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  3. Investigating the available technologies for desulfurization of naphtha from the distillation tower and simulating its process

Investigating the available technologies for desulfurization of naphtha from the distillation tower and simulating its process

Number of pages: 117 File Format: word File Code: 31837
Year: 2013 University Degree: Master's degree Category: Biology - Environment
Tags/Keywords: Catalytic reactor - Desulfurization - Desulfurization - Diesel fuels - Diethanolamine - Emission of suspended particles - Naphtha - process - soot - Sulfur oxides
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  • Summary of Investigating the available technologies for desulfurization of naphtha from the distillation tower and simulating its process

    Dissertation for M.Sc.

    Treatment: Environment

    Abstract
    According to the studies, there are various processes for desulfurization of naphtha, which are very specific parameters to determine the desulfurization method of naphtha There is evidence that the type of sulphurous compounds and operating temperature and pressure are one of the most important determining parameters of the naphtha desulfurization method. One of the most harmful compounds in naphtha is H2S, CO2 and COS, the most important of which is COS. Likewise, in this research, a process of naphtha desulfurization (DMD) with the addition of diethanolamine has been simulated by HYSYS software. The purpose of DMD process design is to remove mercaptans from one direction and remove H2S and CO2 from another direction. The mercaptans in this process include M-Mercaptan and E-Mercaptan. The DMD process includes two catalytic reactors and two-phase and three-phase separators. The purpose of the catalytic reactor is to convert COS to H2S and CO2, and at the output of the second catalytic reactor in the opposite direction of the process, we added diethanolamine to the process, and based on the integrity of the process, the amount of COS, H2S and CO2 output from the process has decreased so much that almost 0.1 of the CO2 and H2S of the process has left the two-phase flash and the rest has been returned as input to the first catalytic reactor. The purpose of the three-phase separator is to remove light hydrocarbons and mercaptans from the output of the three-phase light liquid phase, and the purpose of the two-phase separator is to remove H2S and CO2. Approximately 0.032 and 0.02 of M-Mercaptan and E-Mercaptan exited from the first catalytic reactor from the two-phase flash. The ratio of M-Mercaptan and E-Mercaptan output from two-phase flash to three-phase flash is 0.05 and 0.03, respectively.
    Key words: process, desulfurization, naphtha, diethanolamine and integrity

    Introduction:

    Today, oil and its derivatives provide approximately 37% of the world's energy consumption and 90% of the fuel for highway transportation such as (cars, buses and trucks) and non-road transportation systems such as (trains, ships and agricultural equipment). However, these systems cause the emission of polluting particles [1] and the emission of polluting gases such as SOx and NOx, which cause environmental problems. Sulfur is one of the main pollutants in oil and its products, especially diesel or gas oil, which causes solid pollutants, soot, and SOx gas pollutants during combustion. Soot is the main cause of black and harmful smoke and vapors coming out of the exhaust, which has a huge contribution to air pollution. Also, the presence of small amounts of sulfur in engine fuel leads to failure and inactivation of catalytic converters and reduces their efficiency and ability to oxidize harmful compounds such as carbon monoxide, hydrocarbons and volatile organic substances. In this regard, in order to reduce the harmful effects of these pollutants, environmental laws and regulations have been established in many countries of the world to reduce the sulfur content of petroleum products, especially diesel and diesel, and convert them into products with a very low sulfur content [2] (for example, 10-15 ppm in the case of diesel) and it is becoming stricter every day [1] in order to reduce the amount of emissions. Suspended particles (soot) and sulfur oxides international organizations established regulations to limit the amount of sulfur in diesel fuel. In November 1990, the United States Environmental Protection Agency [3] (US-EPA) required all motor vehicles that used diesel fuels to use diesel fuel with a maximum sulfur content of 500 ppmW from October 1993, which is known as low sulfur diesel fuel [4] (LSD). In January 2001, these conditions were announced in a stricter form. In early June 2006, the International Organization mandated refineries to reduce the sulfur content of motor vehicle fuel to 15 ppmW, known as Ultra Low Sulfur Diesel (ULSD).As of early December 2010, all diesel fuels used on highways must be ULSD type. Another type of diesel fuel is also used in non-road, rail and marine transportation systems. Prior to 2004, no specific limit was set by the EPA for the amount of sulfur in nonroad diesel fuel. Of course, the industrial applications of this type of diesel were excluded and a limit of up to 0.5% ppmW (5000) was considered. In June 2004, EPA established new standards for this diesel fuel. A two-step process to reduce the amount of sulfur for non-road diesel fuel was established as follows:

    a) up to 500 ppmW from June of the year 2007

    b) Up to 15 ppmW from June 2010

    Similarly, the amount of sulfur for fuel used in rail and marine systems was limited to 500 ppmW from June 2007, while this amount was set at 15 ppmW for June 2012 It is. naphtha and COS is the most harmful one. Thus, in this research a Naphta desulfurization (Demercaptanization of Distillate) was simulated using HYSYS software and adding diethanolamine. The purposes of designing the DMD process are twofold: 1) Demercaptanization and 2) removing CO2 and H2S. M-Mercaptan and E-Mercaptan are the Mercaptanized compounds of the process. DMD process includes two catalytic reactors and biphasic and triphasic separators. The catalytic reactor converts COS to CO2 and H2S. And diethanolamine is added as the input at the second catalytic reactor. The amount of output H2S, COS and CO2 was reduced because of process integration, that 10% of process H2S and CO2 was removed through the biphasic flash and the reminder was restored to the preliminary catalytic reactor as the input. The triphasic separator removes the light carbohydrates and the mercaptans from the light liquid phase and the biphasic reactor removes the CO2 and H2S and a negligible amount of mercaptans will exit the biphasic separator as liquid which won't hamper the project. About 0.032 and 0.02% of M-mercaptan and E-mercaptan were removed by the primarily catalytic reactor at the biphasic flash, respectively. The amount of output M-mercaptan and E-mercaptan of the biphasic flash to the triphasic reactor was 0.05 and 0.03, respectively.

    Keywords: process, Sulfurization, naphtha, diethanolamine and integration.

  • Contents & References of Investigating the available technologies for desulfurization of naphtha from the distillation tower and simulating its process

    List:

    Abstract..1

    Introduction..2

    Chapter One: General

    (1-1) The effect of sulfur on vehicle emissions. 10

    (1-2) The effects of sulfur on diesel engines and pollution control technology. 11

    (1-3) Origin Sulphur. 12 (1-4) Types of sweetening methods. 13 (1-4-1) Doctor sweetening. 14 (1-4-2) Copper chloride sweetening. 15 (1-4-3) Hypochlorite process. 17 (1-4-4) molecular sieve process. 18

           (1-4-5) washing with soda solution. 20

            (1-4-6) Merax process. 22

    (1-4-9) Hydrogen refining. 42

    Chapter two: Review of past research

    Chapter three: Analysis and review of the naphtha desulfurization process (DMD)

    (3-1) Definition. 67

    (3-2) Process design and simulation. 68

    (3-3) Features HYSYS.68

    (3-4) Simulation applications. 69

    (3-5) Similar software. 69

    (3-6) Research process. 70

    (3-6-1): Library studies. 70

    (3-6-2): Simulation of naphtha desulfurization process by HYSYS software. 72. (3-7) general results of the DMD process. 88. Chapter four: discussion and conclusion. Conclusions and suggestions to continue the work in the future. 113. Sources and sources. List of Persian sources. 115. List of non-Persian sources. 116. English abstract. 118. Source: [1] Salehi (Marjan), Hosseini (Seyd Mohsen)-1390 Desulfurization - the second science and technology conference of modern technologies in the oil refining industry - Isfahan - page 5-13

    ] 3 [Maqsoudi Saeed-1378- removal of sulfur from the cuttings between oil distillation by biological method- PhD thesis- Faculty of Chemical and Petroleum Engineering- Sharif University of Technology- second chapter- pages 29-31

    ]4 [Ahmadi Saman- 1391- knowledge tips About gasoline and its knowledge - Petronet online encyclopedia

    ] 10 [Bazmi (Mansour), Tagherian (Morteza), Mohammad Beigi (Khashayar)- 2013- The process of demercaptanization of oil cuttings - Research Institute of Oil Industry, Process Engineering Unit - 9th National Congress of Chemical Engineering (University of Science and Technology)

    ] 12 [Nazim Bekai (Hadi), Voshoghi (Manochehar), Alamzadeh (Iran)-1381- Gasoline desulfurization by Rhodococcus P32c1 bacterium immobilized on a polymer base- Iranian Journal of Chemistry and Chemical Engineering- Volume 25- Number 3- Page 9

    ]19 [Bazmi (Mansour)- Tagherian (Morteza)-1382- Mercaptanization of NGL and LPG gasoline feeds Development Engineering Research Institute of Oil Industry Research Institute - Journal of Oil Industry Equipment - Number 2 - Pages 3-5

    ]20 [Shahsund (Akbar), Indesh (Amir) - 1387 - New methods of sulfur recovery in oil and gas industries - 12th National Congress of Chemical Engineering of Iran. 

    ] 21 [Habibpour (Soltan Ali), Kamrova (Hamid Reza), Halimi Far (Gholam Hossein)-2013- Presenting a method with the aim of improving the performance of the sweetening unit of Ilam Gas Refinery using pinch technology- 4th International Conference on Heat Exchangers

    ] 22[Dar Gahi Zaboli, Maleeha. 2015- Simulation and optimization of gas condensate refining processes and converting them into products with higher added value. Master thesis

    ]26 [Rahimi (Masoud)-Madaeni (Siavash), 2018, optimization of a new natural gas sweetening unit, 9th National Congress of Chemical Engineering of Iran, Iran University of Science and Technology, pages 10-14

        

     

     

    Non-Persian sources:

    [2] Keennedy (j),(2002)-Clean Diesel fuel implementation workshop –Hoston, Texas, USA

    [5] Sublette, K. L. and N. D. Sylvester, 1987, "Oxidation of hydrogen sulfide by Thiobacillus

    denitrificans: desulfurization of natural gas Biotechnology and Bioengineering, p:249-257.

    [6] Meyers(R.A)-1996-Hand book of petroleum refining processes, second edition-MC Graw Hill-p:132-134

    [7] Tanaka, H., (2004). Process forProcess for producing hydrofining catalyst. United States Patent 6,689,712.

    February 10.

    [8] Neathery, J.K.(1996)- Model for flue-gas desulfurization in a circulating dry scrubber,

    AICHE Journal 42 , 259–268.

    [9] Oliazadeh, M, Huang, J.H.1995; Application of solvent extraction for the separation of molybdenum from nano-crystalline cobalt electrodeposition effluents Authors

    W4, R.T. ; Source: Proceedings of the TMS Fall Extraction and processing conference, Vol. 1,

    [11].sharipov(A.kh). (1994). Demercaptanization of fuels and liquefied gases in the presence of cobalt polyphthalocyanine. Chemistry and technology of fuels and oils. No: 30.

    [13]. Vildanov(A.F),. Arkhireeva(I.A), Gorokhova(S.A).(1988) "High temperature naphtha desulfurization using a low metal and partially deactivated catalyst" - Vestnik MGU, Ser.2. Khimia, vol.29. No. 6, p.614.

    [14] Campos-Martin(J.M.), Capel-Sanchez(M.C), Perez-Presas(P), Fierro(J.L.G).

    (2011), Oxidative Processes of Desulfurization of Liquid Fuels

     Instituto de Cat?lisis y Petroleoqu?mica, CSIC, Marie Curie 2, Madrid, Cantoblanco, E-28049

    [15] Weinzierl(K); Karger(R), both of Dortmund-(1980)- METHOD FOR OPERATING A FLUE GAS DESULFURIZATION- L. & C. Steinmiiller GmbH

    [16] Mazgarov(A.M) (2000/01), NEW PROCESS AND CATALYST FOR CRUDE, FUEL AND WASTE WATER   VNIIUS, Kazan, Russia. ISSN1311-8978

    [17] Xuemei (CHU). Yufeng (HU), Jiguang (LI), Qianqing. (L.G), Yansheng (LIU). CHINESE JOURNAL OF CATALYSIS, Volume 32, Issue 5, p 707-715

    [23] Weyda, H. kohler, E. (2003). Modern refining concepts on naphtha isomerization to modern gasoline manufacture. catalysis today [serial online] 81 - p:51-55

    [24] A.G. Akhmadullina, L.N. Orlova, I.K. Khrushcheva and others, 1989. Mercaptides transformation during the catalytic oxidation with molecular oxygen in aqueous alkaline solutions. Journal of Applied Chemistry, No.1, p. 53-57. [25] Brink, P. J., Feb 1994, Catalyst for the Selective Oxidation of Sulfur Compounds to Elemental Sulfur, Process for Preparing Such a Catalyst and Method for the Selective Oxidation of Sulfur Compounds to Elemental Sulfur, US Patent. No 5,286,697,.

    [26] G. Xu, Q. Guo, T. Kaneko, (2000)., A new semi-dry desulfurization process using a

    powder-particle spouted bed, Advances in Environmental Research 4, p9–18.

    [27] X. Ma, T. Kaneko, T. Tashimo, et al(2000). Use of limestone for SO2 removal from flue gas in the semidry FDG process with a powder-particle spouted bed, Chemical Engineering

    Science 55p: 4643–4652.

    [28] J.K. Neathery, (1996)  Model for flue-gas desulfurization in a circulating dry scrubber,

    AICHE Journal 42,p: 259–268.

    [29] C.Y. Chu, S.J. Hwang, (2002), Attrition and sulfation of calcium sorbent and solids

    Circulation rate in an internally circulating fluidized bed, Powder Technology 127

    p:185-195.

Investigating the available technologies for desulfurization of naphtha from the distillation tower and simulating its process
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