Response surface statistical optimisation of zeolite-X/silica by hydrothermal synthesis

  • Philip DoumitEmail author
  • Malcolm W. Clark
  • Lachlan H. Yee
  • Andrew Rose
Chemical routes to materials


A hydrothermal alkaline synthesis of self-supporting zeolites from co-generation boiler sugar cane bagasse ash (SCBA) was measured by X-ray powder diffraction (XRD) scan yields (scan area percentages) method. A factorial design and a response surface statistical method were used to optimise the synthesis method. Temperature, NaOH concentration and aluminium/silica (Al/Si) ratio were determined to be the most influential factors in controlling zeolite-X yields, and these three variables were included in a response surface model (RSM) with a central composite design (CCD). The RSM model indicates that optimal zeolite-X formation conditions are 72.5 °C, 5 M NaOH and an Al/Si ratio of 3:5. The RSM/CCD matrix established an efficient statistical modelling of zeolite synthesis optimisation with the fewest possible number of experiments. Scanning electron microscopy examination shows that SCBA particles (20–100 µm) are covered with zeolite crystallites (0.3–0.8 µm in size) producing a self-supporting structure. XRD analyses show a dominance of zeolite-X (33.6%), with zeolite-A (4.7%), and an average Al/Si ratio of 4:5 that is close to published values. The Brunauer–Emmett–Teller (BET) apparent specific surface area measured 228 m2 g−1 (P/Po = 0.045), and ≈ 90% of the micro-porosity distribution is associated with ≈ 7 Å internal micropore, which is typical of zeolite-X. The self-supporting, composite nature and large effective grain size of the zeolites reported in this work opens a number of uses for the materials produced.



The authors are grateful for the financial support, including a PhD scholarship for P. Doumit, provided by Sugar Research Australia (SRA; formally SRDC, Sugar Research Development Corporation) via the SRDC grant SCU03. Financial support was also provided by Australian Biorefining Pty. Ltd., as an industry partner to the SRDC grant SCU03. Many thanks are also extended to the staff and students at the School of Environment Science and Engineering, Southern Cross University, who assisted in the laboratory work for data collection.


This study was funded by SRDC Grant Number SCU03.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2019_3913_MOESM1_ESM.docx (1.8 mb)
Supplementary material 1 (DOCX 1815 kb)


  1. 1.
    Deepchand K (2001) Commercial scale cogeneration of bagasse energy in Mauritius. Energy Sustain Dev 5(1):15–22Google Scholar
  2. 2.
    Payá J, Monzó J, Borrachero MV, Díaz-Pinzón L, Ordóñez LM (2002) Sugar-cane bagasse ash (SCBA): studies on its properties for reusing in concrete production. J Chem Technol Biotechnol 77(3):321–325Google Scholar
  3. 3.
    Sales A, Lima SA (2010) Use of Brazilian sugarcane bagasse ash in concrete as sand replacement. Waste Manage 30(6):1114–1122Google Scholar
  4. 4.
    Teixeira SR, Pena AFV, Miguel AG (2010) Briquetting of charcoal from sugar-cane bagasse fly ash (SCBFA) as an alternative fuel. Waste Manage (Oxford) 30(5):804–807Google Scholar
  5. 5.
    Teixeira SR, De Souza AE, De Almeida Santos GT, Vilche Peña AF, Miguel ÁG (2008) Sugarcane bagasse ash as a potential quartz replacement in red ceramic. J Am Ceram Soc 91(6):1883–1887Google Scholar
  6. 6.
    Usman A, Raji A, Hassan M, Waziri N (2014) Production and characterisation of aluminium alloy-bagasse ash composites. J Mech Civ Eng 11(4):38–44Google Scholar
  7. 7.
    Soltani N, Bahrami A, Pech-Canul MI, González LA (2015) Review on the physicochemical treatments of rice husk for production of advanced materials. Chem Eng J 264:899–935Google Scholar
  8. 8.
    Kalapathy U, Proctor A, Shultz J (2000) A simple method for production of pure silica from rice hull ash. Bioresour Technol 73(3):257–262Google Scholar
  9. 9.
    Le Blond JS, Horwell CJ, Williamson BJ, Oppenheimer C (2010) Generation of crystalline silica from sugarcane burning. J Environ Monit 12(7):1459–1470Google Scholar
  10. 10.
    Cordeiro GC, Toledo Filho RD, Tavares LM, Fairbairn EdMR (2009) Ultrafine grinding of sugar cane bagasse ash for application as pozzolanic admixture in concrete. Cem Concr Res 39(2):110–115Google Scholar
  11. 11.
    Clark MW, Despland LM, Lake NJ, Yee LH, Anstoetz M, Arif E, Parr JF, Doumit P (2017) High-efficiency cogeneration boiler bagasse-ash geochemistry and mineralogical change effects on the potential reuse in synthetic zeolites, geopolymers, cements, mortars, and concretes. Heliyon 3(4):e00294Google Scholar
  12. 12.
    Kaewamatawong T, Kawamura N, Okajima M, Sawada M, Morita T, Shimada A (2005) Acute pulmonary toxicity caused by exposure to colloidal silica: particle size dependent pathological changes in mice. Toxicol Pathol 33(7):745–751Google Scholar
  13. 13.
    Affandi S, Setyawan H, Winardi S, Purwanto A, Balgis R (2009) A facile method for production of high-purity silica xerogels from bagasse ash. Adv Powder Technol 20(5):468–472Google Scholar
  14. 14.
    Purnomo CW, Salim C, Hinode H (2012) Synthesis of pure Na–X and Na–A zeolite from bagasse fly ash. Micropor Mesopor Mat 162:6–13Google Scholar
  15. 15.
    Shah B, Tailor R, Shah A (2011) Adaptation of bagasse fly ash, a sugar industry solid waste into zeolitic material for the uptake of phenol. Environ Prog Sustain Energy 30(3):358–367Google Scholar
  16. 16.
    Deer WA, Howie RA, Zussman J (1992) An introduction to the rock forming minerals, 2nd edn. Pearson Education Limited, EssexGoogle Scholar
  17. 17.
    Deer WA, Howie RA, Zussman J (1966) An introduction to the rock forming minerals. Longman, HarlowGoogle Scholar
  18. 18.
    Baerlocher C, McCusker LB, Olson D (2007) Atlas of zeolite framework types, 6th edn. Elsevier, AmsterdamGoogle Scholar
  19. 19.
    Georgiev D, Bogdanov B, Krasimira A, Markovska I, Hristov Y (2009) Synthetic zeolites–structure, classification, current trends in zeolite synthesis review. In: Economics and society development on the base of knowledge, BulgariaGoogle Scholar
  20. 20.
    Chester A, Derouane EG (2010) Zeolite characterization and catalysis, 1st edn. Springer, BerlinGoogle Scholar
  21. 21.
    Breck DW, Eversole WG, Milton RM, Reed TB, Thomas TL (1956) Crystalline zeolites, the properties of a new synthetic zeolite, type A. J Am Chem Soc 78(23):5963–5972Google Scholar
  22. 22.
    Sherman JD (1999) Synthetic zeolites and other microporous oxide molecular sieves. In: Proceedings of the national academy of science USA, geology, mineralogy, and human welfare, Irvine, CA, vol 7, pp 3471–3478Google Scholar
  23. 23.
    Htun M, Htay M, Lwin M (2012) Preparation of Zeolite (NaX, Faujasite) from pure silica and alumina sources. In: International conference on chemical processes and environmental issues (ICCEEI’2012) July 15–16, SingaporeGoogle Scholar
  24. 24.
    Somerset V, Petrik L, Iwuoha E (2005) Alkaline hydrothermal conversion of fly ash filtrates into zeolites 2: utilization in wastewater treatment. J Environ Sci Heal A 40(8):1627–1636Google Scholar
  25. 25.
    Alberts J, Newman M, Evans D (1985) Seasonal variations of trace elements in dissolved and suspended loads for coal ash ponds and pond effluents. Water Air Soil Pollut 26(2):111–128Google Scholar
  26. 26.
    Muniz JG, Ramirez A, Robles JM, Melo P, Bocardo JC, Martinez AM (2010) Synthesis and characterization of high silica zeolites from coal fly ash (CFA): two cases of zeolite syntheses from the same waste material. Latin Am Appl Res 40:323–328Google Scholar
  27. 27.
    Prasad B, Maity S, Sangita K, Mahato AK, Mortimer RJG (2012) Studies on synthesis and characteristics of zeolite prepared from Indian fly ash. Environ Technol 33(1):37–50Google Scholar
  28. 28.
    Ahmaruzzaman M (2010) A review on the utilization of fly ash. Prog Energ Combust 36(3):327–363Google Scholar
  29. 29.
    Louis B, Ocampo F, Yun HS, Tessonnier JP, Pereira MM (2010) Hierarchical pore ZSM-5 zeolite structures: from micro- to macro-engineering of structured catalysts. Chem Eng J 161(3):397–402Google Scholar
  30. 30.
    Ocampo F, Yun HS, Pereira MM, Tessonnier JP, Louis B (2009) Design of MFI zeolite-based composites with hierarchical pore structure: a new generation of structured catalysts. Cryst Growth Des 9(8):3721–3729Google Scholar
  31. 31.
    Kovo AS (2012) Effect of temperature on the synthesis of zeolite X from ahoko Nigerian kaolin using novel metakaolinization technique. Chem Eng Commun 199(6):786–797Google Scholar
  32. 32.
    Ruen-ngam D, Rungsuk D, Apiratikul R, Pavasant P (2009) Zeolite formation from coal fly ash and its adsorption potential. J Air Waste Manage 59(10):1140–1147Google Scholar
  33. 33.
    Querol X, Alastuey A, Fernández-Turiel J, López-Soler A (1995) Synthesis of zeolites by alkaline activation of ferro-aluminous fly ash. Fuel 74(8):1226–1231Google Scholar
  34. 34.
    Pophale R, Daeyaert F, Deem MW (2013) Computational prediction of chemically synthesizable organic structure directing agents for zeolites. J Mater Chem 1(23):6750–6760Google Scholar
  35. 35.
    Itani L, Liu Y, Zhang W, Bozhilov KN, Delmotte L, Valtchev V (2009) Investigation of the physicochemical changes preceding zeolite nucleation in a sodium-rich aluminosilicate gel. J Am Chem Soc 131(29):10127–10139Google Scholar
  36. 36.
    Tarley CRT, Silveira G, dos Santos WNL, Matos GD, da Silva EGP, Bezerra MA, Miró M, Ferreira SLC (2009) Chemometric tools in electroanalytical chemistry: methods for optimization based on factorial design and response surface methodology. Microchem J 92(1):58–67Google Scholar
  37. 37.
    Ahmadi M, Vahabzadeh F, Bonakdarpour B, Mofarrah E, Mehranian M (2005) Application of the central composite design and response surface methodology to the advanced treatment of olive oil processing wastewater using Fenton’s peroxidation. J Hazard Mater 123(1–3):187–195Google Scholar
  38. 38.
    Vicente G, Coteron A, Martinez M, Aracil J (1998) Application of the factorial design of experiments and response surface methodology to optimize biodiesel production. Ind Crop Prod 8(1):29–35Google Scholar
  39. 39.
    Velmurugan R, Selvamuthukumar S (2015) Development and optimization of ifosfamide nanostructured lipid carriers for oral delivery using response surface methodology. Appl Nanosci 6:1–15Google Scholar
  40. 40.
    Dutta JR, Dutta PK, Banerjee R (2004) Optimization of culture parameters for extracellular protease production from a newly isolated Pseudomonas sp. using response surface and artificial neural network models. Process Biochem 39(12):2193–2198Google Scholar
  41. 41.
    Matlob AS, Kamarudin RA, Jubri Z, Ramli Z (2012) Response surface methodology for optimizing zeolite Na-A synthesis. Arab J Sci Eng 38(7):1713–1720Google Scholar
  42. 42.
    Musyoka NM, Petrik LF, Gitari WM, Balfour G, Hums E (2012) Optimization of hydrothermal synthesis of pure phase zeolite Na–P1 from South African coal fly ashes. J Environ Sci Health A Tox Hazard Subst Environ Eng 47(3):337–350Google Scholar
  43. 43.
    Karami D, Rohani S (2009) Synthesis of pure zeolite Y using soluble silicate, a two-level factorial experimental design. Chem Eng Process Process Intensif 48(8):1288–1292Google Scholar
  44. 44.
    Anderson M, Whitcomb P (2007) DOE Simplified: practical tools for effective experimentation, 2nd edn. CRC Press, New YorkGoogle Scholar
  45. 45.
    Aslan N (2008) Application of response surface methodology and central composite rotatable design for modeling and optimization of a multi-gravity separator for chromite concentration. Powder Technol 185(1):80–86Google Scholar
  46. 46.
    Anderson M, Whitcomb P (2005) RSM simplified: optimizing processes using response surface methods for design of experiments. Productivity Press, New YorkGoogle Scholar
  47. 47.
    Talero R, Trusilewicz L, Delgado A, Pedrajas C, Lannegrand R, Rahhal V, Mejía R, Delvasto S, Ramírez FA (2011) Comparative and semi-quantitative XRD analysis of Friedel’s salt originating from pozzolan and Portland cement. Constr Build Mater 25(5):2370–2380Google Scholar
  48. 48.
    Chipera SJ, Bish DL (2013) Fitting full X-ray diffraction patterns for quantitative analysis: a method for readily quantifying crystalline and disordered phases. Adv Mater Phys Chem 3:47–53Google Scholar
  49. 49.
    Smith F (1999) Industrial applications of X-Ray diffraction. CRC Press, New YorkGoogle Scholar
  50. 50.
    Bae YS, Yazaydin AO, Snurr RQ (2010) Evaluation of the BET method for determining surface areas of MOFs and zeolites that contain ultra-micropores. Langmuir 26(8):5475–5483Google Scholar
  51. 51.
    Genc-Fuhrman H, Bregnhoj H, McConchie D (2005) Arsenate removal from water using sand-red mud columns. Water Res 39(13):2944–2954Google Scholar
  52. 52.
    Clark MW, Munro L, Samed AJF, McConchie DM (2006) Best D Bauxsol™ based barriers for the treatment of metal contaminated ground waters. In: 5th ICEG environmental geotechnics: opportunities, challenges and responsibilities for environmental geotechnics, pp 110–117Google Scholar
  53. 53.
    Thuadaij P, Pimraksa K, Nuntiya A (2012) Synthesis of high cation exchange capacity faujasite from high calcium fly ash. Aust J Basic Appl Sci 6:194–208Google Scholar
  54. 54.
    Porcher F, Souhassou M, Dusausoy Y, Lecomte C (1999) The crystal structure of a low-silica dehydrated NaX zeolite. Eur J Mineral 11(2):333–343Google Scholar
  55. 55.
    Imaizumi K, Matsuda N, Otsuka M (2003) Coagulation/phase separation process in the silica/inorganic salt systems (1)—observation of state transformation. J Mater Sci 38(13):2979–2986. Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Environment Science and EngineeringSouthern Cross UniversityLismoreAustralia
  2. 2.Marine Ecology Research CentreSouthern Cross UniversityLismoreAustralia
  3. 3.Southern Cross GeoScienceSouthern Cross UniversityLismoreAustralia

Personalised recommendations