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Authors: Phillip K. Niccum - KBR Maureen F. Gilbert - KBR Michael J. Tallman - KBR Chris R. Santner - KBR Publication / Presented: 2001 NPRA Meeting Date: March 18, 2001
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History of Fluid Catalytic Light Olefins Production During the latter 1930's, propylene and butylene were largely supplied as a byproduct of thermal cracking of petroleum, and the major use of these light olefins was for the manufacture of gasoline using catalytic polymerization (3). During WW II, fluid catalytic cracking was developed for the production of high octane aviation gasoline and C4's (isobutylene and butadiene precursors for a new and rapidly expanding U.S. synthetic rubber industry as the supply of natural rubber was being cut-off).
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Waxy Gas Oil Feedstock over Commercial Equilibrium FCC Catalysts 950 F cracking temperature at constant conversion
Yields Hydrogen, wt% C1 + C2s, wt% Propylene, vol% Propane, vol% i-Butane, vol% n-Butane, vol% Butylenes, vol% C5+ Gasoline, vol% LCO, vol% Bottoms, vol% Coke, wt% Gasoline Octane RON Clear
Amorphous Catalyst 0.08 3.8 16.1 1.5 7.9 0.7 12.2 55.5 4.2 15.8 5.6
Zeolite Catalyst 0.04 2.1 11.8 1.3 7.2 0.4 7.8 62.0 6.1 13.9 4.1
94.0
89.8
In the 1970's after introduction of zeolite catalyst, FCC unit design and operation evolved to regain some of the lost octane and light olefin yield, primarily with higher reactor operating temperature and riser cracking (5). Increasing reactor temperatures increased light olefin yield, but this came at the expense of increased yield of dry gas, a lower value FCC product. During the 1980's Mobil introduced two new technologies with application to increasing the production of light olefins and octane while limiting incremental dry gas production: (1) Mobil developed ZSM-5 catalyst additive to crack low octane (linear) gasoline boiling range olefins and paraffins into light olefins, and (2) Mobil invented Closed Cyclones which minimize product vapor residence time between the riser outlet and the main fractionator. Refinery Options for Production of Petrochemical Feedstocks In March 1998, Kellogg (now Kellogg Brown & Root (KBR)) and Mobil (now ExxonMobil) introduced the MAXOFIN FCC Process for maximization of propylene yield from FCC feed-
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Some of these options for increasing petrochemicals feedstock production from existing FCC units are further discussed below:
Recovery of refinery grade propylene typically requires investments in a depropanizer (C3/C4 splitter), metering systems, storage tanks, railcar/tank truck loading facilities, or pipeline connections. Recovery of chemical grade propylene would typically include investments in a propylene splitter in addition to the other facilities described above. Production of polymer grade propylene is an even more expensive option, but one with potentially higher return. In addition to the investments listed above, this option would typically include addition of a deethanizer tower as well as COS/Arsine removal reactors and dryers. Hydrogenation reactors may also be required to meet the tight specific ations on dienes/acetylenes. Production of 99.9 vol% purity petrochemical grade ethylene requires the addition of still more fractionation towers as well as equipment designed to remove associated contaminants such as acetylene, water, oxygen, carbon monoxide, sulfur and nitrogen compounds. Design of a low temperature FCC vapor recovery system to meet all these requirements will more than double the cost of a VRU installation relative to that of a traditional absorption oil based VRU system. Alternatively, a dilute ethylene stream may be sent directly to a nearby petrochemical plant for use as feed to an ethylbenzene unit or steam cracker gas recovery system.
Balancing Supply and Demand The relative production Figure 3: Process Characteristics rates of propylene and Relative production of ethylene vs. propylene ethylene from units in the Orthoflow FCC refinery and petrochemical plant are key considera100.0 C3 , C4 & Liquid Feed Steam Cracker tions in refinery / petroEthane Feed chemical plant integration. Steam Cracker Within each type of proc10.0 ess unit, selection of feedstock and operating conSUPERFLEX ditions, as well as catalyst MAXOFIN systems where applicable, 1.0 can dramatically alter light olefin production rates FCC and propylene to ethylene ratio (P/E). Figure 3 0.1 shows typical propylene 1 10 100 and ethylene yield charPropylene Yield, wt% acteristics of various processing options, including data on steam cracking for reference. Although propylene demand is high, refiners are still cautious about committing large capital investments for propylene production alone because of the historically large swings in propylene-fuels margins. A recent study by CMAI estimated the margin and Return on I nvestment (ROI) for installation of facilities for recovering polymer grade propylene from exAM-01-61 Page 5
600
US Cost US Margin ROI
80 70 60 50 40 30 20 Percent ROI
10 0
Figure 4 summarizes the margins and resultant ROI estimated for U.S. refiners over the period of 1994 through 2004, and shows the variability in the recovered propylene margin during the period. The data in the figure show a strong recovery from lower margin levels experienced during the 1998 and 1999 time frame. The data also suggest that now is a very good time to invest in propylene recovery facilities that can come on steam to take advantage of the peak expected in 2003 and 2004.
MAXOFIN FCC The proprietary MAXOFIN FCC Process, licensed by KBR and depicted in Figure 5, is designed to maximize the production of propylene from traditional FCC feedstocks and selected naphthas. The process increases propylene yield relative to that produced by conventional FCC units by combining the effects of MAXOFIN3 catalyst additive and proprietary hardware, including a second high severity riser designed to crack surplus naphtha into incremental light olefins.
FCCs will supply much of increased Propylene demand MAXOFIN combines advanced catalyst & hardware
High ZSM-5 MAXOFIN-3 Additive KBR Orthoflow Hardware
u
In addition to processing recycled light naphtha and C4 LPG, the riser also can accept naphtha from elsewhere in the refinery complex, such as coker naphtha streams, and upgrades these streams into additional light olefins. Olefinic streams, such as coker naphtha, convert most readily into light olefins with the MAXOFIN FCC process. Paraffinic naphthas, such as light straight run naphtha, also can be upgraded in the MAXOFIN FCC unit, but to a lesser extent than olefinic feedstocks.
ZSM-5
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The following table shows the result of MAXOFIN pilot tests which demonstrates the flexibility of the MAXOFIN Process with respect to propylene to ethylene ratio. The tests were performed on a single feedstock while operating conditions and catalyst formulation differ between the runs. This flexibility allows the MAXOFIN unit performance to be tailored to the needs of the refinery/petrochemical complex. Table 3 MAXOFIN FCC Circulating Pilot Plant Data
Hydrocracked Gas Oil Feedstock
The number of product streams, the degree of product fractionation and several other aspects of the vapor recovery process will differ from unit to unit, depending on the market requirements of the application. Design of a vapor recovery unit to produce polymer grade ethylene and propylene products includes consideration of several factors not typically addressed in FCC VRU design.
The cold fractionation train begins with a Depropanizer system, followed by a Demethanizer, Deethanizer and ethylene-ethane Splitter. Polymerization fouling is minimized in both columns as a consequence of the low operating temperatures. Facilities are required to remove impurities from the process gas and to prevent freezing and hydrate formation in low temperature operations. In the recycle tower, the heavy gasoline components (200 F +) are removed from the overhead C4s and lighter gasoline components. The C4s and lighter gasoline comp onents from the recycle tower overhead are recycled to the MAXOFIN FCC reactor. The Deethanizer separates the feed to the column into an overhead C2 stream and a bottom C3 stream. The overhead C2s are routed to the C2 splitter, where polymer grade ethylene product is produced. The feed to C3 Splitter comes from the bottoms of the Deethanizer. duces a polymer-grade propylene product from the mixed C3 feed. This column pro-
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SUPERFLEX can be used in concert with a steam cracker to increase the product P/E of the petrochemical cracking complex. Ultimate olefin plant propylene to ethylene (P/E) ratios for a low severity naphtha steam cracker are typically limited to 0.60 to 0.65. However, with SUPERFLEX, new plants can be designed for P/E ratios of about 0.80. Using the SUPERFLEX process within the olefins complex provides a higher ultimate value as shown in the table below: Table 5 SUPERFLEX/Steam Cracker Integration Steam Cracker Complex Material Balance (KTPA) Feed: Naphtha Products: Ethylene Propylene Fuel Gas Gasoline P/E Ratio Without SUPERFLEX 1891 700 419 327 390 0.60 With SUPERFLEX 1995 700 535 299 421 0.76
Economic analyses show that the alternate including the SUPERFLEX reactor in the olefins complex has about a 1 year simple payout on gross margin for a plant designed to produce 700 KTPA ethylene. SUPERFLEX technology is also available as a standalone unit with its own separation section. Both Arco and KBR have extensively piloted process performance for SUPERFLEX. KBRs inhouse pilot facilities are available for evaluating client feedstocks.
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References 1. 2. 3. Steven J. Zinger; The Critical Role of the Refinery in the Propylene Market; 2000 World Petrochemical Conference; Houston, Texas; March 29 30, 2000. Steven J. Zinger, Chemical Market Associates, Inc.; e-mail, September 2000 C.E. Jahnig, D.L Campbell, and H.Z. Martin; History of Fluidized Solids Development at Exxon; Fluidization, Ed John R. Grace and John M. Matsen, Perseus Books, January 1980 J.J. Blazek; Oil & Gas Journal; 1971 E.L. Whittington, J.R. Murphy, and I.H. Lutz; Catalytic Cracking Modern Designs; American Chemical Society, New York Meeting, August 27 to September 1, 1972. Phillip K. Niccum, Rik B. Miller, Alan M. Claude, Michael A. Silverman, Nazeer A. Bhore, Ke Liu, Girish K. Chitnis and Steven J. McCarthey; MAXOFIN: A Novel FCC Process for Maximizing Light Olefins using a New Generation of ZSM-5 Additive; NPRA Paper AM-98-18; San Francisco, California; March 15-17, 1998 Maureen F. Gilbert, Michael J. Tallman, William C. Petterson, and Phillip K. Niccum; Light Olefin Production from SUPERFLEXSM and MAXOFIN FCC Technologies; ARTC Petrochemical Conference, Kuala Lumpur, Malaysia, February 2001.
4. 5. 6.
7.
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