis distillate
Number of
carbon
atoms
Alkanes
Dienes
Olefins
Cycloalkanes
Arenes
Total
5
0,8
0,89
4,91
0,19
0
6,79
6
0,22
0,41
3,87
0,41
32,94
37,85
7
0,25
0,14
0,84
0,45
11,23
12,91
8
0,12
0,08
0,18
0,48
9,75
10,61
9
0,04
0,1
0,04
0,15
7,56
7,89
10
0,03
0,11
9,07
0,4
5,23
14,84
11
0,18
0,69
2,95
0
0,47
4,29
12
0
0,15
1,84
0
0
1,99
Total
1,64
2,57
23,7
2,08
67,18
97,17
Volume 04 Issue 09-2024
29
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
Fractions of naphthalene and its homologues were
isolated from heavy pyrolysis resins by dealkylation
and rectification. Naphthalene is produced using local
raw materials, which has a positive effect on the
efficiency of the entire process of processing heavy
pyrolysis resins. At the same time, the main problem of
the efficient use of heavy pyrolysis products is
associated with asphaltenes and mechanical impurities
in their composition. The isolated products from heavy
pyrolysis oils are odorless and depend on the
composition of the feedstock. Pyrocondensates from
heavy pyrolysis products containing indene and
naphthalene allow the synthesis of phthalic anhydride
on their basis [7].
Table 2. Qualitative and quantitative composition of heavy pyrolysis resin samples
№
Substance
Number,
%
Degree of
compliance
Retention
time, minutes
1
Indene
9,33
93
12,30
2
1-methylindene
8,96
96
14,72
3
Naphthalene
41,51
90
15,47
4
1-methylnaphthalene 8,61
97
17,59
5
2-methylnaphthalene 16,25
96
17,34
6
1-ethylnaphthalene
1,77
90
18,78
7
1,6-
dimethylnaphthalene
1,71
95
19,18
The qualitative and quantitative composition of heavy
pyrolysis resin samples was studied. The studies were
carried out using an Agilent 5977-A gas chromatograph
with a 30 m × 0.25 mm column, and the composition of
the prepared sample was analyzed by chromatograph
mass spectrometry. The results are presented in Table
2.
In the construction industry, superplasticizers are used
to control the process and formation of the structure,
as well as the rheological properties of organic
chemical additives - concentrated suspensions, which
allows for targeted changes in the fluidity of mixtures
of raw materials and the properties of finished
products.
Based on this, a superplasticizer based on naphthalene
obtained from secondary raw materials of production
was synthesized in the course of the work. The
resulting hydrolyzed polyacrylonitrile, synthesized
superplasticizer and diluted superplasticizer were
analyzed by UV spectroscopy (see Figure 1).
Volume 04 Issue 09-2024
30
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
A) Hydrolyzed polyacrylonitrile;
B) Synthesized superplasticizer;
C) Molten superplasticizer.
Dry building materials were selected for testing
superplasticizers: PS400 D-20 Portland cement,
gypsum, and cement with a high aluminum content.
The effect of superplasticizers on the properties of
these products was studied (see Table 3).
Table 3. Test results for cement with synthesized superplasticizer
Superplasticizers were added in quantities of up to 1%
by weight of the binder. Adding superplasticizers in
quantities greater than 1% in most cases resulted in a
decrease in cement strength.
№
Mass of
cement, g
Amount of
additives by
weight of cement,
%
Water-
cement
ratio
Average
density
g/cm³
Density
1
100
-
0.31
2.065
25
2
100
0.05
0.30
2.05
25
3
100
0.2
0.29
2.142
27
4
100
0.5
0.28
2.12
28
5
100
0.8
0.27
2.15
30
6
100
1
0.27
2.192
31
Volume 04 Issue 09-2024
31
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
Table 4. Test results of cement pastes with synthesized superplasticizer and high
aluminum content
The analysis of the obtained results shows that when
adding a superplasticizer to the mass at a constant
water-cement ratio, the strength of the product
increases, and the average density of cement particles
increases with an increase in the amount of
superplasticizer. This indicates the strength of the
cement mixture and the improvement of its
performance characteristics.
As can be seen from Table 4, when adding a
superplasticizer, the fluidity of cement with a high
aluminum content is 13 cm. Comparison of these
results with conventional cement compositions
showed an increase in plasticity. According to literary
data, this is due to the high content of tricalcium
aluminate.
A
study
of
the
production
of
superplasticizers based on pyrocondensate-pyrolysis
products was carried out, and cement mixtures with
superplasticizers were examined. Their results are
given in Table 5.
Table 5. Test results of the synthesized superplasticizer and gypsum pastes
1
№
Mass of
cement, g
Amount of
additives by
weight of cement,
%
Water-
cement ratio
Average
density
g/cm³
Density
1
100
-
0.43
6
37
2
100
0.02
0.43
6
38
3
100
0.2
0.43
7
42
4
100
0.5
0.43
8
45
5
100
0.8
0.43
11
50
6
100
1
0.43
13
54
7
100
1
0.39
6
66
1
№
Mass of
cement, g
Amount of additives
by weight of cement,
%
Water-
cement ratio
Average
density
g/cm³
Density
1
100
-
0.5
8
11.6
2
100
0.03
0.5
8
16.1
3
100
0.2
0.5
9
15
4
100
0.5
0.5
10
13.3
Volume 04 Issue 09-2024
32
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
The analysis of the results showed that the distinctive
feature of the superplasticizer is that when it is used,
normal setting of the cement mixture occurs with the
formation of a fine-crystalline structure. Also,
according to the X-ray analysis of the binder samples,
superplasticizers do not affect the composition of
hydrated phases on the cement surface.
Figure 1. XRF spectrometer for superplasticizers
At the same time, the superplasticizer also has a
medium plasticizing effect. With an increase in the
amount of superplasticizer, the density increases from
11.6 MPa to 16.1 MPa. With an increase in the amount of
additives in relation to the mass of gypsum from 0.2%
to 1%, the density of the mixture decreases from 15 to
11 MPa.
CONCLUSIONS
5
100
0.8
0.5
11
12
6
100
1
0.5
13
11
Volume 04 Issue 09-2024
33
American Journal Of Applied Science And Technology
(ISSN
–
2771-2745)
VOLUME
04
ISSUE
09
Pages:
26-33
OCLC
–
1121105677
Publisher:
Oscar Publishing Services
Servi
The main content of the pyrolysis distillate is 67.18%
arene with a number of carbon atoms from 6 to 12 and
23.7% olefins, which allows the separation of
naphthalene and indene from the distillate.
Naphthalene, indene and their homologues were
isolated from the composition of heavy pyrolysis oils of
gas processing plants, and plasticizers for concrete and
cement were also obtained. At the same time, the
influence of catalysts of various compositions on
superplasticizers in the process of extracting indene
and naphthalene from heavy pyrolysis products was
investigated and analyzed. The chemical composition
of heavy pyrolysis distillate, the qualitative and
quantitative composition of heavy pyrolysis oil samples
and the results of testing cement with the synthesized
superplasticizer were studied. The structure of the
obtained substances and their physicochemical
properties were confirmed using various methods.
REFERENCES
1.
Павлович Л.Б., Андреиков Е.И. Улучшение
производства
фталевого
ангидрида
из
нафталина промышленного класса. *Коксы
Химия*, 2013, № 9, с. 59–
62.
2.
Романова Н.А., Леонтьева В.С., Хрекина А.С.
Производство коммерческого нафталина путем
переработки каменноугольной смолы. *Кокс и
Химия*, 2018, т. 61, № 11, с. 453–
456. ©
AllertonPress, Inc., 2018. Оригинальный русский
текст опубликован в *Коксы Химия*, 2018, № 1
1,
с. 36–
40.
3.
Саху Б.М., Бера В.В., Кумар Р., Баник Б.К., Бора П.
Полияроматические
углеводороды
(PAHs):
структуры, синтез и их биологический профиль.
*CurrentOrganicSynthesis*, т. 17, вып. 8, 2020, с.
625
–
640.
4.
Ша Ш., Ванг М., Цай Ц., Ши Ц., Сяо Ю. Влияние
структуры полиуксуснойсуперпластификатора
на его производительность в цементных
материалах —
Обзор. *Construction and Building
Materials*,
т.
233,
2020.
https://doi.org/10.1016/j.conbuildmat.2019.117257.
5.
Зиядуллаева К.Х., Нурманов С.Э., Мухиддинов
Б.Ф., Кодиров О.Ш., Вапоев Х.М. Катализатор
окисления ВК
-10-
2 для производства фталевого
ангидрида
из
нафталина.
*Национальная
ассоциация ученых (НАУ)*, № 61, 2020, с. 46–
49.
6.
Зиядуллаева К.Х., Нурманов С.Э., Курбанова
А.Дж., Ахмедова Н. Технологические
основы
приготовления
и
изучение
свойств
катализаторов
при
получении
фталевого
ангидрида на основе нафталина. *Universum:
технические науки*, научный журнал, № 8(89),
Часть 2, Изд. «МЦНО», 2021, с. 37–
43.
7.
Кодиров О.Ш., Зиядуллаева К.Х. Элементный
анализ
синтезированных катализаторов на
основе оксида ванадия и бентонита. *Бухара*,
2020, с. 457–
459.
8.
Батраков В.Г. Модифицированные бетоны.
Теория и практика. М.: Технопроект, 1998. 768 с.
9.
Гамалий Е.А. Комплексные модификаторы на
основе эфиров поликарбоксилата и активных
минеральных
добавок
для
тяжелого
конструкционного бетона: дис. канд. тех. наук,
Челябинск, 2009. 217 с.
10.
Ибрагимов Р.А. Тяжелые бетоны с комплексной
добавкой на основе эфиров поликарбоксилатов:
дис. канд. тех. наук, Казань, 2011. 184 с
.
11.
Рамачандран В.С. Добавки в бетон. Справочное
пособие. М.: Стройиздат, 1988. 244 с.
12.
Рамачандран
В.С.
Применение
дифференциального термического анализа в
химии цементов. М.: Стройиздат, 1977. 408 с
