Journal of Materials Science

, Volume 50, Issue 23, pp 7568–7582 | Cite as

Conversion of waste animal bones into porous hydroxyapatite by alkaline treatment: effect of the impregnation ratio and investigation of the activation mechanism

  • Unai Iriarte-Velasco
  • Irene Sierra
  • Lorena Zudaire
  • Jose L. Ayastuy
Original Paper


Microporous biochars, mainly composed by hydroxyapatite (HAp), were prepared from animal waste bones. In this study, a three-step procedure including pre-pyrolysis, chemical treatment with NaOH, KOH and K2CO3, and pyrolysis was investigated. The effects of the activation agent and its concentration were analysed by N2 adsorption–desorption, SEM, EDX, FTIR, and XRD techniques. The activation mechanism was investigated by TG-MS. FTIR and XRD data confirm that the obtained biochars were mainly composed of HAp. K2CO3 was the most effective with porosity being increased by 30 % (up to 234 m2/g) compared to non-alkali-treated sample. New pores were generated mainly in the microporous range. Analysis of the pyrolysis gases by MS revealed that the main effect of the alkali treatment is the incorporation of OH ions, which then react with bone matrix to generate porosity. Other gas-phase reactions, such as reverse WGS and methanation reactions, promoted by K2CO3, may be involved in the activation process. In contrast, KOH caused little modification of the HAp structure. Statistical analysis supported the relationship among the release of certain compounds during pyrolysis and the textural properties of the final material.


Gasification K2CO3 Textural Property Impregnation Ratio Bone Char 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors wish to thank the Basque Government (UFI 11/39 (UPV/EHU) and S-PE13UN100 (SAI13/254)) for their financial support.

Supplementary material

10853_2015_9312_MOESM1_ESM.doc (100 kb)
Supplementary material 1 (DOC 100 kb)


  1. 1.
    Yan Y, Dong X, Sun X et al (2014) Conversion of waste FGD gypsum into hydroxyapatite for removal of Pb2+ and Cd2+ from wastewater. J Colloid Interface Sci 429:68–76CrossRefGoogle Scholar
  2. 2.
    Goodman PA, Li H, Gao Y et al (2013) Preparation and characterization of high surface area, high porosity carbon monoliths from pyrolyzed bovine bone and their performance as supercapacitor electrodes. Carbon 55:291–298CrossRefGoogle Scholar
  3. 3.
    Kim Y, Lee YJ (2014) Characterization of mercury sorption on hydroxylapatite: batch studies and microscopic evidence for adsorption. J Colloid Interface Sci 430:193–199CrossRefGoogle Scholar
  4. 4.
    Banat F, Al-Asheh S, Mohai F (2000) Batch zinc removal from aqueous solution using dried animal bones. Sep Purif Technol 21:155–164CrossRefGoogle Scholar
  5. 5.
    Rezaee A, Rangkooy H, Jonidi-Jafari A et al (2013) Surface modification of bone char for removal of formaldehyde from air. Appl Surf Sci 286:235–239CrossRefGoogle Scholar
  6. 6.
    Chakraborty R, RoyChowdhury D (2013) Fish bone derived natural hydroxyapatite-supported copper acid catalyst: Taguchi optimization of semibatch oleic acid esterification. Chem Eng J 215–216:491–499CrossRefGoogle Scholar
  7. 7.
    Perego C, Millini R (2013) Porous materials in catalysis: challenges for mesoporous materials. Chem Soc Rev 42:3956–3976CrossRefGoogle Scholar
  8. 8.
    Cheung CW, Chan CK, Porter JF et al (2001) Combined diffusion model for the sorption of cadmium, copper, and zinc ions onto bone char. Environ Sci Technol 35:1511–1522CrossRefGoogle Scholar
  9. 9.
    Doostmohammadi A, Monshi A, Salehi R et al (2012) Preparation, chemistry and physical properties of bone-derived hydroxyapatite particles having a negative zeta potential. Mater Chem Phys 132:446–452CrossRefGoogle Scholar
  10. 10.
    Sobczak A, Kowalski Z, Wzorek Z (2009) Preparation of hydroxyapatite from animal bones. Acta Bioeng Biomech 11:23–28Google Scholar
  11. 11.
    Hassan SSM, Awwad NS, Aboterika AHA (2008) Removal of mercury(II) from wastewater using camel bone charcoal. J Hazard Mater 154:992–997CrossRefGoogle Scholar
  12. 12.
    Murillo YS, Giraldo L, Moreno JC (2011) Porous materials obtained from chicken and pork bones for the adsorption of 2,4-dinitrophenol. Afinidad 68:447–452Google Scholar
  13. 13.
    Rezaee A, Ghanizadeh G, Behzadiyannejad G et al (2009) Adsorption of endotoxin from aqueous solution using bone char. Bull Environ Contam Toxicol 82:732–737CrossRefGoogle Scholar
  14. 14.
    Moreno-Pirajan JC, Gomez-Cruz R, Garcia-Cuello VS et al (2010) Binary system Cu(II)/Pb(II) adsorption on activated carbon obtained by pyrolysis of cow bone study. J Anal Appl Pyrolysis 89:122–128CrossRefGoogle Scholar
  15. 15.
    Rojas-Mayorga CK, Silvestre-Albero J, Aguayo-Villarreal IA et al (2015) A new synthesis route for bone chars using CO2 atmosphere and their application as fluoride adsorbents. Microporous Mesoporous Mater 209:38–44CrossRefGoogle Scholar
  16. 16.
    Lillo-Ródenas MA, Cazorla-Amorós D, Linares-Solano A (2003) Understanding chemical reactions between carbons and NaOH and KOH: an insight into the chemical activation mechanism. Carbon 41:267–275CrossRefGoogle Scholar
  17. 17.
    Phan NH, Rio S, Faur C et al (2006) Production of fibrous activated carbons from natural cellulose (jute, coconut) fibers for water treatment applications. Carbon 44:2569–2577CrossRefGoogle Scholar
  18. 18.
    Dimovic S, Smiciklas I, Plecas I et al (2009) Comparative study of differently treated animal bones for CO2+ removal. J Hazard Mater 164:279–287CrossRefGoogle Scholar
  19. 19.
    Brzezińska-Miecznik J, Haberko K, Sitarz M et al (2015) Hydroxyapatite from animal bones—extraction and properties. Ceram Int 41:4841–4846CrossRefGoogle Scholar
  20. 20.
    Iriarte-Velasco U, Ayastuy JL, Zudaire L et al (2014) An insight into the reactions occurring during the chemical activation of bone char. Chem Eng J 251:217–227CrossRefGoogle Scholar
  21. 21.
    Šljivić-Ivanović M, Smičiklas I, Milenković A et al (2015) Evaluation of the effects of treatment factors on the properties of bio-apatite materials. J Mater Sci 50:354–365. doi: 10.1007/s10853-014-8594-4 CrossRefGoogle Scholar
  22. 22.
    Gunawardane RP, Annersten H (1987) Fertilizer from Eppawela apatite: conversion using alkali hydroxide and quartz. J Natl Sci Counc Sri Lanka 15:117–132Google Scholar
  23. 23.
    Babic BM, Milonjic SK, Polovina MJ et al (1999) Point of zero charge and intrinsic equilibrium constants of activated carbon cloth. Carbon 37:477–481CrossRefGoogle Scholar
  24. 24.
    Iriarte-Velasco U, Sierra I, Cepeda EA et al (2015) Methylene blue adsorption by chemically activated waste pork bones. Color Technol 131:322–332CrossRefGoogle Scholar
  25. 25.
    Wei S, Zhang H, Huang Y et al (2011) Pig bone derived hierarchical porous carbon and its enhanced cycling performance of lithium–sulfur batteries. Energy Environ Sci 4:736–740CrossRefGoogle Scholar
  26. 26.
    Hassenkam T, Fantner GE, Cutroni JA et al (2004) High-resolution AFM imaging of intact and fractured trabecular bone. Bone 35:4–10CrossRefGoogle Scholar
  27. 27.
    Landi E, Tampieri A, Celotti G et al (2000) Densification behaviour and mechanisms of synthetic hydroxyapatites. J Eur Ceram Soc 20:2377–2387CrossRefGoogle Scholar
  28. 28.
    Reyes-Gasga J, Martínez-Piñeiro EL, Rodríguez-Álvarez G et al (2013) XRD and FTIR crystallinity indices in sound human tooth enamel and synthetic hydroxyapatite. Mater Sci Eng 33:4568–4574CrossRefGoogle Scholar
  29. 29.
    Ślósarczyk A, Paszkiewicz Z, Paluszkiewicz C (2005) FTIR and XRD evaluation of carbonated hydroxyapatite powders synthesized by wet methods. J Mol Struct 744–747:657–661CrossRefGoogle Scholar
  30. 30.
    Merry JC, Gibson IR, Best SM et al (1998) Synthesis and characterization of carbonate hydroxyapatite. J Mater Sci Mater Med 9:779–783. doi: 10.1023/A:1008975507498 CrossRefGoogle Scholar
  31. 31.
    Figueiredo MM, Gamelas JAF, Martins AG (2012) Characterization of Bone and Bone-Based Graft Materials Using FTIR Spectroscopy. In: Theophanides T (ed) Infrared spectroscopy-life and biomedical sciences. Intech, Open Science, RijekaGoogle Scholar
  32. 32.
    Puziy AM, Poddubnaya OI, Martínez-Alonso A et al (2002) Synthetic carbons activated with phosphoric acid: I. Surface chemistry and ion binding properties. Carbon 40:1493–1505CrossRefGoogle Scholar
  33. 33.
    Shen Z, Xue R (2003) Preparation of activated mesocarbon microbeads with high mesopore content. Fuel Process Technol 84:95–103CrossRefGoogle Scholar
  34. 34.
    Deng H, Li G, Yang H et al (2010) Preparation of activated carbons from cotton stalk by microwave assisted KOH and K2CO3 activation. Chem Eng J 163:373–381CrossRefGoogle Scholar
  35. 35.
    Etok S, Valsami-Jones E, Wess T et al (2007) Structural and chemical changes of thermally treated bone apatite. J Mater Sci 42:9807–9816. doi: 10.1007/s10853-007-1993-z CrossRefGoogle Scholar
  36. 36.
    Yala S, Khireddine H, Sidane D et al (2013) Surface modification of natural and synthetic hydroxyapatites powders by grafting polypyrrole. J Mater Sci 48:7215–7223. doi: 10.1007/s10853-013-7538-8 CrossRefGoogle Scholar
  37. 37.
    Tanaka H, Watanabe T, Chikazawa M (1997) FTIR and TPD studies on the adsorption of pyridine, n-butylamineand acetic acid on calcium hydroxyapatite. J Chem Soc Faraday Trans 93:4377–4381CrossRefGoogle Scholar
  38. 38.
    Prabowo B, Umeki K, Yan M et al (2014) CO2–steam mixture for direct and indirect gasification of rice straw in a downdraft gasifier: Laboratory-scale experiments and performance prediction. Appl Energy 113:670–679CrossRefGoogle Scholar
  39. 39.
    Chen C, Cheng W, Lin S (2003) Study of reverse water gas shift reaction by TPD, TPR and CO2 hydrogenation over potassium-promoted Cu/SiO2 catalyst. Appl Catal A 238:55–67CrossRefGoogle Scholar
  40. 40.
    Yasukawa A, Kandori K, Ishikawa T (2003) TPD-TG-MS study of carbonate calcium hydroxyapatite particles. Calcif Tissue Int 72:243–250CrossRefGoogle Scholar
  41. 41.
    Purevsuren B, Avid B, Narangerel J et al (2004) Investigation on the pyrolysis products from animal bone. J Mater Sci 39:737–740. doi: 10.1023/ CrossRefGoogle Scholar
  42. 42.
    Bansode A, Tidona B, von Rohr PR et al (2013) Impact of K and Ba promoters on CO2 hydrogenation over Cu/Al2O3 catalysts at high pressure. Catal Sci Technol 3:767–778CrossRefGoogle Scholar
  43. 43.
    Zong N, Liu Y (2012) Learning about the mechanism of carbon gasification by CO2 from DSC and TG data. Thermochim Acta 527:22–26CrossRefGoogle Scholar
  44. 44.
    Soni CG, Wang Z, Dalai AK et al (2009) Hydrogen production via gasification of meat and bone meal in two-stage fixed bed reactor system. Fuel 88:920–925CrossRefGoogle Scholar
  45. 45.
    Acharya CK, Jiang F, Liao C et al (2013) Tar and CO2 removal from simulated producer gas with activated carbon and charcoal. Fuel Process Technol 106:201–208CrossRefGoogle Scholar
  46. 46.
    Mckee DW (1983) Mechanisms of the alkali-metal catalyzed gasification of carbon. Fuel 62:170–175CrossRefGoogle Scholar
  47. 47.
    Lillo-Ródenas MA, Juan-Juan J, Cazorla-Amorós D et al (2004) About reactions occurring during chemical activation with hydroxides. Carbon 42:1371–1375CrossRefGoogle Scholar
  48. 48.
    Robau-Sánchez A, Aguilar-Elguézabal A, Aguilar-Pliego J (2005) Chemical activation of Quercus agrifolia char using KOH: evidence of cyanide presence. Microporous Mesoporous Mater 85:331–339CrossRefGoogle Scholar
  49. 49.
    Mao Z, Yang X, Zhu S et al (2015) Effect of Na+ and NaOH concentrations on the surface morphology and dissolution behavior of hydroxyapatite. Ceram Int 41:3461–3468CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Unai Iriarte-Velasco
    • 1
  • Irene Sierra
    • 1
  • Lorena Zudaire
    • 1
  • Jose L. Ayastuy
    • 2
  1. 1.Department of Chemical Engineering, Faculty of PharmacyUniversity of the Basque Country UPV/EHUVitoriaSpain
  2. 2.Department of Chemical Engineering, Faculty of Science and TechnologyUniversity of the Basque Country UPV/EHULeioaSpain

Personalised recommendations