Skip to main content
SpringerLink
Log in

Prins condensation for the synthesis of isoprene from isobutylene and formaldehyde over sillica-supported H3SiW12O40 catalysts

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

The Prins condensation of isobutylene with formaldehyde over scillica-supported silicotungstic acid catalysts has been investigated. The catalysts were characterized via XRD, FTIR, Py-IR, NH3-TPD and TG–DSC techniques. It was found that the catalyst with 5 wt% silicotungstic acids loading exhibited the best isobutene conversion and isoprene selectivity, and excessive silicotungstic acid was not conducive to improve the catalytic performance. It was proposed that the concentration and strength of acid sites could affect the catalytic properties. An appropriate amount of weak Lewis acid sites were the active site for the condensation of isobutene with formaldehyde, and the medium-strong acid sites could cause the side reactions and coke deposits.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Dang Z, Gu J, Yu L, Zhang C (1991) Vapor-phase synthesis of isoprene from formaldehyde and isobutylene over CuSO4–MOx/SiO2 catalysts. Reac Kinet Mech Cat 43:495–500

    Article  CAS  Google Scholar 

  2. Hamamoto Y, Mitsutani A (1965) Method of producing conjugated diolefins. US Patent 3 221 075

  3. Mitsntani A (1966) Process for the manufacture of isoprene and isobutene. US Patent 3 284 533

  4. Krzywicki A, Wilanowicz T, Malinowski S (1979) Catalytic and physico-chemical properties of the Al2O3–H3PO4 system, I. Vapor phase condensation of isobutylene and formaldehyde—the Prins reaction. React Kinet Catal Lett 11:399–403

    Article  CAS  Google Scholar 

  5. Dang Z, Ding S (1987) Investigation of the surface characteristics and catalytic activity of SbxOy/SiO2 catalysts for vapor-phase synthesis of isoprene from isobutylene and formaldehyde. J Mol Catal, in Chinese 3:146–152

    Google Scholar 

  6. Dumitriu E, Gongescu D, Hulea V (1993) Contribution to the study of isobutene condensation with formaldehyde catalyzed by zeolites. Heterog Catal Fine Chem III:669–676

    Google Scholar 

  7. Dumitriu E, Hulea V, Chelaru C, Hulea T (1994) Selective synthesis of isoprene by Prins condensation using molecular sieves. Zeolites Relat Microporous Mater 84:1997–2004

    CAS  Google Scholar 

  8. Dumitriu E, On DT, Kaliaguine S (1997) Isoprene by Prins condensation over acidic molecular sieves. J Catal 170:150–160

    Article  CAS  Google Scholar 

  9. Dumitriu E, Hulea V, Fechete I (1999) Prins condensation of isobutylene and formaldehyde over Fe-silicates of MFI structure. Appl Catal A 181:15–28

    Article  CAS  Google Scholar 

  10. Sushkevich VL, Ordomsky VV, Ivanova II (2012) Synthesis of isoprene from formaldehyde and isobutene over phosphate catalysts. Appl Catal A 441–442:21–29

    Article  Google Scholar 

  11. Ivanova I, Sushkevich VL, Kolyagin YG, Ordomsky VV (2013) Catalysis by coke deposits: synthesis of isoprene over solid catalysts. Angew Chem 125:13199–13202

    Article  Google Scholar 

  12. Jin D, Hou Z, Luo Y, Zheng X (2006) Synthesis of dimethyldiphenylmethane over supported 12-tungstophosphoric acid (H3PW12O40). J Mol Catal A 243:233–238

    Article  CAS  Google Scholar 

  13. Alsalme AM, Wiper PV, Khimyak YZ, Kozhevnikova EF, Kozhevnikov IV (2010) Solid acid catalysts based on H3PW12O40 heteropoly acid: acid and catalytic properties at a gas–solid interface. J Catal 276:181–189

    Article  CAS  Google Scholar 

  14. Ning L, Ding Y, Chen W (2008) Glycerol dehydration to acrolein over activated carbon-supported silicotungstic acids. Chin J Catal 29:212–214

    Article  CAS  Google Scholar 

  15. Zhu WC, Wang LX, Liu SY, Wang Z (2008) Characterization and catalytic behavior of silica-supported copper catalysts prepared by impregnation and ion-exchange methods. React Kinet Catal Lett 93:93–99

    Article  CAS  Google Scholar 

  16. Wang LX, Zhu WC, Zheng DF (2010) Direct transformation of ethanol to ethyl acetate on Cu/ZrO2 catalyst. Reac Kinet Mech Cat 101:365–375

    Article  CAS  Google Scholar 

  17. Zhu X, Li X, Jia M, Liu G, Zhang W, Jiang D (2005) Vapour-phase selective O-methylation of catechol with methanol over Ti-containing aluminium phosphate catalysts. Appl Catal A 282:155–161

    Article  CAS  Google Scholar 

  18. Su WG, Wang SG, Ying PL, Feng ZC, Li C (2009) A molecular insight into propylene epoxidation on Cu/SiO2 catalysts using O2 as oxidant. J Catal 268:165–174

    Article  CAS  Google Scholar 

  19. Miyaji A, Echizen T, Nagata K, Yoshinaga Y, Okuhara T (2003) Selective hydroisomerization of n-pentane to isopentane over highly dispersed Pd-H4SiW12O40/SiO2. J Mol Catal A 201:145–153

    Article  CAS  Google Scholar 

  20. Zhao L, Zhao Y, Wang S (2012) Hydrogenation of dimethyl oxalate using extruded Cu/SiO2 catalysts: mechanical strength and catalytic performance. Ind Eng Chem Res 51:13935–13943

    Article  CAS  Google Scholar 

  21. Shen L, Feng Y, Yin H (2011) Gas phase dehydration of glycerol catalyzed by rutile TiO2-supported heteropolyacids. J Ind Eng Chem 17:484–492

    Article  CAS  Google Scholar 

  22. Zhu S, Zhu Y, Gao X, Mo T, Zhu Y, Li Y (2013) Production of bioadditives from glycerol esterification over zirconia supported heteropolyacids. Bioresour Technol 130:45–51

    Article  CAS  Google Scholar 

  23. Chen LF, Noreña LE, Navarrete J, Wang JA (2006) Improvement of surface acidity and structural regularity of Zr-modified mesoporous MCM-41. Mater Chem Phys 97:236–242

    Article  CAS  Google Scholar 

  24. Zhang YQ, Wang SJ, Wang JW, Lou LL, Zhang C, Liu SX (2009) Synthesis and characterization of Zr-SBA-15 supported tungsten oxide as a new mesoporous solid acid. Solid State Sci 11:1412–1418

    Article  CAS  Google Scholar 

  25. Jia AZ, Li J, Zhang YQ, Song YJ, Liu SX (2008) Synthesis and characterization of nanosized micro-mesoporous Zr–SiO2 via ionic liquid templating. Mater Sci Eng, C 28:1217–1226

    Article  CAS  Google Scholar 

  26. Atia H, Armbruster U, Martin A (2008) Dehydration of glycerol in gas phase using heteropolyacid catalysts as active compounds. J Catal 258:71–82

    Article  CAS  Google Scholar 

  27. Zhou W, Cao M, Su S (2013) A newly-designed polyoxometalate-based plasmonic visible-light catalyst for the photodegradation of methyl blue. J Mol Catal A 371:70–76

    Article  CAS  Google Scholar 

  28. Hutchings GJ, Hudson ID, Bethella D, Timms DG (1999) Novel synthesis of isoprene from 3-methylbutan-2-one using phosphate catalysts. Chem Commun 16:1489–1490

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21473074), the Natural Science Foundation of Science and Technology Department of Jilin Province (20130101015JC), Jilin Province Science and Technology research plan (key scientific research project). (No.: 20150204020GX).

Author information

Authors and Affiliations

  1. Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Jiefang Road 2519, Changchun, 130021, People’s Republic of China

    Xue Yu, Wanchun Zhu, Qiang Bao, Dongdong Cheng, Yanyang Xia, Zhenlu Wang & Wenxiang zhang

  2. Jilin Institute of Chemical Technology, Jilin, 132022, People’s Republic of China

    Xue Yu

  3. First Hospital of Jilin University, Changchun, 130021, People’s Republic of China

    Shubo Zhai

Authors
  1. Xue Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wanchun Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shubo Zhai
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Qiang Bao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dongdong Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yanyang Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhenlu Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Wenxiang zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Zhenlu Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yu, X., Zhu, W., Zhai, S. et al. Prins condensation for the synthesis of isoprene from isobutylene and formaldehyde over sillica-supported H3SiW12O40 catalysts. Reac Kinet Mech Cat 117, 761–771 (2016). https://doi.org/10.1007/s11144-015-0946-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-015-0946-9

Keywords

Search

Navigation