UOP LCO Upgrading For Added Value Improved Returns Tech Paper
UOP LCO Upgrading For Added Value Improved Returns Tech Paper
UOP LCO Upgrading For Added Value Improved Returns Tech Paper
Vasant P. Thakkar, Suheil F. Abdo, Visnja A. Gembicki and James F. Mc Gehee UOP LLC Des Plaines, Illinois, USA
INTRODUCTION
LCO IN THE CLEAN FUELS REFINERY
As refiners plan to meet regulations for clean fuels, one of the many considerations they face is the disposition of light cycle oil (LCO). It is a poor diesel fuel blending component due to its poor engine ignition performance and its high sulfur. Beyond middle distillate blending, LCO has also historically been used as a blend-stock into heavy fuel oil for viscosity adjustment. This opportunity is also becoming constrained by declining demand for heavy fuel oil. In the overall context of a high conversion, clean-fuels refinery, light cycle oil is an issue, both in terms of product blending and product-value maximization. In addition to the use of conventional hydrotreating, high pressure hydrocracking units have historically been used to crack LCO into naphtha and lighter products. These units are relatively high in capital cost, consume large quantities of hydrogen, and the naphtha product requires reforming before blending to gasoline. This paper will address an alternative LCO processing solution to the growing demand for clean fuels and product slate flexibility with much lower capital investment.
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CHARACTERIZATION OF LCO
The total worldwide installed FCC capacity is approximately 14 million BPSD, with an overall production of about 3 million BPSD of LCO. The majority of FCC capacity is in North America, followed by Europe and Asia. Operating severity varies depending upon the market. For example, North American refiners operate their FCC units at high severity to maximize gasoline AM-05-53 Page 2
production with LCO yield of less than 20%, whereas European refiners operate a lower severity for greater LCO production. Cracked products such as LCO and coker distillates have a considerably lower cetane value compared to straight run distillates derived from most of the worlds crude sources. LCO cetane ranges from 15-25, compared to 40-60 for the straight run distillates produced from the same crude. The sulfur content in average light cycle oils can range from 0.2 to 2.5 wt%. A detailed sulfur speciation of LCO shows that a significant portion of the sulfur is found in alkyldibenzothiophenes (DBT), which are relatively difficult to desulfurize by hydrotreating. The aromatics content of LCO from FCC units in a normal gasoline-oriented operation can be as high as 80 wt-%. The organic nitrogen is almost entirely composed of non-basic aromatic compounds, such as carbazoles, with a concentration range of 100-750 ppm. The components of LCO boil in the diesel range with a 95% point of 360C or higher, representing thermally stable cracked hydrocarbons that are not further reacted in the FCC process. Over 70% of the aromatic hydrocarbons present in LCO have two rings, while the remainder is typically evenly split between single ring and 3-plus ring aromatics. Two and 3+ ring aromatics combust poorly in the diesel engine. They have very low cetane values and are the root cause of the low blending quality of LCO. It is necessary to saturate and open the di-aromatic rings to increase the fuel value of products from LCO upgrading. These reactions are a fundamental pathway in hydrocracking reaction chemistry and thus this process is ideal for converting LCO to a higher quality diesel product. Single ring aromatics boiling in the gasoline range are excellent high octane components in the gasoline pool. Aromatic ring manipulation is the key to producing higher value gasoline and diesel.
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UNIONFINING PROCESS
Table 1 shows an inspection of a typical LCO sample containing 0.7 wt-% sulfur. Approximately 300 ppm of the sulfur is contained in molecules that are very difficult to desulfurize by hydrotreating. As a result, hydrotreating LCO to improve its diesel pool blending characteristics is a challenge not only from the standpoint of its high aromatics content but also due to the nature of its sulfur species. Hydrotreating LCO to reduce its sulfur content to an ultra-low level requires high severity operation. However, high pressure hydrotreating results in over saturation of aromatics and inefficient use of hydrogen for only a modest cetane improvement. Some triand higher ring aromatics are converted to lower aromatics but the total aromatic content of the LCO still remains high and relatively little cetane improvement is realized. Figures 1 and 2 show that even at low pressure there is significant conversion of polyaromatics to monoaromatics and most of the cetane boost is accomplished at low hydrotreating pressures. As pressure is increased to promote deep desulfurization, little further increase in cetane takes place. Another important aspect of LCO upgrading is that in the absence of significant conversion of aromatics through cracking reactions, the saturation reactions proceed only to their equilibrium limit. A typical temperature and pressure range of most hydrotreaters places a ceiling on how far the cetane index of the LCO can be improved via simple partial saturation of aromatic rings. In summary, hydrotreating of LCO for deep sulfur removal requires relatively high pressure and hydrogen consumption, yet achieves only limited improvement in cetane number, total aromatics, and density. Table 1
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Figure 1
Figure 2
Cetane Number
30
Sulfur at 10 ppm
HC 190 CATALYST
HC 190 catalyst was shown to be well suited to accomplish the desired chemistry for partial conversion LCO hydrocracking. It is designed to provide significantly higher activity than the current naphtha hydrocracking catalysts. For example, its performance on a cracked stock blend, containing light cycle oil, shows about 15oF higher activity and higher naphtha yield at equivalent hydrogen consumption compared to current commercial catalysts. It has demonstrated superior performance in pilot plant tests for partial conversion of LCO by maximizing retention of single ring aromatics, thus producing a higher octane naphtha product. It also produces diesel with very low sulfur levels.
LCO Feed Fractionation HT HC MU Gas Off Gas HPS LPS RG Compressor LPG
ULSG Gasoline
ULSD Diesel
The feedstock is processed over a pretreatment catalyst and then hydrocracked in the same stage. The products are subsequently separated without the need for liquid recycle. The advantage of the LCO Unicracking process is that it can be designed for lower pressure operation. The pressure requirement will be somewhat higher than high severity hydrotreating but significantly lower than a conventional partial conversion and full conversion hydrocracking unit design. The upgraded middle distillate product makes a suitable ultra-low sulfur diesel (ULSD) blending AM-05-53 Page 6
component. The naphtha product from low-pressure hydrocracking of LCO has ultra-low sulfur and high octane and can be directly blended into the ultra-low sulfur gasoline (ULSG) pool. Thus, the LCO Unicracking process offers excellent flexibility to increase the value of LCO by upgrading its products to ULSG and ULSD blending targets.
ANALYTICAL TECHNIQUES
Recent advances in hydrocarbon analysis have made it possible to speciate distillate fuels at the molecular level. UOP has developed a technique, which uses comprehensive gas chromatography, also called GCxGC, that enables resolution of hydrocarbon species in a threedimensional map. One axis distinguishes by boiling point, the second axis distinguishes by polarity, and the vertical axis measures the relative concentration (Figures 4 and 5). This type of graphical representation significantly enhances the understanding of complex hydrocarbon mixtures like LCO. Advanced procedures to analyze and interpret this data are being developed at UOP and have been crucial in understanding the fundamental chemistry and pathways associated with different catalysts and reaction conditions. It will allow more precise feedstock characterization and facilitate better understanding and control of the desired molecular transformations Figure 4
Feed
3-ri ng a rom atic s
bz
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b e eb
nC13
nC15
nC17
nC19
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Product
3-ri ng a rom atic s
bz
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nC13
nC15
nC17 nC19
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Figure 6
R1
X
R1 CH3 CH3 CH3
R2
(H
Un de sir yd ro ed ge : na
X
tio
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R2
H3C
Typical cracked product characteristics using HC 190 catalyst are listed in Table 2. It can be seen that the high activity and unique cracking characteristic of HC 190 catalyst enable good Table 2
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aromatic retention in the gasoline range product as demonstrated by the high research octane number. The diesel range product contains less then 10 ppm sulfur and low aromatic content, well within ULSD fuel specification limits. Its cetane index ranges from 6 to 8 numbers higher than the LCO feed. Extended stability tests of more than six months of continuous operation at low pressure have confirmed excellent catalyst stability while maintaining the cracking conversion and product qualities. Stable yields of products were obtained over the entire period, with slight improvement observed in the gasoline octane with time on stream.
REFINERY APPLICATIONS
The potential impact of LCO Unicracking employed in a typical US refinery was examined by comparing it against the alternative of deep LCO desulfurization by high pressure hydrotreating.
Gasoline Pool
Treated FCC gasoline Hydrotreated light straight run naphtha Reformate Alkylate (to premium) Purchased MTBE (to meet oxygen specification for RFG) Butanes for RVP adjustment LCO Unicracking unit gasoline
Diesel Pool
Jet Fuel blending components Kerosene Hydrotreated kerosene Ultra-low sulfur diesel components Hydrotreated kerosene Hydrotreated straight run diesel LCO Unicracking unit diesel or hydrotreated LCO (case study) AM-05-53 Page 10
All process units were sized to be consistent with the design crude oil capacity, and assumed to operate at typical conditions for a US refinery. The new LCO Unicracking unit or the hydrotreating unit cases were sized at a 20,000 bpsd capacity. The gasoline and diesel pools were blended to meet the 2006 US quality regulations. In order to reflect the next wave of diesel regulations, the diesel pool blend was based on harmonized on-road and off-road diesel specifications, i.e. the entire pool must attain an ultra low sulfur level of 15 ppm or less. The estimated quantities and qualities of the blended gasoline and diesel products are detailed in Table 3. The results show that both solutions, i.e. the LCO Unicracking process or high pressure hydrotreating will enable production of acceptable ultra-low sulfur diesel which can be entirely blended into the diesel pool. Due to selective chemistry of the LCO Unicracking process however, this route produces 3-5 points higher cetane index than the hydrotreating route. Both routes produced a cetane index in excess of the 2006 specification. By employing the LCO Unicracking solution, the refiner will be better prepared for expected future upward changes in the cetane specifications. Additionally, LCO Unicracking process yields a high octane and ultra low sulfur gasoline, which can be blended directly into the gasoline pool without jeopardizing the pool specifications for octane, sulfur, or aromatics. The small amount of naphtha produced in the hydrotreating case is sent to a reformer prior to blending into the pool. Due to the high octane of the gasoline produced via the LCO Unicracking process, the overall refinery pool octane is not changed by direct blending of this product into the pool. The installation of an LCO Unicracking unit increased gasoline production by about 10% while decreasing the diesel production by 13% compared to the hydrotreating unit option. The addition of an LCO Unicracking unit has the benefit of varying diesel/gasoline slate to meet the refiners seasonal demand. Table 3
Refinery Gasoline and Diesel Pool Yields and Qualities As a Function of the LCO Upgrading Option
Type of LCO Upgrading Gasoline pool: Volume, BPSD RONC / MONC Sulfur, ppm ULSD Pool: Volume, BPSD Cetane Index Sulfur, ppm Hydrotreating LCO Unicracking Process
Process Economics
Type of LCO Upgrading Unit Capacity, BPSD Yield, Lt and Hvy Naphtha, wt-% Yield, ULSD, wt% Estimated ISBL Investment Cost, $M 10 yr NPV, $M Simple Payout, yrs
The LCO Unicracking project produces a very attractive positive 10 yr NPV of $203M and results in a simple payout of two years. LCO hydrotreating option has a negative NPV and a payout time of six years, i.e. it is a stay-in-business solution imposed by the regulatory requirements. The sensitivity analysis of the two solutions was done using two comparative parameters; price differential between ULSD and LCO, and a price differential between gasoline and ULSD. The results are depicted in Figures 7 and 8. It is shown that the LCO Unicracking solution retains the same advantage over the hydrotreating solution for a range of price differentials. As expected, the Unicracking solution advantage increases as the price differential between gasoline and diesel increases. It should be noted that this analysis is specific to market where gasoline is a higher priced product, as for example, in the US. A somewhat different case study was described recently in another publication which was focused on the European refinery setting and market pricing (1).
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Figure 7
Figure 8
10 Yr NPV, $MM
NPV(HC)
NPV(HT)
CONCLUSIONS
LCO is a distressed refinery stream with limited future disposition options without further significant upgrading. Refiners will have to consider investments in technology to upgrade the LCO to higher value transportation fuels as they prepare for clean fuels production and increased market demand in the future. In this paper we have announced our new, commercially available technology, the LCO Unicracking process, ideally suited for production of ULSD and ULSG blendstocks from LCO at relatively mild conditions. The unique selectivity characteristics of our new HC-190 catalyst are also an important enabler in the new process. The LCO Unicracking process makes efficient use of hydrogen by employing advanced catalytic know-how to selectively increase the hydrogen content of the diesel range product while minimizing saturation of aromatics in the naphtha range. The process economics for a US based refinery have shown that the investment in an LCO Unicracking unit yields superior NPV and provides a good payout compared to a conventional hydrotreating solution.
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REFERENCES
1. V. P. Thakkar, V.A. Gembicki, D. Kocher-Cowan, S. Simpson, LCO Unicracking Technology A Novel Approach for Greater Added Value and Improved Returns, ERTC, 2004 2. Crude Oil Prices, EIA petroleum marketing Monthly, www.eia.gov 3. Product prices obtained from historical North American data of Platts, and CMAI, www.platts.com, and www.cmaiglobal.com
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