CC BY
19
AZ9RBAYCAN KIMYA JURNALI № 4 2016
53
UDC 665.6/.7
THERMOCATALYTIC CONVERSION PROCESS OF HEAVY GASOIL OF CATALYTIC CRACKING AND ITS MIXTURE WITH COTTONSEED OIL
T.A.Mammadova, M.M. Abbasov, N.V.Hasankhanova, S.K.Aliyeva, X.Sh.Teyubov, T.S.Latifova, R.T.Adilov, A.A.Alizade*, V.M.Abbasov
Yu.Mamedaliyev Institute of Petrochemical Processes, NAS of Azerbaijan * Azerbaijan State University of Oil and Industry
Received 04.07.2016
The production process of (C2-C4) low molecular weight olefins as a result of thermocatalytic conversion of the fraction heavy gasoil of catalytic cracking (HGCC) and its mixture with cottonseed oil in the temperature range of 550-7000C has been investigated. It is faund that at result the thermocatalytic conversion of pure HGCC fraction at 7000C, the increase of 16.1-16.4 and 6.3-6.1% have been recorded for the yield of ethylene and propylene respectively. When 10% of cottonseed oil is added to this fraction in the presence of Omnikat-210P and Omnikat-210P/halloysite mixture catalysts in 7000C, 3-2.8 and 0.6-1.4% of mass increases have been observed for ethylene and propylene respectively.
Keywords: catalytic cracking, heavy gasoil, ethylene, propylene, halloysite, low molecular weight olefins.
Introduction
Low molecular weight olefins are considered as major products of petrochemical industry and ethylene, propylene and butylenes are used as main olefins. Extending petroleum refining, efficient usage as well optimization and improvement of the quality of petroleum products are one of the most actual problems. Currently, besides ethylene, the demand for propylene is increasing day by day [1]. The increment for the demand of ethylene and propylene are 3.7 and 4.7% respectively per year. In order to eliminate the deficiency of propylene, the production should reach 7%. Taking into consideration of extending petroleum refining problem, the usage of miscellaneous heavy petroleum fractions for this process has a great importance.
On the other hand, the usage of renewable feedstock types are one of the most actual problems due to the shortage of petroleum reserves. Currently, vegetable oils are the widespread feedstock type among the renewable resources for the production of different fuel and petrochemical products [2-4]. A number of investigations are being operated
for the direct application of renewable resources to petrochemical industry and research of deep catalytic cracking process [1, 2].
Experimental
In this proceeding, the thermocatalytic conversion of pure heavy gasoil fraction which is obtained from catalytic cracking process (HGCC) and its mixture with cottonseed oil in the temperature range interval of 550-7000C has been investigated. Omnikat-210P and its mixture with halloysite-natural nanotube have been used as catalysts in Baku Oil Refinery named after H.Aliyev.
Halloysites-natural nanotubes and Omnikat-210P - synthetic zeolite have been used as catalysts for deep catalytic cracking process of heavy gasoil fraction. On the other hand, this mixture has been used in contact pyrolysis process which is one of the main industrial pyrolysis types and is operated by solid heat carrieers for providing heat surface. The mentioned catalyst contains 10% (by mass) halloysite [3].
When halloysite is added to Omnikat-210P catalyst, the production yield of olefins increases for all temperature intervals.
54 THERMOCATALYTIC CONVERSION PROCESS OF HEAVY GASOIL
Results
The yields of gases produced by using Omnikat-210P and halloysite are illustrated in Table 1.
As it is obvious from the table, the maximum yield for ethylene has been observed at 7000C by using Omnikat-210P and Omnikat-210P/halloysite mixture catalysts with 22.423.1%. For propylene, it was 16.5-17.1%. Halloysite is used as a heating surface at high temperatures and has an advantage for this process. When the results of the process at 5500C is compared with the process at 7000C, 16.1-16.4% and 6.3-6.1% of improvement can clearly be seen for the yield of ethylene and propylene respectively by using 0mnikat-210P
and 0mnikat-210P/halloysite mixture.
When 10% of vegetable oil is added to refined feedstock, the yields of both ethylene, propylene, as well as total olefin gases increase (Table 2).
As it is obvious from Table 2, the addition of 10% of cottonseed oil to HGCC at 7000C increases the yield of ethylene and propylene to 25.4-25.9 and 17.1-7.8% respectively, by using 0mnikat-210P and Omnikat-210P/halloysite mixture. According to catalyst, 3-2.8 and 0.6-1.4% of increases have been recorded for ethylene and propylene respectively. The addition of halloysite to catalyst causes 0.4-1.1 and 0.1-1.3% of increases for ethylene and propylene respectively.
Table 1. The hydrocarbon content of the gases produced by thermocatalytic conversion of HGCC by using Omnikat-
210P (I) and its mixture with halloysite (II)
Hydrocarbon content of gases, mas. % Catalysts
I II I II I II I II
Temperature of the process, 0C
550 600 650 700
methane 1.7 1.9 3.6 3.8 6.8 7.2 8.2 8.7
ethane 1.6 1.2 1.8 1.6 2.4 1.8 2.8 2.4
ethylene 6.3 6.7 10.2 11.6 18.5 19.5 22.4 23.1
propane 2.65 2.3 1.2 1.4 1.8 1.6 2.0 1.9
propylene 10.2 11.0 13.4 14.3 14.5 15.1 16.5 17.1
butane 1.6 1.8 1.4 1.0 1.7 1.4 1.8 1.6
E butylenes 2.45 2.4 4.4 4.2 3.0 4.3 5.0 7.0
Sum 26.5 27.3 36.0 37.9 48.7 50.9 58.7 61.8
E olefin con- taining gases 18.95 20.1 28.0 30.1 36.0 38.9 43.9 47.2
Hydrocarbon content of gases, mas.% Catalysts
I II I II I II I II
Temperature of process, 0C
550 600 650 700
methane 1.9 2.1 4.0 4.3 7.1 7.2 8.6 8.7
ethane 1.5 1.4 2.1 1.9 2.6 1.5 3.0 2.1
ethylene 6.8 7.2 11.1 12.2 21.7 22.4 25.4 25.9
propane 3.0 2.7 1.4 1.8 2.0 1.2 2.2 1.6
propylene 11.0 11.3 14.1 15.4 15.6 15.4 17.1 17.8
butane 1.8 1.7 1.2 1.3 1.4 1.6 1.6 1.4
E butylenes 2.3 2.8 4.6 3.9 2.0 4.4 5.9 7.9
Sum 28.3 29.2 38.5 40.8 52.4 53.7 63.8 65.4
E olefincontaining gases 20.1 21.3 29.8 30.1 39.3 42.2 48.4 51.6
Table 2. The content of hydrocarbon gases obtained from thermocatalytic conversion of heavy gasoil of catalytic cracking which contains 10% vegetable oil by using Omnikat-210P (I) and its mixture with halloysite (II)
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2016
T.A.MAMMADOVA et al.
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References
1. Жагфаров Ф.Г., Григорьева Н.А., Лапидус А.Л. Новые катализаторы процесса пиролиза // Химия и технология топлив и масел. 2005. № 2. С. 41-43.
2. Nishino J., Itoh M., Fujiyoshi H., Uemichi Y. Catalytic degradation of plastic waste into petrochemicals using Ga-ZSM-5 // Fuel. 2008. V. 87. P. 3681-3686.
3. Nakamura D. Special report: ethylene capacity rising, margins continue to suffer // Oil Gas J. 2002. No 4. P. 265-278.
4. Suarez P.A.Z., Meneghetti S.M.P., Meneghetti M.R., Wolf C.R. Transformation of triglycerides into fuels, polymers and chemicals: some applications of catalysis in oleochemistry // Quim Nova. 2007. V. 30. P. 667-676.
KATALÍTÍK KREKÍNQÍN AGIR QAZOYLUNUN VO ONUN PAMBIQ YAGI ÍLO QARI§IGININ
TERMOKATALÍTÍK ÇEVRILMOSÎ
T.A.Mamm3dova, M.M.Abbasov, N.V.Hasanxanova, S.K.Oliyeva, X.§.Teyyubov, T.S.Latifova,
R.T.Adilov, O.A.Olizad3, V.M.Abbasov
Katalitik krekinq prosesindan alinmiç (KQKA) agir qazoyl fraksiyasinin tamiz halda va onun pambiq yagi ils qariçiginin 550-7000C temperatur intervallarinda termokatalitik çevrilmasi naticasinda C2-C4 açagi molekullu olefinlarinin alinma prosesi tadqiq olunmuçdur. KQKA fraksiyasinin tamiz halda 7000C temperaturda termokatalitik çevrilmasi zamani Omnikat-210P va Omnikat-210P/halloizit qariçiq katalizatorlari istifada olunduqda uygun olaraq etilenin çiximinda 16.1-16.4%, propilenda isa 6.3-6.1% kütartim olmuçdur. Bu fraksiyaya 10% pambiq yagi alava olunduqda 7000C-da Omnikat-210P va Omnikat-210P/halloizit qariçiq katalizatorlari içtirakinda uygun olaraq etilenin 3-2.8%; propilenin isa 0.6-1.4% kütla artmasina sabab olmuçdur.
Açar sözlar: katalitik krekinq, agir qazoyl, etilen, propilen, halloizit, a§agi molekullu olefmhr.
ТЕРМОКАТАЛИТИЧЕСКОЕ ПРЕВРАЩЕНИЕ ТЯЖЕЛОГО ГАЗОЙЛЯ КАТАЛИТИЧЕСКОГО КРЕКИНГА И ЕГО СМЕСИ С ХЛОПКОВЫМ МАСЛОМ
Т.А.Мамедова, М.М.Аббасов, Н.В.Гасанханова, С.К.Алиева, Х.Ш.Теюбов, Т.С.Лятифова,
Р.Т.Адилов, А.А.Ализаде, В.М.Аббасов
Исследован процесс получения низкомолекулярных олефинов C2-C4 в результате термокаталитического превращения фракции тяжелого газойля каталитического крекинга (ТГКК) в чистом виде и его смеси с хлопковым маслом в интервале температур 550-700°С. Выявлено, что при термокаталитическом превращении ТГКК с использованием катализатора Омникат-210П и его смеси с галлоизитом (Омникат-210П/галлоизит) при температуре 7000С прирост выходa этилена составляет 16.1-16.4%, а выхода пропилена - 6.3-6.1 мас.% Добавление 10% хлопкового масла в состав ТГКК в идентичных условиях приводит к дополнительному приросту выходa этилена и пропилена на 3-2.8 и 0.6-1.4 мас.% соответственно.
Ключевые слова: каталитический крекинг, тяжелый газойль, этилен, пропилен, галлоизит, низкомолекулярные олефины.
