Science and Technology of Novel Process For Deep Desulfurization of Oil Refinery Streams

Fuel 82 (2003) 607631 www.fuelrst.
com
Review Article
Science and technology of novel processes for deep desulfurization of oil renery streams: a reviewq
I.V. Babich*, J.A. Moulijn
Faculty of Applied Sciences, Delft University of Technology, Delft ChemTech, Julianalaan 136, 2628 BL Delft, The Netherlands Received 15 March 2002; revised 15 July 2002; accepted 9 October 2002; available online 14 November 2002
Abstract Oil renery related catalysis, particularly hydrodesulfurization (HDS) processes, is viewed as a mature technology and it is often stated that break-throughs are not to be expected. Although this could be a justied compliment to those who developed this area, at the same time it could also stie potential new ideas. The applicability and perspectives of various desulfurization technologies are evaluated taking into account the requirements of the produced fuels. The progress achieved during recent years in catalysis-based HDS technologies (synthesis of improved catalysts, advanced reactor design, combination of distillation and HDS) and in non-HDS processes of sulfur removal (alkylation, extraction, precipitation, oxidation, and adsorption) is illustrated through a number of examples. The discussed technologies of sulfur removal from the renery streams lead to a wealth of research topics. Only an integrated approach (catalyst selection, reactor design, process conguration) will lead to novel, efcient desulfurization processes producing fuels with zero sulfur emissions. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Oil renery; Sulfur removal; Hydrodesulfurization
1. Introduction A modern renery is a highly integrated industrial plant, the main task of which is to efciently produce high yields of valuable products from a crude oil feed of variable composition. Employing different physical and chemical processes such as distillation, extraction, reforming, hydrogenation, cracking and blending the renery converts crude oil to higher value products. The main products are liquid petroleum gas, gasoline, jet and diesel fuels, wax, lubricants, bitumen and petrochemicals. Energy and hydrogen for internal and external use are also produced in a renery. Currently, reneries meet changing societal needs concerning product specications and quality by upgrading existing technologies and continuously developing advanced technologies [1]. Changes in rening processes
* Corresponding author. Present address: Faculty of Chemical Technology, University of Twente, Postbus 217, 7500 AE, Enschede, The Netherlands. Tel.: 31-53-489-35-36; fax: 31-53-489-46-83. E-mail address: i.v.babych@ct.utwente.nl (I.V. Babich). q Published rst on the web via fuelrst.comhttp://www.fuelrst.com
are made in response to external driving forces taking into account the inherent limitations of the renery (Fig. 1). Environmental restrictions regarding the quality of transportation fuels produced and the emissions from the renery itself are currently the most important issues, as well as the most costly to meet. The primary goal of the recently proposed regulations (by the Directive of the European Parliament [2] and the Environmental Protection Agency (EPA) Clean Air Act (Tier 2) [3]) is to reduce the sulfur content of transportation fuels. The CO2 emitted by the renery into the atmosphere is limited by the Kyoto protocol [4]. According to various estimation models, $10 15 billions in the European renery industry and up to $16 billion in US and Canadian reneries will be invested in direct response to the new environmental clean-fuel legislation [5,6]. Gasoline, diesel and non-transportation fuels account for 75 80% of the total renery products. Most of the desulfurization processes are therefore dealing with the streams forming these end products. Sulfur present in the fuels leads to SOx air pollution generated by vehicle engines. In order to minimize the negative health and environmental effects of automotive exhaust emissions,
0016-2361/03/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 1 6 - 2 3 6 1 ( 0 2 ) 0 0 3 2 4 - 1
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I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631
Fig. 1. External and internal factors inuencing modern reneries.
the sulfur level in motor fuels is minimized. New sulfur limits of 30 50 ppm for gasoline and diesel marketed in the European community and the USA will be introduced starting from January 1, 2005 [2,3,5,7,8]. Germany has even passed legislation limiting the sulfur in diesel and gasoline to 10 ppm as of November, 2001 [9]. In fact, zero-emission and, as a consequence, zero levels of S are called for worldwide in coming 5 10 years. Such ultra low-sulfur fuels requirements have consequences for the renery. Efciency of the desulfurization technologies becomes a key point. Conventional hydrodesulfurization (HDS) processes cannot currently produce such zero sulfur level fuels, while maintaining other fuel requirements such as oxygen content, vapor pressure, benzene content, overall aromatics content, boiling range and olen content for gasoline, and cetane number, density, polynuclear aromatics content, and distillation 95% point for diesel fuel [2,3,5,7,8]. 1.1. Gasoline Gasoline is formed by blending straight run naphtha (isomerate, reformate and alkylate products), naphtha from uid catalytic cracking (FCC) units and coker naphtha. Most sulfur in gasoline comes from the FCC naphtha. Treatment of FCC gasoline is, therefore, essential. The sulfur content of the other gasoline forming renery streams is not a problem for the current environmental regulations, but to produce gasoline of # 30 ppm S the renery will be obliged to treat them as well. A relatively high level of sulfur removal can be reached by using conventional or advanced CoMo and NiMo catalysts. However, simultaneous hydrogenation of olens should be minimized because it reduces the octane number. Also aromatics are not desired in the nal gasoline product. Process applicability is determined by its efciency in terms of end product yield and specications. Instead of further improving traditionally applied catalysis-based HDS technologies in small steps, now might be the right time for advanced desulfurization technologies which provide effective sulfur removal and simultaneously increase the octane number.
1.2. Diesel Diesel fuel is formed from straight run diesel, light cycle oil from the FCC unit, hydrocracker diesel, and coker diesel. Nowadays, diesel is desulfurized by hydrotreating all blended renery streams. To get diesel with less sulfur content the hydrotreating operation has to be more severe. For straight run diesel, sulfur removal is the only point of concern in hydrotreating since the other diesel specications (e.g. cetane number, density, and polyaromatics content) are satisfactorily met. Hydrocracker diesel is usually relatively high in quality and does not require additional treatment to reduce the sulfur content. As with gasoline, the diesel produced by the FCC and coker units contains up to 2.5 wt% sulfur. Both the FCC and coker diesel products have very low cetane numbers (slightly above 20), high densities, and high aromatics and polyaromatics content (about 80 90%). In addition to being desulfurized, these streams must be upgraded by high pressure and temperature processes requiring expensive catalysts. Another problem is that at high temperature the hydrogenation dehydrogenation equilibrium shifts toward aromatics. As with gasoline desulfurization, there are many options for developing and applying advanced desulfurization technologies with simultaneous upgrading to higher diesel specications. 1.3. Non-transportation fuels Non-transportation fuels are formed from vacuum gas oils and residual fractions from coking and FCC units. The sulfur content requirement for non-transportation fuels is less strict than for gasoline and diesel because industrial fuels are used in stationary applications where sulfur emissions can be avoided by combustion gas cleaning processes. In particular, high temperature solid adsorbents based on zinc titanate [10 12] or manganese/alumina [13 15] are currently receiving much attention. In practice, the major process is the capture of SOx with CaO producing CaSO4 [16 19]. Of course, for non-transportation fuels
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HDS technologies can also be applied without considering other fuel specications that must be met for gasoline and diesel fuels. It is also important to note that in some cases the HDS process requirements are between those for transportation and non-transportation fuels. For instance, in large ships and power plants ample space is available for dedicated equipment aiming at reduction of emission of SOx and soot that makes the requirement to sulfur content less strict. It has to be expected that the sulfur level requirements will become more and more strict in the near future, approaching zero sulfur emissions from burned fuels. The next generation of engines, especially fuel cell based engines, will also require fuels with extremely low (preferably zero) sulfur content. Therefore, scientists and engineers involved in improving current renery technologies and developing advanced technologies should shoot for complete sulfur removal from renery products. The applicability of various desulfurization technologies should be evaluated taking into account all requirements for the produced fuels. The most effective options for ultra deep desulfurization should be chosen since removing all sulfur from the fuels might be too expensive or result in renery CO2 emissions which are too high [9,20]. The aim of this paper is to analyze different desulfurization technologies for crude oil and renery streams and to formulate challenges for innovative research. We purport that break-through innovations in oil renery related desulfurization are still possible. The desulfurization processes currently employed in some reneries and in semi-commercialized and laboratory proven approaches are discussed. Special attention is paid to development and application of new desulfurization reactors and some examples of advanced options for reactor design are mentioned. In a separate chapter, structured monolithic catalytic reactors are discussed since they can be readily applied to desulfurization processes.
2. Classication of desulfurization technologies There is a no universal approach to classify desulfurization processes. The processes can be categorized by the fate of the organosulfur compounds during desulfurization, the role of hydrogen, or the nature of the process used (chemical and/or physical). Based on the way in which the organosulfur compounds are transformed, the processes can be divided into three groups depending on whether the sulfur compounds are decomposed, separated from renery stream without decomposition, or both separated and than decomposed (Fig. 2). When organosulfur compounds are decomposed, gaseous or solid sulfur products are formed and the hydrocarbon part is recovered and remains in the renery streams. Conventional HDS is the most typical example of this type of process. In other processes, the organosulfur compounds are simply separated from the renery streams. Some processes of this type rst transform the organosulfur compounds into other compounds which are easier to separate from the renery streams. When streams are desulfurized by separation, some desired product can be lost and disposal of the retained organosulfur molecules is still a problem. In the third type of process, organosulfur compounds are separated from the streams and simultaneously decomposed in a single reactor unit rather than in a series of reaction and separation vessels. These combined processes, which provide the basis for many technologies currently proposed for industrial application, may prove very promising for producing ultra-low sulfur fuels. Desulfurization by catalytic distillation is the fascinating example of this type of process. Desulfurization processes can be also classied in two groups, HDS based and non-HDS based, depending on the role of hydrogen in removing sulfur. In HDS based processes, hydrogen is used to decompose organosulfur compounds and eliminate sulfur from renery streams while non-HDS based processes do not
Fig. 2. Classication of desulfurization processes based on organosulfur compound transformation.
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Fig. 3. Desulfurization technologies classied by nature of a key process to remove sulfur.
require hydrogen. Different combinations of renery streams pre- or post-distilling treatments with hydrotreating to maintain desired fuel specications can also be assigned as HDS based processes since HDS treatment is one of the key steps. The two above-mentioned classications overlap to some extent. Most sulfur elimination processes, with the exception of selective oxidation, are HDS based. The organosulfur compound separation processes are usually non-HDS based since they do not require hydrogen if concentrated sulfur-rich streams are not subsequently hydrotreated. Finally, desulfurization processes can be classied based on the nature of the key physico-chemical process used for sulfur removal (Fig. 3). The most developed and commercialized technologies are those which catalytically convert organosulfur compounds with sulfur elimination. Such catalytic conversion technologies include conventional hydrotreating, hydrotreating with advanced catalysts and/or reactor design, and a combination of hydrotreating with some additional chemical processes to maintain fuel specications. Technologies of this type are discussed further in the Section 3. The main feature of the technologies of the second type is the application of physico-chemical processes different in nature from catalytic HDS to separate and/or to transform organosulfur compounds from renery streams. Such technologies include as a key step distillation, alkylation, oxidation, extraction, adsorption or combination of these processes. These processes will be discussed in Section 4.
3. Catalysis based HDS technologies 3.1. Conventional HDS: catalysts and reactivity Catalytic HDS of crude oil and renery streams carried out at elevated temperature and hydrogen partial pressure
converts organosulfur compounds to hydrogen sulde (H2S) and hydrocarbons. Detailed analysis of the HDS process is presented in the literature [21,22] so we discuss only the general aspects here. The conventional HDS process is usually conducted over sulded CoMo/Al2O3 and NiMo/Al2O3 catalysts [21]. Their performance in terms of desulfurization level, activity and selectivity depends on the properties of the specic catalyst used (active species concentration, support properties, synthesis route), the reaction conditions (sulding protocol, temperature, partial pressure of hydrogen and H2S), nature and concentration of the sulfur compounds present in the feed stream, and reactor and process design. Organosulfur compounds are usually present in almost all fractions of crude oil distillation. Higher boiling point fractions contain relatively more sulfur and the sulfur compounds are of higher molecular weight. Therefore, a wide spectrum of sulfur-containing compounds should be considered from the viewpoint of their reactivity in the hydrotreating processes. In Table 1 some of the organosulfur compounds of interest, namely, mercaptans, suldes, disuldes, thiophenes and benzothiophenes (BT), and their alkylated derivatives are mentioned with the proposed mechanism of sulfur removal. Of course, for deep desulfurization of renery streams, polynuclear organic sulfur compounds are also of interest. However, as they are rather stable under conventional HDS conditions we decided not to list them in Table 1. Moreover, their desulfurization reaction pathway is more complex compared with alkylated dibenzothiophene, and is not well understood. The reactivity of organosulfur compounds varies widely depending on their structure and local sulfur atom environment. The low-boiling crude oil fraction contains mainly the aliphatic organosulfur compounds: mercaptans, suldes, and disuldes. They are very reactive in conventional hydrotreating processes and they can easily be completely removed from the fuel. Other processes like
I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631 Table 1 Typical organosulfur compounds and their hydrotreating pathway Type of organic sulfur compound Mercaptanes Suldes Disuldes Thiophene Chemical structure R SH R1 SR2 R1 SSR2 Mechanism of hydrotreating reactiona R S H H2 ! R H H2 S R1 S R2 H2 ! R1 H R2 H H2 S R1 S S R2 H2 ! R1 H R2 H H2 S
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Benzothiophene
Dibenzothiophene
Reaction pathway for alkylated thiophene, benzothiophene and dibenzothiophene is similar to the reaction of nonalkylated counterparts.
Merox can be applied to extract mercaptans and disuldes from gasoline and light renery streams [23]. For higher boiling crude oil fractions such as heavy straight run naphtha, straight run diesel and light FCC naphtha, the organosulfur compounds pre-dominantly contain thiophenic rings. These compounds include thiophenes and benzothiophenes and their alkylated derivatives. These thiophene containing compounds are more difcult than mercaptans and suldes to convert via hydrotreating. The heaviest fractions blended to the gasoline and diesel pools bottom FCC naphtha, coker naphtha, FCC and coker dieselcontain mainly alkylated benzothiophenes, dibenzothiophenes (DBT) and alkyldibenzothiophenes, as well as
polynuclear organic sulfur compounds, i.e. the least reactive sulfur compounds in the HDS reaction. HDS of model organosulfur compounds as well as industrial fuels have been the subject of many investigations (see, for example, [21,22,24 29]). As reaction conditions, reactor type, catalyst, and feed composition vary from study to study, the observed data do not always agree. However, some general conclusions about reaction mechanism and catalyst efciency can be made based on the published data. HDS of thiophenic compounds proceeds via two reaction pathways (Table 1). Via the rst pathway the sulfur atom is directly removed from the molecule (hydrogenolysis pathway). In the second pathway the aromatic ring is
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hydrogenated and sulfur is subsequently removed (hydrogenation pathway). Both pathways occur in parallel employing different active sites of the catalyst surface. Which reaction pathway pre-dominates depends on the nature of the sulfur compounds, the reaction conditions, and the catalyst used. At the same reaction conditions, DBT reacts preferably via the hydrogenolysis pathway whereas for DBT alkylated at the 4 and 6 positions both the hydrogenation and hydrogenolysis routes are signicant [26,28]. The reactivity of sulfur compounds in HDS follows this order (from most to least reactive): thiophene . alkylated thiophene . BT . alkylated BT . DBT and alkylated DBT without substituents at the 4 and 6 positions . alkylated DBT with one substituent at either the 4 or 6 position . alkylated DBT with alkyl substituents at the 4 and 6 positions [25,29]. Deep desulfurization of the fuels implies that more and more of the least reactive sulfur compounds must be converted. Since from study to study the parameters of the HDS process differ, the reported values of catalyst activity and selectivity vary a lot. For example, in a continuous-ow reactor, a NiMo catalyst was found to be more active than a CoMo catalyst for desulfurizing 4,6-dimethyldibenzothiophene (DMDBT) [30]. In contrast, desulfurization of the same sulfur compounds in a batch reactor has been reported to be more efcient with a CoMo catalyst [31]. However, despite the differences in the experimental data, some general conclusions about the performance of NiMo and CoMo based catalysts can be made [21,22]. Conventional CoMo catalysts are better for desulfurization via the hydrogenolysis pathway since the CoMo hydrogenation activity is relatively low and, as a result, relatively little hydrogen is consumed. This makes CoMo catalysts attractive in HDS of unsaturated hydrocarbon streams like FCC naphtha. In contrast, NiMo catalysts possess high hydrogenation activity. Therefore, they are preferable for HDS of renery streams that require extensive hydrogenation.
3.2. Advanced HDS: catalyst, reactor and processing Deep desulfurization of renery streams becomes possible when the severity of the HDS process conditions is increased. Unfortunately, more severe conditions result not only in a higher level of desulfurization but also in undesired side reactions. When FCC gasoline is desulfurized at higher pressure, many olens are saturated and the octane number decreases. Higher temperature processing leads to increased coke formation and subsequent catalyst deactivation. It is also important to note that in practice the severity of the operating conditions is limited by the HDS unit design. Instead of applying more severe conditions, perhaps HDS catalysts with improved activity and selectivity can be synthesized. Ideal hydrotreating catalysts should be able to remove sulfur, nitrogen and, in specic cases, metal atoms from the renery streams. At the same time they must also improve other fuel specications, such as octane/cetane number or aromatics content, which are essential for high fuel quality and meeting environmental legislation standards. Hydrotreating efciency can also be increased by employing advanced reactor design such as multiple bed systems within one reactor, new internals in the catalytic reactor or new types of catalysts and catalyst support (e.g. structured catalysts). The best results are usually achieved by a combination of the latter two approaches, namely, using an appropriate catalyst with improved activity in a reactor of advanced design. 3.2.1. Advanced HDS catalysts To improve catalyst performance, all steps in the catalyst preparationchoice of a precursor of the active species, support selection, synthesis procedure and post-treatment of the synthesized catalystsshould be taken into account. Different approaches have resulted in new catalyst formulations (Fig. 4) and some examples are considered here. Applying a new catalyst manufacturing technology, Akzo Nobel introduced in 1998 new, highly active CoMo
Fig. 4. Different approaches to improve HDS catalyst performance [3236, 4050].
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and NiMo catalysts [51 53] referred to as STARS (Super Type II Active Reaction Sites). Under usual HDS operating conditions, these catalysts are claimed to desulfurize renery streams down to 2 5 ppm of sulfur and to signicantly reduce polyaromatic content and improve the cetane number and density of diesel fuels. Both CoMo and NiMo catalysts can be used for deep desulfurization but their efciency is determined by the feedstock properties [51]. The CoMo STARS catalysts are preferable for streams with relatively high sulfur levels of 100 500 ppm and perform better than NiMo catalysts at low pressure. In contrast, the NiMo STARS catalysts are especially suitable for fuels with low sulfur levels (below 100 ppm) at high pressure. Commercial results of STARS catalysts are reported to be promising. They show a stable high level of desulfurization during a long-term run of 400 days on stream. The CoMo STARS catalyst makes it possible to run a conventional HDS unit with output sulfur levels of 10 20 ppm for feed rates up to 30% higher than those for which the unit was designed without revamping the equipment [53,54]. Another Akzo Nobel catalyst preparation technology has been claimed to result in extremely active hydrotreating catalyststhe so-called NEBULA catalysts (NEBULA, NEw BULk Activity) [55]. In these catalysts, which are also active in sulded form, the active phase and the carrier are different in nature from conventional HDS catalysts. The hydrogen consumption is relatively high and these catalysts are suitable for diesel hydrotreating both at medium severity conditions and at high pressure. NEBULA catalysts have already been applied in two commercial units. A similar approachto enhance catalyst activity by modifying the preparation routewas employed by Criterion Catalysts and Technologies and resulted in Criterions CENTINEL catalyst family [56]. The CENTINEL catalysts are claimed to combine superior hydrogenation activity and selectivity. At lower H2 pressures and for high sulfur content streams, CoMo CENTINEL catalysts are preferable. For high H2 pressures and low sulfur content (below 50 ppm) NiMo CENTINEL catalysts are more useful. Combining new types of active catalytic species with advanced catalyst supports such as ASA (amorphous silica alumina) [37,38] can result in extremely high desulfurization performance. The application of ASA-supported noble metal based catalysts for second-stage deep desulfurization of gas oil is an example [37,38]. The Pt and PtPd catalysts are very active in the deep HDS of pre-hydrotreated straight-run gas oil under industrial conditions. These catalysts are able to reduce sulfur content down to 6 ppm while simultaneously reducing aromatics to 75% of their initial amount [57]. The PtPd/ASA catalysts are excellent for feeds with low or medium sulfur content and low aromatics levels (Fig. 5). At higher aromatics levels, the Pt/ ASA catalysts perform better than PtPd/ASA. At high sulfur levels, the ASA supported noble metal catalysts are
Fig. 5. Classication of ASA based catalysts for deep HDS of the feed of different composition [57].
poisoned by sulfur and NiW/ASA catalysts become preferable for deep sulfur removal and dearomatization. Application of noble metal catalysts for deep HDS is limited by their sulfur resistance. Therefore, noble metal catalysts are usually used when most of the organosulfur compounds and H2S have been removed from the process stream. A new concept of HDS catalyst design has been proposed to increase the sulfur resistance of noble metal hydrotreating catalysts [39]. The proposed catalyst is bifunctional. It combines catalyst supports with bimodal pore size distribution (e.g. zeolites) and two types of sulfur resistant active sites. The rst type of active sites, placed in large pores, is accessible for large organosulfur compounds and is sensitive to sulfur inhibition (sulfur resistant sites of the type I). The second type of active sites, placed in small pores, is not accessible for organosulfur compounds and is stable against poisoning by H2S (sulfur resistant sites of type II). Since hydrogen can easily access the sites located in the small pores, it can be adsorbed dissociatively and transported between pore systems to regenerate the poisoned metal sites of type I. Auto regeneration is ensured, so the HDS activity remains high even for feeds with high sulfur content. The concept looks very interesting, although successful application has not yet been demonstrated. Moreover, a number of questions of scientic interest should be solved. Appropriate design of active sites of different sulfur resistance is one of the key feature of this concept. Supports with appropriate texture and surface chemistry must be developed. For example, monolith supports with washcoats of regular structure (discussed in Section 5) might be attractive. 3.2.2. New reactor systems 3.2.2.1. Counter-current operation. Aside from improving the catalysts, upgrading hydrotreating equipment is an option. Conventionally used hydrotreating reactors are xed-beds with co-current supply of oil streams and hydrogen, resulting in unfavorable H2 and H2S concentration proles through the reactor. Due to high H2S concentration at the reactor outlet, the removal of the last ppm S is inhibited. Counter-current operation can provide a more preferable concentration prole. In counter-current reactor operation
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mode, the oil feed is introduced into the reactor at the top and hydrogen is introduced at the bottom of the reactor, in the place where its presence is most desired. H2S is removed from the reactor at the top, avoiding possible recombination of H2S and olens at the reactor outlet. A commercial example of this approach is the hydrotreating process based on SynSat Technology, which combines Criterions SynSat catalysts and ABB Lummus reactor technologies [58,59]. The general process scheme is shown in Fig. 6. In the rst stage, the feed and hydrogen co-currently contact the catalyst bed and the bulk of the organosulfur compounds is converted. This is followed by the removal of H2S from the reactant ow. The second stage of the reactor system operates in the counter-current mode providing more favorable concentration proles of H2S and H2 over the length of the reactor. Such a conguration allows for application of catalysts that are intrinsically very active but sensitive to sulfur poisoning, such as the noble metal based catalysts. The Scanraffs SynSat gas oil hydrotreating unit in Sweden uses a noble-metal catalyst in the second stage of the process. Industrial application of SynSat Technologies illustrates the ability of the counter-current approach not only to remove sulfur, but also to remove nitrogen and aromatics as well. It was reported that a sulfur level of 1 ppm and an aromatics level of 4 vol% could be attained [58]. 3.2.2.2. Ebullated bed reactors. The ebullated bed reactor [60] is an example of other types of reactors aimed at HDS of heavy renery streams, processing of which results in very fast catalyst deactivation due to coke formation. This type of reactor also has good heat transfer so overheating of
the catalyst bed is minimized and less coke forms. An ebullated bed is used by a.o. IFP (Institut Francais du Petrole, France) in the so-called T-Star process to desulfurize heavy feedstocks such as deep cut heavy vacuum gas oils, coker gas oils, and some residues [61]. In this unit, the catalyst particles are uidized by the feed and hydrogen and are therefore well mixed with the feed stream. Bed plugging and channeling are avoided and the unit operates nearly isothermally with a constant low-pressure drop. It is also very convenient that the catalyst activity can be controlled by adding and withdrawing catalyst particles. In comparison with xed-bed HDS catalysts, the additional requirement for T-Star catalysts is that they be mechanically stable and resist attrition. Integration of the T-Star process with inline hydrotreating produces diesel with less than 50 ppm sulfur and FCC feed with 1000 1500 ppm sulfur, which will result in FCC gasoline sulfur of 30 50 ppm [61]. As an example of the processes employing a special reactor design and modied catalyst system for HDS of a large variety of feedstocks, the so-called Prime processes (Prime-G, Prime-G , and Prime-D) developed by IFP must be mentioned [62,63]. They combine mild operating conditions with relatively high space velocities utilizing a dual catalyst system. The Prime HDS technology results in minimal olen saturation in the case of FCC gasoline desulfurization, and polyaromatics reduction and cetane number improvement in the case of gas oils treatment. The Prime technology enables over 98% desulfurization of the entire FCC naphtha cut. Prime reactors t easily into any renery conguration and currently ve units are in operation. 3.2.3. Combinations of hydrotreating with other reactions Sulfur removal by HDS processes is usually accompanied by other hydrogenation reactions, which are particularly undesired for FCC gasoline streams where olens are present. Olen saturation during hydrotreating results in octane loss of the nal gasoline pool. Different options of FCC gasoline treatment before or after desulfurization in the HDS unit can be considered to compensate for the loss of octane. 3.2.3.1. Aromatizing and hydrotreating. Aromatizing of the cracked gasoline before HDS treatment was proposed by Phillips Petroleum Co. [64]. By combining pre-aromatization of FCC gasoline streams with conventional HDS, sulfur content decreases from 300 to 10 ppm and the octane number increases from 89 to 100. Despite almost complete olen saturation, octane is boosted by increasing the aromatics amount in the end product up to 68 wt%. However, it is fair to state that a high level of aromatics in the nal product makes application of the proposed technology less attractive since new environmental rules require a limited amount of aromatics in the gasoline.
Fig. 6. Co-current/counter-current Syn Technology process scheme.
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3.2.3.2. Hydrotreating and octane boosting (ISAL process1). The ISAL process, which was specially developed for hydrotreating FCC gasoline, combines conventional HDS with post-treatment of the products to minimize the decrease in octane number [65 67]. As in conventional hydrotreating, it saturates olens present in the feed, but the resulting octane loss is compensated by octane-enhancing reactions. The key point of the process is the catalyst formulation. Due to improved catalyst desulfurization activity and nitrogen and sulfur tolerance, the ISAL process employs one xed-bed reactor unit with the catalyst system divided in a multiple bed conguration. For example, typically combination of CoMoP/Al2O3 and GaCr/H-ZSM-5 catalysts is applied [68]. The ow scheme of the ISAL process is similar to that of a conventional hydrotreating process. As a result, the ISAL process can be easily implemented as a new process unit or as a revamp of existing hydroprocessing units. It was very efcient at reducing sulfur from 1450 ppm in a naphtha feed to 10 ppm in the nal product with almost no decrease in octane number [67,68]. 3.2.4. Catalytic distillation To avoid octane loss with deeper desulfurization, the FCC gasoline stream can be fractionated by distillation before desulfurization and each fraction can be desulfurized at appropriately severe conditions. This option is efcient since the olens are mainly concentrated in the low-boiling fraction of the FCC naphtha whereas the sulfur compounds are mainly present in the high-boiling fraction. Moreover, the nature of sulfur compounds in light and heavy naphtha fractions is different and, therefore, they can be hydrotreated advantageously at different selective conditions, preserving olens in the nal product. But realizing this approach requires multiple hydrotreating reactorsone reactor per fraction. Combining distillation and reaction in a single vessel is a breakthrough. The elegant technology of sulfur removal employing distillation and HDS (catalytic distillation (CD)) has been introduced by CDTech Company [69 71]. The process is based on simultaneously desulfurizing and splitting the FCC naphtha stream into fractions with different boiling points. The simplied CDHDS process ow is shown in Fig. 7. The main feature of the process is that, depending on the FCC naphtha properties and desired product specication, a distillation column is loaded with a hydrotreating catalyst at different levels of the column or throughout the whole column. Desulfurization conditions are different for light and heavy fractions, their severity being nicely controlled by the boiling temperature of the naphtha fraction. The lighter fractions, which contain most of the olens and easily removable sulfur compounds, are subjected to
1 The name of the technology comes from isomerization and Salazar name of the technology inventor.
Fig. 7. Simplied ow scheme for CDHDS based technology.
desulfurization at lower temperatures at the top of the column. That leads to higher desulfurization selectivity and less hydrocracking and/or saturation of olenic compounds. The higher boiling portions, containing heavily desulfurized sulfur compounds, are subjected to desulfurization at higher temperatures at the bottom of the distillation column reactor. The reaction zone cannot overheat since the heat released during the HDS reaction is used to boil the hydrocarbon stream. This leads to nearly perfect heat integration. The CDHDS process efciency has been demonstrated at Motivas Port Arthur, Texas Renery with the application of a commercially available catalyst loaded in a proprietary distillation structure provided by CDTech [72]. Over the rst four months of operation, the technology showed a stable desulfurization level of about 90% with an average octane number loss of less than 1. To improve process feasibility and increase product yield a two stage CDTechw process including CDHydro (production of sweet light cut naphtha with very low mercaptan content and increased octane) and CDHDS processes has been proposed [70,71]. It is claimed that the technology of CDTechw is about 25% less expensive than the conventional HDS process, making it very attractive for reneries.
4. Non-HDS based desulfurization technologies Technologies that do not use hydrogen for catalytic decomposition of organosulfur compounds are discussed here as non-HDS based desulfurization technologies. The following approaches are considered to be attractive for attaining high levels of sulfur removal by shifting the boiling point of sulfur-containing compounds, separating by extraction or adsorption, and decomposition via selective oxidation.
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Fig. 8. The OATS process ow scheme.
4.1. Shifting the boiling point by alkylation When the boiling temperature of organosulfur compounds is shifted to a higher value, they can be removed from light fractions by distillation and concentrated in the heavy boiling part of the renery streams. British Petroleum used this approach in a new advanced technology process for desulfurizing FCC gasoline streamsolenic alkylation of thiophenic sulfur (OATS) [73 75]. The process employs alkylation of thiophenic compounds via reaction with olens present in the stream:2
As a result the boiling temperature of the sulfur containing hydrocarbon compounds increases. In comparison with thiophene (boiling point around 85 8C), alkylated thiophenes such as 3-hexylthiophene or/and 2-octylthiophene have a much higher boiling point (221 and 259 8C, respectively). This enables them to be easily separated from the main gasoline stream by distillation. The high-boiling compounds produced can be blended into the diesel pool and desulfurized by conventional hydrotreating as the octane number is not important for diesel. The OATS technology consists of a pre-treatment section, an OATS reactor, and a product separation unit (Fig. 8) [73].
2 If CH3I or AgBF4 is used as an additional alkylation agent, Salkylsulfonium salts are formed and sulfur is removed from fuel oil as precipitates [76,77]. As a result, fuel oil can be desulfurized to less than 30 ppm S. The desulfurization level can be further increased by increasing the alkylating agent/sulfur ratio. Taking into account the high cost of alkylating agents, this approach does not seem to be economically feasible on an industrial scale. Another disadvantage is the decrease in olen concentration due to their reaction with the alkylating agents.
Thiophenic sulfur is alkylated in an OATS reactor employing acidic OATS catalysts such as BF3, AlCl3, ZnCl2, or SbCl5 deposited on silica, alumina or silica alumina supports [78]. After the OATS reactor, the feed is sent to a conventional distillation column where it is separated into a light sulfur-free naphtha and a heavy sulfur-rich stream. The light naphtha is directly sent to the gasoline pool and the heavy stream is preferably hydrotreated. The hydrotreater is not an essential part of the OATS technology, but its application after the fractionator increases the product yield. Employing the OATS technology, over 99.5% of the sulfur can be removed from the gasoline stream [74,79]. Demonstration experiments showed sulfur reduction in gasoline from 2330 ppm to less than 20 ppm with only two octane number loss [74]. Another advantage of the OATS process is that less hydrogen is consumed since only a relatively low volume of the FCC gasoline stream is hydrotreated. The efciency of the OATS process can be limited by competing processesalkylation of aromatic hydrocarbons and olen polymerization. Fortunately, under the conditions employed alkylation of the sulfur-containing compounds occurs more rapidly than that of aromatics. One of the disadvantages of the OATS process is that the alkylated sulfur compounds produced require more severe hydrotreating conditions to eliminate sulfur. To our knowledge, there is no information in the open literature about catalyst durability and other key process characteristics. It seems that many issues must be studied and proven before OATS technology can be commercialized. 4.2. Desulfurization via extraction Extractive desulfurization is based on the fact that organosulfur compounds are more soluble than hydrocarbons in an appropriate solvent. The general process ow is
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shown in Fig. 9. In a mixing tank, the sulfur compounds are transferred from the fuel oil into the solvent due to their higher solubility in the solvent. Subsequently, the solvent fuel mixture is fed into a separator in which hydrocarbons are separated from the solvent. The desulfurized hydrocarbon stream is used either as a component to be blended into the nal product or as a feed for further transformations. The organosulfur compounds are separated by distillation and the solvent is recycled. The most attractive feature of the extractive desulfurization is the applicability at low temperature and low pressure. The mixing tank can even operate at ambient conditions. The process does not change the chemical structure of the fuel oil components. As the equipment used is rather conventional without special requirements, the process can be easily integrated into the renery. To make the process efcient, the solvent must be carefully selected to satisfy a number of requirements. The organosulfur compounds must be highly soluble in the solvent. The solvent must have a boiling temperature different than that of the sulfur containing compounds, and it must be inexpensive to ensure economic feasibility of the process. Solvents of different nature have been tried, among which acetone, ethanol [80], polyethylene glycols [81], and nitrogen containing solvents [82] showed a reasonable level of desulfurization of 50 90% sulfur removal, depending on the number of extraction cycles. The GT-DeSulfSM process is an example of desulfurization technology based on organosulfur compound extraction [83]. This process separates the organosulfur compounds and aromatics from FCC naphtha by extractive distillation using a blend of solvents. A desulfurized/dearomatised olen rich gasoline stream and an aromatic stream containing the sulfur compounds are formed after treatment in a GT-Desulf reactor. The rst stream is directly used as a gasoline blend stock. Unfortunately, available literature does not contain any information on the level of sulfur removal from the treated stream. The aromatics fraction with the sulfur compounds is sent to a HDS reactor. After treatment in the HDS reactor, aromatics recovery is proposed as an additional option to increase economic efciency of the process. The authors pointed out that
the GT-DesulfSM process is economically favorable due to an integrated approach to the renery processing (segregated sulfur removal and aromatics recovery) and lower hydrogen consumption since less FCC naphtha is treated in the HDS reactor. The efciency of extractive desulfurization is mainly limited by the solubility of the organic sulfur compounds in the solvent. Solubility can be enhanced by choosing an appropriate solvent taking into account the nature of the sulfur compounds to be removed. This is usually achieved by preparing a solvent cocktail such as acetone ethanol [80] or a tetraethylene glycol methoxytri glycol mixture [81]. Preparation of such a solvent cocktail is rather difcult and intrinsically non-efcient since its composition depends strongly on the spectrum of the organosulfur compounds present in the feed stream. Solubility can also be enhanced by transforming the organic sulfur compounds to increase their solubility in a polar solvent. One way to do this is by selective oxidizing the organic sulfur compound (thiophene, BTs, DBTs) to sulfones possessing higher polarity. This type of desulfurization process can be also considered as oxidative desulfurization technology. They are mentioned here because they employ liquid/liquid extraction to separate sulfur-containing compounds from renery streams. 4.2.1. Desulfurization via conversion and extraction Conversion/extraction desulfurization (CED) technology began in 1996 when Petro Star Inc. combined conversion and extraction to remove sulfur from diesel fuel [84,85]. Before liquid/liquid extraction, the fuel is mixed with an oxidant (peroxoacetic acid). The oxidation requires a stoichiometric amount of the oxidant and proceeds at temperatures below 100 8C at atmospheric pressure. In laboratory-scale experiments straight-run diesel fuel with 4200 ppm S was treated to below 10 ppm S [84]. Other fuel specications like cetane number, API gravity and aromatics content were also improved. Reducing the oxidant cost is one way to improve the economic feasibility of this technology. Again, a solvent cocktail should be more suitable than an individual solvent, but additional investigations are required to determine
Fig. 9. General process ow of extractive desulfurization.
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the appropriate composition. The processes for deep extract treatment to recover sulfur from the concentrated sulfur-rich extract and to return most of the hydrocarbons to the product stream must be developed to enhance the CED process performance. 4.2.2. UniPure aromatic sulfur reduction technology [86] The UniPure process is also based on oxidizing aromatic sulfur compounds before extracting them. The main difference from the CED technology is that an aqueous phase is applied along with a dissolved oxidation catalyst. Organosulfur compounds are claimed to be converted to sulfones at nearly atmospheric pressure and mild temperature (up to 120 8C) within short residence times (about 5 min) [86]. After separation of the aqueous and oil streams, the process follows the same scheme as the CED process. The sulfur level is reported to be reduced from 270 to 2 ppm sulfur. Pilot plant tests have been planned for the second half of 2001. Oxidation of the organosulfur compounds is the main limiting step of the conversion/extraction desulfurization technologies. Kinetics of the oxidation reaction can be improved by employing photons or ultrasound. In the following sections, this will be treated more in detail. 4.2.3. SulphCo desulfurization technology3 [87,88] The SulphCo technology applies ultrasound energy to oxidize sulfur compounds in a water fuel emulsion containing a hydrogen peroxide catalyst.4 Similar to the CED and UniPure technologies, the SulphCo process operates at 70 80 8C under atmospheric pressure. The residence time for the ultra-sound reactor is reported to be only 1 min. No detailed discussion of the mechanism of the desulfurization reaction is currently available. The authors claim desulfurization efciencies for crude oil and diesel up to 80 and 98% sulfur removal, respectively. For light diesel fuels, the proposed technology meets the 10 ppm S requirement. The SulphCo process is reported to be economically feasible. In accordance with the preliminary estimation of Betchel Corp. scientists, the SulphCo unit will cost about 50% of what an equivalent hydrotreater would cost [88]. The rst ultrasonic desulfurization unit has been installed at the IPLOM petroleum renery near Genoa in Italy. It showed continuous and successful desulfurization of diesel fuel at a rate of up to 350 bbl per day.3 No detailed discussion of the mechanism of the desulfurization reaction is currently available. The authors
http://www.sulphco.com/technology.htm Ultrasonic energy can be also used for catalytic HDS of thiophene. There is only one preliminary report about ultrasound desulfurization of thiophene water ethanol mixture employing Ni/Al2O3 or Ni/ZnO catalysts at low temperature and atmospheric pressure [89]. The combination of ultrasound and catalyst results in water decomposition to provide hydrogen for thiophene desulfurization. The reported desulfurization level is about 30 40 mol% of thiophene conversion.
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do not disclose details of the process because of pending patents and because they are still optimizing some stages of the process, like elucidation of the mechanism of oxidation reactions under ultra-sound excitation, optimization of the solvent and catalyst composition. 4.2.4. Desulfurization by extractive photochemical oxidation Another desulfurization method combines photochemical reactions with extraction of the organosulfur compounds into an aqueous-soluble solvent [90 93]. The sulfur containing hydrocarbons are suspended in an aqueous-soluble solvent and irradiated by UV or visible light in a specially designed photoreactor. This results in the oxidation of the sulfur compounds. The polar compounds formed are rejected by the non-polar hydrocarbon phase and are concentrated in the solvent. Photochemical reaction is assisted by a photosensitizer 9,10-dicyanoanthracene (DCA). Acetonitrile, which provides relatively high solubility of initial and oxidized sulfur compounds, was found to be the most suitable solvent. After photooxidation, the solvent and the hydrocarbon phases are separated, as in extractive desulfurization. In addition, the recovery of aromatics from the solvent and recovery of the photosensitizer from the solvent and desulfurized hydrocarbon stream must be done to increase product yield and economic efciency. Aromatics are usually recovered by liquid liquid extraction using light parafnic solvents and are subsequently blended into the desulfurized fuel stream [91,93]. DCA is removed by adsorption, using a silica gel as an adsorbent. It can be returned to the process after desorption with aqueous solution of acetonitrile. All of these processes are rather common renery processes (though not all of the chemicals are common) that can be easily integrated into the renery and do not require special equipment or conditions. This photooxidation method showed a high selectivity to remove sulfur from light oils [90,91], catalytic-cracked gasoline [92], and vacuum gas oils [93]. The sulfur content in commercial light oil can be reduced to below 50 ppm [91]. For fuels with higher aromatics content, efciency is slightly lower but it was claimed that above 99% of the sulfur was removed from a vacuum gas oil [93]. At the present stage, the extractive photooxidation desulfurization process is rather far from being widely applied in industry. There are a number of problems that have to be solved to make the process technically and economically feasible. A solvent has to be carefully selected from the viewpoint of sulfur compounds solubility and aromatic rejection. Combination of a solvent and a photosensitizer has to be optimized to increase the rate of the organosulfur compounds phototransformation. Some opportunities for improvement of separation processes still exist, in particular the DCA recovery. It is promising to
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stabilize a photosensitizer on the surface of a solid carrier without losing its ability to accelerate photooxidation of the sulfur compounds. This will simplify the general process ow, eliminating the process of photooxidant recovery from the fuel oils and the solvent. Also the reactor design is not standard. It remains to be proven that reasonable photon efciency can be obtained. 4.3. Desulfurization by precipitation Desulfurization by precipitation is based on the formation and subsequent removal of insoluble charge-transfer complexes. Preliminary experiments were reported for a model organosulfur compound (4,6-DMDBT, referred to as DBT) in hexane and gas oil, using 2,4,5,7-tetranitro-9uorene (TNF) as the most efcient p-acceptor [94,95]. A suspension of the p-acceptor and sulfur containing gas oil was stirred in a batch reactor where insoluble chargetransfer complexes between p-acceptor and DBT derivatives formed. The consecutive steps include ltration to remove the formed complex from gas oil and the recovery of the p-acceptor excess using a solid adsorbent. Currently the efciency is very low. One treatment results in the removal of only 20% of the present sulfur. Moreover, there is a competition in complex formation between DBT compounds and other non-sulfur aromatics that results in low selectivity for DBT removal. The experimental results reported are not very informative because the role of other compounds that might form pcomplexes (aromatics, N-compounds) has not been studied. Moreover, a large overstoichiometric amount of TNF is used to provide good complexing and its excess should be removed from the oil stream afterwards. It seems interesting to introduce a complexing agent into a solid organic or inorganic matrix. This would simplify the process since the ltration and p-acceptor recovery steps are avoided. 4.4. Selective oxidative desulfurization
compounds will only be separated and their treatment will be done elsewhere). If transformation of the sulfur compounds is combined with distillation, the process scheme might be similar to catalytic distillation desulfurization (CDTech). The possibility of selective oxidation of hydrocarbon streams with different oxidizing agents (peroxides, peracids, molecular oxygen, and air) followed by thermal decomposition of oxidized sulfur compounds were already described more than 30 years ago [97]. Organosulfur compound oxidation to gaseous sulfur compounds in the presence of methanol has also been proposed. Sulfur is released mainly as SO2 at low temperatures, and some H2S is formed if the temperature of decomposition is above 300 8C. However, efciency of the process was low as only about 40% sulfur removal was reported. Direct selective oxidation of organosulfur compounds to gaseous sulfur products and hydrocarbons is also an option. Using oxygen or air rather than hydrogen to remove sulfur from renery streams is attractive due to the availability of the reacting gas and its low price. The main issues of the direct selective oxidation process are operation safety and the formation of by-products (CO2, CO, etc.). We checked the thermodynamic feasibility of selective oxidation of thiophene and benzothiophene assuming the formation of SO2 and hydrocarbons using air as an oxidant. It appears to be thermodynamically feasible within a temperature interval relevant for a renery (typically 200 400 8C). It should be noted that, due to the reaction stoichiometry, either bonded or molecular hydrogen is needed. Otherwise the reactions resulting in sulfur elimination will be accompanied by the formation of unsaturated compounds that can lead to undesired polymerization or coke formation. Water can be considered as one possible hydrogen source, taking into account the availability and safety. To make this process efcient, appropriate catalysts with high selectivity for oxidation and decomposition must be identied. 4.5. Desulfurization by adsorption on a solid sorbent
Generally, desulfurization by selective oxidation consists of two main steps: oxidation of sulfur compounds and subsequent purication [96]. Some of the processes employing oxidation as one of the key steps (CED, SulphCo, UniPure, photochemical desulfurization) have already been discussed as the extraction-based processes. In the meantime, other methods like distillation, adsorption or thermal decomposition can be used for separating oxidized sulfur containing compounds from fuel streams. To our knowledge, there is no information in the open literature about combination of selective oxidation and distillation to remove sulfur. But this approach is feasible, in principle, because the oxidation of sulfur compounds to sulfoxides or sulfones increases their boiling temperature. The oxidative distillation desulfurization process will be very similar to normal distillation if organosulfur
Desulfurization by adsorption (ADS) is based on the ability of a solid sorbent to selectively adsorb organosulfur compounds from renery streams. Based on the mechanism of the sulfur compound interaction with the sorbent, ADS can be divided into two groups: adsorptive desulfurization and reactive adsorption desulfurization. Adsorptive desulfurization is based on physical adsorption of organosulfur compounds on the solid sorbent surface. Regeneration of the sorbent is usually done by ushing the spent sorbent with a desorbent, resulting in a high organosulfur compound concentration ow. Reactive adsorption desulfurization employs chemical interaction of the organosulfur compounds and the sorbent. Sulfur is xed in the sorbent, usually as sulde, and the S-free hydrocarbon is released into the puried fuel stream. Regeneration of the spent
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sorbent results in sulfur elimination as H2S, S, or SOx, depending on the process applied. Efciency of the desulfurization is mainly determined by the sorbent properties: its adsorption capacity, selectivity for the organosulfur compounds, durability and regenerability. 4.5.1. Adsorptive desulfurization Adsorptive desulfurization was studied by Salem and Hamid [98,99] for removing sulfur from naphtha with a 550 ppm initial sulfur level in a batch reactor using activated carbon, zeolite 5A, and zeolite 13X as solid adsorbents. Activated carbon showed the highest capacity, but a low level of sulfur removal. Zeolite 13X was superior for sulfur removal from low sulfur streams at room temperature. Therefore, a two-bed combination was proposed for industrial application. The rst bed contains activated carbon and is able to remove up to 65% of the sulfur at 80 8C. The second bed is loaded with zeolite 13X and provides almost 100% sulfur recovery at room temperature if the sorbent/feed ratio is about 800 g/l. No data about sorbent regeneration were presented. Activated carbon, zeolites, CoMo catalysts, and silica alumina sorbents were tested for adsorptive desulfurization of a mid-distillate stream with 1200 ppm S in a xed bed reactor [100]. The process was specially aimed at the elimination of refractory 4- and 4,6-substituted dibenzothiophenes which are pre-dominantly present in the feed after hydrotreatment. Activated carbon was claimed to possess good desulfurization performance at 100 8C for 75 min. It is not possible to estimate the sorbent capacity from the data given. To regenerate the sorbent, the column was ushed with toluene. Sorbent capacity was completely restored within 2 h of ushing at 100 8C. 4.5.2. IRVAD process An adsorption-based desulfurization technology called IRVAD (combination of the inventor name IRVine and ADsorption) was developed by Black and Veatch Pritchard engineering company [101 104]. It is targeted to remove a wide spectrum of organosulfur compounds from various renery streams including FCC gasoline. A simplied process scheme is shown in Fig. 10.
The process is based on moving bed technology and uses a solid sorbent, which is counter-currently brought into contact with a sulfur-rich hydrocarbon stream. The desulfurized hydrocarbon stream is produced at the top of the adsorber whereas the spent sorbent is withdrawn at the bottom. The spent sorbent is circulated into the reactivator where organosulfur compounds and some adsorbed hydrocarbons are desorbed from the sorbent surface. The regenerated sorbent is recirculated back to the adsorber. The IRVAD process employs alumina based selective sorbents produced by Alcoa Industrial Chemicals. To increase sorbent capacity and selectivity the initial support was modied with an inorganic promoter [104]. However, the sorbent formulation is not disclosed. The process operates up to 240 8C, at low pressure with a hydrocarbon/sorbent weight ratio of about 1.4. The reactivation process requires slightly higher temperature. No hydrogen is required so sulfur removal is not accompanied by undesired olen saturation. The efciency of the IRVAD process was demonstrated in pilot plant experiments for FCC feedstock (1276 ppm S) and coker naphtha (2935 ppm), providing at least 90% reduction in sulfur content [101]. The performance of the IRVAD process is limited by the sorbent capacity and its afnity for sulfur compounds. As adsorption of dibenzothiophene molecules occurs parallel to the surface of the catalyst via the p-electron of the aromatic ring [105], the sorbent capacity is rather low. As a result, a high amount of sorbent is required for effective operation of the desulfurization units. In the adsorptive desulfurization processes, organosulfur compounds are only concentrated. Additional downstream treatment, preferably high-pressure hydrotreating, is required to eliminate sulfur. Efciency of the process can be increased by optimizing the sorbent properties in order to improve hydrocarbon recovery during the reactivation treatment. Some of the operating parameters, such as adsorbent particle size, number of adsorption reactivation steps, weight ratio of the hydrocarbon feed to the adsorbent, appropriate adsorption, and reactivation temperature, must also be optimized before commercial application is possible. Work on the IRVAD process is currently discontinued because of a time limit to nalize the technology before
Fig. 10. Simplied adsorptive desulfurization process ow.
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the new sulfur levels are introduced in Europe and the US [106].
4.5.3. Reactive adsorption desulfurization (Phillips S Zorb sulfur removal technology) The general desulfurization pathway of sulfur removal by reactive adsorption desulfurization can be described by the following scheme [107]:
The sulfur atom is removed from the molecule and is bound by the sorbent. The hydrocarbon part is returned to the nal product without any structural changes. Employing the principle of reactive adsorption, Phillips Petroleum Co., USA has proposed the so-called Phillips S Zorb technology to remove sulfur from gasoline and diesel fuels5 [108,109]. The S Zorb process is based on uid bed technology and the ow scheme is very similar to the IRVAD technology, but operating conditions are more severe T 340 410 8C; P 2 20 bar to provide good kinetics of the process. It is claimed that the process removes about 98% of the sulfur from gasoline (feed 1100 ppm, product 25 ppm) with only 3% decrease in olen concentration (0.5 1.5 octane number loss) and almost 100% hydrocarbon recovery [108]. Less hydrogen is consumed than in conventional hydrotreating processes and the requirements for hydrogen purity are not so strict. S Zorb application for diesel fuels is now under development and test results have conrmed the high level of sulfur removal [110]. The process was proven on laboratory scale in October 1999. An industrial pilot plant was designed between October 1999 and February 2000, and commercial start-up was planned in March 2001 at the Phillips Petroleum Co. renery in Texas [108,109]. The key point of the S Zorb processthe composition of S Zorb sorbentis not fully revealed, but it can be assumed that zinc and other metal oxides on suitable supports can be used in the process [109]. Zinc oxide is mentioned as the main component of the desulfurization sorbent described in patents assigned to Phillips Petroleum Co. [111,112]. The sorbent also contains alumina, silica and nickel oxide. 4.5.3.1. Thermodynamic analysis of reactive adsorption desulfurization. The potential applicability of different metal oxide sorbents in reactive adsorption can be evaluated from the results of thermodynamic modeling of the desulfurization process. We calculated the equilibrium
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composition of the reacting system from the criterion that equilibrium at constant temperature and pressure is reached if the total Gibbs energy is at a minimum with respect to all possible changes in composition. The gas phase was simulated by the presence of the model organic sulfur compound thiophene6 in a H2/N2 mixture. Several types of metal oxides, namely bulk or supported ZnO, MoO3, NiO, Co3O4, and MnO, were considered as sorbent candidates. All sorbents show relatively favorable equilibrium data in the desulfurization of thiophene. The obtained equilibrium compositions for bulk ZnO sorbent as a function of temperature at normal total gas pressure are presented in Fig. 11 as an example. It is observed that with an excess of hydrogen (H2/thiophene 10) thiophene decomposition is thermodynamically feasible over a large temperature range (Fig. 11(a)). Up to 900 K, the equilibrium composition contains less than 50 ppm S. All sulfur is xed in the sorbent as ZnS (not shown in Fig. 11, because of the scale limit). The role of the hydrogen in reactive adsorption desulfurization can be claried from thermodynamic modeling as well. With a stoichiometric ratio of hydrogen to thiophene in the reacting mixture, the process does not result in a high desulfurization level (Fig. 11(b)). Only when hydrogen is in excess (H2 to thiophene ratio above stoichiometric), is thiophene desulfurized almost completely. These data should not be considered as evidence that a lot of hydrogen is consumed, but they show that hydrogen still plays a very important role in the process. To clarify the role of H2 the mechanism of organosulfur compound decomposition has to be determined experimentally and kinetics have to be determined. From earlier work, we expect that the kinetics are fast [113]. Conventional Ni Mo/Al2O3 and Ni/Al2O3 HDS catalysts have been experimentally tested in reactive adsorption desulfurization of kerosene [114]. The oxide form of the Ni Mo/Al2O3 catalyst has been shown to exhibit a higher desulfurization activity in reactive adsorption in comparison with the sulded analogue under hydrotreating conditions. It provides a very high level of kerosene desulfurization in pure hydrogen. However, the catalyst sulfur capacity is limited by the amount of active phase that can be sulded (Ni Mo). We have estimated that, for a feed with 100 ppm S at LSHV equal to 1 h21, the catalyst will be overloaded by sulfur in less than one month. Of course this is a rather short time for conventional industrial application and a tailored process conguration including regeneration is, therefore, required. Reduced Ni/Al2O3 catalysts have shown even higher activity in the adsorptive desulfurization in comparison with
Thiophene was chosen since it was reported to posses the lowest reactivity in the reactive adsorption process among alkyl thiophenes and benzothiophenes [108]. This is clear evidence that sulfur removal in the reactive adsorption occurs via a mechanism different from hydrotreating mechanism (hydrogenation/hydrogenolysis of organosulfur compounds). Benzothiophene and dibenzothiophene show similar, even more favorable, results in thermodynamic modeling.
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http://www.fuelstechnology.com/sulfur_removal.htm
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Fig. 11. Thermodynamic modeling of the equilibrium composition in the reactive adsorption desulfurization process. Solid sorbent: ZnO; organosulfur compound: thiophene. (a) H2/thiophene 10:1; (b) H2/thiophene 1:1.
the oxide Ni Mo catalysts, but their life time on stream is limited by the limited suldation capacity of the nickel surface layer [115]. Different options to regenerate the sulfur-poisoned Ni surface species have been tested [116, 117]. The best performance has been observed for Ni/ZnO system. Due to its higher sulfur accepting potential, ZnO in this system is acting as an acceptor of sulfur that is released during regeneration of sulded nickel surface species. The overall mechanism can be tentatively described by the scheme in Fig. 12. Based on the data of Tawara et al. [114 117], a mechanism for the Z Sorb sorbent can be proposed and the role of the sorbent components can be claried. ZnO, which provides the high sulfur capacity, has to be the main component of the sorbent. Alumina and silica can be used to increase the mechanical strength and attrition resistance of the sorbent. Also, NiO promotes the decomposition of organic sulfur compounds [118,119]. Optimal composition of the Ni/ZnO sorbent is determined by the balance between the poisoning rate and the regeneration rate and is found to be equal to 13 wt% Ni. It has been reported that less than 0.03 ppm of sulfur was
present in the efuent during one year for a kerosene feed containing 51 ppm of sulfur LSHV 0:27 h21 : The main limitation of the reactive adsorption desulfurization process is connected with quick overloading of the sorbent in the case of renery streams with high sulfur content. High sulfur content requires either a large amount of sorbent or a suitable process conguration based on fast kinetics of the deactivation regeneration reactions. Both sorbent capacity and sorbent performance can be optimized by appropriate composition of the sorbent applied. For low sulfur containing streams (usually concerning removal of the last ppm S) reactive adsorption requires treatment of large volumes of sulfur diluted reactant. This results in a high energy penalty due to pumping of the hydrocarbons through the reactor. In this case, it seems very efcient to apply structured low-pressure drop reactors and to combine reactive adsorption desulfurization with processes such as catalytic distillation or extraction, which preconcentrate sulfur. The list of processes discussed above is not complete. Many other processes are already applied or almost ready for industrial application. We limited ourselves to the discussion
Fig. 12. Mechanism of reactive adsorption desulfurization process.
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of processes that are attractive for ultra-deep desulfurization of renery streams but still have some scientic challenges that need to be addressed.
5. Monolith reactor/catalysts for renery stream desulfurization For successful development of advanced desulfurization technologiesHDS as well as non-HDS basedboth the catalyst and the reactor should be close to perfect. A fascinating option for highly efcient and innovative technologies arises from a combination of different functions in single units, performing more functions simultaneously [120]. Structured monolithic reactors will play a key role in the design of novel processes based on multifunctional reactors [121]. Depending on the point of view, a monolith can be considered to be a reactor or a catalyst: the borders between catalyst and reactor vanish [122,123]. A large experimental program dealing with the application of monolith-based catalysts/reactors in different chemical processes is carried out at Delft University of Technology. Examples of very high activity and selectivity have been reported [124 127]. Various types of monolithic catalysts can be distinguished (Fig. 13). Ceramic monoliths are by far the most used. Analogous systems are also produced from corrugated metal sheets. The optimal morphology and structure depends on the specic application. For desulfurization, ceramics are probably to be preferred because of their high resistance to corrosion by H2S. Monolithic catalysts can be prepared in various ways. They can be produced by direct extrusion of support material (often cordierite is used, but various types of clays or typical catalyst carrier materials such as alumina are also used) or of a paste also containing catalyst particles (e.g. zeolites, V-based catalysts) or a precursor of catalyst active species (e.g. polymers for carbon monoliths). An advantage of this route is that the catalyst loading of the reactor can be high.
Alternatively, catalysts, supports, or their precursors can be coated onto a monolithic support structure by washcoating. The ceramic monolith that is being used as a support structure for the catalyst is macroporous. This facilitates the anchoring of washcoat layers. There is a mass of literature and patents on coating and a variety of preparation procedures can be applied. It is expected that, in an evolutionary way, better and better catalysts will be produced. Washcoating was successfully applied with the strongly acidic polymeric catalyst Naon and with BEA zeolite in several acid catalyzed reactions [128]. Monoliths are the dominant catalyst structures for threeway catalysts in cars [129 131], selective catalytic reduction catalysts in power stations [132,133], and for ozone destruction in airplanes. Application of structured catalysts for desulfurization processes can also be highly advantageous in comparison with common catalysts and reactors. Monoliths are applicable not only for single-phase processes, but it has become clear that they are often preferable for multiphase processes. If Taylor ow through a single tube is ensured, the diffusion limitations for gas liquid processes can be reduced due to internal liquid recirculation during their transport through a channel (Fig. 14). This results in one order of magnitude faster mass transfer than in conventional reactors. What makes monoliths practically attractive for different chemical processes and, particularly, for desulfurization? The large open frontal area and straight channels result in an extremely low pressure drop essential for end-of-pipe solutions. The straight channels also prevent the accumulation of dust. That makes monolith catalyst/reactors applicable in desulfurization processes currently employing moving or ebullated bed reactors (like T-Star or reactive adsorption). Compared to random packed beds, monolithic reactors exhibit more ideal reactor behavior resulting in higher conversion and selectivity. This is particularly important for deep desulfurization. Monolith based reactors are very favorable for processes that benet from a counter-current operation, especially for equilibrium limited reactions and when product inhibition is
Fig. 13. Monolithic structures of various shapes. Square channel cordierite structures (1), (3), (5), (6), internally nned channels (2), washcoated steel monolith (4).
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Fig. 14. Taylor ow through a single tube. Left: picture of airwater ow, middle: schematic representation of the gas and liquid slugs, right: CFD velocity pattern in a liquid slug showing the liquid recirculation.
strong [134]. Examples are hydrotreating processes like HDS, hydrodenitrogenation (HDN), and hydrocracking. This operation mode could be achieved in a packed bed only if particles were large or ow rates were low (Synsat process [135]). Deep desulfurization is a good example of a reaction where the concentration prole in counter-current operation is more optimal from a reaction kinetics point of view. Also more active catalysts that are more susceptible to H2S poisoning and are consequently not suitable for co-current operation (e.g. noble metals) can be used in the last part of the reactor (catalyst proling). Overall counter-current operation leads to deeper desulfurization with smaller catalyst units or to larger throughputs [136]. From an engineering point of view, easy scale-up and the potential for high safety of monolith reactors are also appealing. The main issues are the design of optimal monolithic structures and dedicated inlet and outlet systems to ensure optimal distribution of the ow through the channels. Monoliths are industrially produced in large numbers by extrusion and washcoating. This leads to the attractive situation that although they are sophisticated structures, they are commercially available at reasonable costs. The interesting points are to demonstrate that the theoretically outlined advantages are indeed present. These advantages of monoliths over classical reactors include larger reactor productivity, better selectivity control, and higher efciency, thus better catalyst utilization, easy scale-up and high safety. The fact that the catalyst is
xed in the reactor and that pressure drops are low are also obvious advantages. Sattereld [137] already demonstrated that monoliths enable deeper removal of sulfur and nitrogen compounds. Almost a decade later, the rst industrial application of a monolithic reactor was developed by Akzo Nobel for the hydrogenation step in the anthraquinone process. This work includes a lot of pioneering developments from the Anderson group [138 141]. More examples of current applications of monoliths in selective hydrogenation in gas liquid systems can be found [121,142,143]. Monoliths can also be used as low-pressure drop and low-energy consuming contacting devices to efciently bring reactants into contact with the solid catalyst. They can be applied in stripping, extraction, evaporation, drying and distillation, in co- as well as in counter-current modes. The combination with catalysis is then obvious to arrive at a multifunctional reactor system in which reactions take place with controlled reactant addition or product removal. These applications are not restricted to gaseous or liquid phases, but also solid phases can be applied. The straight channels of monoliths are ideal for xed or moving bed applications. In this case, existing catalysts can be applied. The nned channel could be considered as a structured trickle bed reactor where longer residence times can be achieved than in a straight channel monolith. Blocks of monoliths lled with particles may be applied in catalytic distillation or three levels of porosity reactors [144], replacing the catalyst bales used in the CDTech process [123]. Channels lled with a single particle string have much better solid ow characteristics than a packed bed, so application of monoliths as moving bed reactors is seducing. This opens a wide range of applications for monoliths, including desulfurization. Of course, monoliths have disadvantages. They are, at this moment, more expensive than conventional compacted catalysts. In xed bed operation, they will have to exhibit a sufciently long lifetime. In quickly (irreversibly) deactivating reactions, they will not be used. Monolithic and other structured catalysts exhibit favorable properties with respect to convenience in practical application with their high production rates, high selectivity and low energy consumption. Monoliths exhibit large exibility concerning operation conditions. They are well suited for optimal semi-batch, batch, continuous and transient processing. Different catalytic reactions can be combined, catalytic conversion can be joined with in situ separation, heat integration is possible, all leading to process intensication. In the short term, catalytic monoliths will be applied to replace trickle bed reactor and slurry phase operations in view of the better overall conversion and selectivity performance. Monoliths allow for the efcient use of small sized catalyst particles, e.g. zeolites, and are substantially exible with respect to catalyst inventory in a reactor. Multifunctional reactor operations like reactive
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stripping or distillation are challenging applications which are not far out of reach for monoliths. Several options exist for application of monoliths in oil reneries. They include, but are not limited to, gas phase processes for removal of the last ppm S from gasoline and efuent gases; gas liquid phase processes aimed at deep desulfurization, denitrogenation and dearomatization and hydrocracking (co- and counter-current) employing catalytic distillation, reactive stripping and reactive adsorption; and gas liquid solid processes like moving bed application for hydrodemetalization and sulfur removal by reactive adsorption. Catalyst preparation and extrusion should be developed further for specic applications, optimizing the structure and active phase distribution. Hydrodynamics and transport processes have to be described better to design reliable processes. In many of the processes described above, monolithic reactors can be fruitfully applied.
6. Desulfurization technologies: evaluation at the renery level To produce fuels satisfying the new environmental legislation concerning sulfur levels, reneries need to consider desulfurization of all streams that are used in end fuel products. Places where desulfurization units have to be installed and their exact conguration are determined by the nature of the renery stream to be desulfurized, its sulfur content, and the desired product specications. A simplied ow scheme of an oil renery is shown in Fig. 15 with the possible locations for desulfurization units. Only streams forming the main end fuel products are shown. Processes to convert vacuum residue into more valuable products such as
gasoline, naphtha, diesel, etc. are not shown in Fig. 15, although desulfurization of these streams is also required. Their desulfurization is similar to that of gasoline, kerosene and diesel streams produced by distillation (straight run) or FCC units. It is fair to state that a renery does not initially produce the right products with the right specications. In particular, the FCC unit produces the wrong products: although the boiling points are in the desired range, for practical use they are too high in aromatics and sulfur content. Thus, the FCC products used for gasoline blending have to be upgraded extensively without reducing octane number. The alternative of applying the FCC products for diesel fuel is even more problematic because aromatics have very low cetane numbers. In this case, extensive hydrogenation is unavoidable. This applies to a much lesser extent to hydrocracking. In that case, the products contain much lower concentrations of sulfur compounds and the aromatic content is lower. In the future reneries will be much more based on hydrocracking than on FCC. This could lead to the conclusion that research related to the upgrading of current renery streams is not advisable. However, this is not the case for two reasons. Firstly, FCC units are very robust and protable. For several decades to come they will play a major role in the conversion of crude oil into desired products. Secondly, they are complementary to hydrocracking and their robustness makes them very exible. In view of the fact that better and better catalysts are being developed, it might well be that FCC will maintain a prominent position in the future. Moreover, FCC in principal might be used for modern feedstock, such as biomass. Also in that case upgrading of products by hydroprocessing might be required.
Fig. 15. Simplied ow scheme of an oil renery with possible locations of hydrotreating units.
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6.1. Light stream desulfurization Desulfurization of straight-run streams like straight run gasoline, naphtha and middle distillate can be easily done by conventional hydrotreating employing CoMo and/or NiMo catalysts (desulfurization units 1 3 in Fig. 15) since the sulfur compounds present are rather reactive under HDS conditions. Moreover, hydrogen consumption is not high because of the low content of olens and aromatics. Finally, the other fuel specications aside from sulfur content are not strict since before they are blended most streams are additionally treated to improve the nal products properties. Of course, application of more active HDS catalysts will be benecial for the renery in terms of deeper conversion of sulfur containing compounds, lower operating temperature and pressure, and higher space velocity. Replacement of conventional HDS by the non-HDS technologies does not seem to be very attractive in this case. However, when the last sulfur traces have to be removed, advanced processes, reactors, and catalysts might be required. Application of extractive or adsorptive desulfurization in addition to conventional HDS can be benecial for removing the last ppm from the streams satisfying essentially zero emission requirements. As an option, the consecutive conguration of the conventional hydrotreating and desulfurization by reactive adsorption or extractive separation/oxidation can be proposed. This is also important for reneries that are not able to increase sulfur removal using more severe conditions due to limitations in the reactors operating conditions. 6.2. Heavy stream desulfurization Deep desulfurization of heavy atmospheric gas oil, vacuum gas oil and products of the transformation of vacuum residue is more difcult because of the higher sulfur content and lower reactivity of sulfur compounds in heavy streams. It becomes even more difcult, taking into account that some other fuel specications such as octane or cetane numbers should not be changed or should even be improved via additional reactions. Generally, for FCC oriented reneries, three options can be considered: desulfurization of streams before the FCC unit (FCC feed pre-treatment; unit 4 or hydrocracking unit in Fig. 15), FCC in situ desulfurization (not shown), and FCC product stream desulfurization (FCC post-treatment; units 5 and 6 in Fig. 15). 6.2.1. FCC feed pre-treatment Desulfurization of FCC feed is a costly process and requires severe operating conditions but it provides benets for FCC unit operation as well as for FCC unit products. The reduction of sulfur in FCC feed reduces SOx emissions from FCC units and lowers sulfur in the full range of FCC products. If a relatively high level of sulfur removal from the FCC feed is achieved post FCC, desulfurization can be
avoided or simplied. Considering the differences in chemical composition of the feed and FCC products, it is obvious that FCC pre-treatment requires much less hydrogen than conventional HDS post-treatment requires. Usually, FCC pre-treatment can be done by hydrotreating the FCC feed or by partial-conversion/high pressure hydrocracking. Conventional HDS catalysts with specially modied pore structure can be employed in combination with a staged catalyst bed. Ideally, the catalysts should provide demetalization, desulfurization/denitrogenation and dearomatization of the FCC feed. Among the non-HDS based technologies, the application of extractive/oxidative desulfurization looks attractive. However, the main problem is that in the disposal/transformation of eliminated sulfur containing compounds and solvent/oxidant recovery some products can be lost. From this point of view, selective oxidation by oxygen to gaseous sulfur products and hydrocarbons looks more promising, but development of appropriate catalysts is still a big issue. Adsorptive desulfurization does not look very promising for FCC feed pre-treatment because the high sulfur content will result in fast sorbent overloading and short time of the adsorption-regeneration cycle. 6.2.2. In situ FCC desulfurization To our knowledge, there are no processes and technologies proposed to combine catalytic cracking and desulfurization in one reactor unit. Application of the conventional HDS catalysts is not promising for FCC in situ desulfurization. Hydrogenation of sulfur containing compounds is not feasible under FCC conditions. Nevertheless, selective catalytic cracking of sulfur compounds like thiophenes, benzothiophenes, and dibenzothiophenes, resulting in formation of easily desulfurized sulfur compounds (H2S, suldes, etc.), is theoretically possible. The development of catalysts with high enough activity and selectivity in a cracking process is a key point of catalytic FCC in situ desulfurization. Adsorptive separation is another option to be tested for in situ desulfurization. Taking into account the FCC operation conditions, only reactive adsorption can provide the desired level of sulfur removal. It might be possible to nd sorbents that selectively interact with organosulfur compounds capturing sulfur and releasing the hydrocarbon part. One of the options is to use S Zorb or similar sorbents inside a FCC unit, but their inuence on the cracking process itself should be studied in detail. It would be very useful if regeneration of the sorbent would take place at the same conditions as the regeneration of the conventional FCC catalyst to simplify the regeneration step of a FCC unit operation. However, the production of diluted SOx streams might not be attractive. 6.2.3. FCC products desulfurization Desulfurization of FCC product streams is currently the most widely used approach to meet new environmental
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legislation. In the case of FCC gasoline, the main trick is to remove sulfur and simultaneously preserve, or even improve, the octane number. Conventional HDS has rather limited capabilities for this because of extensive olen saturation under HDS operating conditions. Therefore, alternative desulfurization technologies located at the position of unit 5 in Fig. 15 are promising. As an option, HDS-based technologies coupled with additional pre- or post-treatment of the feed to compensate for octane loss can be considered. The ISAL and OATS processes have proven their capability to reduce sulfur with very little octane loss. Integration of these processes into a renery scheme requires installation of additional reactor units for isomerization or alkylation, respectively. Simultaneous fractionation and hydrotreating, like the CDTech process, also looks very attractive for FCC gasoline desulfurization. Adsorptive and extractive/oxidative sulfur removal technologies should still prove their efciency at the industrial level. Fortunately, the potential capabilities of these technologies regarding sulfur removal and protection of other stream specications attract attention of scientists and engineers and promise the further development and improvement of these processes. FCC diesel desulfurization (desulfurization unit 6 in Fig. 15) can be done by HDS, using proper process conditions, catalysts with advanced activity and improved formulation, and new reactor and process designs. This integrated approach should result in efcient deep desulfurization of the feed and upgrading of other diesel specications like increase of cetane number and decreases in polynuclear aromatics and density. A wide range of non-HDS approaches can also be used for deep diesel desulfurization. This concerns adsorptive desulfurization and extractive/oxidative separation technologies. To be efciently applied they should be directed to the removal of heavy sulfur compounds like DBT and its alkylated forms. In general, the proposed options for deep desulfurization can be grouped as following. Separation of S-compounds without upgrading them to useful products leads to yield losses and environmental problems. This might be realistic only as a nishing step. When separation involves stoichiometric reactions (in order to increase polarity, making separation easier) the process will be inefcient and environmentally unfavorable. Transformation of S-compounds with sulfur elimination is traditionally the technology of choice. A lot of experience exists in HDS, both in catalyst development and process design. Usually sulfur is removed from the organic compounds and transformed into H2S. The normal process step is conversion of the formed H2S into elemental sulfur by the Claus process. Much work is carried out in improving this process. Elegant processes have also been proposed in which H2S is transformed in valuable products such as methanethiol [146,147]. These processes are beyond the scope of this review.
One might wonder if hydrogenation is the most logical technology. In fact, biodesulfurization is advocated by some research groups. On the one hand, those processes generally require large reactor volumes and in that sense they are less attractive. On the other hand, they are based on oxidation with air oxygen and that makes them relatively inexpensive. Moreover, the conditions are mild. Oxidation might also be feasible in chemocatalysis. The advantages could be comparable to those in bioprocessing: not only cheap reactant but also mild conditions because, intrinsically, oxygen is expected to be much more reactive than hydrogen. Exploratory thermodynamic calculations showed that this process is feasible, in principle. This is a highly unknown area. At present, it is not clear whether oxidation technology can be realized efciently at the industrial level. When separation is combined with a reaction several attractive processes have been described. This can be realized by coupling two process steps (for instance, an adsorption and a desorption column) or by integrating the two steps in one vessel in a multifunctional reactor. The major representative of this class of processes that has already proven its value is catalytic distillation. To a lesser extent, this applies to reactive adsorption. In practice, catalytic distillation is currently limited to strictly HDS reactions, but new processes are investigated, such as the OATS process where an alkylation step aids separation. It is conceivable that oxidative desulfurization may also be carried out in a multifunctional reactor. When reaction/regeneration cycles are carried out in two separate units many possibilities can be imagined. In the case of solids recirculation (comparable to FCC units), it should be realized that circulation of solids is very costly and a major requirement will be that a high loading (kgadsorbed/ kgadsorbent) is realized.7 In all processes discussed, adequate chemical reaction engineering has a lot to offer. In particular, structured catalytic reactors have high potential. In many respects, both for gas and for gas liquid systems, structured reactors outperform the conventional reactors such as slurry and trickle bed reactors. Monoliths are promising structured reactors. In gas liquid applications they exhibit high production rates, high selectivity (for serial kinetics), and close to plug ow behavior. They allow counter-current operation for common industrial conditions. They can also be used in multifunctional reactors for processes such as catalytic distillation. They are an option for many processes mentioned before. Their usefulness in counter-current operation also makes them a potential candidate in catalytic distillation. In transient adsorption processes, structured
These processes focus on desulfurization. However, also nitrogen removal is also essential. Here, the same line of reasoning can be followed. Nitrogen compounds might be removed by adsorption, or even reactive removal adsorption of N might be an option. Removal of nitrogen compounds can also greatly help deep HDS.
7
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reactors can be designed that exhibit a low-pressure drop and a fast response. This makes them attractive for reactive adsorption for deep desulfurization. The same applies to processes based on circulating solids. In that case, structured reactors are associated with much less friction and attrition. They even allow for the combination of a catalytic structured reactor with a circulating solid with a separation function. In the above analysis, the renery is where the processes of sulfur removal take place. Occasionally, it is proposed to carry out the desired reaction outside of the renery. This could be in storage tanks, in piping, or even at the well. There exists an analogy with coal gasication. This is done in well-dened reactors, but underground gasication is theoretically possible and has appealed to many. Underground gasication of coal is not really a success story, but for the case of oil it is more promising, because oil is a uid whereas coal is a solid. Due to its uid nature, oil is relatively easily handled. Possible commercialization of these technologies will increase the value of crude oil before its production. The renery will benet from elimination of hydrotreating steps during processing. The renery will become simpler with less hardware employed and fewer potential safety hazards. A number of scientic questions should be addressed before downhole catalytic upgrading of crude oil becomes reality, namely the placement of the catalysts into an appropriate zone of the well, mobilization of the reactants (crude oil, H2, and CO) at the catalyst surface, and creation optimal process conditions ( p, T ). Feasibility of each of these options has been proven separately and their application into a unied underground process still remains problematic [145]. In the production well the oil should pass a reactor and the S- and metalcontaining molecules should stay in the well. However, we do not expect that it will be easy to develop an attractive desulfurization process. There might be a place for small down-scaled reneries at remote places. In that case, dedicated catalysts and reactors should be developed. We did not consider such a development in this review. Development of new biocatalytic systems of sufcient activity and stability for crude oil desulfurization might be attractive in the future. Taking into account the fast progress
Table 2 Challenging research topics in desulfurization of renery streams Advanced HDS Noble metal catalysts Selection Mechanism Kinetics Catalytic distillation Design Experimental validation Processes at mild conditions Optimal reactor
in biotechnology, sulfur removal by biocatalysts during crude oil transportation is not science ction. At the renery site, biocatalytic processes might also be considered. We expect that the size of the plants required will be large and, in the terms of process intensication, we expect that compact chemical reactors will also be more attractive in the future. Nevertheless, we realize that predicting the future is not the strongest point of scientists and engineers; so, this eld should be closely watched.
7. Challenging research topics The above discussed technologies of sulfur removal from renery streams leads to a wealth of research topics. Not all of them are challenging, of course. Several topics have the character of demonstration of known science. The most challenging ones are given in Table 2. Only an integrated approach (catalyst selection, reactor design, process conguration) will lead to efcient desulfurization processes that will produce fuels with zero sulfur emission. In HDS based technologies, less room for breakthroughs exists. Noble metal based catalysts with high sulfur tolerance and sufcient kinetics in sulfur removal seems to be the most challenging option for improvement of the HDS based technologies. Application of catalytic distillation in combination with HDS sulfur removal is also attractive. Reactive adsorption is applicable at almost all points of the renery where desulfurization is required. Due to the very high exibility in the reactor design and process conditions, reactive adsorption can be easily adapted to streams with different properties and compositions. The ability to remove the last ppm sulfur makes reactive adsorption also attractive as the nishing step in the fuel production, for instance, for the gasoline stream from the reformer. Development of reactive adsorption based desulfurization technologies should rst be oriented towards the rational selection of sorbent/catalysts formulation taking into account the nature of the sulfur compounds, hydrocarbon composition, and nal product specications. Sorbent development should be accompanied by evaluation
Reactive adsorption Selection sorbent Thermodynamics Kinetics regeneration Process design
Oxidative desulfurization Thermodynamic evaluation Conditions Air versus oxygen Catalyst selection Exploratory Kinetics Process design Optimal reactor
Optimal reactor
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of the kinetics of sulfur removal processes and design of optimal reactor conguration. Selective oxidation of sulfur compounds into hydrocarbons and volatile sulfur products might also be also attractive for desulfurization. Substitution of expensive hydrogen, which is normally used in desulfurization, by air will bring about high economical benets. Thermodynamic feasibility of this process in the presence of different catalytic systems should be evaluated. Based on that, the perspective catalyst compositions should be selected and their applicability has to be demonstrated by the experiments. Other approaches to sulfur removal, such as extractive desulfurization, look less attractive since the involvement of an additional phase leads to large plants and limited efciency. The same applies for oxidative extraction, in which in addition to the solvent an oxidant is required in addition to the solvent, although recycling might reduce the amounts consumed. Table 2 is not meant to be exhaustive. New ideas will most certainly emerge, while some of those presented here will be skipped from further research.
Acknowledgements We thank Dr S. Eijsbouts (Akzo Nobel, The Netherlands) and Prof. J.A.R. van Veen (Shell Research and Technology Centre, The Netherlands) for fruitful discussions during the review preparation. The authors wish to thank to Dr Tracy Gardner (Delft University of Technology, The Netherlands) for help with the review preparation.
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Science and Technology of Novel Process For Deep Desulfurization of Oil Refinery Streams

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Fuel 82 (2003) 607631 www.fuelrst.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 1. External and internal factors inuencing modern reneries.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 2. Classication of desulfurization processes based on organosulfur compound transformation.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 3. Desulfurization technologies classied by nature of a key process to remove sulfur.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 4. Different approaches to improve HDS catalyst performance [3236, 4050].

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 6. Co-current/counter-current Syn Technology process scheme.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 7. Simplied ow scheme for CDHDS based technology.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 8. The OATS process ow scheme.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 9. General process ow of extractive desulfurization.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 10. Simplied adsorptive desulfurization process ow.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Fig. 12. Mechanism of reactive adsorption desulfurization process.

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

Reactive adsorption Selection sorbent Thermodynamics Kinetics regeneration Process design

I.V. Babich, J.A. Moulijn / Fuel 82 (2003) 607631

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