Role of FCC catalyst in renery protability

By switching to a rare earth-free FCC catalyst, a rener raised its output of premium grade gasoline and increased its operating margin
Ivan Chavdarov, Dicho Stratiev, Ivelina Shishkova and Rosen Dinkov Lukoil Neftohim Burgas JSC Vladimir Jegorov Grace Catalysts Technologies Petko Petkov University Prof Dr Assen Zlatarov Burgas

he FCC unit is the main contributor (RVP) of gasoline from the FCC unit correlates (51-52%) to the refinery gasoline pool of to the content of C4 hydrocarbons in the gasothe Lukoil Neftohim Burgas refinery in line, with lower RVP values obtained by Bulgaria, with the next largest contributor being producing more C4 at the expense of gasoline. the reformer (about 27%). The gasoline sensitiv- Optimising the FCC gasoline RVP during the ity (research octane number minus motor octane winter season (RVP was reduced from 60 to 50 number [RON MON]) from the FCC unit and kPa) and increasing the C4 olefins yield (leading reformer is about 12 and 11 numbers, respec- to a higher MON in alkylate production) resulted tively, resulting in an overall MON shortage in in an additional improvement in refinery the refinery gasoline pool. Considering MTBE economics by a five-figure number (US $/y). has a MON of 94-97, alkylate a MON of 93 (both of which are produced from C4 olefins) and FCC Lukoil Neftohim Burgass FCC unit gasoline a MON of about 82, increasing the Commercial investigations were carried out on production of C4 olefins at the expense of gaso- the FCC unit, which consists of a feed hydroline in the FCC unit will increase the MON of the treater section, the FCC reactor and regenerator, overall gasoline pool. as well as the main fractionator Physical and chemical properties of A catalyst selection was and vapour recovery sections. The hydrotreated vacuum gas oil feedstock performed with the objective FCC reactor is equipped with the for Lukoil Neftohim Burgas FCC unit of increasing MON. Grace modern UOP VSS riser terminaDensity at 20C, g/cm3 0.895 proposed the REsolution catation device and the UOP Optimix Sulphur content, wt% 0.3 lyst, which was trialled in the feed injection system. Typical feed Total nitrogen, wt ppm 800 FCC unit and subsequently for the FCC unit is hydrotreated Content of Ni and V, wt ppm max 1.0 Conradson carbon, wt% max 0.1 led to an increase in gasoline vacuum gas oil distilled from Refractive Index at 20C 1.4994 MON by 0.5 numbers. This Urals crude, of which the physical ASTM D 1160 distillation 5 vol% 357 allowed the refinery to and chemical properties are 10 vol% 376 increase the production of shown in Table 1. 50 vol% 438 90 vol% 509 automotive gasoline by 1.3%, 95 vol% 532 and to increase the share of Optimisation of FCC catalyst K-Factor 12.13 premium automotive gasoline technology Molecular weight (Goosens) 369 Hydrogen content (ConocoPhillips) 12.5 from 68% to 73%. This In response to rapidly inflating Aromatic carbon content resulted in an annual six-figrare earth metal prices in 2011, (ConocoPhillips) 17.02 Gasoline precursors (LNB) 79.5 ure improvement in refinery Grace developed the REpLaCeR economics. series of rare earth-free FCC cataThe Reid vapour pressure Table 1 lysts. The REsolution catalyst

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Physical and chemical properties of e-cats used in the study

E-cat properties Supplier 1 Grace Catalyst X REsolution Apparent bulk density (ABD), g/cm3 0.85 Total surface area, m2/g 159 147 Matrix surface area, m2/g 55 51 Zeolite surface area, m2/g 104 96 Particle size distribution, % 0-20 m 0.1 2 0-40 m 1.8 5 0-80 m 46 45 0-149 m 94 Average particle size, mm 83 84 Unit cell size, 24.29 24.27 Al2O3, wt% 40.5 44.2 RE2O3, wt% 1.35 0.38 Na2O, wt% 1.15 0.28 Fe, wt% 0.61 0.42 V, wt ppm 206 208 Ni, wt ppm 25 63 Cu, wt ppm 25 8

Yield structure in Lukoil Neftohim Burgass FCC unit

Product, wt% Supplier 1 Grace Catalyst X REsolution Dry gas (C2-) 3.8 3.5 Total C3s 8.0 8.2 Total C4s 14.0 13.8 Gasoline (C5-195C) 51.1 51.2 LCO (195-296C) 9.8 10.3 HCO (296-360C) & slurry 9.0 8.9 Coke 4.3 4.1 Conversion 81.2 80.8

Table 4

tional rare earth based catalysts. To date, there have been more than 15 successful applications of the REsolution catalyst in the EMEA region. Based on laboratory, pilot plant and commercial data Table 2 using Catalyst X from Supplier 1, Lukoil Neftohim Burgas switched to the Grace Operating conditions in Lukoil Neftohim Burgass FCC unit REsolution catalyst in 2011, with the objective of increasing Operating conditions Supplier 1 Grace the FCC gasoline MON. As Catalyst X REsolution Flow rates Table 2 shows, the REsolution Hydrotreated feed, t/h 220 229 catalyst differs significantly Unhydrotreated feed, t/h 11 7 from the previous catalyst, Recycle, t/h 2 5 primarily in terms of rare earth Dispersion steam, kg/h 3000 3435 Riser steam, kg/h 2000 2000 content, which is 16 times Stripping steam, kg/h 5881 6200 lower than in the catalyst from 3 Air ow rate, kNm /h 134 118 Supplier 1. Even though Fresh catalyst ow, t/d 2 2 REsolution is a rare earth-free Catalyst to oil ratio 8.1 7.9 Temperatures, C catalyst, the e-cat still contains Combined feed temperature 317 331 a small amount of rare earth, Riser temperature 535 533 as the inventory was not 100% Regenerator dense phase temperature 668 668 changed out. Typical FCC unit Regenerator dilute phase temperature 678 677 Air temperature 179 184 operating conditions from periSteam temperature 262 247 ods using Catalyst X and the Grace catalyst are shown in Table 3 Table 3. Table 4 shows the yield strucbelongs to this series and is based on the rare ture for FCC products obtained using Catalyst X earth-free Z-21 zeolite. Within each family of and the REsolution catalyst. The slightly higher REsolution catalysts, the ability to inde- conversion obtained with Catalyst X is due to the pendently adjust the activity and selectivities of higher catalyst to oil ratio resulting from the zeolite and matrix, as well as the ratio of higher outlet temperature and lower feed zeolite/matrix activity, enables maximum temperature used in this period. The catalyst formulation flexibility. For low metal applica- consumption rate was the same for both tions, REsolution catalysts are proven to match, catalysts, at 0.350 kg catalyst addition per ton and even improve on, the performance of tradi- of feedstock. Generally, both catalysts

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displayed very similar product Product properties in Lukoil Regular A-92 Premium A-95 selectivities. Neftohim Burgass FCC unit Super A-98 Gasoline A-93 Table 5 shows the FCC product properties from Lukoil Product, wt% Supplier 1 Grace Catalyst X Catalyst X REsolution Neftohim Burgas. Compared to 2% Gasoline Catalyst X, the REsolution cata29% MON 81.7 82.2 RON 94.0 94.0 lyst provided FCC gasoline with RVP, kPa 55.1 57.9 an increased MON of 0.5 FIA hydrocarbon numbers. This can be explained Composition, vol% Saturates 37.8 41.7 with the increased aromatics in 1% Olens 39.2 32.5 68% gasoline. It is well known that Aromatics 23.0 25.8 C3s, wt%: increased hydrogen transfer Propylene 80.8 78.8 activity results in the increased Propane 17.9 20.9 REsolution C4s, wt%: conversion of olefins and naph2% i-butane 33.5 39.5 thenes to paraffins and 25% i-butylene 17.3 16.0 aromatics. Conventional undern-butane 6.7 7.6 Total olens 56.3 53.3 standing of typical FCC catalysts would explain that a lower rare Table 5 earth content and smaller unit 73% cell size (as found in the REsolution catalyst) should Based on operational data result in decreased hydrogen from the FCC unit, the economic transfer activity. However, the Figure 1 Renery gasoline grades efficiency of using both catalysts data shown in Table 5 demon- produced by Lukoil Neftohim Burgas from different suppliers was strate that the REsolution using Catalyst X and the REsolution determined by applying a refinery model, which uses software catalyst displayed higher hydro- catalyst for linear programming by gen transfer activity, resulting in a lower olefin content of FCC gasoline, as well as Honeywell (RPMS). The results from RPMS the C4 and C3 fractions. This is due to the Z-21 demonstrate that replacing Catalyst X with the Grace catalyst results in an increased profit of technology utilised in this catalyst. Figure 1 shows how the proportion of different 4% for the overall oil refining operations of grades of automotive gasoline within the gaso- Lukoil Neftohim Burgas. This demonstrates the line pool changed when switching from Catalyst important role that the FCC catalyst plays in X to the REsolution catalyst. The REsolution refining operations profitability. catalyst increased the proportion of premium gasoline A-95 from 68% to 73% at the expense Optimisation of FCC gasoline Reid vapour pressure of the regular grade. Figure 2 highlights the structure of the gaso- A significant parameter of FCC gasoline is Reid line pool using Catalyst X and the REsolution Vapor Pressure (RVP),1 which increases linearly catalyst. Catalyst X produced FCC gasoline with with an increasing amount of C4 components. a RON of 94 and a MON of 81.7, resulting in a Lukoil Neftohim Burgas performed a commergasoline pool with a RON of 95 and a MON of cial test operating with two different RVP values 84.2, which complies with the requirements of of FCC gasoline. Table 6 shows how the yield of standard EN228:2012 for RON but not MON. FCC products changed when switching from an Switching to the REsolution catalyst increased RVP of 60 kPa to 50 kPa, with the yield of C4s the MON of FCC gasoline from 81.7 to 82.2, increasing by 0.6 wt% at the equal expense of resulting in a final MON of 84.5 for the gasoline gasoline. The effect of operating with two different RVP pool with the RON unchanged. Since FCC gasoline accounts for the majority of the gasoline values on the refinery gasoline grades produced pool (over 50 vol%), the FCC catalyst clearly has is shown in Figure 3. The total amount of autoa significant impact on the octane number of the motive gasoline produced by the refinery decreased by 0.18 wt%, while overall LPG total gasoline pool.

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Regular A-92

Catalyst X
1.9 vol%; RON 94.0; MON 81.7 51.7 vol% RON 93.1 MON 81.7 53.6 vol% RON 94.0

REsolution
7.0 vol%; RON 94.0; MON 82.2 51.7 vol% RON 94.0 44.7 vol% RON 93.1

Premium A-95 Super A-98

RVP = 60kPa
1% 28%

MON 82.2 Prime-G MON 82.2 Prime-G MON 81.7 FCC gasoline unit unit 27.7 vol%; RON 99.9; MON 89.0

26.7 vol%; RON 99.9; MON 89.0

Reformate

11.1 vol%; RON 97.2; MON 93.2

Alkylate

10.9 vol%; RON 96.8; MON 93.1

71%

4.2 vol%; RON 63.2; MON 60.2

Straight-run naphtha

5.1 vol%; RON 63.2; MON 60.2

RVP = 50kPa
1% 26%

4.4 vol%; RON 112.0; MON 93.0

Methyl tertiary 4.2 vol%; RON 118.0; MON 94.0 butyl ether
0.1 vol%; RON 108.0; MON 93.0

0.01 vol%; RON 108.0; MON 93.0

Bioethanol

Gasoline pool RON 95.0 MON 84.2

Gasoline pool RON 95.0 MON 84.5

73%

Figure 2 Structure of gasoline pool at Lukoil Neftohim Burgas using Catalyst X and the REsolution catalyst

Figure 3 Effect of changing the RVP on renery gasoline grades produced during the Resolution catalyst period

production increased by 3.7 wt%. This resulted in an increase of Premium A-95 production from 71% to 73% at the expense of the Regular A-92 grade. Reducing the RVP from 60 kPa to 50 kPa improved refinery profitability by about 2.5%.

higher production of alkylate, which resulted in the production of 2% more premium grade gasoline.
References 1 Watanbe K, Nagai K, Aratani N, Saka Y, Chiyoda N, Mizutani H, Techniques for octane enhancement in FCC gasoline, 20th Annual Saudi-Japan Symposium, Dhahran, December 2010. 17. Montgomery J A, Guide to Fluid Catalytic Cracking, Part 1, 1993. Ivan Chavdarov is a Chemical Engineer in the Process Engineering department of Lukoil Neftohim Burgas, Bulgaria. His activities are focused on guiding the operation of the units of the FCC complex, troubleshooting support and optimisation of the performance of the FCC complex. Email: Chavdarov.Ivan.S@neftochim.bg Dicho Stratiev is Chief Process Engineer with Lukoil Neftohim Burgas. He holds a MS in organic chemistry engineering, and a PhD and a DSc in petroleum rening from the Burgas University Assen Zlatarov. He has authored more than 130 papers. Email: Stratiev.Dicho@neftochim.bg Ivelina Shishkova is R&D Department Manager with Lukoil Neftohim Burgas.

Summary

It has been demonstrated that the FCC catalyst is an excellent tool for improving overall refinery profitability. Optimising FCC technology by switching to the Grace REsolution catalyst led to an FCC yields at different gasoline increase in the FCC gasoline RVP values MON by 0.5 points, which allowed the refinery to produce Product, wt% RVP 5% more premium grade 60 kPa 50 kPa Dry gas 5.32 5.30 gasoline. C s 7.10 7.15 3 The overall refinery margin C4s 12.65 13.25 was improved further by optiGasoline 50.61 50.01 misation of the FCC gasoline LCO 11.01 11.04 HCO 5.10 4.92 RVP. A reduction in the RVP Slurry 4.00 4.10 from 60 to 50 kPa resulted in Coke 4.21 4.23 an increase in LPG production Conversion 79.89 79.94 by 3.7% at the expense of gasoline pool reduction. The higher FCC C4 yield led to Table 6

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She holds a MS in organic chemistry engineering and a PhD in petroleum rening from Soa Chemical and Technological and Metallurgical University, and has authored more than 20 technical papers. Email: Shishkova.Ivelina.K@neftochim.bg Rosen Dinkov is the Quality Manager in the Process Engineering department of Lukoil Neftohim Burgas. His research interests include crude oil characterisation, bio/conventional fuels blends characterisation and modelling of renery distillation processes. He holds a MS in organic chemistry engineering from Burgas University and a PhD in the technology of fossil and synthetic fuels from the University of Chemical Technology and Metallurgy, Soa. Email: Dinkov.Rosen.K@neftochim.bg Vladimir Jegorov is the Sales Development Manager for Grace in the CIS region. Prior to joining Grace, he was an FCC process engineer at the Mazheikiai renery in Lithuania.

Petko Petkov is a full professor and rector of the Burgas University Assen Zlatarov. He teaches in the social science department in the eld of oil rening and lubricants, and has authored more than 180 scientic papers and ve books. Email: PST_Petkov@abv.bg

LINKS
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