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Fuel Processing Technology 86 (2005) 1335 – 1350 www.elsevier.

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Comparisons of FCC product yields and qualities between reactors using Canadian heavy feeds
Siauw H. Nga,T, Adrian Humphriesb, Craig Fairbridgea, Yuxia Zhuc, Chandra Khulbea, Thomas Y.R. Tsaid, Fuchen Dinge, Jean-Pierre Charlandf, Sok Yuig
National Centre for Upgrading Technology, 1 Oil Patch Drive, Devon, Alberta, Canada T9G 1A8 b Akzo Nobel Catalysts LLC., 2625 Bay Area Boulevard, Suite 250, Houston, TX 77058, USA c Research Institute of Petroleum Processing, 18 Xue Yuen Road, PO Box 914, Beijing 100083, China d National Dong Hwa University, Hualien 974, Taiwan, ROC e University of Petroleum, Beijing 102249, China f CANMET Energy Technology Centre-Ottawa, 1 Haanel Drive, Ottawa, Ontario, Canada K1A 1M1 g Syncrude, Research Centre, 9421-17 Avenue, Edmonton, Alberta, Canada T6N 1H4 Accepted 1 January 2005
a

Abstract This study describes the effects of two catalysts, an octane-barrel and a bottoms-cracking catalyst, on the catalytic cracking of 10 oil-sands bitumen-derived feeds in fixed- and fluid-bed microactivity test (MAT) units, an Advanced Cracking Evaluation (ACE) unit, and a continuous riser pilot unit. This is part of a comprehensive study of the cracking behavior of Canadian vacuum gas oils. In general, at an equivalent catalyst/oil ratio, conversions decreased in the order ACE N fixed-bed MAT N fluid-bed MAT among the batch reactors. Between a batch reactor and the continuous riser, there existed a good correlation for a given product yield as well as for a given product quality, at a specific conversion. For the oil-sands-derived vacuum gas oils, the bottoms-cracking catalyst containing rare-earth-exchanged Y zeolite (REY) with a large-pore active matrix was more effective than the catalyst containing the rare-earth-exchanged ultrastable Y (REUSY) and ZSM-5 zeolites with an active matrix. The overall distribution of feed sulfur in cracked products, and the relationship

T Corresponding author. Tel.: +1 780 987 8709; fax: +1 780 987 5349. E-mail address: sng@nrcan.gc.ca (S.H. Ng). 0378-3820/$ - see front matter. D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2005.01.020

Advanced Cracking Evaluation (ACE) unit 1.V. Ng et al. nitrogen. With parts or all of the same feeds. through pipelines.g. Syncrude has been striving for a better quality of SSB. very aromatic).1336 S. producing an SCO called bSyncrude Sweet BlendQ or bSSB. with specific interest in the heavy gas oil (HGO) or vacuum gas oil (VGO). which are described below. Riser results were reported previously [1].H. This paper focuses on objectives (2) and (3). including the United States. is the world’s largest oil-sands bitumen upgrader. and an Advanced Cracking Evaluation (ACE) unit. and nitrogen in MAT liquid product fractions and compare these values with those obtained from the pilot plant. which is usually used by refiners as a fluid catalytic cracking (FCC) feed.1. Introduction Canadian oil-sands bitumen is a mixture of immature and complex hydrocarbons rich in chemical impurities (e. Canadian heavy feeds. 2. Experimental The test program was composed of three studies.e. a comprehensive FCC program consisting of several series of microactivity (MAT) tests in fixed. sulfur. Keywords: FCC yields. Syncrude Canada Ltd. HT-VIR—hydrotreated virgin VGO . 2. / Fuel Processing Technology 86 (2005) 1335–1350 of the sulfur content of feed with that of light cycle oil (LCO). Because of the high viscosity. and vanadium) and low in hydrogen-tocarbon ratio (i. HCB—hydrocracker bottoms VGO 2..and fluid-bed reactors). D 2005 Elsevier B. (2) to compare cracking yields obtained from different reactor systems including riser. All rights reserved. Oil-sands bitumen. Study 1—establishing riser operating conditions and comparison of cracking performances between riser and fixed-bed MAT This study involved the following 10 feeds: 1. Alternatively. MAT (with fixed. nickel. In 1998. confirmed the findings reported in the literature.Q Over the years. Syncrude evaluated 10 existing and potential VGOs in a riser pilot plant. the bitumen can be upgraded to a light and bottomless synthetic crude oil (SCO) that is of pipeline quality as far as the viscosity and contents of sediment and water are concerned. [2] and (3) to develop analytical techniques for determination of aromatics.. The objectives of the test program were threefold: (1) to provide guidance for the pilot plant operation. the bitumen can only be transported through pipelines after being mixed with suitable diluents such as natural gas condensates and naphthas.and/or fluidbed reactors was conducted at the National Centre for Upgrading Technology (NCUT). Microactivity test (MAT) unit. sulfur. Canadian heavy crudes are delivered from western provinces (mostly Alberta) to other regions.

it was assumed that the temperature effect on MAT yields was negligible and that one regression could be applied to the same set of data points obtained at three different temperatures. used in this program. 9. equipped with collection systems for gas and liquid products was used to crack the 10 feeds. some runs were repeated later. Based on concentrations of gasoline precursors [3].2.and fluid-bed MAT reactors and method development to characterize MAT liquid Five feeds of various ranks (HCB. 4. HT-DA. / Fuel Processing Technology 86 (2005) 1335–1350 1337 3.S. respectively. 10. a specially designed liquid receiver with extra large volume (300 mL) was used to collect over 99 wt.% of liquid products that were free of contamination by wash solvents (e. Table 1 summarizes the feed properties. which illustrates that a decrease of 20 8C will cause less than 10% absolute change in yield (relative to the yield at 520 8C and 5. The fixed-bed version is based on ASTM D 5154. 8. A fixed-bed MAT unit (Zeton Automat IV). Since the reaction temperature range was rather small (F10 8C at 510 8C). total nitrogen. 2. For each feed.. HT-C. and fluid bed runs involving HT-DA. Total liquid products (TLPs) from fixed-bed runs involving HT-C and DA-BIT. The reactor was loaded with 4 g of CAT-A with 30 s catalyst contact time for all runs. 5. while the fluid-bed version is being developed by ASTM.H. and an intensive discussion on feed properties. except for dry gas due to its small yield. In this study. which is more widely used by the catalyst industry. However. the feed qualities in terms of the capacities to produce gasoline were ranked [4] in a descending order from feed 1 to feed 10. This is shown in Table 3. Study 2—comparison of cracking performances between fixed. Note that the majority of the MAT runs were performed at 510 8C. as shown above.and fluid-bed reactors at 510 8C and 30 s oil injection time with 5 g of CAT-A. 7. RZ—Rainbow Zama crude VGO HT-LCF—hydrotreated LC-Finer VGO HT-C—hydrotreated coker VGO HT-DA—hydrotreated DA-BIT (see bfeed 10Q below) VIR—untreated virgin VGO LCF—untreated LC-Finer VGO DA-LCF—deasphalted oil VGO from LC-Finer resids DA-BIT—deasphalted oil VGO from bitumen. and microcarbon residue (MCR).g. Some of the cracking characteristics in Study 1 have been reported previously [4–7]. and DA-BIT) were cracked in the MAT unit using both fixed. a specially configured gas . More detailed characteristics and history of the feeds. Coke deposited on the catalyst after cracking was determined by in situ combustion through the use of a CO2 absorber. (2) hydrocarbon types of gasoline [PIONA analyzer. CS2). were characterized (without prior separation) for: (1) simulated distillation (ASTM 2887). HRO 610 (HRO) and catalyst A (CAT-A). Table 2 gives the properties of the equilibrium catalysts. VIR.4]. 6. three runs were conducted at 510 8C and one and two runs at 500 and 520 8C. The omission of the temperature effect can be justified by the rather low sensitivity of the MAT yields to temperature in this study.5 C/O). can be found elsewhere [1. Ng et al.

9 0.9 0.7 1.8 2.3 13. wppm V.3 58.562 2150 4290 0.3 52.0 1.% Ni.8 0.1 0.2 63.9 0.0 2.7 Saturates + monoaromatics.7 7.9284 12.37 11.7 5.1 26.5 13.0 2.0 0. Ng et al.2 1.1 6. and (3) boiling-point distributions of aromatics (GC with a mass-selective detector—GC-MSD).9252 13.8 0.0 15.61 4.8643 0.9 35.5397 1.9430 0.1 46.556 3050 35.669 460 981 0 0 0 17.8 21.764 800 9170 0.8 38.619 2450 7040 2.0 0.9642 11.1 68.5 0.0 24.9 6.9 4. % Aniline point.8 74.0 22.7 0.8 99.1 0.6 1.3 9.6 0.4 20.8 20.4 1.3 1.8 29.2 1.2 10.7 0.4 1.8 1.5 12.1 1.1 2.1 0.5324 1.532 3370 13.3 8.6 45.8 63.7 6.4747 1. / Fuel Processing Technology 86 (2005) 1335–1350 1 HCB 2 3 4 5 6 7 8 LCF 9 10 HT-VIR RZ HT-LCF HT-C HT-DA VIR DA-LCF DA-BIT 0.5153 2. .% 90.6 12.1338 Table 1 Feedstock properties Feed number Feed name Density at 15 8C.2 1.6 7.8 58.0 4.3 34.6 22.8 55.8 26.1 25.2 47.4 6.2 35.892 0 b10 0.7 9.1 1.3 6.7 51.5370 4.1 3.8 1.5 36.7 11.7 1.4 12. nitrogen (GC with an Antek nitrogen chemiluminescence detector—GC-NCD).3 24.0 73.50 0 0 24.4 11.3 2.6 25.0 30.5 4.9712 0.200 3.0 MSD.4 7.1 29.0 0.6 1. wt. chromatograph (GC) with a prefractionator].5393 10.4 4.0 1.6 0.4 5.3 3.7 11.4 7. 8C Refractive index at 20 8C 343 8CÀ by simdist.9776 11.8 1.5 1.4 7.8 24.8 59.0 0.7 2.4967 1.7 2.1 1.2 2.5 8.7 3.7 5.% Hydrocarbon type by Saturates Paraffins Cycloparaffins Aromatics MonoDiTriTetra.8 1.3 3.7 3.% 524 8C+ by simdist. and sulfur (GC with Sievers sulfur chemiluminescence detector—GC-SCD).5 29.0 50.3 1.1 1.5323 1.400 5. g/ml Hydrogen.8 1.2 2.4 1.1 6.4 11. wt.9 28.9 29.2 36.0 2.7 6.5 8.7 14.7 1.6 2. wppm Total sulfur. wt.8988 0.7 1.7 61.5 1.500 0.04 0 0 4.1 3.2 30.6 1.638 1090 880 0.9 0.5 2.549 1930 32.1 16.0 65.0 6.5269 1.4 42.7 1.6 13.9 61.2 8.9] and published [9–11].9562 0.7 29.4 21. wt.and greater Aromatic sulfur 2-Ring compounds 3-Ring compounds 4-Ring compounds unidentified Polar compounds Gasoline precursorsa a S.08 0 0 14.5 5.500 0. Partial results from Study 2 have been orally presented [8.8 5.3 6. wppm MCR.4 1.4 57.0 25.1 56.6 11. wt.% H/C atomic ratio Total nitrogen.02 0 0 20.5 5.1 0.9 3.9 77.9 3.5 3.9 65.7 97.9511 0.7 4.0 5.4 71.2 1.2 0.5130 19.8 38.1 28.2 1.6 6.1 4.6 7.0 7.4 38.1 11.24 0 0 30.4 1.0 0.0 10.7 3.4 23.4 62.2 0.1 4.9 75.4 5.6 81. wppm Aromatic carbon.3 52.1 4.9 11.536 4020 15.6 5.5 14.4 3.3 89.2 0.1 64.6 61.40 4.3 27.5 1.33 0 0.H.

7 1. m2/g Zeolite/matrix (Z/M) Micropore volume.1 2. wppm HRO 610 24.1 18. Ng et al.% Dry gas LPG Gasoline LCO HCO Coke Conversion a Absolute differencea relative to yield at 520 8C and 5.28 13 150 100 50 2.% (on catalyst) RE2O3.9 n/a 49. In addition.62 0.0 5. wt. wt.4 16. wt. / Fuel Processing Technology 86 (2005) 1335–1350 Table 2 Equilibrium catalyst properties Catalyst X-ray diffraction Unit cell size (fresh). Am SiO2.37 101 147 0. 2 Unit cell size (equilibrium). TLPs collected with the improved liquid receiver were characterized as in Study 2.78 n/a 10. Study 3—catalyst effects on product yields and qualities Three feeds of special interests (HT-C. wt. HT-DA.21 7.4 6.5 44.1 6. m2/g Average pore diameter. .66 24.5 55. m2/g Matrix surface area.45 67. % 15. and VIR) were cracked at 30 s catalyst contact time with 7 g of equilibrium catalysts (CAT-A and HRO) at 510 8C (530 8C for HT-DA) in the MAT unit using the fluid-bed reactor.5 C/O (average of 10 feeds). wt.67 291 314 2.6 0.53 65.S.5 0.35 n/a 148 65 83 0.66 242 434 1339 CAT-A n/a 24.7 39. mL/g Zeolite content.6 0. wt.19 1. m2/g Zeolite surface area. 2 Water absorption Pore volume. 2 Zeolite content.5 C/O (average of 10 feeds). wt.22 61 109 0. mL/g Pore area.31 79. wt.7 Based on yields at 500 and 520 8C in Study 1 using CAT-A.% TiO2. wppm V.% Al2O3.31 n/a 0.7 1. the three feeds were also Table 3 Sensitivity of fixed-bed MAT yields to temperature Yield at 520 8C and 5.9 9.8 0.05 15.H. wt.4 5.% Nitrogen adsorption–desorption Total surface area.2 2. wt.% Fe2O3.56 13.5 1.% Hg porosimetry Pore volume. mL/g Average particle size.85 17.00 0.% RE2O3.% (on zeolite) Na2O.% Ni.3.

the adsorption and desorption rates of hydrocarbons). HRO was characterized by: (1) higher rare-earth content on zeolite (17.8 wt. Ng et al.e. (2) lower zeolite content and lower zeolite surface area.14].% for CAT-A) that increased its stability and activity.H. Results and discussion 3. but higher matrix surface area with a much lower zeolite/matrix (Z/M) ratio (0.5 vs. 1. Comparison of product yields between MAT unit and riser reactor In spite of fundamental differences in reactor design and operations. Fig. the MAT unit can be a useful tool to predict riser performance. wt % 9 8 R = 0.1340 S. / Fuel Processing Technology 86 (2005) 1335–1350 cracked with the same two catalysts in the ACE unit [2]. Correlation of MAT dry gas (open symbols) or coke (closed symbols) yield with their corresponding riser counterpart at the same conversion (from Study 1 involving fixed-bed MAT and CAT-A).946 LCF DA-LCF DA-BIT 1 0 0 1 2 3 4 5 6 7 8 9 10 RISER DRY GAS OR COKE YIELD.00 for CAT-A).1.. 3. These properties suggested that HRO was a bottoms-cracking catalyst containing rare-earth-exchanged Y zeolite (REY) while CAT-A was an octane-barrel catalyst containing rare-earth ultra-stable Y zeolite (REUSY) mixed with a small amount of ZSM-5 for octane enhancement. 109 2 average pore diameter for CAT-A) that provided greater access to heavy molecules that needed to be precracked. compared with CATA. 70. and (3) larger matrix opening (147 vs. . Table 2 shows that. In Study 1.78 vs. and 81 wt.971 2 HCB RZ HT-VIR HT-LCF 7 6 5 4 VIR 1:1 line HT-DA HT-C 3 2 R2 = 0. MAT data at 55. Partial results from Study 3 have been reported [5. wt % Fig. which measures the relative mass transfer rates of hydrocarbons into and out of the catalyst pores (i. Recently. 65. 1 10 MAT DRY GAS OR COKE YIELD.13. 7.% conversion were plotted against their riser counterparts reported previously [1]. the ACE unit has gained popularity as a tool for laboratory FCC studies. HRO is a large-pore catalyst developed by Akzo Nobel Catalysts LLC based on a special catalyst assembly technology to give a high Akzo accessibility index [12]. 2.

This indicated that the catalyst poisoning (by coke) was less severe in a fluidized 65 MAT GASOLINE OR HCO YIELD. In all cases. 3 shows a good linear relationship. higher conversion than fluid-bed MAT (from which the results represented by thin trendlines) for all feeds because of the more intimate contact between oil molecules and catalyst particles within a reaction period in a fixed-bed reactor. with 0. At a given C/O ratio. 3.961 1:1 line HCB HT-VIR RZ HT-LCF HT-C HT-DA 30 25 20 15 10 5 5 10 15 20 25 30 35 40 45 50 55 60 65 R 2 = 0. 2). 2. However. 4 shows the increase in conversion with catalyst/oil ratio (C/O) for five feeds (HCB. HT-DA. Both studies involved CAT-A at 510 8C. VIR. Fig. Ng et al. and VIR [13]. in general. HT-C. The imperfect linear correlations have been explained before [6. fixed-bed MAT (from which the results represented by thick trendlines) gave.650.and fixed-bed MAT units (Study 2). and two feeds (HT-C and VIR) cracked in the ACE unit (Study 3).992 R 2 value. one can calculate the individual predicted riser yields from their corresponding MAT yields.920 DA-BIT VIR LCF DA-LCF RISER GASOLINE OR HCO YIELD. wt % 60 55 50 45 40 35 R 2 = 0. for all products between the predicted and actual riser yields. The similar plot for gasoline or heavy cycle oil (HCO) gave R 2 N 0.2. a good correlation was also observed in Study 3 involving fluid-bed MAT and riser for feeds HT-C. The correlation of MAT liquefied petroleum gas (LPG) or light cycle oil (LCO) yield with their respective riser counterpart was less impressive. HT-DA. fixed-bed MAT gave lower conversion for the three feeds (HCB. . Similarly.920 (Fig.7].946. did not overlap the 1:1 line due to the differences in unit operation and design. Correlation of MAT gasoline (closed symbols) or HCO (open symbols) yield with their corresponding riser counterpart at the same conversion (from Study 1 involving fixed-bed MAT and CAT-A). But from the linear relationships. HT-C and VIR) that were low in microcarbon residue (MCR). representing the data points. with R 2 value being ~ 0. and DA-BIT) cracked in both fluid.H. Cracking performances in MAT and ACE units Fig. at about or below 4 C/O ratio. wt % Fig. the trend lines.S. / Fuel Processing Technology 86 (2005) 1335–1350 1341 depicts the linear relationship for dry gas or coke yield between riser and fixed-bed MAT with R 2 values greater than 0.

90 HCB (Fixed) HCB (Fluid) HCB (Fixed) HT-C (Fluid) 80 VIR (ACE) HCB (Fluid) HT-DA (Fixed) HT-DA (Fluid) HT-C (Fluid) CONVERSION.H. wt% HT-C (Fixed) HT-C (ACE) HT-DA (Fluid) 70 HT-C (ACE) DA-BIT (Fixed) 60 VIR (Fluid) HT-DA (Fixed) VIR (Fluid) 50 DA-BIT (Fluid) VIR (Fixed) VIR (ACE) 40 VIR (Fixed) HT-C (Fixed) DA-BIT (Fluid) DA-BIT (Fixed) 30 2 4 6 8 10 12 14 C/O RATIO.651 0. . 3.86 0.30 3.75 1.992 GASOLINE LCO HCO 20 10 COKE 0 0 10 20 30 40 50 60 70 ACTUAL RISER YIELD.75 1. Correlation of predicted riser yield with actual riser yield at the same conversion (from Study 1 involving fixed-bed MAT and CAT-A.971 2 50 40 dry gas LPG gasoline LCO HCO coke trend line and 1:1 line DRY GAS 30 LPG R 2 = 0.946 0.23 b -0. wt % 60 all feed: a 1. Ng et al.14 0. 4.08 1.34 -5. wt % Fig.08 0. Variation of conversion with C/O ratio for feeds cracked in MAT (Study 2) and ACE (Study 3) reactors with CAT-A at 510 8C.1342 70 S.655 0.78 R 0. / Fuel Processing Technology 86 (2005) 1335–1350 predicted riser yield = a x MAT yield + b PREDICTED RISER YIELD.83 -2. g/g Fig.920 0.961 0.60 5.

3 14. .7 19. with their individual counterparts from the riser at 55 and 65 wt. % À13. the corresponding fluid-bed MAT yields and the yields of LPG and gasoline from ACE could be maintained within 15% relative. 4 also shows that.3 21.8 11.2 33. Nitrogen in the LCO fractions from the MAT was consistently lower by about 50% for the three feeds.% conversion.2 8.1 6.1 16. Comparison of product qualities between MAT unit and riser reactor Table 5 shows that in Study 2.2 4.9 À0.7 18.8 14.7 Study 2. Another reason for coke differences was that ACE was operated at a shorter catalyst contact time (b15 s) than MATs. It was found later that after cracking. and the lowest yields of coke and LCO.3 14. ACE gave the highest yields of converted products (except coke) and HCO.9 3. possibly caused by the calibration problem in the analysis of MAT samples.7 0.7 15.S.% conversion among reactors using CAT-A Reactor Dry gas HT-C VIR LPG HT-C VIR Gasoline LCO VIR HCO Coke VIR HT-C VIR HT-C HT-C VIR HT-C 13.6 37. HTDA. Bias 2 (%) = [ACE À MAT (fixed bed)] / MAT (fixed bed) Â 100. Table 4 shows a yield comparison at 65 wt. Bias 1 (%) = [MAT (fluid bed) À MAT (fixed bed)] / MAT (fixed bed) Â 100.1 1. Between the two MAT units.3.3 37. N. some minute but consistent amount of heavy product (HCO) was condensed and not recovered at the bcoldQ spot near the exit of the reactor. the reduced poisoning effect on the fluid bed was masked.5 MAT (fixed bed)a 2.2 7.0 Bias 2d.7 18.0 À62. relative to the fixed-bed MAT yields. the order of conversion corresponded with that of the feed rank [4].7 15. with a few exceptions. and equivalent yield in LPG.2 MAT (fluid bed)a ACEb 2. In any reactor.8 41.%) at 65 wt.2 38. % a b c d 13.% conversion among the three reactors for HT-C and VIR.9 À 1.8 17. / Fuel Processing Technology 86 (2005) 1335–1350 1343 bed with even distribution of poisons than in a fixed bed with accumulation of poisons at the top of the bed. for the same feed.7 2. the product analyses (S.5 1. and aromatics) of HT-C. resulting in lower coke deposit on catalyst according to the Voorhies equation [15]. the fixed-bed reactor gave higher yields in dry gas and LCO.3 13. slightly higher or equivalent yield in coke.8 10.4 31.5 À19.8 4.7 À68.7 21.3 22.0 2.3 À2. at the same C/O ratio.2 9.and fluid-bed MATs had much higher coke yields than ACE due partially to some imperfect conditions of MAT reactors in the early stage of operations. Table 4 Comparison of yields (wt.7 Bias 1c.0 8. Study 3.6 5. Ng et al.5 À9.H.7 43.2 À21. In general.0 2. 3.1 14.0 12. and DA-BIT from the MAT compared reasonably well. Fig. with the conversion curves parallel to their counterparts from the fixed-bed MAT. For the two high-MCR feeds (HT-DA and DA-BIT). except for the two deasphalted oils (HT-DA and DA-BIT) with high MCR and sulfur.0 14. This was picked up later as bcokeQ at a higher reactor temperature (600 8C) during catalyst in situ regeneration. Both fixed. lower yields in gasoline and HCO.8 7. In general. ACE (from which the results represented by trendlines of medium thickness) gave the highest conversion for the same feed.6 42.6 À3.5 43.8 14.8 À27.

76 0.4.10 N. a nonhydrotreated feed. to yield H2S. or molecular reduction. LCO always gave the highest aromatics concentration due to the more stable nature of its precursors (mostly diaromatics) compared with those of HCO.76 520 333 1040 1060 90. Variation of product qualities with conversion With the low cost and simple operation of the MAT unit. wt.1344 S. Ng et al. / Fuel Processing Technology 86 (2005) 1335–1350 Table 5 Comparison of product qualities between MAT unit and riser reactor using CAT-A Product Analyses Reactor Gasoline S. and VIR in Study 3 [14] (Table 5).76 4.2 89. .09 0.9 84.1 83.10 1282 1603 839 1040 1060 760 0. ! The unique concave sulfur curves for DA-BIT (much less pronounced for HT-DA).2 1.75 0. cracked in a fixed-bed MAT reactor in Study 2.% MAT 1.96 3.85 3.63 3.14 4.H.57 1.% conversion a HT-C 50 64 HT-DA 646 410 55 wt.70 1.28 0.71 3.42 0.92 4. wt.22 1.22 1. HT-DA.50 0.7 Riser 88. conversion plot (Fig. 5): At a given conversion.92 1.81 0. wppm MAT 540 461 541 Riser 1110 1000 900 Aromatics. A good agreement in product analyses between the fluid-bed MAT and the riser was also obtained for HT-C.0 79.16 0. in three liquid fractions.67 Riser 0.63 3. Study 3 (fluid-bed MAT for all feeds).41 0.92 4238 4286 3399 3400 2990 2500 0. which might form coke.49 0.% conversion b HT-C 70 53 HT-DA 710 570 VIR 4600 5500 65 wt.15 4378 4639 3517 3100 3530 2000 Study 2 (fixed-bed MAT for HT-C and DA-BIT but fluid-bed MAT for HT-DA).65 3. one could afford to perform a detailed study that might reveal useful information.66 3.06 N.% MAT 0. wppm MAT 3500 3210 3815 Riser 3400 2990 2980 55 wt.44 0.8 94.09 0.15 1. 3.% conversion a HT-C 72 53 HT-DA 632 570 DA-BIT 6971 6600 65 wt.43 0.% conversion b HT-C 50 64 HT-DA 610 410 VIR 3900 4900 a b 0.7 HCO S.41 0.81 Riser 1. or coke formation) and the sulfur augmentation (through enrichment of sulfur-containing aromatics or molecular reduction). 6): This observation indicates the balances.96 4.% MAT 88.55 0.0 78.49 0.37 1437 1750 916 1110 1000 750 0. Figs. in a sulfur vs.14 4000 3621 3100 3530 0. between the sulfur removal (by decomposition of sulfur species.62 3. wppm MAT Riser LCO S. The following summarizes the interesting observations: ! The enrichment of aromatics in the three fractions of DA-BIT liquid product as conversion increased (Fig. wt. 5–8 show the effects of conversion on product qualities for feed DA-BIT.3 84.

. wt % Fig. Effect of conversion on aromatics concentration of product cut for DA-BIT cracked in fixed-bed MAT with CAT-A at 510 8C (Study 2). Effect of conversion on sulfur concentration of product cut for DA-BIT cracked in fixed-bed MAT with CAT-A at 510 8C (Study 2). wppm 10000 35000 LCO 8000 30000 6000 25000 HCO 4000 20000 2000 56 58 60 62 64 66 68 15000 MAT CONVERSION.S. wt % 80 LCO 75 70 65 HCO 60 55 56 58 60 62 64 66 68 MAT CONVERSION. / Fuel Processing Technology 86 (2005) 1335–1350 95 1345 90 Gasoline 85 AROMATICS. 16000 50000 14000 45000 Gasoline 12000 40000 SULPHUR. Ng et al. 6. wt % Fig.H. 5.

Ng et al.1–9.5 wt. In Study 3. for steric reasons. Here.% and decreased HCO yield by 3. Effect of catalyst pore size on product yields Modern commercial FCC catalysts are formulated with 10–50 wt. 7). a specially designed catalyst.H. 7. Akzo Nobel HRO.% of highly active zeolites [16] containing a maximum pore size of about 7. from entering the zeolite cage for cracking. However. ! The increase in density of DA-BIT gasoline at higher conversion.1346 S. / Fuel Processing Technology 86 (2005) 1335–1350 ! Similar balances among the reactions involving nitrogen compounds in the three liquid fractions of DA-BIT (Fig. HT-C and VIR were cracked at 510 8C. These molecules are precluded. Table 6 shows that at 65 wt.%.0–3.% conversion. . and HTDA was cracked at 530 8C. wppm 400 2500 LCO 300 2000 200 1500 HCO 100 1000 0 56 58 60 62 64 66 68 500 MAT CONVERSION. 8). HRO significantly increased the yield of liquid fuels (gasoline + LCO) by 7. using both catalysts HRO and CAT-A. in bitumen feeds. Effect of conversion on nitrogen concentration of product cut for DA-BIT cracked in fixed-bed MAT with CAT-A at 510 8C (Study 2). a matrix with mesopores (30–500 2) or macropores (500 2 +). modern design of FCC catalysts requires a wide-pore non-zeolitic component. showing the gradual depletion of crackable saturates and unsaturates (olefins) in this fraction (Fig. 3.5 2 [17]. Dry 700 4000 600 3500 Gasoline 500 3000 NITROGEN. wt % Fig. compared with CAT-A.5.6 wt. some heavy hydrocarbon species with boiling points 850 8F + (454 8C +) have kinetic diameters ranging from 10 to over 100 2 [17]. with high accessibility to large hydrocarbon molecules demonstrated the important role of the large-pore catalyst in cracking Canadian bitumen feeds. for pre-cracking the large oil molecules. Thus.

H. wt.9 5.% coke) Table 6 Catalyst effect on product yield at 65 wt. wt.825 1347 DENSITY @ 15.30 À2.1 68.% Coke.1 À3.5 60.92 1.5 À3.4 42.%.82 1. spent catalysts with less than 1 wt.45 À2.13 9.1 À0.82 À1.% Gasoline.7 5.3–0.5 21.4 45.% LPG. g/mL 0.59 À0.3 48.07 2.61 0.4 46.77 9.63 À3.3 11.1 3.84 9..2 21.9 8.3 69.3 wt.1 42.68 À3. Feed sulfur distribution in FCC products The amounts of sulfur in H2S and coke are usually difficult to determine accurately due to (1) the abundance of olefins in product gas.92 À0.82 9.10 1.14 12.34 À3.5 7.0 3.6 À1. / Fuel Processing Technology 86 (2005) 1335–1350 0.32 VIR CAT-A Difference HRO 6.5 7.% a HT-C HRO 8.97 0.1 41.% LCO.6–3. Ng et al. .% Delta coke. wt. 3. and (2) the restricted small amounts of samples (i.28 0.6 °C. Effect of conversion on gasoline density for DA-BIT cracked in fixed-bed MAT with CAT-A at 510 8C (Study 2).3 23.6 60.83 CAT-A Difference 12.0 À1.% HCO.0 13. which may react with H2S.15 Study 3 (fluid-bed MAT for all feeds).5 68.69 0.4 17. wt. gas yield was also decreased by 0.0 7.66 3.820 0.84 2.5 18.2 20.35 2.6 9.82 1.44 13.5 13.% conversiona Feed Catalyst C/O ratio Dry gas.71 3. wt % Fig.9 7.6 wt.S.9 16.11 HT-DA CAT-A Difference HRO 10. wt. however. The corresponding LPG yield. wt.0 61.%.43 0.28 0.810 55 57 59 61 63 65 67 69 MAT CONVERSION.9 wt.4 7. 8.11 12.6.% Gasoline + LCO.7–1. wt.8 3.53 À0.2 14.815 0.0 17.e.%. wt. was lower by 2.18 0.6 4.1 4.1 7.1 À3. and coke yield by 0.

57 0. LCO. .2 17.13 0.5 Gasoline 5.10 0.35 1.4 4.0 22.51 0. wt.%) Feed name Feed sulfur.% concentration Riser at 70 wt.67 3.10 CAT-A CAT-A 0.75 0.95 0.% MAT at 55 wt. LCO sulfur concentrations Letzsch and Ashton [20] reported that.54 3.52 3.73 0. but it was safe to assume 5 wt. as a rule of thumb.% concentration Riser at 81 wt.7 48.001 0.37 1.3 LCO 23.92 0.66 0.9 51.41 0.87 0. In general.49 0.55 0.42 3.% concentration Riser at 65 wt.50 0. required by modern analytical instruments for sulfur analysis.0 4.% concentrationa MAT at 65 wt.3 47.10 3.70 3. 3.13 0. the results agreed with the findings reported in the literature [19].66 0.43 3.70 0. but fluid-bed MAT for HT-DA).76 3.63 0.% concentration Average a b HCB HT-VIR RZ HT-LCF HT-C HT-DA VIR LCF DA-LCF DA-BIT 0.% concentrationa Averagea MAT at 65 wt.0 21. / Fuel Processing Technology 86 (2005) 1335–1350 Table 7 Feed sulfur distributions in FCC products for virgin VGOa (wt.03 0. Ng et al.%) Catalyst HRO 610 CAT-A HRO 610 CAT-A a Conversion 60 60 65 65 Coke 5. Thus.25 1.1348 S.46 3. [18].7 20.0 5. Study 3 (fluid-bed MAT for all feeds).9 Study 3 (fluid-bed MAT for all feeds).45 3.01 b0.43 0. uncertainty existed in estimating the feed sulfur distribution in coke for HT-C and HT-DA.71 0.45 0. This was also observed in our work.74 1. High sulfur in coke was found for hydrotreated feeds by Huling et al.% conversion.54 1.10 1.10 Study 2 (fixed-bed MAT for HT-C and DA-BIT.% concentrationb MAT at 65 wt. The feed sulfur distributed in gasoline. a nonhydrotreated feed [19].10 0.10 3.44 0. LCO has approximately the same sulfur content as the feed for many FCC units.9 4. in Study 3.54 1.09 CAT-A HRO CAT-A CAT-A CAT-A CAT-A b0.H.3 HCO 21. and HCO could be readily calculated.0 H2 S 45. Table 8 Sulfur concentration in LCO (wt.0 5. regardless of the cracking units and catalysts used (Table 8).67 b0.42 4. while the balance was counted as the sulfur in H2S.01 0.9 24.70 0. respectively.53 0.13 0.0 17.0 5.% concentrationb Averageb Riser at 55 wt. Table 7 shows the feed sulfur distributions at 60 and 65 wt.% for VIR.7.

the LCO produced had approximately the same sulfur content as the feed. Yui. Ring. At a given conversion. 1. Z. Sponsored by Chemical Industry and Engineering Society of China. Oil Gas J. N. at the same conversion and for the same feed. Fisher. Yui. the order of conversion corresponded with that of the feed rank except for the deasphalted oils. 65 (1990) 189 – 210. ! Regardless of the cracking units and catalysts used. ! To achieve higher yields of valuable distillates when cracking oil-sands-derived VGOs.X. L.H. S. 96 (3) (1998) 43 – 51. I. among which LCO had the highest aromatics concentration. and nitrogen of each product fraction from the MAT were comparable in magnitude with their individual counterparts from the riser. J. S. Conclusions ! MAT yields. correlations existed among the fixed. Appl. ACE gave the highest conversion for the same feed. Catal.and fluid-bed MAT units and the ACE for each product yield.H. vol. Matsumoto. A. contents of aromatics.. C.S. Wallenstein. A. Compared with the MAT. Harding. Partial funding for this research has been provided by Syncrude Research.P. Ding. R. and the Alberta Energy Research Institute. could be correlated with the corresponding riser pilot plant results. S.H. irrespective of reactor types and catalysts used. respectively. . 01-51–01-58. F. Catal. the Canadian Program for Energy Research and Development (PERD). HRO–a bottoms-cracking catalyst containing REY zeolite and a large-pore active matrix–was more suitable than CAT-A. Acknowledgments The authors wish to thank the analytical laboratory of the National Centre for Upgrading Technology (NCUT) for its technical support. Appl. although their absolute values could be different. ! In general. ! The feed sulfur distribution in cracked products for VIR feed agreed well with those reported in the literature. Humphries. scope 01. D. pp. Ng. References [1] [2] [3] [4] [5] S. China. Aromatics concentration increased with conversion in all three liquid product fractions. In any reactor. an octane-barrel catalyst containing REUSY/ ZSM-5 zeolites and an active matrix. Yui. Wang. S.H. Y.and nitrogencontaining species. the Alberta Research Council. Yang. Ng. A 203 (2000) 23 – 36. Sasaki. Ng et al. American Institute of Chemical Engineers. Zhu. and National Natural Science Foundation of China: Beijing. The observed changes in sulfur and nitrogen with conversion were the net results from the reaction balances involving sulfur. fixed-bed MAT gave higher conversion than fluid-bed MAT for all feeds except at low C/O for the low-MCR feeds. Proceedings of the Third Joint China/USA Chemical Engineering Conference. ! At a given C/O ratio. / Fuel Processing Technology 86 (2005) 1335–1350 1349 4. Energy Fuels 18 (1) (2004) 160 – 171. 2000. Fairbridge. Haas. Y. sulfur.

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