Reaction Kinetics, Mechanisms and Catalysis

, Volume 114, Issue 2, pp 639–660 | Cite as

Hydrogenation of pinene on spent fluid cracking catalyst supported nickel: Langmuir–Hinshelwood kinetic modelling

  • Linlin Wang
  • Huiqing Guo
  • Xiaopeng Chen
  • Yingying Huang
  • Pengpeng Zhang
Article
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Accepted:

Abstract

The kinetics for the pinene hydrogenation to pinane, the transformation of renewable biomass to useful chemicals, using spent fluid catalytic cracking catalyst (SFCC) supported nickel (Ni/SFCC), has been extensively investigated without any organic solvent, in the temperature range 373–393 K and the hydrogen pressure of 2–6 MPa in the absence of diffusional limitation. The non-noble metal catalyst was synthesized by incipient wet impregnation method and characterized by SEM, XPS and ICP. The catalytic effects of various parameters (catalyst weight, temperature and hydrogen pressure) on the reaction were reported, and the novel catalyst exhibited good activity. 17 kinds of Langmuir–Hinshelwood surface reaction mechanisms for the hydrogenation of pinene were proposed and derived. The best model described the experimental data with physically meaningful parameters was obtained by parameter diagnostics and a non-linear regression analysis, in which the surface reaction of adsorbed hydrogen atoms and pinene molecules over nickel catalyst was the rate-controlling step during the entire hydrogenation process. The activation energy of pinene surface hydrogenation to pinane was 118 ± 2.61 kJ mol−1 calculated from the Arrhenius plot.

Keywords

Spent FCC Pinene Supported Ni catalysts Langmuir–Hinshelwood model Kinetics 

Abbreviations

a

Constant

A

Pinene

b

Constant

bi

Apparent adsorption equilibrium constant of component i, L mol−1

c

Constant

CA0

Initial concentration of pinene, mol L−1

Ci

Concentration of component i, mol L−1

C1, C2

Intrinsic parameters

D

Pinane

F

F-test function

Ft

Tabled values of F-test

H

Hydrogen

k

Reaction rate constant, min−1

K

Equilibrium constant of surface reaction

PH

The pressure of hydrogen, MPa

r

Rate of reaction, mol min−1 L−1

X

The conversion of pinene

Greek letters

αH

The apparent solubility coefficient of hydrogen in pinene, mol L−1 MPa−1

θi

Fraction of vacant active sites of various type of component i

θv

Fraction of vacant active sites of nickel catalyst

ρ2

Correlation coefficient of model

*

Active nickel site

Subscripts

i

Component in the mixture

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Notes

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant No. 31060102), the Guangxi Natural Science Foundation (Grant Nos. 2014GXNSFDA118010 and 2013GXNSFAA0190507), and the Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology.

References

  1. 1.
    Piang-Siong W, Pascale DC, Corinne LD, Alain SCS, William H (2012) Ind Crops Prod 35:203–210CrossRefGoogle Scholar
  2. 2.
    Liao YH, Liu QY, Wang TJ, Long JX, Ma LL, Zhang Q (2014) Green Chem 16:3305–3312CrossRefGoogle Scholar
  3. 3.
    Corma A, Huber GW, Sauvanaud L, Connor PO (2007) J Catal 247:307–327CrossRefGoogle Scholar
  4. 4.
    Pakdel H, Sarron S, Roy C (2001) J Agric Food Chem 49:4337–4341CrossRefGoogle Scholar
  5. 5.
    Yang GD, Liu Y, Zhou Z, Zhang ZB (2011) Chem Eng J 168:351–358CrossRefGoogle Scholar
  6. 6.
    Ko SH, Chou TC, Yang TJ (1995) Ind Eng Chem Res 34:457–467CrossRefGoogle Scholar
  7. 7.
    Chouchi D, Gourgouillon D, Courel M, Vital J, Nunes da Ponte M (2001) Ind Eng Chem Res 40:2551–2554CrossRefGoogle Scholar
  8. 8.
    Casella ML, Santori GF, Moglioni A, Vetere V, Ruggera JF, Iglesias GM, Ferretti OA (2007) Appl Catal A: Gen 318:1–8CrossRefGoogle Scholar
  9. 9.
    Milewska A, Banet Osuna AM, Fonseca IM, Nunes da Ponte M (2005) Green Chem 7:726–732CrossRefGoogle Scholar
  10. 10.
    Simakova IL, Solkina Y, Deliy I, Warna J, Murzin DY (2009) Appl Catal A: Gen 356:216–224CrossRefGoogle Scholar
  11. 11.
    Deliy I, Simakova I (2008) Russ Chem Bull 57:2056–2064CrossRefGoogle Scholar
  12. 12.
    Behera B, Ray S, Siddhart S (2009) Catal Today 141:195–204CrossRefGoogle Scholar
  13. 13.
    Gonzalez MR, Pereyra AM, Torres Sánchez RM, Basaldella EI (2013) J Colloid Interf Sci 48:21–24CrossRefGoogle Scholar
  14. 14.
    Psarras AC, Iliopoulou EF, Kostaras K, Lappas AA, Pouwels C (2009) Microporous Mesoporous Mater 120:141–146CrossRefGoogle Scholar
  15. 15.
    Al-Jabri K, Baawain M, Taha R, SAl-Kamyani Z, Al-Shamsi K, Ishtieh A (2013) Constr Build Mater 39:77–81CrossRefGoogle Scholar
  16. 16.
    Okatsu H, Morrill MR, Shou H, Barton DG, Ferrari D, Davis RJ, Agrawal PK, Jones CW (2014) Catal Lett 144:825–830CrossRefGoogle Scholar
  17. 17.
    Gryglewicz S, Śliwak A, Ćwikła J, Gryglewicz G (2014) Catal Lett 144:62–69CrossRefGoogle Scholar
  18. 18.
    Todic B, Bhatelia T, Froment GF, Ma MP, Jacobs J, Davis BH, Bukur DB (2013) Ind Eng Chem Res 52:669–679CrossRefGoogle Scholar
  19. 19.
    Wang LL, Chen XP, Sun WJ, Liang JZ, Xu X, Tong ZF (2013) Ind Crops Prod 49:1–9CrossRefGoogle Scholar
  20. 20.
    Torras-Claveria L, Berkov S, Codina C, Viladomat F, Bastida J (2014) Ind Crops Prod 56:211–222CrossRefGoogle Scholar
  21. 21.
    Ruppert AM, Niewiadomski M, Grams J, Kwapinski W (2014) Appl Catal B 145:85–90CrossRefGoogle Scholar
  22. 22.
    Yang M, Ling Q, Rao RC, Yang HX, Zhang QY, Liu HD, Zhang AM (2013) J Mol Catal A: Chem 380:61–69CrossRefGoogle Scholar
  23. 23.
    Gupta A, Buddie Mullins C, Goodenough JB (2013) J Power Sources 243:817–821CrossRefGoogle Scholar
  24. 24.
    Gao HP, Tian JJ, Kong H, Yang PX, Zhang WF, Chu JH (2013) Surf Coat Tech 228:162–166CrossRefGoogle Scholar
  25. 25.
    Ko SH, Chou TC (1993) Ind Eng Chem Res 32:1579–1587CrossRefGoogle Scholar
  26. 26.
    Devulapelli VG, Weng HS (2009) Catal Commun 10:1638–1642CrossRefGoogle Scholar
  27. 27.
    Borgna A, Hensen EJM, van Veen JAR, Niemantsverdriet JW (2004) J Catal 221:541–548CrossRefGoogle Scholar
  28. 28.
    Levenspiel O (1999) Chemical reaction engineering, 3rd edn. Wiley, NewYorkGoogle Scholar
  29. 29.
    Brahme PH, Doralswamy LK (1976) Ind Eng Chem Process Des Dev 15:130–137CrossRefGoogle Scholar
  30. 30.
    Logan SR (1996) Fundamentals of chemical kinetics. Addison-Wesley Longman Ltd, LondonGoogle Scholar
  31. 31.
    Twaiq F, Nasser MS, Onaizi SA (2014) Reac Kinet Mech Cat 112:477–488CrossRefGoogle Scholar
  32. 32.
    Kittrell JR, Hunter WG, Mezaki R (1966) AIChE J 12:1014–1017CrossRefGoogle Scholar
  33. 33.
    Helfferich FG (2004) Kinetics of multistep reactions. Elsevier, AmsterdamGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2015

Authors and Affiliations

  • Linlin Wang
    • 1
  • Huiqing Guo
    • 1
  • Xiaopeng Chen
    • 1
  • Yingying Huang
    • 1
  • Pengpeng Zhang
    • 1
  1. 1.School of Chemistry and Chemical EngineeringGuangxi University Key Laboratory for the Petrochemical Resources Processing and Process Intensification Technology of GuangxiNanningPeople’s Republic of China

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