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IBP1299_12 AUXILIARY UNITS FOR REFINING OF HIGH NITROGEN CONTENT OILS: PREMIUM II REFINERY CASE Paolo C.

Nicolato1, Rafael Pinotti2

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Resumo A Petrobras tem investido constantemente em seu parque de refino com o objetivo de aumentar a produção de combustíveis mais limpos e estáveis, além de ampliar sua capacidade de processamento de petróleos mais pesados e com maiores teores de contaminantes. O enxofre e o nitrogênio são os principais heteroátomos presentes no petróleo. Estes são responsáveis por algumas propriedades indesejadas dos combustíveis, como corrosividade e instabilidade, e também emitem poluentes quando queimados. Processos de hidrotratamento e hidrocraqueamento são projetados para a remoção destes contaminantes, além de ajustar outras propriedades dos combustíveis, gerando como subprodutos correntes de gases ácidos e águas ácidas, ricos em H2S e NH3, normalmente enviados para as unidades de Tratamento de Águas Ácidas e Recuperação de Enxofre. A regeneração da amina utilizada para o tratamento de correntes leves de hidrocarbonetos, como gás combustível e GLP, também gera gases ácidos que também devem ser enviados para as Unidades de Recuperação de Enxofre. Na medida em que o teor de amônia nas correntes ácidas aumenta, alguns parâmetros de projeto devem ser ajustados para evitar o aumento das emissões da Refinaria. As unidades de Recuperação de Enxofre devem prover a destruição adequada da amônia presente em sua carga. As unidades de Tratamento de Águas Ácidas devem prover uma segregação adequada das correntes de ácido sulfídrico e amônia, sempre que necessário. Os sistemas de Regeneração de Aminas devem ter um procedimento adequado para evitar a concentração de NH3 na solução amínica. Este artigo apresenta algumas soluções de projeto comumente aplicadas na indústria petrolífera, analisa alguns aspectos relacionados à Refinaria Premium II e como ela está sendo desenvolvida de forma a auxiliar ao parque de refino brasileiro a atender as futuras demandas de regulamentações ambientais e de mercado. Abstract Petrobras is constantly investing on its refining park in order to increase the production of clean and stable fuels and to be capable to process heavier oils with high contaminants content. Sulfur and nitrogen are the main heteroatoms present in petroleum. They are responsible for some undesirable fuels properties like corrosivity and instability, and also emit pollutants when burnt. Hydrotreating and hydrocracking processes are designed to remove these contaminants and adjust other fuel properties, generating, as byproduct, sour gases and sour water streams rich in H2S and NH3, which are usually sent to Sour Water Treatment Units and Sulfur Recovery Units. The regeneration of the amine used for the light streams treatment, as fuel gas and LPG, also generates sour gas streams that must be also sent to Sulfur Recovery Units. As the ammonia content in the sour streams increases, some design parameters must be adjusted to avoid increasing the Refinery emissions. Sulfur Recovery Units must provide proper NH3 destruction. Sour Water Treatment must have a proper segregation between H2S and ammonia streams, whenever desirable. Amine Regeneration Systems must have an efficient procedure to avoid the ammonia concentration in the amine solution. This paper presents some solutions usually applied to the Petroleum Industry and analyses some aspects related to Premium II Refinery Project and how its design will help the Brazilian refining park to meet future environmental regulation and market demands.

______________________________ 1 Process Engineer – Petrobras 2 M.Sc., Process Engineer - Petrobras

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1. Introduction
The Brazilian refining park was built based on the importing of light oil and on the production of fuels with high sulfur content and few restrictions regarding product quality. As the domestic petroleum production increased, along with the demand for more stable and clean products, the Brazilian refining scheme evolved accordingly, in order to be able to process heavier oils with higher contaminants content and meet more severe product specifications. For these reasons Petrobras Refineries have invested, for example, in Delayed Coker units, which help to increase the refining profit, by converting heavy streams into lighter ones. Many Hydrotreating units were also implemented in order to meet diesel, kerosene and naphtha specifications. In this context Hydrocracker units have become an attractive alternative to convert heavier petroleum fractions into high quality products, and will be implemented in three of the new Petrobras Refineries scheduled for startup in this decade: Comperj (Itaboraí – RJ), Premium I (Bacabeira – MA) and Premium II (Caucaia – CE). Petrobras is also building another Refinery in Pernambuco, RNEST, which will be able to process 230 mi bpd of diesel with 10 ppm of sulfur in another refining scheme, without a Hydrocracker Unit. Together, these four new refineries will process 1,295 million bpd of crude, producing mainly low sulfur content diesel, according to the new regulation regarding products quality. Figure 1 illustrates future requirements for cleaner fuels. Restricted specification regarding fuels sulfur content requires investments on refining.
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Figure 1. Sulfur content specification evolution Petrobras increased its diesel and kerosene production in 17,1 millions of barrels in 2010, by means of operational adjustments and some REVAMP projects. A Delayed Coker Unit and a Coker Naphtha Hydrotreatment Unit were built in Henrique Lage Refinery (REVAP) in São José dos Campos, SP. A total of fourteen new Units focused on products quality improvement were concluded in 2011, and the S50 diesel started to be commercialized in 56 new cities. The 2012 Petrobras budget forecasts more than R$ 33 billion invested on the modernization and enlargement of the current refining park, improvement of the fuels quality and increase in Petrochemicals participation. This paper is structured as follows: in section (2) some oil characteristics are listed, a macroflux of the nitrogen components from crude in a refinery is described and the commonly evolved units are highlighted; in section (3) the Auxiliary Units special design criteria regarding nitrogen content and the problems caused by ammonia concentration increase are presented; in section (4) Premium II refining scheme and auxiliary units basic characteristics are described and a conclusion is presented in section (5).

2. Nitrogen compounds removal and destination processes
The design of a refining scheme has to take into account the oils characteristics, which varies according to its origin, as well as the expected products specifications. Some of the oil’s main characteristics which influence a refinery design are the density, viscosity, ASTM distillation curve, resins and asphaltenics concentration and contaminants content (mainly sulfur and nitrogen). The characteristics of the market that the refinery will supply are equally important to the definition of the units that will maximize the production of a specific fuel, for example. In general, Arabic oils have high API and high sulfur content; some Nigerian ones are light and with low sulfur content. Brazilian oil from Campos Basin has high density and low sulfur content. The oil recently prospected from the pre-salt layer seems to have medium API and low sulfur content. As for the nitrogen content, Brazilian oils are particularly rich, compared with oils from other countries. Table 1 shows different characteristics regarding density and contaminants content of oils commonly processed in Brazilian Refineries, ordered according to their API. 2

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Table 1. Typical oils processed in Brazil Low / Sulfur High content Nitrogen (% w) Content 0,06 Low 0,44 High 1,93 Low 0,06 Low 0,53 High 2,90 Low 0,31 High 1,23 High Low / Sulfur High content Nitrogen (% w) Content 0,11 Low 0,74 High 0,72 High 0,40 Low 0,58 High 0,14 Low 0,90 High 0,05 Low

Oil Alagoano Albacora - P-31 Arabian light Baiano-Mistura Barracuda - P-43 Basrah light Fazenda Alegre Fazenda Belém

ºAPI 42,2 28,3 33,5 36,5 24,9 30,8 13,2 12,7

Oil Golfinho Marlim - P-33 Marlim - P-37 Medanito Roncador - P-52 Sergipano-mar Siri Urucu

ºAPI 37,0 19,9 22,8 36,8 28,3 43,7 12,3 48,5

Nitrogen compounds are responsible for some catalyst poisoning, product instabilities, disturbances in the middle distillates color and deposits precipitation due to thermal degradation. Although nitrogen concentration is not directly controlled in the main fuels specifications, its effects are. So it must be removed from fuels, as sulfur is. If a fuel has high nitrogen content, the washed gum content is higher, the induction period is smaller and the tendency of color change is higher as well. Basic nitrogen components, thiophenols, olefins and organic acids are precursors of these kinds of degradations. The gasoline specification defines that washed gum content must be less than 5 mg/100 ml and induction period greater than 360 min, at 100ºC, according to standard laboratory procedures. The aviation kerosene must have current gum content less than 7 mg / 100 ml and Diesel has its oxidation stability monitored, for example. A crude oil is considered to have high nitrogen concentration if its total mass fraction is greater than 0,25%. Premium I and II Refineries are designed to process a mixture of Albacora and Marlim oils, which has more than 0,35% (mass) of total nitrogen. The first step to avoid unexpected crude high ammoniacal nitrogen content in oil is to comply with the appropriate petroleum production procedures. It is not desirable for the Basic Sediment and Water (BSW) content to exceed the design value, normally smaller than 1%. The ammoniacal nitrogen typical content from the Cabiúnas and the Caravelas oils associated water vary between 100 mg/L to 900 mg/L, for example. Distillation unit is normally the first process unit of a refinery. This unit consists on a physical fractionating of the oil components according to their respective boiling points. Lighter components are removed in the top of distillation towers, where there is normally an injection of water to wash the columns top section in order to avoid the precipitation of ammonia salts. The ammonia content in crude normally represents a very small fraction of the nitrogen content in oil. Ammonia is normally carried by the wash water and it is removed in the distillation towers top vessels, after column condensers, due to its affinity with the aqueous phase. The other nitrogen compounds are distributed in the distillate cuts according to their boiling points. The distillation streams will be destined to product treatment units or to conversion units, according to the refining scheme. The nitrogen compounds in heavier streams from Distillation Unit, directed to Delayed Coker Units, for example, are cracked into lighter cuts that may be directed to the hydrotreatment or hydrocracking units. Some ammonia and cyanide may be formed, and they will also be removed with the sour water in the fractionator tower top vessel. In hydroprocessing units, the nitrogen in oil attached to organic molecules is partially converted into ammonia due to hydrocracking. Aliphatic amines and nitriles are easily converted in hydrotreating units. The nitrogen in aromatics heterocyclics compounds, common in gasoils, are more difficult to remove, demanding most severe conditions as higher partial hydrogen pressure, higher temperatures and smaller hydrocarbon flowrates through reactors. Hydrodenitrogenation (HDN) process usually requires more severe operational condition than the hydrodessulfurization (HDS) process. The gaseous streams from hydrotreating and hydroconversion units are rich in hydrogen, light hydrocarbons, methane and ethane for example, hydrogen sulfide (H2S) and ammonia (NH3). These streams may be treated in amine extractors and absorption towers, in order to reduce the contaminants concentration thus allowing them to be used as fuel gas, or to increase the hydrogen concentration of the recycle gas, for example. The aqueous amine solutions commonly used for gases and LPG treatment are DEA (diethanolamine) and MDEA (methyl-diethanolamine). MDEA is more selective for the absorption of H2S than for other gases. The ammonia is not directly absorbed by amines, but it has affinity to the aqueous phase, so it may be concentrated in the absorbent solution. The rich amine with high H2S content from the acid gases absorption is regenerated by means of heating, releasing the rich sour gas on the top of the 3

Rio Oil & Gas Expo and Conference 2012 regeneration tower, while the regenerated amine at the bottom of the tower. The Figure 2 shows a simple configuration of an Amine Regeneration Unit. It consists, basically, on a rich amine vessel, the amine regeneration tower and the lean amine filters.

Figure 2. Amine Regeneration System Scheme Sour Water Treatment Units receive the aqueous streams from main process units, generated by the direct injection of water in the process or by the condensation of steam injected or generated by the process. The water is stripped so the H2S and ammonia may be properly directed, while the water is sent to a Waste Water Treatment Unit. The rectification is done by indirect heat of the sour water on a tower reboiler or by the direct injection of steam in the tower, under a certain pressure. The segregation of the hydrogen sulfide and the ammonia may be interesting according to the strategy developed to treat these gases. This segregation is influenced by the refining scheme adopted and by the crude contaminant contents and it is important to define the number of towers of this unit. The Figure 3 shows a simple configuration of a single tower Sour Water Treatment unit. This system basically consists on a feed storage and stabilization tank and the stripper column. If the segregation between hydrogen sulfide and ammonia is desired, the sour water is rectified in two columns. A vessel for gases and/or oil removal may also be installed in this unit.

Figure 3. Sour Water Stripping simple scheme The acid gases from the amine regenerator towers and from sour water strippers are then sent to sulfur recovery units, NH3 converter or SNOx Units, so the refinery sulfur oxides and nitrogen oxides emissions fits federal and environmental regulations and local parameters. Sulfur Recovery Units (SRUs) aim to convert H2S into commercial sulfur, normally by Modified Claus processes, which consist on a partial combustion of the hydrogen sulfide followed by catalytic reactors to produce elementary sulfur. When ammonia is expected in the acid gas stream, the design of the unit has to be adjusted accordingly. Some SRU may be followed by Tail Gas Treatment Units to increase the sulfur recovery. These units produce sulfur with high purity, a tail gas with low contaminants content and may also export steam. The Figure 4 illustrates a simple scheme of a Sulfur Recovery Unit. It consists basically on a furnace where part of the H2S is converted into sulfur by Claus Reactions, followed by a heat recovery boiler. The conversion of the 4

Rio Oil & Gas Expo and Conference 2012 hydrogen sulfide is complemented in the reaction loops, compounded by heaters, reactors and sulfur condensers. The tail gas is burnt in an incinerator.

Figure 4. Sulfur Recovery Unit simple schemes Ammonia converters are usually designed to process ammonia rich gaseous stream with flow rates that do not economically justify the installation of new process units to recover it on a commercialized product. They are designed according to pre-established criteria of destruction / conversion of the contaminants, and complying with environmental restrictions. It shall convert ammonia into N2 and water, minimizing the formation of nitrogen oxides. SNOx units are multi-pollutants systems for acid and combustion gases treatment, especially for those with very high ammonia concentration, for which LowNOx incinerator burners would not provide a suitable conversion. This technology consists of a catalytic process that converts sulfur and nitrogen oxides into sulfuric acid and N2, respectively. The first SNOx Unit applied in a Brazilian refinery is being built for RNEST, in Pernambuco, designed to refine oils with ultra high contaminant content, like Carabobo and Marlim.

3. Nitrogen impacts on auxiliary units and possible solutions
Although amine treatment, sour water treatment and sulfur recovery units are the usual destination for contaminated streams, they are not typically designed for high nitrogen concentration. The Sour Water Treatment Units may be typically distinguished by those with one tower and with two towers. On single tower units, the sour water is stripped on a unique stage, where hydrogen sulfide and the ammonia are removed together. This case demands a downstream process unit capable to deal with both gases. There are still too few licensors that design Sulfur Recovery Units for acid gas streams with more than 30% molar of NH3. If the ammonia content of acid gases stripped from sour water is higher than 30%, it may be necessary to design a sour water treatment unit with two columns, or to design a SNOx Unit for sour gases treatment, for example. There are also other possibilities like the destination of the acid gases to SNOx Units. The two towers unit produces a rich H2S stream and a rich NH3 stream. Premium II Non-phenolic Sour Water Treatment Unit segregates these two gaseous streams. The H2S stripping occurs first under higher pressure than the ammonia, due to its easier removal. The operational issue of these kinds of units is that the cut point to promote the proper fractionation between these toxic gases is very sensible. As the sulphide gas removal is maximized, the ammonia begins to be removed in the first tower. On the other hand, it is not desirable to have high H2S content in the second tower, because it will be sent to the ammonia converter, what would increase SOx refinery emission. The ammonia removed from the second tower carries also a lot of steam due to its difficulty to be removed. The total flow rate of the gas stream leaving the second tower is higher, which leads to larger equipments downstream. If the ammonia content in the sour water increases, it becomes more difficult to specify the NH3 concentration on the stripped water, which demands more thermal duty from the reboilers and bigger equipments downstream, reflecting on investments and operational costs. One of the design criteria for the Sour Water Treatment Unit is the ammonia content of the stripped water, normally between 10 mg/kg to 50 mg/kg. The ammonia that is not removed from the stripped water is usually sent to the Waste Water Treatment Unit (WWTU) which has limited capacity to deal with this component. The ammonia content in refinery’ effluent may be out of specification if a large amount of ammonia is sent to the WWTU. The effluent 5

Rio Oil & Gas Expo and Conference 2012 ammoniacal nitrogen concentration is limited in 5,0 mg/L according to Brazilian federal regulation. Higher concentrations may cause eutrophication on the river that receives the effluent. Different strategies may be evaluated to minimize the impacts of higher ammonia concentration on the operational and investment costs of the refinery. Depending on the amount of this toxic gas its recovery may be interesting, but usually the quantity of ammonia produced on a refinery is much smaller than the amount produced by a fertilizer plant, for example. RNEST will have a SNOx Unit to treat most of the acid gases generated in the refinery, and will produce ammonia for commercial purposes. It’s important to highlight that RNEST is designed to process ultra heavy oils with very high contaminants content, when compared to Premiums’ feed. Petrobras’ Sulfur Recovery Units used to be typically designed to deal with ammonia free acid gases streams, with a tolerance of a 0,5% molar maximum content. This limitation exists because the ammonia destruction on the SRU furnaces demands higher temperatures, not commonly reached on the typical process. Theses systems demand the segregation of the gases from the Sour Water Systems (SWSs) and the operational control of the first stripping tower is very important for the stability of the SRU. The gaseous stream from the second tower is usually sent to an ammonia converter. The ammoniacal gases from the second tower of non-phenolic SWS of Premium II will be sent to ammonia converters. The first sour water stripper tower operational control is not very easy because the reboilers thermal duty is much greater than the condensers’. Small increases on the heat supplied to the reboilers to increase the H2S removal may not be properly absorbed by the condenser, leading to higher ammonia sent to SRUs. Soda solution may be injected on the second sour water stripping tower to ease ammonia removal and to reduce the amount of vapor in the respective gaseous stream. On the other hand, excessive soda solution injection may have deleterious consequences for stripped water reuse and in effluent treatment. The stripped water reuse with high soda content in the SWS may fix the H2S on water, interfering on its removal. The pH control on the WWTU is a key parameter to maintain a steady operation and assure the refinery’s effluent specification. Recent projects of Petrobras Sulfur Recovery Unit furnaces were designed with a pre-chamber. Premium II SRU furnace is an example. The acid gas feed flow rate is divided before entering the furnace in order to increase the burner temperature. The air flow provided to SRU furnace is stoichiometrically controlled in order to assure the proper conversion for the Claus reactions. By segregating the acid gas flow, the hydrogen sulfide that will not be burned is fed on a second chamber, so it does not steal the heat of the combustion to heat itself, providing higher burner temperatures, ideal to destroy ammonia. Normally the maximum molar concentration of ammonia on the acid gas to SRU is between 25% and 30%. For these cases it is possible to have a single tower for the sour water stripping, since the petroleum nitrogen content allows it. Some different strategies may be used to provide higher SRU burner chamber temperatures and ammonia destruction. ZareNezhad and Hosseipour (2007) evaluate different alternatives for increasing the reaction furnace temperature by chemical equilibrium calculations. Fuel gas injection on the acid gas feed may substantially increase the reaction temperature, although it also demands more air flow and promotes the formation of more CS2 as well, which may reduce the sulfur recovery and increase refinery emissions. Hydrocarbon pass through the furnace is also possible, which may cause the catalytic bed plugging by coke formation. This strategy is normally used only when the existing furnace temperature is close to the inferior threshold temperature. In order to avoid the formation of CS2 due to the fuel injection, a relatively new concept was developed consisting on the pre-burner of the fuel gas on a different burner with air excess. The temperature increase is normally limited to the metallurgy design of the piping and the presence of the combustion gases (CO2 and H2O) can increase the corrosion of steel equipments. The indirect air preheat or the acid gas preheat is an efficient way of improving the chamber temperature, but normally limited to the materials temperature design (for carbon steel piping the maximum operating temperature might be between 300ºC and 350ºC). The utility normally used for the pre-heating is the steam available on the unit. The use of oxygen enriched air is common for acid gases with low H2S content processing, but it has been also applied to improve the furnace temperature to allow ammonia destruction. This use is normally restricted to this utilities’ availability and it requires a special care in order to avoid the oxygen pass through the furnace, leading to the formation of SO3, which may cause the catalytic bed deactivation. The enrichment of the acid gas feed may be the most efficient way of improving the SRU furnace temperature, but it has to be foreseen in the design of the auxiliary units. Higher acid gas concentration in the sulfur recovery unit provides higher temperature, not to mention equipments size reduction. The ammonia in amine absorption and regeneration systems may also be an operational problem. The top section of Amine regeneration towers tends to concentrates ammonia, due to its affinity to the aqueous phase. High NH3 in amine stripper reflux may cause upsets in the stripper control, stripper flooding, increase of the condenser and reboilers duties, precipitation of ammonium salts, severe corrosion and fouling of exchangers. Ammonia must be removed from the tower condenser lines, which is usually done by dialysis. In order to do it, a continuous flow of wash water is injected in the top section of amine stripper. This water replaces the vapors lost with acid gases stream and also dissolves part of the NH3 of the gaseous phase. If the ammonia concentration increases, the 6

Rio Oil & Gas Expo and Conference 2012 dialysis flow must increase as well, and the effluent treatment units have to be able to deal with more contaminated aqueous streams. This solution may not be economically attractive as ammonia concentration increases, since it will demand larger water and amine volume replacements and also larger equipments in Waste Water Treatment Units. Different projects concepts shall be considered in order to avoid the scale up of effluent treatment units. The dissolution of ammonia on the amine stream may be minimized actuating primarily on the absorption columns. Gaseous streams to be treated with MDEA or DEA contain ammonia, especially those from high severity hydrotreatment units. These gas streams may be pre-washed with stripped water, before the absorption with amine, since the ammonia has great affinity with water and the solution of the hydrogen sulfide is small. The water used for the gas washing may be then sent to Sour Water Treatment Units. This scheme requires an extra column or a vessel before each absorption tower and also increases the volume flow to SWS, which means larger equipments, more utilities consumptions and increase of the thermal duty of reboilers and condensers. If the absorption of ammonia in the amine system can not be minimized, it may be possible to modify the traditional amine regeneration scheme by a two columns scheme, similar to the sour water rectification. This design will be applied to Premium II Amine Regeneration Unit. It consists on the selective rectification of the acid gases absorbed by the amine, like H2S and CO2, and the rectification of the ammonia diluted on the water. The flow to the second column consists only by the reflux stream from the first tower. The segregated rectification demands more investments for the amine regeneration system and may be interesting only for cases with high ammonia concentration. In this case the H2S rich gas and NH3 rich gas may be sent to Sulfur Recovery Units; if the H2S content in the second stream is small, the ammonia will be sent to an ammonia converter.

4. Premium II Refinery scheme
Premium II Refinery will be built in Caucaia, in Ceará state, with a capacity of 300 000 barrels per day of crude oil. It will be able to produce Euro V quality diesel, with very small concentration of sulfur (10 ppm w) and high cetane number, which is the main product of the refinery. Figure 5 illustrates the macroflux of the main process and auxiliary units.

Figure 5. Premium Refining Scheme 7

Rio Oil & Gas Expo and Conference 2012 The refining scheme consists on five main process units: one Atmospheric and Vacuum Distillation Unit; one Delayed Coker Unit; two Hydrotreatment Units (one to treat diesel and another one to treat coker naphtha and kerosene) and one hydrocracking unit. Two Hydrogen Generation Units will supply its demand for the hydrotreatment units and the hydrocracking unit, which consumes more than the half of the total hydrogen production of the refinery. The Hydrocracking Unit converts heavy streams into lighter ones, converting more than 75% of its feed into diesel and kerosene. The hydrorrefining total capacity corresponds to 81,7% of the distillation capacity, a value greater than the average of Petrobras refining park. This means that the fuels and derivates generated in the refinery have high quality, with very low contaminants’ content, which calls for a high demand on the Auxiliary Units, in order for the refinery to comply with environmental regulations and to guarantee a proper disposal of the by-products of the treatments. The Sour Water Treatment Unit consists on two systems that remove acid gases and ammoniacal gases separated and another system with only one stripping column. The sour water generated in Distillation and Delayed Coker Unit is treated in the SWS with one single tower. The sour water from de hydroprocessing Units is stripped in the other SWS, where two gas streams are generated, one rich in H2S and another rich in NH3. The Amine Regeneration Unit (ARU) is an integrated system that will regenerate the MDEA solution used for all the absorption and extraction of acid gases from light hydrocarbon streams. The absorbers and extractor towers are located in the main process units. There are two trains of sulfur recovery units, capable to account for about 20% of the total Petrobras current production of sulfur. The SRU will receive the acid gases generated in ARU and in the Sour Water Treatment Unit. The Unit contains also two ammonia converter for the ammoniacal gases generated in two of the three Sour Water Treatment Systems. Premium II Refinery is designed to process high nitrogen content oil, and most of it is removed in the hydrotreatment and hydrocracking. These units work under severe conditions, with very high hydrogen partial pressure and elevated temperatures. Most part of the nitrogen is converted into ammonia, which follows to the auxiliary units. If all the ammonia were removed together with the hydrogen sulfide in the Sour Water Systems, its concentration would be greater than 30% molar, which is normally the maximum acceptable value for a Sulfur Recovery Unit design with pre-chamber. The ammonia gas stripped from the non-phenolic sour water is then sent to ammonia converter, such a way the ammonia concentration in SRU feed is kept under the maximum concentration. In order to assure the proper destruction of the ammonia in SRU furnace pre-chamber, the acid gas feed is preheated with steam; the auxiliary units are designed so the acid gas is rich on the compounds intended for destruction. Hydrogen sulfide corresponds more than 65% of the feed composition and ammonia is less than 25%. The amount of H2S and H2O in ammoniacal gas is reduced by the inclusion of a third column in the sour water system, where this stream is washed with stripped water. As a consequence, the size of lines and ammonia converter are smaller and the refinery emissions are reduced as well. The ammonia is removed from the amine system through a second stripper in the amine regeneration condenser circuit. The elevated concentration of this nitrogen compounds justifies the investment on additional equipment.

5. Conclusion
The processing of domestic oil with high nitrogen content, together with more tight environmental regulations on refinery and fuels emissions, have had a great impact on the design of new hydroprocessing and auxiliary units. Premium II Refinery will be able to cope with these new constraints, producing cleaner fuels and generating by-products (gaseous emissions, liquid effluents and sulfur) within limits specified by new environmental laws. This paper has stressed the role of auxiliary units in reading the goals of a refinery adapted to the new reality of the oil industry.

6. Acknowledgements
The authors thank Glenda Rangel Rodrigues, Roberto Carlos Pontes Bittencourt, Solange Lins Klein, Mario José Dias Tavares and Caio Veiga Penna Delgaudio for the helpful discussions and disposal to review this paper, making relevant contributions.

7. References
ANP, Agência Nacional do Petróleo. Legislação, available at <http://www.anp.gov.br/?id=478>, acessed in April 17th, 2012. KELLER, A.E., CUMMINGS, A.L., Grime doesn’t pay. Brimstone Sulfur Recovery Suumposium, Vail Colorado, 2004 8

Rio Oil & Gas Expo and Conference 2012 PETROBRAS, Relatório de Sustentabilidade, 2010. PETROBRAS, Divulgação dos Resultados 4o trimestre de 2011 e exercício de 2011 (legislação societária), 2012. PINOTTI, R.; ARAÚJO, M. A. S. Managing Sulfur in Brazilian Oil Refining Industry: Present and Future. Rio Oil & Gas Expo and Conference, 2010. PINOTTI, R.; DELGAUDIO, C., Hidrorrefino e Enxofre no Parque de Refino de Petróleo Brasileiro: Evolução e Perspectivas. Revista Petro & Química, Ano XXXIV, nº 337, p. 50-53, 2011. SPEIGH, J.G., The Refinery of the Future, p.315-340, 2011. ZARENEZHAD, B., HOSSEINPOUR, N. Evaluation of different alternatives for increasing the reaction furnace temperature of Claus SRU by chemical equilibrium calculation. Applied Thermal Engineering, v.28, p. 738-744, 2008.

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