A novel fluid catalytic cracking process for maximizing iso-paraffins: From fundamentals to commercialization

Abstract

The maximizing iso-paraffins (MIP) developed by RIPP has improved gasoline quality to meet the demand of motor gasoline specification. A concept that two different reaction zones include cracking zone and conversion zone is proposed as the fundamental of MIP by research on fluid catalytic cracking (FCC) reaction chemistry. Based on the concept, the MIP process is featured by applying a novel sequential two-zone riser in conjunction with proprietary catalyst and engineering technique. The developed MIP process can not only improve gasoline yield or gasoline plus propylene yields but also produce gasoline with a higher content of iso-paraffins and a lower content of sulfur. A minimum octane number loss is achieved when MIP gasoline is treated by downstream desulfurization technology (RSDS/S Zorb). The combination of MIP and RSDS/S Zorb processes creates a very competitive route, which is different from the technical route used by other developed countries, to upgrade the quality of motor gasoline with the lowest economic costs in China. In just one decade, the processing capacity of MIP units has accounted for about 60% of the domestic total processing capacity of FCC units. The MIP process is gradually becoming a new generation of FCC technology.

Key words： gasoline; iso-paraffins; FCC; desulfurization; octane number

References

1 Flank W H, Abraham  M A, Matthews  M A. In Innovations in Industrial and Engineering Chemistry. Washington DC: American Chemical Society, 2008, 189–249

2 Sadeghbeigi R. Fluid Catalytic Cracking Handbook. 3th ed. Waltham: Elsevier Inc, 2012, 2–3

3 Bos A N R,  Tromp P J J,  Akse H N. Conversion of methanol to lower olefins. Kinetic modeling, reactor simulation and selection. Industrial & Engineering Chemistry Research, 1998, 34(11): 3808–3816

4 Dharia D, Lomg  J, Xu Y H,  Zhang J S,  Batachari A,  Yuan E, Gim  S, Xu S. Consider new processes for clean gasoline and olefins production. Hydrocarbon Processing, 2011, 9: 85–90

5 Chen J W, Xu  Y H. Catalytic Cracking Processing and Engineering. 3th ed. Beijing: Sinopec Press, 2015, 64–69 (in Chinese)

6 Xu Y H, Zhang  J S, Long  J. A modified FCC process MIP for maximizing iso-paraffins in cracked naphtha. Petroleum Processing and Petrochemicals, 2001, 32(8): 1–5 (in Chinese)

7 Xu Y H, Zhang  J S, Long  J, He M Y,  Xu H, Hao  X R. Development and commercial application of FCC process for maximizing iso-paraffins (MIP) in cracked naphtha. Engineering and Science, 2003, 5(5): 55–58 (in Chinese)

8 Scherzer J. Ocatne-enhancing, zeolitic FCC catalysts: Scientific and technical aspects. Catalysis Reviews. Science and Engineering, 1989, 31(3): 215–354

9 Xu Y H. Study on the effect of hydrogen transfer reaction on olefin conversion. Petroleum Processing and Petrochemicals, 2002, 33(1): 38–41 (in Chinese)

10 Tao L X. Hydride transfer reaction in catalytic reaction. Acta Petrolei Sinica, 2008, 24(4): 365–369 (Petroleum Processing Section)

11 Rochettes B M D,  Marcilly C,  Gueguen C,  Bousquet J. Kinetic study of hydrogen transfer of olefins under catalytic cracking conditions. Applied Catalysis, 1990, 58(1): 35–52

12 Guisnet M, Gnep  N S. Mechanism of short-chain alkane transformation over protonic zeolites. Alkylation, disproportionation and aromatization. Applied Catalysis A, General, 1996, 146(1): 33–64

13 Boronat M, Corma  A. Are carbenium and carbonium ions reaction intermediates in zeolite-catalyzed reactions? Applied Catalysis A, General, 2008, 336(1-2): 2–10

14 Xu Y H, Zhang  J S, Ma  J G, Long  J. Controllability of cracking reaction in MIP process. Acta Petrolei Sinica, 2004, 20(3): 1–6

15 Jiang W B, Long  J, Chen B Y,  He M Y. Development of RMI cracking catalyst tailored for MIP technology processing paraffin base feedstock. Petroleum Processing and Petrochemicals, 2004, 35(12): 8–12 (in Chinese)

16 Gong J H, Xu  Y H, Xie  C G, Long  J, Jiang W B,  Qiu Z H. Development of MIP technology and its proprietary catalysts. . China Petroleum Processing and Petrochemical Technology, 2009, 2: 1–8

17 Tammera R F, Jones  E N, Smalley  C G, Deis  P A, Chen  A U, Gurciullo  C S. FCC reactor and riser design for short contact-time catalytic cracking of hydrocarbons. US Patent, 9358516, 2016-07-06

18 Yan J S, Long  J, Tian H P. Microstructure analysis of alumina sol and acidified pseudoboehmite. Petroleum Processing and Petrochemicals, 2004, 35(12): 33–36 (in Chinese)

19 Song H T, Da  Z J, Zhu  Y X, Tian  H P. Effect of coke deposition on the remaining activity of FCC catalysts during gas oil and residue cracking. Catalysis Communications, 2011, 16(1): 70–74

20 Song H T, Jiang  W B, Da  Z J. Reaction behaviors of normal hydrocarbons over FCC catalyst matrices. Acta Petrolei Sinica, 2003, 19(3): 14–19 (in Chinese)

21 Shen N Y, Chen  B Y, Song  H T, Jiang  W B. Development of RMI-II catalyst tailored for MIP technology processing intermediate base feedstock. Petroleum Processing and Petrochemicals, 2006, 37(9): 1–5 (in Chinese)

22 Yang J, Xie  X D, Cai  Z, Xu Y H. Commercial trial of MIP-CGP process. Petroleum Processing and Petrochemicals, 2006, 37(8): 54–59 (in Chinese)

23 Xu Y H, Zhang  J S, Xu  H, Hao X R. Commercial application of a novel FCC process for maximizing iso-paraffins in cracked naphtha. Petroleum Processing and Petrochemicals, 2003, 34(11): 1–6 (in Chinese)

24 Xu Y H. Advance in China fluid catalytic cracking (FCC) process. Scientia Sinica (Chimica), 2014, 44(1): 13–24 (in Chinese) 

25 Xu Y H. Chemistry & Process of Catalytic Cracking. Beijing: China Science Press, 2013, 277–279 (in Chinese)

26 Xu Y H, Qu  J H, Yang  Y T, Xu  L. Analysis of octane number and composition characteristics of MIP naphtha. Petroleum Processing and Petrochemicals, 2009, 40(1): 10–14 (in Chinese)