Optimization of the Operating Conditions of a Refinery Using High Percentages of Heavy Crude Oil.

A. Perez Instituto Mexicano del Petrleo, Mexico City E. Zelaya CADIT, Universidad Anhuac, Mexico City Abstract.
Many different types of crude oils are extracted from Mexican wells and mixed to produce commercial mixtures that are well known and highly demanded in the export market. These mixtures are also used as feed in Mexican refineries. However, to make the best out of our refineries, crude oils should be mixed according to the particular characteristics of each refinery. It is also possible to define optimal operating conditions for a particular refinery as a function of the crude mixture. Processing of heavy crude in existing refineries can not be significantly increased because of limitations such as: a decrease in the yield of light products, equipment metal restrictions, and greater environmental impact. However, it is our belief, that the efficiency of the oil industry can be significantly increased. This paper visualizes one approach: improving the productivity of individual refineries in order to increase heavy crude refining capacity and reduce costs. We develop an optimization model of a typical FCCconfiguration refinery and analyze alternative ways of improving heavy crude processing efficiency. Our modeling efforts concentrate on the selection of the ideal mixture of crude and on hydrotreating and catalytic cracking of atmospheric and vacuum gas oils.

Introduction
The demand for gasoline is affected by many factors including quality of available crude oils and environmental regulations influencing finished products. The demand for lighter products and middle distillates has grown steadily as a result of transportation demand and the lack of economically viable alternatives. Optimum conversion capacity provides refiners with flexibility to process heavy crudes and acts as a hedge against high-cost light crudes. This flexibility is required to be more competitive in the marketplace. However, the refiner must select the appropriate process configuration that best fits the combination of crude supply and market demands. The principal rationale for upgrading gasoline, particularly for production of low sulfur gasoline, is to observe new stringent regulations on gasoline fuel quality1-3. Changes in regulations governing gasoline composition continue to focus on reducing sulfur levels. Examples include those counties like USA and Canada, that mandating 30 ppm S, will become effective between 2004-2006, and 50 ppm S will be required in the EU in 20054, 6. The overall impact of such regulations on the makeup of the USA and Mexico gasoline pool can be illustrated in Figure 1, which combines historic and forecast specification to levels of sulfur in gasoline. In 2001, with new regulations in several northern European countries, and overall growth in demand, low sulfur gasoline will likely make up about 3.3 thousands of barrels per day (MBD), or about 17% of worldwide production5. The problems faced by refiners in meeting these extremely low sulfur levels are to deeply desulfurize fluid cat cracked (FCC) feedstock or naphta (which contributes in most of 90% of total sulfur gasoline) with out loss of octane6. The Petroleum refining industry has rapidly developed and deployed new processes and catalyst to accomplish low sulfur in FFC naphta. This studied visualizes one approach: improving the productivity of individual refineries in order to increase heavy crude refining capacity and reduce costs. We develop an optimization model of a typical FCC-configuration refinery and analyze alternative ways of improving heavy crude processing efficiency. Our modeling efforts concentrate on the selection of the ideal mixture of crude and on hydrotreating and catalytic cracking of atmospheric and vacuum gas oils. In this paper, we will provide an update on recent progress in the fluid cat cracked process, including a variety of options that have been explored to get low sulfur gasoline. We will also present pilot plant results and review several options to FCC process optimization and a

description of our model. Finally, this paper will present the main results in optimization model applications.

USA

1994 Automotive vehicle technology Sulfur in the pool Start Tier 1

1996 Tier 1 Journey 160,000 km Rank: 0 1,000 ppm Average 300

2004 25%

2005 50%

2006 75%

2007 100%

2008 50%

2009 100%

Tier 2 cars Journey 192,000 km Average 120 Aver. 80

Tier 2 heavy Average 30

Mexico

2001 Tier 1 Automotive with out vehicle guaranteed technology journey Sulfur in the pool Average 700 Mexico city 400 20%

2002 40%

2003 60%

2004 80%

2005 100%

2006

2009 2011

Tier 1 Journey 80,000 Km. Average 300

Tier 2 Introduction phase

Average 50

Figure 1. New environmental regulations

Fluid catalytic cracking feedstock

Fluid catalytic cracking, better know as FCC, is one of the most important and complicated processes in petroleum refining. This unit is considered the primary conversion process in an integrated refinery. Many refiners use FCC-configurations, where FCC units are the key to profitability in that successful operation of the unit can determine whether or not a refiner can stay in business and remain competitive in todays market. Although the mechanical configuration of individual FCC units may be arranged differently, their main purpose of the unit is to convert high-boiling petroleum fractions called Gas Oil to high-value, highoctane gasoline and heating oil. It is important to note that, worldwide, about 45% of all gasoline produced comes from the FCC and ancillary units, such as the alkylation unit. Gas Oil is the portion of crude oil that boils in the 330-550C range and contains a diversified mixture of paraffins, naphthenes, aromatics, and olefins. This process has a remarkable history of adapting to continual changes in market demands. The gas oil to a conventional cat cracker comes primarily from the atmospheric column (heavy atmospheric heavy gas oil AHGO), the vacuum tower (light and heavy vacuum gas oil VLGO & VHGO), and the delayed coker unit, or H-Oil unit, or other residue processing units. Refiners are faced with processing many different types of crude oil. As market conditions and crude quality fluctuate, so do cat cracking feedstock properties. Two feeds with similar boiling point ranges may exhibit dramatic differences in cracking performances and product yields. Because of these variable conditions, often the only constant in FCC operations is the continual change in the feedstock quality. FCC feed characterization is one of the most important requirements of cat cracking. Understanding feed properties and knowing their impact on unit performance are essential to optimization of FCC

process, just as troubleshooting, catalyst selection, and subsequent process evaluation. Knowing the effects of a feedstock on unit yields, a refiner can purchase the feedstock that would maximize profitability. It is not uncommon for many refiners to purchase raw crude oils or FCC feedstock without knowing their impact on unit operations. At times, this lack of knowledge can cause unit shutdowns for several weeks7.

Mexican crude oils

Crude oil exports are one of the most important sources of income in Mexico. As a result, emphasis has traditionally been placed on maximization of the quantity available for export rather than on efficient refining of oil. Since the vast majority of light oils produced in Mexico are exported, Mexican refineries are forced to process the heavier crude. The total design capacity of the Mexican refining system is 1.48 million barrels per day8. This design capacity could be used to process 33% of heavy crude oil, equivalent to 488 thousand barrels per day. However, to process the future production of heavy crude from the Cantarell field in Campeche, Mexico (800 thousand-barrel per day), current capacity will have to be increased by 45%9. Istmo light crude was chosen as the reference feedstock for this study, as it is processed worldwide and provides a good reference for the technical and economic comparisons. The Mexican Maya crude, on the other hand, illustrates the specialized refining techniques necessary to maximize transportation fuels and minimize fuel oil production when processing extremely contaminated crudes. The results in figure 2 illustrate differences in the properties of several gas oil from these kings of Mexican crude oils. The most efficient refineries around the world rely on some type of optimization model and many works on this subject have been published in the specialized literature10, 11. In this paper, we draw on some of those works to develop a linear optimization model of a refinery with facilities for hydrotreating of intermediates and an FCC unit for cracking of gas oil. We analyze the operating conditions for feeds ranging from light crudes like Istmo to the heavy Maya, including 10 mixtures of Istmo and Maya. As in previous optimization models12, we rely on extensive information obtained from a pilot plant and a full scale refinery.

Methodology
The experimental part was developed in two stages. In the first stage, gas oil resulting from processing different mixtures of crude oil at the atmospheric and vacuum distillation units was obtained. In the second stage, several mixtures of heavy and light gas oils were processing in HDT and FCC pilot plants.

Pilot plant runs

Desulfurization activity was measured in a HDT pilot plan with a continuos flow reactor operating at 90 kg/cm2 pressure and 380C. The reactor was operated in isothermal mode by an independent temperature control of a three-zone electric furnace. The axial temperature profile of the catalysts bed was measured by three thermocouples located in a thermowell mounted at the center of the reactor. All tests were made at a liquid-space-velocity of 1.0 hr-1, and with a hydrogen flow rate of 5000 standard cubic feet per barrel (scf/bbl) (0.0718 l/s at STP). For all tests the catalyst was presulphided with H2S prior to the above gas oils treatment. The several mixtures of gas oils and hydrogen were directed upwards through the reactor over a fixed bed of catalyst. The gas oil produced was processed in a FCC pilot plant, where the operating conditions were adjusted to resemble those of an industrial unit. Tests run are conducted to evaluate performance of a 40,000 BPD FCC unit. The feed to the unit were mixtures of gas oil from the atmospheric and vacuum unit. Products from the pilot plant are fuel gas, LPG, gasoline, LCO, and decanted oil. This plant were operating at 450 C in riser outlet, 3.3 kPa in reactor dome and reactor flow rates of 900 ml/hr.

Analytical and evaluation methods

The distillation was determined by True Boiling Point (ASTM-D-2892). This method was used to characterize the distribution between naphtha and distillates. The sulfur content of each fraction was determined by an X-ray fluorescence technique (ASTM-D-4294).

24 Gas Oil, vol.% yield

FCC feed, Sulfur, wt.%

2 1.8 1.6 1.4 1.2 1

22 20 18 16 14 12 10 32.5 31.7 30.4 29.4 28.0 27.0 25.8 24.8 23.5 22.5 21.1

1.4 1.7 1.9 2.2 2.4 2.7 2.9 3.1 3.4 3.6 3.8 Crude Oil, Sulfur, w t.%

Crude Oil, API

FCC feed, Ni+V, ppmw

3 2.5 2 1.5 1 0.5 0 66 96 127 156 183 213 243 271 301 330 359 Crude Oil, Ni+V, ppm w

FCC feed, Ramsbotton, wt.%

3.5

0.3 0.25 0.2 0.15 0.1 0.05 0 4.1 4.9 5.4 5.6 7.0 7.7 8.3 9.7 9.8 10.9 11.7

Crude Oil, Ram sbotton Carbon, w t.%

Figure 2. Gas oils yield and properties from several Mexican crudes

The optimization model

Our modeling efforts concentrate on the selection of the ideal mixture of crude and on hydrotreating and catalytic cracking of several mixtures of gas oils. The three purposes of our analysis are as follows: Profit maximization, Heavy crude feed maximization and Gasoline yield maximization

A profit maximization objective function is used to analyze the three objectives. Objective function

NP = PF f X f PR r U r OP r , p Z r , p + OPG r , e A r , e , " dist"Z r , " dist " f r e r r p

Material balance constraints Crude oils

A
p

r , " crude" , p

Z r , p + U r 0 r CR

Intermediates

A
p

r, i, p

Z r , p W r , i , f 0 r CR, i CI , f BP
f

Capacity constraints This set of constraints defines the capacity of our productive units: Distillation unit HDT FCC 270,000 BPD 25,000 BPD 40,000 BPD

B
p r

m, p

Z r , p K m m

Crude oil purchases constraints A limit of 270,000 BPD is imposed on daily crude oil purchases. This is in fact the capacity of our refinery

U r UR r r
Blending balance constraints This set of constraints defines the ways in which gasoline components can be mixed to obtain blended gasoline (reformate, alkylate, cat cracker naphta, etc).

X f = W r , i , f
r i

Quality constraints Sulfur content in blended gasoline is limit to 30 ppmw.

ATC
r i

r, i, q

Wr, i, f Q f , q X f

f QS , q

The resulting model has 395 equations and 4152 variables. The GAMS modeling system is used.

Results and discussion

The optimization model was run for multiple situations. The most relevant results are presented in Tables 1 and 2. Table 1. Yield of final gasoline in Barrels per Day (BPD) Final product Gasoline I 96,271 II 73,230 III 83,487 IV 63,313 V 75,638 VI 58,247 VII 63,373

Table 2. Process economics in thousands of Dollars Net income Sales Revenue Crude cost Operating cost Total cost I 7,123.2 14,541.1 7,311.6 106.2 7,417.8 II 5,424.1 11,816.5 6,293.7 98.7 6,392.4 III 6,290.3 12,685.8 6,293.7 101.7 6,395.4 IV 4,167.6 9,885.8 5,610.6 107.6 5,718.2 V 5,207.9 10,930.2 5,610.6 111.7 5,722.3 VI 3,625.3 8,855.8 5,097.6 133.0 5,230.6 VII 4,057.5 9,290.2 5,097.6 135.2 5,232.8

I. Light oil
Our first optimization run is intended to find the type of crude and the blend of final products that maximize net income. The results show that production should be totally based on the light Istmo. Although HDT capacity is fully utilized, sensitivity analysis shows additional capacity is unnecessary.

II. Crude with 70% Istmo, 30% Maya, and with HDT capacity of 25,000 BPD
This is the most commonly used feed in Mexican refineries. HDT capacity is fully utilized and our sensitivity analysis indicates that it would pay to increase it.

III. Crude with 70% Istmo, 30% Maya, and with an HDT capacity of 50,000 BPD
Only 91% of the HDT capacity of 50,000 BPD is utilized. However, the increase in net income resulting from the added HDT capacity is $866,252 per day. This fully justifies the investment required to double HDT capacity.

IV. Crude with 30% Istmo, 70% Maya, and with HDT capacity of 25,000 BPD
HDT capacity is fully utilized. The advantages of increasing HDT capacity are discussed in run V.

V. Crude with 30% Istmo, 70% Maya, and with HDT capacity of 50,000 BPD
HDT capacity of 50,000 BPD is fully utilized. The increase in net income resulting from the added HDT capacity is $1,040,316 per day. This fully justifies the investment required to double HDT capacity.

VI. Maya with HDT capacity of 25,000 BPD

HDT capacity is fully utilized.

VII. Maya with HDT capacity of 50,000 BPD

Only 71% of HDT capacity of 50,000 BPD is used. However, the increase in net income resulting from the added HDT capacity is $432,200 per day. This fully justifies the investment required to double HDT capacity.

Concluding remarks
As a consequence of new stringent regulations on gasoline fuel quality; where this environmental regulations requiring 30-50 ppm sulfur in gasoline will take effect soon in many countries. A lot of refinery investments in hydroprocessing facilities for gas oils upgrading will be required in the next years. The main results were, for light oil, the most abundant products are gasoline in first place. However, for the case of the mixtures of light with heavy oils, gas oils (FCC feedstock) being the main product. The reason for these lies behind the limits imposed on the viscosity and sulfur of fuel oil. For the light Istmo, small amounts of kerosene and jet fuel mixed with cracked gas oil and vacuum residuum are enough to reach the desired viscosity. The mixtures of light and heavy oil require large quantities of kerosene and jet fuel (all of the production in cases IV and V) to satisfy the viscosity specification. When 100% heavy oil is used, not enough kerosene and jet fuel are produced to be blended with the highly viscous vacuum residuum and some of it remains unused. It should be noted

that there is a high demand of fuel oil in Mexico for use in power plants, but some countries need more fuel oil with less sulfur and metals; because, environmental specifications will be more stronger with toxic emissions.

Definition of symbols Zr, p Xf Ur Wr , i , f Km PR r PF f UR r OPG r , e A r, c, p O P r, p ATC r , i , q Q B m, p References

1. Annual Energy Outlook 2000, Energy Information Administration (EIA), Washington, D.C., Dec 1999. 2. R.E. Dymond, World Markets for Petroleum, Hydrocarbon Processing, Sep. 1991. 3. Murphree, E.V., Fischer, H.C.M., Fluid cattalytic cracking of premium fuels, Pet. Ref., 22, No. 11, 1943. 4. Bienstock, M.G., Draemel, D.C., Terry, P.H., and Shaw, D.F., Modernizing FCCUs for improved profitability, AIChE Annual Meeting, Chicago, No. 1990. 5. Burnett, P., Huff, G., European Refining Technology Conference, Rome, Italy, Nov 15, 2000. 6. Rheaume, L., and Ritter, R.E., Fluid catalytic cracking: role in modern refining, ACS Symp. Ser. 375 (M.L. Occelli, ed.), American Chemical Society, Washington, D.C. 1988. 7. Speight, J., (1998), The chemistry and technology of petroleum, third edition, Marcel Dekker, Inc. New York, US 8. Memories, (1999), Mexican Petroleum, Mexico City. 9. Meyers, R.A., (1997), Handbook of petroleum refining processes, second edition, McGraw-Hill, New York, USA. 10. Pontuario, (1998), Secretary of Energy, Mexico, Mexico City. 11. Seo,J.W. et. Al. (2000), Design optimisation of crude oil distillation, Chem. Eng. Technol. 23 (2000) 2. 12. Zelaya de la Parra, E. (2000), Optimisation of a Process for the Solvent Fractionation of Palm Oil Using a Model Based on Interpolation of Experimental Data, Chem. Eng. Technol. 23 (2000) 2. process level final sales purchase of crude oil blending process level initial capacity prices of crude oils prices of final products upper bound on crude oils operating cost of intermediates input output coefficients operating cost attributes for blending by crude quality attribute capacity utilization