P ROCESS T ECHNOLOGY U PDATE

Desulfurization Process

Optimizing The Cat Feed Hydrotreater/FCCU Complex With Detailed Simulation Tools
RICHARD LEE (Senior Consultant, KBC Advanced Tecnologies, Inc.), ERNEST LEUNENBERGER (Senior Consultant, KBC Advanced Tecnologies, Inc.), ROBERT POWELL (Manager, Process Model Development, KBC Advanced Tecnologies, Inc.) Based on a paper presented at the ERTC Computing Conference, June 2001, Paris, France
Overview

A new simulation tool has been commercialized by KBC Advanced Technologies, Inc. and AEA TechnologyHyprotech. Known as the HYSYS.Refinery, this tool provides significant advances in three areas: First, the ability to simulate multiple refinery units with detailed representations of both the reactor and separation sections. Previously, reactor units had to be simulated in isolation, with reaction effluent streams carried manually from unit simulation to unit simulation. Second, the ability to model large sections of the whole refinery in one simulation. This was previously possible only with linear program (LP) models with their attendant shortcomings overly simplistic linear representation and limited availability and transferability of key refinery stream properties. Third, the ability to build such simulations in a reasonable amount of time, with reasonable effort and reasonable (non-expert) simulation experience and skills. To illustrate these points, a study project was initiated to develop a realistic simulation of an FCC and its upstream gas oil hydrotreater (HTR). The overall objective was to create a tool from which multiple case studies could be easily developed to study the effects of varying hydrotreater severity and FCC conversion on the product yields, properties and economics of the hydrotreater/FCC complex. A final objective was the optimization of the entire operation. The selection of the cat feed hydrotreater/FCC combination as a processing and economic unit is especially interesting for the following reasons: The benefits of the hydrotreater are largely realized at the FCC. Optimization of the hydrotreater or the FCC in isolation provides only limited operational guidance. Both the hydrotreater and the FCCU can be consid ered conversion units in this process scheme. Though the hydrotreater has a smaller conversion window of operation, there is flexibility to convert
32 World Refining July/August 2001

incrementally 1020 vol% FCC feed to diesel. Thus, conversion may be shifted from one unit to the other. The best severity for the hydrotreater is not intuitively obvious. Higher severities produce diminishing amounts of lower-sulfur, lower-nitrogen FCC feed. However, aromatic content (a key gas oil property for FCC feed) first decreases, then increases as the limitations of naphthene/aromatic equilibrium impose themselves on the hydrotreater operation at elevated reactor temperature. Even without the ability to alter the feedstock composition, optimization of the FCCU is always an interesting exercise best left to a process model. The complexity of the unit results from the need of the unit to continuously regenerate its own catalyst while operating at conditions that produce just the amount of coke needed to operate the process. Combined with the normal FCC constraints of air blower, regenerator temperature, etc., optimization of this unit calls for the application of a mathematical model and an optimization algorithm. Finally, with the current emphasis on sulfur reduction in both gasoline and diesel, the effects of varying HDS severity upstream of the FCCU are especially interesting in investigating pre-treatment/posttreatment options.

Reactor Unit Models

Reaction unit models utilized in the study were KBC Profimatics VGO HTR-SIM for the hydrotreater operation and FCC-SIM for the cat cracker simulation. VGO HTR-SIM is a detailed kinetic model licensed by KBC to refining company clients for detailed process studies and process monitoring. It has been licensed for use on more than 55 commercial hydrotreater units. FCC-SIM is licensed by KBC for analysis and optimization of FCC units. This model contains a detailed kinetic representation of the riser/reactor and regenerator sections of the process. FCC-SIM has been licensed for use on more than 160 commercial units worldwide.
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P R O C E S S T E C H N O L O G Y U P D AT E

The main fractionators for both the hydrotreater and the FCC unit were simulated using KBCs DISTOP model. This model is a shortcut section-by-section distillation model that predicts real-world fractionation volume interchanges between adjacent products. It has been made a component of HYSYS.Refinery.
Pseudocomponents

One of the technical challenges of combining reactor models and flowsheets is the translation of pseudocomponents used in the reactor model to those used in the flowsheet and vice versa. Reactor models used in the refining industry have normally utilized broad boiling range pseudocomponent lumps. For example, FCC-SIM uses the following reactant/product lumps: Slurry Gas (C1-C4) Coke Naphtha Unconverted Gas Oil LCO These lumps represent the reactant/products for the basic reaction of the FCC model (i.e., cracking). HTR-SIM utilizes a carbon number pseudocomponent approach, C1 thru C80. The integer carbon numbers span boiling ranges between 10 and 17C. Carbon number rather than distillation (volatility) range-based pseudocomponents are more logical and appropriate for modeling reactions. The advantages are that carbon and hydrogen balances are more easily maintained, and the true reaction heat effects are more accurately calculated. In short, the representation of the model more closely represents the reactions that are actually occurring in the reactor, such as: Cracking of C-C bonds to form lower carbon number fragments Transformation of aromatic carbon to naphthenic carbon (hydrotreating) or vice versa (FCC hydrogen transfer) Currently, KBC is developing a carbon number-based version of FCC-SIM, which will complement the suite of carbon number-based models it currently licenses for reforming (REF-SIM), hydrocracking (HTR-SIM, HCR-SIM) and alkylation (ALK-SIM). Regardless of whether the reactor pseudocomponents are broad boiling range or narrow cuts, the effluent must be converted to a series of continuous yield and property curves for the separation modeling in the flowsheet. For the HTR/FCC flowsheet example used here, the reactor effluents from both reactors were converted to a number of such curves, including: Vol% off versus TBP Density versus TBP Sulfur versus TBP Nitrogen versus TBP The HYSYS.Refinery flowsheet is then able to break these down into any pseudocomponent scheme desired. The scheme used in the flowsheet in this example is:
Figure 1A. Hydrotreater flow sheet online.

H2, H2S, H2O, C1-C4: pure components C5+: fixed 10C temperature pseudocomponent cuts

These pure components plus pseudocomponents, defined by boiling range, are appropriate for separation operations based on relative volatility (e.g., flash, multi-stage fractionation). The thermodynamics package selected for the flowsheet also allows calculation of heat transfer via exchangers or fired heaters. The continuous yield and property curves allow the correct calculation of properties generated in any fractionator model (perfect cut, short cut or tray-to-tray) used downstream of the reactors.
HTR/FCC Problem Flowsheet

For the purpose of the study described here, the individual HTR-SIM and FCC-SIM reactor models were first separately tuned and calibrated to match typical commercial unit operations. Calibration is required to allow a first principles reactor model to match an observed units performance. The matching is accomplished by adjusting model parameters tied to the installed catalysts activity, selectivity and stability. Also captured during the calibration are non-idealities in the reactor system, such as divergence from plug-flow (e.g., hydrotreater bed channeling). The flowsheet constructed for this hypothetical problem is shown in Figure 1A. The desulfurized gas oil stream from the HTR unit is internally passed to the FCC unit. Streams in/out are summarized below: In Raw gas oil to HTR Make-up H2 to HTR Raw gas oil to FCC (bypassing HTR) Air to FCC Steam to FCC

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Out Purge/fuel gas from HTR Naphtha from HTR Distillate from HTR FCC flue gas Fuel gas from FCC C3/C4 from FCC Naphtha from FCC LCO from FCC Slurry from FCC Water from FCC As this study is more focused on yields and economics, much of the detail of the true process flow of the units has been dropped for simplification. For example, streams between units have been heated or cooled as required because energy considerations are secondary to the product yields and their economic importance. Also, the full detail of the FCC gas plant has been eliminated in favor of a simple fractionation scheme of a main column and several component splitters. Should more detail be required, the entire gas plant could be simulated using the unit operations of HYSYS.Refinery, including detailed tray-to-tray fractionators, heat exchangers, absorbers and the like. In situations in which the separation section is at or near constraints, this detail may very well be necessary, as these considerations may limit the reactors window of operations.
Case Studies

350.0C (662F). The HYSYS.Refinery case results were captured in an Excel worksheet for easy analysis and charting (Figure 1B). The results from Case 1 (WABT = 355.2C), Case 5 (WABT = 376.6C) and Case 10 (WABT = 400.3C) are shown in Table I (on page 38). As hydrotreater severity is increased, the amount of conversion on the HTR increases about 9%. As a result, the FCC feed decreases from 486 to 435 m3/HR (73,364 to 65,666 bpd). Figure 2 shows the HTR yields of naphtha, diesel and hydrotreated gas oil across all ten cases. The desulfurized gas oil (FCC feed) sulfur decreases from 0.46 wt% to 0.09 wt% (Figure 3 on page 36). However, the crackability of this stream as measured by aromatic carbon content (CA) first improves and then deteriorates as the HTR temperature increases. This is the result of the aromatic/naphthene equilibrium effect on the conversion of aromatics to their saturated counterparts: Naphthene Aromatic +H2
M M

As a prelude to a full-blown optimization, a simpler process study was performed with the flowsheet to observe the response of the HTR/FCC model to variation of the HTR severity over a wide range of reactor temperatures. The raw HTR feedstock characteristics are: HTR Rate 530.0 m3/HR (80,000 bpd) Density 21.87 Deg API (0.9226 sp. gr.) Distillation, TBP, C (F) 1% 276 (530) 10% 360 (680) 30% 422 (792) 50% 462 (864) 70% 501 (934) 90% 553 (1027) 99% 590 (1094) Sulfur, wt% 2.47 Nitrogen, ppm 810 Refractive Index 1.51349 @ 20C Ni/V, ppm 0.11/0.02

Figure 1B. Excel spreadsheet from HYSIS.Refinery.

HTR Yields vs. HTS WABT

100 90 80 70 60 50 40 30 20 10 0 350 355 360 365 370 375 380 385 390 395 400 405

Yield, Vol. %

HTR WABT, Deg C HTR Naph yld wt% HtF

The HTR Weighted Average Bed Temperature (WABT) was varied from 355.2C (671F) to 400.3C (753F) over a series of ten cases. The FCC fed the entire 335C+ (635F) desulfurized gas oil product from the HTR. Riser outlet was held constant at 521.1C (970F) as was preheat temperature at
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HTR Dist yld wt% HtF HT Gas Oil yld wt% HtF

Figure 2. Hydrotreater yields.

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HTR Yields vs. HTS WABT

0.5 0.45

Desult Gas Oil, Wt. % S

0.4 0.35 0.3 0.25 0.2 0.16 0.1 0.05 0 350 355 360 365 370 375 380 385 390 395 400 405

cases is shown in Figure 5. From the standpoint of sulfur content of the FCC products, higher-severity hydrotreatment results in naphtha sulfur reduction from about 400 ppm at the lowest severity (Case 1) to 80 ppm at the highest hydrotreatment severity (Case 10).
Optimization

HTR WABT, Deg C HT Gas O (Sulfur)

In the previous case studies, only one variable (HTR WABT) was manipulated. In order to demonstrate the full capabilities of HYSYS.Refinery, an optimization case was created to maximize the HTR/FCC complex as an integrated economic unit. The independent variables selected for manipulation during the optimization were: HTR WABT FCC riser outlet temperature FCC feed preheat temperature Optional purchase of raw gas oil to be fed directly to the FCC (bypass HTR) Constraints utilized in the problem were: FCC wet gas compressor (170,000 std m3/HR max) FCC air blower (49,000 std m3/HR max) The objective function selected was Profit, using the traditional definition of: Profit = (Value of Products) (Cost of Feeds) (Cost of Utilities/Catalyst) Prices were assumed to be as shown in Table II (page 38). The SQP optimizer included with HYSYS.Refinery was utilized for the optimization. The Base Case was arbitrarily selected to be Case 7 of the previously described parametric study. This case utilized a HTR WABT of 386.5C (728F), a riser of 521.1C (970F) and feed preheat of 350C (662F). The constraints used for the FCC air blower and wet gas compressor were set to those existing at the Base Case conditions. The purchase of raw (unhydrotreated) FCC feed was allowed because it was felt that by not doing so, higher HTR operation would be penalized as a result of lower FCC feed rates. The results of the optimization are shown in Table III (page 39). The optimizer chose to reduce the HTR WABT from 386.5C (728F) to 373.2C (704F) to take advantage of the improved FCC feed quality at an HTR severity corresponding to the region of minimum aromatics content. Lower aromatics in the feed reduces the coking tendency of the feed, and this improves yields and moves the unit away from the air blower constraint. The preheat increase also assists in alleviating this constraint. It appears that the optimizer then raises riser temperature until the wet gas compressor constraint is encountered. Interestingly, the model chooses not to purchase external FCC feed when faced with the blower and wet gas constraints. Profit was increased by about $11,700/day as a result of these moves. Optimum operation nonetheless remains at the point at which the units blower and wet gas compressor operate at maximum.
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Figure 3. Sulfur reduction.

HTR Gas Oil Ca vs. HTR WABT

17.50

Aromatic Carbon, Wt %

17.00 16.50 16.00 15.50 15.00 14.50 14.00 350 355 360 365 370 375 380 385 390 395 400 405

HTR WABT, Deg C

Figure 4. Conversion rate of aromatics by temperature.

FCC Naphtha Yield vs. HTR WABT FCC Naphta Yield, Vol. %
62.00 61.50 61.00 60.50 60.00 59.50 59.00 350 355 360 365 370 375 380 385 390 395 400 405

HTR WABT, Deg C

Figure 5. Naptha yield, cumulative 10 cases.

As temperature increases, the reverse reaction rate increases more rapidly. The maximum conversion of aromatics occurs at about 375C (707F) HTR WABT for this case (Figure 4). The effect on the FCC is that the conversion and naphtha yield both increase and then fall as the feed becomes more aromatic (less crackable). FCC naphtha yield for the ten
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TABLE 1. SIMULATION RESULTS OF HYDROTREATER SEVERITY STUDY

Case 1 (Lo-Sev) HTR Feed rate, m3/HR (bpd) WABT, C (F) Naphtha, vol % FF Distillate, vol % FF Desulfurized gas oil, vol % FF Desulfurized gas oil Density, API (sp. gr.) Sulfur, wt% CA, wt% FCC Feed rate, m3/HR (bpd) Riser outlet, C (F) Preheat, C (F) FCC naphtha, vol % FCC LCO, vol % FCC slurry, vol % FCC naphtha Sulfur, ppm FCC wet gas rate, std m3/HR Regen air rate, std m3/HR

Case 5 (Mid-Sev)

Case 10 (Hi-Sev)

530.0 (80,000) 355.2 (642) 1.35 8.91 91.82 26.15 (0.8975) 0.46 15.00

376.7 (710) 2.46 11.41 88.80 26.90 (0.8933) 0.25 14.50

400.3 (752) 4.59 16.22 82.02 27.16 (0.8918) 0.09 17.04

486.6 (73,455) 521.1 (970) 350.0 (662) 61.42 16.10 8.51 407 50,940 181,170

470.6 (71,040)

434.7 (65,621)

61.44 16.06 8.04 221 49,868 174,309

59.52 17.67 8.91 80 44,957 158,711

TABLE 2. PRICES/COSTS FOR OPTIMIZATION RUN

Make-up HTR H2 Fuel Gas C3 C3= i C4 n C4 C4 FCC Naphtha FCC LCO FCC Slurry HTR Naphtha HTR Distillate Raw Gas Oil Feed Octane BBL

$105.9/ M std m3 ($3.00/MSCF) $24.29/Giga-cal ($6.12/MMBTU) $132.09/m3 ($21.00/BBL) $185.54/m3 ($29.50/BBL) $176.11/m3 ($28.00/BBL) $144.66/m3 ($23.00/BBL) $194.98/m3 ($31.00/BBL) $226.43/m3 ($36.00/BBL) $179.26/m3 ($28.50/BBL) $138.38/m3 ($22.00/BBL) $201.28/m3 ($32.00/BBL) $216.99/m3 ($34.50/BBL) $188.69/m3 ($30.00/BBL) $0.063/Octane-m3 ($0.40/Octane BBL)

Summary

HYSYS.Refinery was utilized to study the potentially large operating window of a typical cat feed hydrotreater/FCCU complex. This real-world situation presents an interesting optimization problem due to the many non-linear responses of those processes and the interaction between the two units. A key factor in the optimization of these units is the point of maximum aromatics conversion in the hydrotreater. Minimizing aromatics tends to maximize FCC conversion, all other things held constant. Using the model, it was determined
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that introducing constraints on the units tended to adjust the operating point around this minimum aromatics point. HYSYS.Refinery is extremely useful in performing parametric studies or optimizations. Once the model is built, case studies can easily be constructed and executed. Though not part of the study presented, other operating questions could be easily answered with the tool, including: How sensitive is the optimum point to product pricing changes? Given several FCC feed streams (SR VGO, coker/visbreaker gas oil, resid) and a limited hydrogen supply, which streams are most economically treated? Should certain streams be severely treated while others are bypassed around the HTR to conserve H2? Will increased hydrotreater reactor volume allow the refinery to meet the new gasoline sulfur specifications? With a fixed hydrogen availability, should a pretreat or post-treat strategy be followed to meet new sulfur product levels? The possibilities of studies with HYSYS.Refinery can also be extended to add the following units to the flowsheet: downstream alkylation, LCO/FCC naphtha hydrotreaters and gasoline/diesel blending; upstream crude/vacuum fractionation, coker/visbreaker units or other sources of feed for the HTR/FCC complex. With the inclusion of the crude/vacuum units, HYSYS.Refinery can be used to study the impact of varying crude slates. Crude assay libraries are linkable to the tool.
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The natural extension of the use of the tool from the simulation of one or two associated units to the entire refinery is obvious. G
About The Authors
HTR Feed rate, m3/HR (bpd) WABT, C (F)

TABLE 3. OPTIMIZATION RESULTS

Base

Optimized

Ernest Leuenberger is a senior modeling Consultant with KBC Advanced Technologies, Inc. in Thousand Oaks, Calif. His main area of specialty is FCC. Prior to joining KBC, he worked for Air Products & Chemicals and Engelhard Corporation, where he supported FCC catalyst marketing and provided technical service. More recently he was employed by ARCO Products Co. as a FCC process specialist, developing simulation models and evaluating alternative operating stratgies. He was a member of the NPRA Q&A panel in 1987.

530.0 (80,000) 381.1 (718 ) 0.0 (0.0) 521.1 (970) 350.0 (662) 170,000 49,000 Base

530.0 (80,000) 373.2 (704) 0.0 (0.0) 520.1 (968) 360.0 (680) 170,000 49,000 Base + $11,700/day

FCC Purchased raw gas oil, m3/HR (bpd) Riser outlet, C (F) Preheat temperature, C (F) FCC wet gas rate, std m3/HR FCC air blower rate, std m3/HR Profit, $/day

Richard Lee is a senior consultant with KBC. He is a chemical engineer who has 23 years of experience in petroleum and chemical industries, the last 19 of which have been focused on providing process engineering and modeling support to numerous refiners around the globe. His responsibilities have included development, implementation and technical support of process models in the reforming, delayed coking, isomerization and sulfur recovery areas. He has linked reactor models to flowsheeting package such as HYSYS and ProII.

Robert Powell is manager of process models for KBC Advanced Technologies, Inc. Thousand Oaks, Calif. Bobs previous work experience includes refinery technical support for Atlantic Richfield Company and economics and refinery planning positions with Tosco Refining. He joined Profimatics, Inc. in 1985 and was involved in process model development for ten years, then joined KBC in 1997 when it acquired Profimatics.