Catalytic processing of the acid tars
Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of u...
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| author | Krymets, Grigorii V. Litynska, Marta I. Melnychuk, Oleksandr V. |
| author_facet | Krymets, Grigorii V. Litynska, Marta I. Melnychuk, Oleksandr V. |
| author_institution_txt_mv | [
{
"author": "Grigorii V. Krymets",
"institution": "National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute» Peremogy Avenu 37\/4, 03056 Kyiv, Ukraine"
},
{
"author": "Marta I. Litynska",
"institution": "National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute» Peremogy Avenu 37\/4, 03056 Kyiv, Ukraine"
},
{
"author": "Oleksandr V. Melnychuk",
"institution": "V.P Kukhar Institute of Bioorganic Chemistry and Petrochemistry of NAS of Ukraine. Kharkivske shosse, 50, Kyiv-02160, Ukraine"
}
] |
| author_sort | Krymets, Grigorii V. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2023-01-20T10:06:12Z |
| description | Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain  volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production. |
| doi_str_mv | 10.15407/kataliz2022.33.084 |
| first_indexed | 2026-03-12T15:50:17Z |
| format | Article |
| fulltext |
84 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
UDC 621.892.213+658.567.1+544.473
https://doi.org/10.15407/kataliz2022.33.084
Catalytic processing of the acid tars
Grigorii V. Krymets1*, Marta I. Litynska1, Oleksandr V. Melnychuk2
1 National Technical University of Ukraine ”Igor Sikorsky Kyiv Polytechnic Institute”,
37, Peremohy prosp., 03056 Kyiv, Ukraine; krimets@xtf.kpi.ua, m.litynska-2017@kpi.ua
2 V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry, NAS of Ukraine,
1, Murmanska Str., Kyiv, 02094, Ukraine; melnichuk@ex.ua
Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining
and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous
substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric
acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of
vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in
spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to
the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important eco-
logical and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization
methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain
volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or
0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid
tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the
case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the
compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and
centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-
gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile
fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also signifi-
cant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the
main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar
distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is
perspective in the context of fuel production.
Keywords: acid tar, catalytic cracking, oil processing, fuel, utilization
____________________________________________________________________________________________________
Introduction
Acid tars are hazardous, non-utilizable solid
wastes with resinous and viscous characteristics and
varying flowability. It is waste from the processing of
coal, petroleum and petrochemicals (oil refining, ben-
zene refining, petroleum fractions refining and alkyla-
tion of isobutane with butenes) [1]. Sulfonation tech-
nologies are among the oldest technological processes
of oil processing that are still used today due to their
high efficiency of removing undesirable substances
and improving the oxidative stability [2]. In the petro-
leum and petrochemical industries sulfuric acid is used
for the removal of metal impurities from spent lubrica-
tion oils, for the removal of unsaturated hydrocarbons
and sulfur-containing compounds from heavy lubricant
fractions, and for the sulfonation of undesirable impu-
rities in benzene (also toluene and xylene) separation
[1, 3]. Thus, acid tars are produced as a result of these
processes.
Acid tars compositions include resinous substan-
ces, organic matter, and polymerization products of
unsaturated hydrocarbons. The presence of free sulfu-
ric acid in acid tars often reaches 70 % by weight [4].
Almost all metals from oil are concentrated in tars and
contents of vanadium and nickel can reach 0.046 and
0.014 %, respectively [4]. For example, tars stored at
the Lviv city landfill contain 20.6 % of carbohydrates,
78.2 % of such components as resins, carbon, carboids,
ash, and oxidation products. The content of sulphuric
acid and sulfonic acids is about 1.2 % [5]. In the case
of the Kozinske forestry the total concentration of sul-
fonic acids in the aqueous extract from the acid tar is
8.9 %. Derivatives of benzene and naphthalene are
among the main species of sulfonyl chlorides in these
acid tars [6].
A lot of countries keep acid tar in the open air in
spent quarries, storage ponds, barns, lagoons or near
landfills. The USA, UK, Netherlands, Belgium, Ger-
many, Latvia, Slovenia, Slovakia, China, Ukraine, and
Каталіз та нафтохімія, 2022, №33 85
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Zimbabwe are among these countries [7, 8]. Storage of
acid tars in open areas (ponds, lagoons, etc.) causes an
increase in regional environmental hazards [7, 9]. It
poses risk or even potential threat to people and to the
environment nearby due to soil, water and air pollution
[1, 8]. The leaching of the acid tars components affects
the ground water and the evolution of gaseous com-
pounds from the acid tars also affects the atmosphere,
which might cause acid rains, which will in turn affect
surface water, flora, and fauna. During storage in
open-air ponds, the chemical composition of the acid
tar changed as a result of the leaching of the acid from
the tar by rainfall, the evolution of SO2, and condensa-
tion of the different substances [1]. There are elevated
concentrations of total organic carbon (TOC), chemi-
cal oxygen demand (COD), chlorides and sulphates in
groundwater in the indication area of these storage
places [8]. Thus, disposal of the acid tars is a very im-
portant ecological and industrial task.
There are a lot of disposal methods for acid tars,
especially thermal (combustion, gasification, etc.), bio-
logical (usage of microorganisms and enzymes),
physico-chemical (separation of different fractions)
and chemical methods (extraction and other approach-
es with usage of chemical reagents) [10].
Combustion is the most widely used process for
acid tar disposal, but this method has some disad-
vantages, including a high concentration of SO2 in
produced gases and a significant content of heavy me-
tals in the ash [2]. In this case, disposal of one type of
waste leads to the production of polluting gas emis-
sions and another type of toxic waste. Also, deacidifi-
cation is necessary before the combustion due to the
high corrosive activity of acid tars.
Acid tar disposal by biodegradation in natural
conditions also has some disadvantages, especially
significant duration of the degradation process; differ-
rent biodegradability due to possible toxicity; the need
for appropriate nutrients; large area requirements; and
complex control of the biodegradation process [2, 11].
Chemical and physico-chemical processes are
very perspective in the context of acid tars disposal
because they produce a lot of important substances
(liquid fuel, coke, asphaltic binders, surfactants, con-
trolled low-strength materials for landfill liner and
landfill daily cover, polycondensates used as basic
stocks for adsorbents, etc.) [3, 12-14]. But chemical
disposal is often relatively expensive due to the use of
chemical reagents and can produce different wastes.
This research is about catalytic cracking and dis-
tillation of the acid tar for fuel production.
Materials and methods
We chose catalytic cracking and distillation as
the utilization methods for acid tar. The acid tar sample
was characterized by the following parameters: free
acid content - 12%, mineral component - 21.3%,
organic component - 66.7%. The main elements of the
organic component are C-62%, H-17%, O-13%, N-
1.5%, S-6.5%. The aim was to obtain the maximum
quantity of volatile fractions from tar. AlCl3 (an-
hydrous) was used as a catalyst during the cracking of
petroleum residues to obtain volatile gasoline fractions
due to its catalytic activity in many organic reactions.
Although the use of aluminum chloride as a catalyst
cannot be called environmentally friendly, it is still
quite popular due to its high efficiency.
Figure 1 demonstrates lab-scale equipment for
tar cracking. Acid tar and anhydrous AlCl3 were put
into a two-necked flask and heated to a temperature of
about 200 °C. The obtained volatile compounds were
concentrated in condensers. The activated carbon tube
was used to hold emitted gases. For cooling and con-
densation, we used water in the Liebig condenser and
air in the Dimrot condenser.
Two different catalyst ratios (0.15 g/g of tar and
0.1 g/g of tar) were used to study the effect of the
amount of catalyst on the acid tar cracking process. We
also carried out a series of distillations of previously
deacidified and centrifuged tar, acid tar without de-
acidification and centrifugation, and previously deaci-
dified tar without centrifugation. For the first distilla-
tion experiment, acid tar was deacidified by calcium
carbonate (CaCO3) to pH 6 and centrifuged (7000 rpm)
for 20 min to separate solid and liquid phases. After
centrifugation, 107.6 mL of liquid fraction was put into
a round-bottomed flask and inserted into a flask heater
for distillation experiment
Fig 1. Tar cracking lab-scale equipment: 1 - tube
with activated carbon; 2 - the Liebig condenser with
ground glass joints; 3 - the Dimrot 3-way air condenser
with ground glass joints; 4 - two-necked flask with
ground glass joints; 5 - thermometer; 6 - flask heater.
86 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
1H NMR technique was used to characterize the
structures of volatile compounds after cracking and
distillation experiments. The spectra were recorded in
CDCl3 solution (the peak at 7.02 ppm) on a Varian
Gemini-2000 (400 MHz) spectrometer using tetrame-
thyl silane as an internal standard.
Results and Discussion
The catalyst ratios (0.15 g AlCl3/g of tar or 0.1 g/g
of tar) had a very significant influence on the number
of volatile fractions and boiling temperature in the acid
tar cracking process. At the catalyst ratio of 0.15 g/g of
tar at the temperature range of 170-220 °С, we ob-
served the beginning of intensive production of white-
yellow vapors, which condensed in the Liebig conden-
ser. During massive condensation, the temperature de-
creased from 210-220 °С to 180-190 °С. The process
duration was 2 hours. In this case, the content of vola-
tile fractions was 14 %. In the experiment with a cata-
lyst ratio of 0.1 g/g of tar, the content of volatile frac-
tions was 5.5 % and the boiling temperature was about
120-140 °С. According to the findings of 1H NMR
research, the main components of volatile fractions in
the case of catalytic cracking were alkanes CH3-
(CH2)n-CH3 (peaks at 0.91 and 1.30 ppm). The compo-
sitions of the volatile fractions were similar to the
compositions of gasoline and diesel fuel. Table 1
demonstrates information about the interpretation of
1H NMR spectra.
Table 1. The interpretation of 1H NMR
spectra of volatile fractions
Peak, ppm Characteristic group
0.91 CH3 at the tertiary atom
1.30 CH2 in the aliphatic chain
2.23 CH3S in the aliphatic chain
2.29 CH3 in aromatic compounds
2.52 CH3S in the aliphatic chain
2.70 CH2 in aliphatic heterocycles
7.02 CDCl3
10.60 COOH
A series of distillation experiments (distillation
of previously deacidified and centrifuged tar, acid tar
without deacidification and centrifugation, and previ-
ously deacidified tar without centrifugation) gave dif-
ferent results for each type of material (Table 2). In the
first case, we observed signals at 0.91, 1.31, 2.23, 2.29,
2.52, 2.70, 7.02, and 10.60 ppm, which were assigned
to CH3 at the tertiary atom, CH2 in the aliphatic chain,
CH3 in aromatic compounds, CH3S in the aliphatic
chain, CH2 in aliphatic heterocycles, CDCl3, and
COOH. In the second experiment the 1H NMR spec-
trum had peaks at 0.92, 1.30, 2.23, 2.29, 2.54, 2.70,
and 7.02 ppm, which were the signals of CH3 at the
tertiary atom, CH2 in the aliphatic chain, CH3 in aro-
matic compounds, CH3S in the aliphatic chain, CH2 in
aliphatic heterocycles, and CDCl3. In the third 1H
NMR spectrum, we also observed peaks at 0.92, 1.30,
2.23, 2.29, 2.54, 2.70, and 7.02 ppm. But the intensi-
ties of these peaks were different for various samples.
Table 2. The compositions of volatile fractions
Sample Component Content, wt. %
Distilled organic phase obtained at the
temperature of 120 ºC from deacidified
and centrifuged tar
Aliphatic (saturated) hydrocarbons (gasoline fractions) ~ 80
Aliphatic sulfur-containing compounds of CH3-S- and
CH2-S-types
~ 10
Saturated heterocycles ~ 3
Aromatic compounds ~ 4
Acid compounds (aliphatic carboxylic acids) ~ 3
Distilled organic phase from acid tar at
the temperature of 170 ºC (without
deacidification and centrifugation)
Aliphatic hydrocarbons ~ 60
Aliphatic S-organic compounds ~ 30
Saturated heterocycles ~ 4
Aromatic compounds ~ 6
Distilled organic phase obtained at the
temperature of 150 ºC from deacidified
tar (without centrifugation) with add-
ing of 50 mL of distilled H2O
Aliphatic hydrocarbons with a predominance of long-
chained hydrocarbons
~ 90
Aliphatic S-organic compounds ~ 8
Aromatic compounds ~ 2
Thus, in distillation experiments (distillation of
previously deacidified and centrifuged tar, acid tar
without deacidification and centrifugation and previ-
ously deacidified tar without centrifugation) aliphatic
hydrocarbons were the main component of volatile
fractions (~ 80, ~ 60 and ~ 90 %, respectively) and
aliphatic S-organic compounds were also present (~
10, ~ 30 and ~ 8 %).
Conclusions
Acid tars are hazardous, non-utilizable solid
wastes with resinous and viscous characteristics and
varying flowability. This type of waste is produced in
the processing of coal, petroleum, and petrochemicals
(oil re-refining, benzene refining, and petroleum frac-
tions refining).
Каталіз та нафтохімія, 2022, №33 87
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Catalytic cracking and distillation were effective
utilization methods for acid tar due to the significant
amounts of volatile fractions obtained from the tar.
AlCl3 (anhydrous) was used as a catalyst during the
cracking of petroleum residues to obtain volatile gaso-
line fractions due to its catalytic activity in many or-
ganic reactions. The catalyst ratios (0.15 g/g of tar or
0.1 g/g of tar) had a very significant influence on the
amount of volatile fractions and boiling temperature in
the acid tar cracking process. According to the findings
of 1H NMR research, the main components of volatile
fractions in the case of catalytic cracking were alkanes
CH3-(CH2)n-CH3. The compositions of these fractions
were similar to the compositions of gasoline and diesel
fuel.
A series of distillation experiments (distillation of
previously deacidified and centrifuged tar, acid tar
without deacidification and centrifugation and previ-
ously deacidified tar without centrifugation) gave dif-
ferent results for each type of material. The first sam-
ple of the distilled organic phase contained 80 % ali-
phatic (saturated) hydrocarbons (gasoline fractions), 10
% aliphatic sulfur-containing compounds of the CH3-S
and CH2-S types, 3 % saturated heterocycles, 4 %
aromatic compounds, and 3 % acid compounds (ali-
phatic carboxylic acids). The distilled organic phase of
the second sample contained aliphatic hydrocarbons
(60 %), aliphatic S-organic compounds (30 %), satu-
rated heterocycles (4 %), and aromatic compounds
(6 %). And the third sample contained aliphatic hydro-
carbons with a predominance of long-chained hydro-
carbons (~ 90 %), aliphatic S-organic compounds
(~ 8 %) and aromatic compounds (~ 2 %).
Thus, both for catalytic cracking and for tar distil-
lation aliphatic hydrocarbons were the main compo-
nent of volatile fractions. According to 1H NMR spec-
tra of distilled organic phases, deacidification of tar
increased the yield of aliphatic hydrocarbons during tar
distillation and decreased production of S-organic
compounds due to its reactions with calcium car-
bonate. It is very relevant in the context of fuel produc-
tion.
References
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Надійшла до редакції 15.07.2022 р.
88 Каталіз та нафтохімія, 2022, №33
ISSN 2707-5796. Catalysis and Petrochemistry, 2022, 33
Каталітична переробка кислих гудронів
Григорій В. Кримець1*, Марта І. Літинська1, Oлександр В. Мельничук2
1Національний технічний університет України «Київський політехнічний інститут імені Ігоря Сікорського», просп. Пе-
ремоги, 37, 03056 Київ, Україна; krimets@xtf.kpi.ua, m.litynska-2017@kpi.ua
2 Інститут біоорганічної хімії та нафтохімії ім. В. П. Кухаря НАН України, Київ, Україна; melnichuk@ex.ua
Кислі гудрони – це відходи переробки вугілля, нафти та нафтохімічних продуктів. До складу кислих гу-
дронів входять смолисті речовини, різноманітні органічні речовини та продукти полімеризації ненасичених
вуглеводнів, а присутність вільної сульфатної кислоти у кислих гудронах часто досягає 70 % за масою. Майже
всі домішки сполук металів, які містяться у нафті, концентруються у гудронах, а вміст ванадію і нікелю може
досягати відповідно 0,046 і 0,014 %. Багато країн зберігають кислі гудрони під відкритим небом у відпрацьо-
ваних кар’єрах, ставках-сховищах або поблизу сміттєзвалищ. Це створює ризики або навіть потенційну загро-
зу для населення та оточуючого середовища внаслідок забруднення ґрунту, води та повітря. Таким чином,
утилізація кислих гудронів є дуже важливим екологічним і промисловим завданням. У цій статті досліджено
каталітичний крекінг та дистиляцію як методи утилізації кислого гудрону. Безводний AlCl3 було використано
у якості каталізатору крекінгу гудронів з метою одержання летких бензинових фракцій. AlCl3 було обрано за-
вдяки його каталітичній активності у багатьох органічних реакціях. Співвідношення маси каталізатору до ма-
си гудрону (0,15 г/г гудрону або 0,1 г/г гудрону) мало дуже значний вплив на кількість летких фракцій і
температуру кипіння суміші в процесі крекінгу. За результатами ЯМР встановлено, що у випадку каталітично-
го крекінгу основними компонентами летких фракцій були алкани CH3-(CH2)n-CH3. Склад цих фракцій схо-
жий на склади бензину та дизельного палива. Серія дослідів по розгонці (попередньо розкисленого та від-
центрифугованого гудрону, не розкисленого та не від центрифугованого кислого гудрону та попередньо роз-
кисленого, але не від центрифугованого гудрону) дала різні результати для кожного типу матеріалу. Аліфати-
чні вуглеводні були основним компонентом летких фракцій (~ 80, ~ 60 і ~ 90 % відповідно), а вміст аліфатич-
них S-органічних сполук також був доволі високим (~ 10, ~ 30 та ~ 8 %). Таким чином, як для каталітичного
крекінгу, так і для розгонки гудрону аліфатичні вуглеводні були основним компонентом летких фракцій. Роз-
кислення гудрону підвищувало вихід аліфатичних вуглеводнів при розгонці та зменшувало утворення
S-органічних сполук за рахунок їх реакцій з кальцієм карбонатом. Це робить метод доволі перспективним в
контексті виробництва палива.
Ключові слова: кислий гудрон, каталітичний крекінг, нафтопереробка, паливо, утилізація
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| id | oai:katalizorgua:article-85 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:17Z |
| publishDate | 2022 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/fd/3711850d0978dc357ef386f6b68c09fd.pdf |
| spelling | oai:katalizorgua:article-852023-01-20T10:06:12Z Catalytic processing of the acid tars Catalytic processing of the acid tars Krymets, Grigorii V. Litynska, Marta I. Melnychuk, Oleksandr V. acid tar; catalytic cracking; oil processing; fuel; utilization кислий гудрон, каталітичний крекінг, нафтопереробка, паливо, утилізація Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain  volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production. Acid tars are wastes from the processing of coal, petroleum, and petrochemicals (oil refining, benzene refining and petroleum fractions refining and alkylation of isobutane with butenes). Acid tar compositions include resinous substances, organic matter, and polymerization products of unsaturated hydrocarbons. The presence of free sulfuric acid in acid tars often reaches 70 % by weight. Almost all metals from oil are concentrated in tars, and the content of vanadium and nickel can reach 0.046 and 0.014 %, respectively. A lot of countries keep acid tar in the open air in spent quarries, storage ponds, barns, lagoons or near landfills. It poses a risk or even potential threat to people and to the environment nearby due to soil, water, and air pollution. Thus, disposal of the acid tars is a very important ecological and industrial task. In this study, we have researched catalytic cracking and distillation as the utilization methods for acid tar. Anhydrous AlCl3 was used as a catalyst during the cracking of petroleum residues to obtain  volatile gasoline fractions due to its catalytic activity in many organic reactions. The catalyst ratios (0.15 g/g of tar or 0.1 g/g of tar) had a very significant influence on the number of volatile fractions and boiling temperature in the acid tar cracking process. According to the results of 1H NMR research, the main components of volatile fractions in the case of catalytic cracking were alkanes CH3-(CH2)n-CH3. The compositions of these fractions were similar to the compositions of gasoline and diesel fuel. A series of distillation experiments (distillation of previously deacidified and centrifuged tar, acid tar without deacidification and centrifugation, and previously deacidified tar without centrifu-gation) gave different results for each type of material. Aliphatic hydrocarbons were the main components of volatile fractions (~ 80, ~ 60 and ~ 90 %, respectively) and the contents of aliphatic S-organic compounds were also significant (~ 10, ~ 30 and ~ 8 %). Thus, both for catalytic cracking and for tar distillation, aliphatic hydrocarbons were the main component of volatile fractions. Deacidification of tar increased the yield of aliphatic hydrocarbons during tar distillation and decreased production of S-organic compounds due to its reactions with calcium carbonate. It is perspective in the context of fuel production. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2022-10-27 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/85 10.15407/kataliz2022.33.084 Catalysis and petrochemistry; No. 33 (2022): Catalysis and petrochemistry; 84-88 Каталіз та нафтохімія; № 33 (2022): Каталіз та нафтохімія; 84-88 2707-5796 2412-4176 10.15407/kataliz2022.33 en https://kataliz.org.ua/index.php/journal/article/view/85/68 Copyright (c) 2022 Catalysis and petrochemistry |
| spellingShingle | кислий гудрон каталітичний крекінг нафтопереробка паливо утилізація Krymets, Grigorii V. Litynska, Marta I. Melnychuk, Oleksandr V. Catalytic processing of the acid tars |
| title | Catalytic processing of the acid tars |
| title_alt | Catalytic processing of the acid tars |
| title_full | Catalytic processing of the acid tars |
| title_fullStr | Catalytic processing of the acid tars |
| title_full_unstemmed | Catalytic processing of the acid tars |
| title_short | Catalytic processing of the acid tars |
| title_sort | catalytic processing of the acid tars |
| topic | кислий гудрон каталітичний крекінг нафтопереробка паливо утилізація |
| topic_facet | acid tar catalytic cracking oil processing fuel utilization кислий гудрон каталітичний крекінг нафтопереробка паливо утилізація |
| url | https://kataliz.org.ua/index.php/journal/article/view/85 |
| work_keys_str_mv | AT krymetsgrigoriiv catalyticprocessingoftheacidtars AT litynskamartai catalyticprocessingoftheacidtars AT melnychukoleksandrv catalyticprocessingoftheacidtars |