01 Survey 4-3

Survey of Petroleum Refining Technology for High-quality (Ultra-low Sulfur Content) Diesel Fuel
Yutaka Mukai, Toshiaki Hisamitsu, Japan Energy Research Center Co., Ltd. Yoshihiro Mizutani, Technology Department, Petroleum Energy Center (PEC)

1.

Background and Goals

The United States and Japan as well have been strengthening their quality requirements for automotive fuels such as diesel fuel in order to prevent air pollution and comply with environmental regulations. In 1994 a uniform European standard for the sulfur content of diesel fuel was established, with the maximum allowable level being 0.2 wt.%. The maximum level was reduced to 0.05 wt.% in 1996, and plans call for the introduction of new regulations that will further lower the allowable sulfur content to 350 wt.ppm in 2000 and 50 wt.ppm in 2005. There is also a trend toward the implementation of quality regulations covering properties other than sulfur, such as polycyclic aromatic compounds, cetane rating, and distillation characteristics. Regulations that took effect in 1993 in the United States mandated a maximum sulfur content of 500 wt.ppm, a cetane index of 40 or greater, and a maximum aromatic content of 35 vol.%. In addition to the sulfur limitation less than 500 wt.ppm, in California, where the air pollution problem is acute, diesel fuel regulations specified a maximum aromatic content of 10 vol.%. The EPA has suggested lowering the maximum acceptable sulfur content for diesel fuel to 15 ppm in June 2006, and this proposal is being hotly debated. In Japan the maximum acceptable sulfur content for diesel fuel has been set at 500 ppm since 1997. When the JIS (Japanese Industrial Standard) is updated in 2004 this is expected to be lowered to 50 ppm, to become effective in January 2005. In the years ahead measures to deal with air pollution from sources such as automobile exhaust are likely to include calls for higher quality diesel fuel with lower sulfur and aromatic content. It is necessary to assume that in future acceptable sulfur content levels will fall significantly below 50 ppm. With this in mind, this survey examines the present state of deep desulfurization technology in Japan and oversea as well as the current status of high-quality diesel fuel production technology. An attempt is made to sketch the future of high-quality diesel fuel production technology and to identify key issues related to the development of such technology.

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2.1

Survey Content and Findings

Trend in Sulfur Content Regulations on Diesel Fuel

Regulations in Japan, the United States, and Europe mandating the maximum sulfur content of diesel fuel are listed below. The next stage maximum value listed for Europe was decided in 1998, and that for Japan was proposed in 2000.
Japan (government proposal) U.S.A. (government proposal) Europe Present 500 ppm 500 ppm 350 ppm Next stage 50 ppm 15 ppm 50 ppm Takes effect 2005 2006 2005

2.2

Present State of Japanese Deep Desulfurization Technology and Ultra-deep Desulfurization

The deep desulfurization process generally used in Japan for diesel fuel is a single-stage process in which hydrodesulfurization reaction takes place in a fixed bed reactor. There is also a two-stage process in use, in which desulfurization reaction takes place at relatively higher temperature in the first stage reactor, and color is improved at a lower temperature in the second stage reactor. The typical feedstock consists of straight-run diesel fuel produced from Middle Eastern crude oil and cracked diesel fuel (mainly LCO) in the ratio of approximately 80% to 20%. The sulfur content of the feedstock is between 1.0 wt.% and 1.5 wt.%, and its T90 (90% distillation temperature) is between 350 and 360C. The characteristics of the various diesel fuel feedstocks used are summarized in Table 2.2.1.

Table 2.2.1 Characteristics of Diesel Fuel Feedstocks

Sample Feedstock Sulfur content Nitrogen content Aromatic content 90% distillation point Cetane index ASTM color (wt%) (wtppm) (vol%) (C) Straight-Run Diesel Fuel 1.22 130 36 348.5 58.0 L0.5 RFCC Diesel Fuel 0.09 290 55 328.0 37.0 L1.5 Thermal Cracked Diesel Fuel 1.38 310 44 365.5 53.0 L5.5

Differences in the type of crude oil used and the distillation characteristics can affect properties such as desulfurization reactivity. The diesel fuel feedstocks used in Japan are mainly straight-run diesel fuel mixed with LCO, derived from Middle Eastern crude oil. In comparison with low-sulfur feedstock produced from North Sea crude oil used in Europe and the United States, the feedstock produced from Middle Eastern crude contains greater amounts of sulfur, total aromatics, and polycyclic aromatics, even for distillates within the same distillation temperature range. Therefore, Middle Eastern feedstock is relatively difficult to process, requiring reactor capacity twice or more that for North Sea feedstock.

Table 2.2.2 Crude Oil Types and Reactor Capacity

Product Sulfur Content (wt.ppm) 50 Feedstock Crude Oil Type Fraction Sulfur content (wt%) Relative reactor capacity Hydrogen partial pressure: 30 kg/cm2 1.0 North Sea Straight-run diesel fuel 0.2 1.25 Middle Eastern Straight-run diesel fuel/20% LCO 1.5 3.4 30 30

Differences in the feedstocks distillation temperature (T90) correspond with large differences in the reactivity. Figure 2.2.1 provides the relationship between reaction temperature and product sulfur content for feedstocks with different cut temperatures: SR-LGO (T90: 359C, sulfur content: 1.17 wt%), 335C cut fraction (T90: 316C, sulfur content: 1.01 wt%), and 305C cut fraction (T90: 287C, sulfur content: 0.81 wt%). Under the same conditions (LHSV: 2, hydrogen partial pressure: 5 MPa) at which the sulfur content of the SR-LGO is reduced to approximately 350 ppm, the sulfur content of the 335C cut fraction is reduced to less than 100 ppm.

Figure 2.2.1

Effect of Feedstock Cut Temperature on Product Sulfur Content

In order to reduce product sulfur content from 500 ppm to 50 ppm, the reactor capacity has to be increased by 2.9 times when processing heavy straight-run diesel fuel, however, the increase in reactor capacity becomes as little as 1.3 times when 95% distillation points reduced from 360C to 340C by substituting feedstock from heavy diesel fuel for summer season to light diesel fuel for winter season (Table 2.2.3).

Table 2.2.3 T95 of Feedstock and Reactor Capacity

Feedstock 95% distillation point Sulfur content Product sulfur content Relative reactor capacity Hydrogen partial pressure: (C) (wt%) (wt.ppm) 50 kg/cm2 Heavy Straight-run Diesel Fuel 360 1.5 500 1.0 50 2.9 1.3 Light Straight-run Diesel Fuel 340 1.0

2.3

Technical Approaches to Deep and Ultra-deep Desulfurization

It is anticipated in Japan that ultra-deep desulfurization for reducing the sulfur content of diesel fuel to 50 ppm or less can be accomplished through the extension of current hydrodesulfurization technology. Some refineries succeeded in satisfying the regulations by modifying their existing equipment, which limited sulfur content of 500 ppm or less and took effect in 1997, are planning next steps such as the construction of additional reactors. And refineries that have already installed new deep desulfurization equipment will be able to cope with by introducing newly developed catalysts without major modifications of facility. Technical approaches to deep and ultra-deep desulfurization that are likely to emerge in the years ahead include; (1) (2) (3) (4) introduction of severer reaction conditions improvement of dispersion of the reaction fluid improvements in catalyst performance development of new processes

2.3.1 Severer Reaction Conditions In addition to increasing the reaction temperature, there are ways to reaction conditions more rigorous as follows; (1) reducing the feedstock/catalyst ratio (2) increasing the hydrogen partial (1) Reducing the Feedstock/Catalyst Ratio The feedstock/catalyst ratio is reduced by decreasing the feed rate, increasing the amount of catalyst loaded in reactors, and building additional reactors. With regard to the case of reducing the product sulfur by building of additional reactors, in order to reduce the sulfur contents to 50 ppm, 30 ppm, and 10 ppm from 500 ppm, reactor capacity has to be increased by 1.9 times, 2.3 times, and 3.4 times, respectively, for processing a feedstock with a sulfur content of 1.5 wt.%, a mixture of straight-run diesel fuel and LCO derived from Middle Eastern crude oil (Table 2.3.1).

Table 2.3.1 Product Sulfur Content and Relative Reactor Capacity

Product sulfur content (ppm) Catalyst Relative reactor capacity Feedstock: Feedstock sulfur content: 500 1.0 50 Co-Mo 1.9 2.3 32 kg/cm2 3.4 1.5wt%, reaction pressure: 30 10

(2)

Increasing the Hydrogen Partial Pressure The hydrogen partial pressure is increased by increasing the reaction pressure, the hydrogen/oil ratio, and the purity of the hydrogen. In the United States the NPC has publicly released the responses of five companiesUOP, IFP, Akzo, Criterion, and Topsoeto questions regarding the modifications of existing desulfurization unit, producing diesel fuel with a sulfur content of 500 ppm, for reducing the product sulfur content. The modification was estimated based on the use of feedstock with a sulfur content of 0.9 wt.%, a specific gravity of 0.861, and a T90 value of 321C. These properties suggest that this feedstock can be desulfurized at milder reaction condition than that for the feedstocks used in Japan. The modifications required to reduce the sulfur content to 30 ppm are summarized in Table 2.3.2. All of them regard an amine scrubber as indispensable facility. UOP and IFP propose to minimize the cut down of LHSV by increasing the purity of circulating hydrogen. On the other hand, the other companies propose to decrease LHSV to the greater extent without increasing the hydrogen purity.

Table 2.3.2 Modification for Reducing the Sulfur Content to 30 ppm from 500 ppm
LHSV Amine scrubber installed Purity of circulating hydrogen (mol%) Ratio of circulating hydrogen (scf/bbl) Catalyst packing method Hydrogen partial pressure: 46 kg/cm2 Current 2 No 75 1,000 Sock UOP 1.5 Yes 90 1,900 Dense IFP 1.45 Yes 91.3 3,649 Sock Akzo 1.08 Yes 75 1,000 Sock Criterion 0.5 Yes 75 1,600 Sock Topsoe 1 Yes 75 1,160 Sock

The modifications for reducing the sulfur contents further to 10ppm are summarized in Table 2.3.3. They require the significant sacrifice of LHSV. In addition, IFP says that a sulfur content level of 10 ppm can not be achieved at existing unit pressure and that new unit must be constructed. Criterion also says that although the data is tentatively shown, new unit is strongly recommended.

Table 2.3.3 Modification for Reducing the Sulfur Content to 10 ppm from 30 ppm
UOP 1.5 0.9 1,900 2,000 46 IFP 1.45 1 3,694 ? 58 Akzo 1.08 0.45 1,000 46 Criterion 0.5 0.4 1,600 1,850 46 Topsoe 1 0.7 1,160 46

LHSV Ratio of circulating hydrogen Hydrogen partial 2 pressure (kg/cm )

2.3.2 Uniform Dispersion of Reaction Fluid To ensure efficient utilization of all the catalyst packed into the reactor it is essential to attain a uniform distribution of the feedstock and hydrogen throughout the entire catalyst layer. The maldistribution may also cause problems, such as occurrence of abnormally high temperature area (hot spots) due to uneven reaction temperature distribution or a rise in pressure differential across the reactor, that force sometimes discontinuance of operation. If the reaction fluid once begins to become deflected within the catalyst layer the normal state is hardly restored. Effective measures to avoid the maldistribution of reaction fluid include improvements of the reactor interior and the catalyst loading method. (1) Distribution Tray When designing a high-performance liquid distribution tray, the following requirements should be borne in mind. The distributor nozzles should be spaced close together. Pressure loss should be minimized. The tray should be configured so as to avoid deflection due to tilting. Operation at a turn down ratio with a high liquid flow volume should be supported. Operation with a wide range of gas-liquid volume ratios should be supported. Good gas-liquid mixture performance is essential. The design should incorporate measures to prevent clogging due to scale, etc. Topsoe has developed a dense pattern flexible tray designed to ensure uniform dispersion. In tests using Topsoes TK 554 catalyst the apparent relative desulfurization activity achieved with it was more than 2.5 times that with a simple chimney tray, and the average reaction temperature was reduced by 25C (Table 2.3.4).

Table 2.3.4 Distribution Tray Effectiveness

Average reaction temperature (C) Feedstock sulfur content (wt%) Product sulfur content (wt%) Relative desulfurization activity Simple Chimney Tray 346 0.7 0.05 1.0 Dense Pattern Flexible Tray 321 0.9 0.035 2.5

(2)

Catalyst Loading Systems If the catalyst is loaded in such a way that the top surface of layer is at an incline on the way of the loading, the catalyst particles become slanted along the inclination. It is known that the oil tends to flow along the inclination and may be deflected by the slanted portions, even if the top surface of the catalyst is packed flat.

In the past, to keep the surface flat during the catalyst loading, the work was halted periodically and the surface was leveled by manpower. However, there were limits to the effectiveness of such techniques, and the frequent interruption of the loading work lowered the efficiency. In order to get around these problems a catalyst loading system has recently been developed that incorporated monitors which allow real-time measurement of the flatness of the catalyst surface without interrupting the work and a catalyst loading machine which is able to constantly control the incline of the surface. 2.3.3 Improvements in Catalyst Performance (1) Improvement of Base Metal Catalysts The performance of molybdenum catalysts has been successively improved up to date. In addition to the desulfurization performance, well-balanced activities related to nitrogen removal, aromatics hydrogenation, cracking, isomerization are demanded to the hydrorefining catalysts for diesel fuel, in order to meet additional requirements for the performance of diesel fuel, such as stability, combustibility, lubricity, etc. other than sulfur content. R&D on the improvement of catalyst performance currently focuses mostly on the properties of carrier such as the porous structure and acidity, as well as the impregnation of metals regarding to the amount of metals and the impregnation methods, including the promoter. (2) Improvement of Precious Metal Catalysts Precious metal catalysts, particularly catalysts incorporating platinum or platinum and palladium, are used in the latter stages of deep-desulfurization process. They have excellent performance in hydrogenation of monocyclic aromatic hydrocarbons and are likely to become more and more important in the years ahead. Work on improvement focuses on increasing hydrogenation activity and resistance to sulfur and nitrogen poisoning while balancing these characteristics. In addition, work is being done to assign appropriate cracking activity to match specific applications. Techniques include the use of inorganic (composite) oxides, such as amorphous alumina, silica alumina, or crystalline silica alumina, as carriers and optimization of the amount of the precious metals and highly-dispersed metal impregnation methods. (3) Development of Catalysts for Deep Desulfurization and Aromatics Hydrogenation The Co-Mo, Ni-Mo, and precious metal catalysts on the market for use in deep desulfurization and aromatics hydrogenation are shown in Table 2.3.5. The performance of the up-to-date molybdenum catalysts is 1.5 times or more that of the catalysts available when deep desulfurization was first introduced. This means that some refineries will be able to produce diesel fuel with a sulfur content of 50 ppm or less only by substituting catalysts.

Table 2.3.5 Catalysts for Deep Desulfurization and Aromatics Hydrogenation

Company Akzo Criterion Topsoe UOP IFP CCIC OCC Co-Mo Type KF-757 DC-160, DC-185, DC-2000 TK-574 N-40, N-108, N-200 HR-416 CDS-LX6 HOP-467 Ni-Mo Type KF-848 DN-200 TK-573, TK-525, TK-555 HC-H, HC-K, HC-P, HC-R, HC-T HR-448 Hop-414 Precious Metal Type KF-200 TK-907, TK-908 AS-250 Platinum type

2.3.4 Development of New Processes New processes under development other than hydrodesulfurization include oxidative desulfurization, bio-desulfurization, and adsorption separation. (1) Oxidative Desulfurization An oxidative desulfurization process called CED (Conversion/Extraction Desulfurization) developed by Petro Star Inc. has been selected as one of projects for development of ultra-clean fuels by the DOE in the United States. In this process sulfur compounds in diesel fuel are selectively oxidized and then extracted using a solvent. Sulfur compounds with lower reactivity in hydrodesulfurization tend to show greater reactivity toward oxidation, and can be eliminated easily by oxidative desulfurization. If feedstock with high sulfur content is directly processed using oxidative desulfurization, large quantities of sulfinyl and sulfonyl compounds are produced as byproducts. However, employment of the process after hydrodesulfurization process holds promise as ways to achieve deep and ultra-deep desulfurization while limiting the hydrogen consumption and the production of the oxidized sulfur compounds. Still, finding ways to dispose of or utilize these oxidized sulfur compounds is an issue. (2) Bio-Desulfurization Enchira Biotechnology (formerly Energy Bio System) has licensed bio-desulfurization technology for diesel fuel to Petro Stars Valdez Alaska refinery. In addition, Enchira Biotechnology has announced that it will be engaged in a three-year project, subsidized by the DOE, that will involve everything from the development of microorganisms to the design of a plant with a capacity of 5,000 barrels per day. (3) Adsorption Separation Another project to develop ultra-clean fuels, subsidized by the DOE, is an adsorption separation process. It is adaptation to diesel fuel from a process for gasoline developed by Phillips (S Zorb). A pilot plant have already succeeded in producing diesel fuel with a sulfur content of 15 ppm or less using this process. In this process sulfur compounds are removed from feedstocks in the form of adsorbate on a specially designed adsorbent, then, decomposed.

Like the above oxidative desulfurization process, this process can be combined with hydrodesulfurization process, and may show promise as deep and ultra-deep desulfurization processes for the future. 2.4 High-quality Diesel Fuel Production Technology

Although diesel fuel with a sulfur content or 10 ppm or less is already commercially available in some particular regions such as urban district in Sweden, the T95 of the fuels is 285C or below, which is as low as the specification for kerosene in Japan. In California in the United States the maximum sulfur content is presently 500 ppm. In addition, regulations stipulate a maximum aromatic content of 10 vol.% and T90 between 290C and 320C. The leading hydrorefining technologies capable of meeting these strict standards on sulfur content and aromatic content are shown in Table 2.4.1.

Table 2.4.1 High-quality Diesel Fuel Production Technology

Process SynSat Ultra Deep HDS MAK Fining MQD Unionfining Deep HDS, HDAr Licensers Criterion, ABB Lummus, Shell Topsoe Mobil, Akzo, Kellogg, Fina UOP IFP

(1)

SynSat Process The SynSat process is one of hydrorefining processes included in Syn-technology. The SynSat process uses either one reactor or two reactors in series and divides the reaction zone into two stages. In the first stage both feed oil and hydrogen flow downward, while in the second stage direction of hydrogen flow can be set upwardly or downwardly depending on conditions. The Syn-technology consist of the following four hydrorefining processes. 1) 2) 3) 4) SynSat HDS: Deep hydrodesulfurization

SynSat HDS/HDA: Deep hydrodesulfurization/Hydrogenation of aromatics SynShift: SynFlow: Improvement of cetane number/Shift of boiling point range Improvement of cold-flow properties

The SynSat process is being used commercially in Sweden, Germany, and the United States. Examples of commercial applications of the SynSat process are listed in Table 2.4.2. In the second stage reactor of the units in Scanraff and Preem refineries in Sweden a precious metal catalyst is used, and oil and hydrogen flow countercurrently. They produce two types of product containing different amount of sulfur, 100 ppm and less than few ppm. It is likely that the second stage reactors are used for production of the latter ultra-low sulfur fuel with low aromaticity from feedstocks with lower T95 and sulfur content.

Meanwhile at Lyondell-Citgo refinery in the United States an existing hydrodesulfurization unit was revamped to two-stage system. The unit employs base metal catalysts and the cocurrent system for feedstock and hydrogen in the second stage. This unit achieved reduction of product sulfur to a level of 5 ppm or less from a feedstock with relatively high sulfur content of 1.38 wt. However, this figure is based on a test operation over a short period of time, and no data concerning catalyst life has been reported.

Table 2.4.2 Commercial Applications of SynSat Process

Company Processing Volume BPSD Scanraff Preem LyondellCitgo 48,000 37,000 50,000 Feedstock Characteristics Sulfur Aroma T95 Density Content Content 3 (wt%) (C) g/cm (vol%) 0.54 323 0.841 22.1 0.34 286 0.827 21.5 0.14 338 0.866 0.1 277 0.827 21.8 1.38 367 0.902 58.2 Product Characteristics Sulfur Aroma Density Content Content 3 (ppm) g/cm (vol%) 100 0.835 11.3 1 0.812 4.4 100 0.858 2 0.815 3 <5 0.861 34.8 Reaction Type Co/Cnt Co/Cnt Co/Co

(2)

Topsoe Ultra Deep HDS process Topsoes Ultra Deep HDS (UDHDS) process is a two-stage process for producing low-sulfur and low-aromatic diesel fuel. It primarily comprises the following four components. 1) 2) 3) 4) First stage reactor: Intermediate stripper: Second stage reactor: Second stage stripper: Ultra-deep desulfurization Hydrogen sulphide elimination Aromatics hydrogenation Boiling point adjustment

In the first stage reactor Ni-Mo catalysts are used. The second stage reactor employs a precious metal catalyst, TK-907. The San Joaquin refinery in the United States provides an example of the commercial application of this process. As shown in Table 2.4.3, the sulfur content is reduced from 0.65 wt.% in the feedstock to 9 ppm in the first stage, then further reduced to 1 ppm in the second stage. Although the detail of feedstock properties and operating conditions are not reported, this unit has been in operation for more than 18 months.

Table 2.4.3 Commercial Application of Topsoe UDHDS Process (San Joaquin refinery)
Density (g/ml) 0.91 0.88 0.87 71 kg/cm2 Sulfur (ppm) 6,515 9 1 Nitrogen (ppm) 775 3 0 Aromatics (vol%) 33 24 3.5 Reaction Temperature (C) 367 287

Feedstock First stage output Second stage output Feedstock T95: 370C Hydrogen partial pressure:

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(3)

MAK Fining process MAK Fining is a hydrorefining process licensed by ExxonMobile, Akzo Nobel, Kellogg, and Total-Fina. It can be designed to match the current diesel fuel standards as well as the upgraded standards in years ahead by combining the following processes and catalysts; 1) 2) 3) UDHDS: HDHDC: HDAr: Ultra-deep hydrodesulfurization (Co-Mo catalyst) Mildhydrocracking of heavy distillate (Ni-Mo catalyst) Hydrogenation of polycyclic aromatic compounds (precious metal catalyst) Dewaxing by hydroisomerization of Paraffin Cold-flow improvement by selective hydrocracking of n-paraffin

4)

MIDW: CFI:

OMV Germany (Burghausen refinery) uses a system combining UDHDS and MIDW. Although the details of the feedstock properties are not clear, diesel fuel with a sulfur content of 10 ppm or less and a cloud point of -11C or less (improvement of 18C) was reportedly being produced. Further, HDHDC with a catalyst using zeolitic carrier was added to the downstream of the system to produce high-quality diesel fuel with lower polycyclic aromatics content, lower density, and lower T95. Properties of feedstock and products processed at a pilot plant of the combination of HDS and HDHDC using a zeolite containing catalyst are shown in Table 2.4.4.

Table 2.4.4 MAK Fining Process (HDS + HDHDC)

Total Aromatics (wt%) Feedstock 356 16,600 39 Case 1 353 25 22 Case 2 349 3 19 Feedstock: Middle Eastern diesel fuel Reaction pressure: 56kg/cm2 T95 (C) Sulfur (ppm) Polycyclic Aromatics (wt%) 15 1.2 0.7 Cetane Number 51 57 58

(4)

MQD Unionfining Process UOPs MQD Unionfining employs either single-stage or two-stage reactor system. It produces high-quality, low-sulfur diesel fuel by combining hydrogenation process with other processes such as hydrocracking, catalytic dewaxing, aromatics hydrogenation and hydroisomerization. The two-stage process consists of a first stage reactor using a base metal catalyst, an intermediate stripper, and a second stage reactor packed with a precious metal catalyst. In the two-stage process it is possible to reduce initial investment and operating costs by installing an intermediate high-temperature, high-pressure stripper and employing a heat integration system. 11

1) Single-stage reaction 2) Two-stage reaction

: : : : :

Hydrogenation (HC-P, R, H, K catalyst) (N-108, 40, 200 catalyst) Hydrogenation + Hydrocracking (HC-24 catalyst) Hydrogenation + Catalytic dewaxing (HC-80 catalyst) Hydrogenation + Aromatics hydrogenation (AS-250 catalyst) Hydrogenation + Hydroisomerization (DW10 process)

At the commercial plant (Unicracking/DW process) in Schwechat refinery of OMV Austria, dewaxed VGO with sulfur content of 20 ppm and flow point of 17.5C is reportedly produced with 75% yield by processing VGO with sulfur content of 0.95 wt.% and flow point of 30C. (5) IFP Prime-D30 Process IFPs Prime-D30 is a process for producing diesel fuel with ultra-low sulfur content, reduced polycyclic aromatic compounds, and a boosted cetane rating. Two-stage hydrogenation is required to accomplish aromatics hydrogenation aimed at increasing the cetane index. In the first stage an Ni-Mo catalyst and comparatively high pressure (6 to 8 MPa) is used to reduce the sulfur content of cracked diesel fuel to 50 wppm or less. After fractional distillation of the reaction products, the diesel fuel fraction containing virtually no sulfur and hydrogen sulphide is sent to the second stage, where aromatics hydrogenation takes place. The precious metal catalyst used in the second stage is a highly active hydrogenation catalyst. It is capable of processing even feedstocks containing significant amounts of sulfur. When LCO with a sulfur content of 1.58 wt.% is subjected to the two-stage process, the sulfur content is lowered to 3 ppm in the first stage, and then the aromatic content is reduced to 1.4% in the second stage, according to reports.

Table 2.4.5 IFP Prime-D30 Process Reaction Example

Feedstock First stage output Second stage output Feedstock: LCO T95 (C) 319 288 283 Sulfur (ppm) 15,800 3 < 0.5 Nitrogen (ppm) 1,100 1 < 0.5 Aromatics (wt%) 66.4 34.2 1.4 Cetane Index 27.5 45 53.4

(6)

Costs of Installing Diesel Fuel Ultra-Deep Desulfurization Equipment Deep and ultra-deep desulfurization of diesel fuel requires either the revamp of existing unit equipment or the installation of new unit equipment. Investment cost of revamping an existing unit to reduce the sulfur content stepwisely from 500 ppm to 20 ppm are shown in Table 2.4.6.

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Table 2.4.6 Costs of Upgrading Conventional Equipment for Ultra-deep Desulfurization

Upgrade Item Standard Catalyst change (50% increase in activity) Gas recycler/scrubber Increasing purity of makeup hydrogen Increased EOR temperature + reactor Reactor Change of operating duration from 2 years to 1 year Sulfur Content (ppm) 500 285 180 140 120 30 20 Amount of Investment ($ million) 1.8 2.4 0.6 1.4

The costs of building a new ultra-deep desulfurization unit, presented by the licensers, are shown in Table 2.4.7. They vary widely, running anywhere between $1,100 and $3,000 per BPSD, depending on the feedstock properties and the refinerys environment. This investment is equivalent to between $60 and $150 million for a plant with a capacity of 30,000 to 40,000 BPSD.

Table 2.4.7 Costs of Installing Diesel Fuel Ultra-deep Desulfurization Equipment

Process SynSat (two-stage) IFP (two-stage) MAK Fining MQD Unionfining IFP HYC Processing Volume (BPSD) 30,000 30,000 35,000 45,000 40,000 Quality Target S: S: S: S: S: 10 ppm, Ar: < 10 ppm 10 ppm, PAH: < 10 ppm, Ar: 2 vol% < 8 vol% 5 vol% Equipment Cost ($/BPSD) 3,330 2,070 1,100 - 2,000 3,310 2,500 - 3,000

< 5 ppm, Cetane rating

3.

Conclusion

Diesel fuel with ultra-low sulfur content is being on the market in some European countries. However, the main feedstock for the ultra-low sulfur diesel fuel is lighter distillates derived from North Sea crude oil, and the like, which is contain comparatively less sulfur, and easier to desulfurize. In addition, the supplied volume is not very large. Consequently, there is a wide gap between the situation in Europe and that in Japan, where the main feedstock is derived from Middle Eastern crude oil with high sulfur content, and where there is a need to process heaver distillates as well. The present survey shows that, even under these more difficult conditions, the production of diesel fuel with a sulfur content 10 ppm or so is technically possible in Japan through a combination of severer reaction conditions, improved catalysts, better equipment, and the development of new processes. However, when considering upgrading existing equipment or installing new equipment it important to take into considerations the status of the existing facilities and deliberate plans for future expansion, because they will make a substantial difference in the future investment cost. When making choices, it will be necessary to consider seriously, in addition to the properties and volume of feedstock, issues such as the anticipated product standards in the future, operating costs, flexibility to changes in the levels of supply and demand. 13

In addition, the immixture of other petroleum products, even in tiny quantities, can have a substantial effect on the sulfur content of the diesel fuel product. For this reason, good cooperation on anti-contamination measures is important from the output of the desulfurization equipment through the pump at the service station, including the storage facilities at the refinery and the distribution and shipping system.
Copyright 2001 Petroleum Energy Center All rights reserved.

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