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Simulation of Hydrodesulfurization Unit for Natural Gas Condensate with High Sulfur Content

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Simulation of Hydrodesulfurization Unit for Natural Gas Condensate with High Sulfur Content View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Springer - Publisher Connector Appl Petrochem Res (2016) 6:25–34 DOI 10.1007/s13203-015-0107-0 ORIGINAL ARTICLE Simulation of hydrodesulfurization unit for natural gas condensate with high sulfur content 1 2 Javad Alaei Kadijani • Elhameh Narimani Received: 8 January 2015 / Accepted: 2 April 2015 / Published online: 29 April 2015 Ó The Author(s) 2015. This article is published with open access at Springerlink.com Abstract The natural gas condensates are composed of Keywords Gas condensates Á Disulfide oils Á Sulfur various components of hydrocarbons and some con- content Á Ultra-Deep Hydrodesulfurization unit Á Petroleum taminants such as hydrogen sulfide, thiols (mercaptans), cuts Á Fractional distillation system and aromatics. Thus, the natural gas condensates could be considered as a fuel resource. This study concerned the Abbreviations simulation of an Ultra-Deep Hydrodesulfurization ANN Artificial neural network (UDHDS) unit plus a distillation section to treat a combi- DEAmine Diethyl amine nation of gas condensate and disulfide oils (DSO) and DEDS Diethyl disulfide produce clean fuel cuts. Gas condensate of South Pars field DMDS Dimethyl disulfide of Iran with high sulfur content was applied to obtain clean DSO Disulfide oil fuel cuts. In order to reduce the sulfur content of this F.B.P. Final boiling point stream to less than 10 ppmw as sulfur, a UDHDS unit was FLR Flare simulated using Aspen HYSYS software package. The HDA Hydrodearomatization clean gas condensate leaving the UDHDS unit (with sulfur HDN Hydrodenitrogenation content \10 ppmw) contains complex mixtures of hydro- HDS Hydrodesulfurization carbon components called petroleum cuts which are iden- IEA International energy agency tified by their boiling points ranges. To obtain the narrow I.B.P. Initial boiling point fractions of butane, light naphtha, heavy naphtha, kerosene, OSBL Outside battery limit and gasoil, a fractional distillation system was simulated. Nm3 Cubic meters @ normal condition (0 °C) The simulation results revealed that the top products of PFD Process flow diagram distillation column, namely butane, light naphtha, and ppmw Parts per million weight heavy naphtha were sulfur free and the sulfur contents of RSM Response surface methodology kerosene and gasoil cuts were 12 and 27 ppmw as sulfur, TBP True boiling point respectively. UDHDS Ultra-Deep Hydrodesulfurization VGO Vacuum gasoil & Elhameh Narimani [email protected] Javad Alaei Kadijani [email protected] Introduction 1 Research Institute of Petroleum Industry (RIPI), Gas Department, West Boulevard of Azadi Stadium, Looking at the world’s growing demand for new energy P. O. Box 14665-1998, Tehran, Iran resources, experts in the field of oil and energy can obvi- 2 School of Chemical Engineering, Iran University of Science ously realize that oil industry has to find new fuel supplies and Technology, P.O. Box 16765-163, Tehran, Iran and upgrade their qualities. The natural gas condensates can 123 26 Appl Petrochem Res (2016) 6:25–34 catch their attention as they contain complex mixtures of studies investigating the simulation and modeling of HDS hydrocarbon components. Natural gas condensate is known plants. The research conducted by S. Bilal et al. [8] focused as a low-boiling mixture of hydrocarbon liquids that are on the simulation of an HDS unit using Aspen HYSYS with present as gaseous components in the raw natural gas pro- the aim of removing impurities such as sulfur and nitrogen duced from many natural gas fields [1]. Therefore, in ad- from raw kerosene. F. Jime´nez et al. [9] carried out com- dition to crude oil, the natural gas condensate can be an puter-aided modeling as a tool for the investigation of si- appropriate resource for oil industry to augment the fuel multaneous Hydrodesulfurization (HDS), Hydrodenitro- production. According to the report of International Energy genation (HDN), and Hydrodearomatization (HDA) of a Agency (IEA), the South Pars/North Dome field, which is vacuum gasoil (VGO) in which reactions took place in in- located in the Persian Gulf, is the world’s largest gas field dustrial reactors. Another study explored the use of different and shared between Iran and Qatar. This field holds an es- artificial neural network (ANN) architectures in creating timated 1800 trillion cubic feet (51 trillion cubic meters) of various models of the HDS process for the prediction of in situ natural gas and some 50 billion barrels (7.9 billion sulfur removal from naphtha [10]. Ultra-Deep Hydro- cubic meters) of natural gas condensates.1 However, the gas desulfurization (UDHDS) process is considered as one of condensate of this field is substantially sour as it is esti- the subbranches of the conventional HDS process which is mated that the sulfur content of gas condensate of South conducted in the severe process conditions and using dif- Pars field is more than 2000 ppmw as sulfur. The sulfur ferent catalyst to obtain the lower amount of sulfur content. content of fuels is currently considered as a major factor In addition to the HDS unit, a distillation system is re- contributing to pollution of the atmosphere. quired to obtain clean cuts. However, the order of these two Accordingly, the U.S. Environmental Protection Agency sections is a problem. Based on a technical recommendation limited the sulfur content of most diesel fuels to 15 ppm study report given by HQCEC, the hydrogenation plus from a level of 500 ppm in 2006. The similar environmental fractionation process to treat naphtha can produce clean regulations in Europe forced petroleum industries to reduce product with high quality and low impurity content com- the sulfur content for on-road diesel fuels from the level of pared with the fractionation plus hydrogenation units. 350–50 ppm by 2005 and to 10 ppm by 2009. Furthermore, Moreover, the energy consumption of these two plants was based on the Euro V criterion, the bound for fuels, in terms approximately equal. In terms of investment, the system of total sulfur content has to be less than 10 ppm as sulfur. capacity of hydrogenation plus fractionation process is The sulfuric compounds in fossil fuels are divided into non- slightly higher than that of the fractionation plus hydro- aromatic and aromatic compounds. The first group includes genation processes [11]. However, in these studies, costs sulfides, disulfides, and mercaptans (thiols) and the second and problems caused by sour petroleum cuts have been one includes thiophenes, benzothiophenes, dibenzothio- ignored. Gas condensate of South Pars field is currently sent phenes, and benzonaphthothiophenes. The former has much to refineries to produce fuel cuts or sold in markets. In both more reactivity than the other sulfuric compounds while the cases, gas condensate with high sulfur content or sour pet- latter, particularly benzothiophenic and dibenzothiphenic roleum cuts can seriously damage pipelines and process derivatives, are difficult to desulfurize. equipment due to corrosion and push up the cost of process. Hydrodesulfurization (HDS) is known as one of the In the present study, it has been assumed that the primary most efficient methods to reduce the sulfur content of hy- design of sulfur removal unit for gas condensate should be drocarbons regarding universal criteria. This process can be based on the UDHDS plant plus a fractional distillation unit. extremely effective in removing both types of sulfuric Regarding the world’s increasing need for clean fuels as compounds. In this plant, the reaction takes place under well as environmental issues resulting from high-sulfur fuel high temperature and high hydrogen pressure in the pres- burning, it was assumed that a new UDHDS unit treating the ence of a catalyst. HDS process can accomplish desul- natural gas condensate of South Pars field and producing the phurization and in the meanwhile it can remove nitrogen ultra-low sulfur fuel cuts from them would attract invest- and metal compounds, and also carry out deoxidation. ments and get back more interests in the universal markets. Based on the advantages of hydrodesulfurization pro- Moreover, this process can protect downstream equipment cess—removing less than 10 ppm sulfur, decreasing the from corrosion and cut down costs of maintenance. Fur- amount of environmental pollutants, increasing the age of thermore, there is an environmental issue which is related to catalysts, simple operation of process unit to name but a the production of disulfide oil. The substance, commonly few—it is considered as an appropriate method to reduce known as disulfide oil (DSO), can comprise 17 different the sulfur content of gas condensate [2–7]. There are some disulfides and trisulfides with monoalkyl chain lengths no greater than C4. Evidence demonstrates that the lowest 1 Data are extracted from APS Review Gas Market Trends. April 2, series member, dimethyl disulfide (DMDS), can display the 2007. highest toxicity. DSO possesses high aquatic toxicity, 123 Appl Petrochem Res (2016) 6:25–34 27 moderate environmental persistence, high repeated dose Table 1 The specification of gas condensate based on TBP toxicity, carcinogenicity, and reproductive/developmental Volume, % TBP (°C)@760 mmHg effects [12]. DSOs (mainly dimethyl and diethyl disulfides) are 5.18 15 formed in considerable amounts in the process of hydro- 11.49 36.1 carbon demercaptanization in refineries. Presently, there is 53.24 150 no practical application for DSO. Furthermore, destruction 63.09 175 of DSO by combustion would lead to the formation of 73.41 215 sulfur dioxide and carbonyl compounds which can pollute 81.76 250 the atmosphere. Fortunately, DSOs are highly active in the 87.01 275 catalytic reaction with hydrogen and they can be easily 95.81 350 removed and converted to alkanes and hydrogen sulfide in 100 360 the hydrodesulfurization process. Therefore, the aim of this study is the simulation of a new UDHDS unit plus a distillation section in South Pars refinery which would treat the natural gas condensate with high sulfur content and produce clean and sellable fuel cuts.
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