Synthesis and Characterization of Fly Ash-Based Geopolymers Activated with Spent Caustic
Abstract
:1. Introduction
2. Experimental
2.1. Materials
2.2. Synthesis of Geopolymers
2.3. Immobilization of Organic Contamination
2.4. Characterization of Geopolymers
3. Results and Discussion
3.1. Compressive Strength
3.2. X-ray Diffraction (XRD)
3.3. Nuclear Magnetic Resolution (NMR) Spectra
3.4. Pore Structure
3.5. Organics Immobilization
4. Conclusions
- (1)
- The spent caustic can partially replace the NaOH to synthesize geopolymers, and the organics in spent caustic can be immobilized in geopolymers. The method can not only make the spent caustic harmless, but also utilize the strong alkalinity of the spent caustic to reduce the cost of preparing the geopolymer.
- (2)
- When the degree of alkalinity is higher than 4 mol/L, the geopolymers prepared by the mixed activator of spent caustic and sodium hydroxide have better 28 days compressive strength than that synthesized with pure NaOH solution, and the highest strength can reach 21.86 Mpa.
- (3)
- With the degree of alkalinity increasing, the immobilization efficiency of organics in geopolymers is improved, and the maximum can reach 84.5%. The organics in the spent caustic will hinder geopolymerization at the initial stage but has little effect on the chemical structure and phase of the final product.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Rahi, M.N.; Jaeel, A.J.; Abbas, A.J. Treatment of petroleum refinery effluents and wastewater in Iraq: A mini review. Proc. IOP Conf. Ser. Mater. Sci. Eng. 2021, 1058, 012072. [Google Scholar] [CrossRef]
- Ntagia, E.; Fiset, E.; Hong, L.T.C.; Vaiopoulou, E.; Rabaey, K. Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery. J. Hazard Mater. 2020, 388, 121770. [Google Scholar] [CrossRef] [PubMed]
- Vaiopoulou, E.; Provijn, T.; Prévoteau, A.; Pikaar, I.; Rabaey, K. Electrochemical sulfide removal and caustic recovery from spent caustic streams. Water Res. 2016, 92, 38–43. [Google Scholar] [CrossRef]
- Alipour, Z.; Azari, A. COD removal from industrial spent caustic wastewater: A review. J. Environ. Chem. Eng. 2020, 8, 103678. [Google Scholar] [CrossRef]
- Su, P.; Zhang, J.; Yang, B. The Current Status of Hazardous Waste Management in China: Identification, Distribution, and Treatment. Environ. Eng. Sci. 2022, 39, 81–97. [Google Scholar] [CrossRef]
- Nunez, P.; Hansen, H.K.; Rodriguez, N.; Guzman, J.; Gutierrez, C. Electrochemical generation of Fenton’s reagent to treat spent caustic wastewater. Sep. Sci. Technol. 2009, 44, 2223–2233. [Google Scholar] [CrossRef]
- Elmi, R.; Nejaei, A.; Farshi, A.; Ramazani, M.E.; Alaie, E. Comparison of two methods of neutralization and wet air oxidation for treating wastewater spent caustic produced by oil refineries. Environ. Monit. Assess. 2021, 193, 854. [Google Scholar] [CrossRef]
- Duxson, P.; Provis, J.L.; Lukey, G.C.; Van Deventer, J.S. The role of inorganic polymer technology in the development of ‘green concrete’. Cem. Concr. Res. 2007, 37, 1590–1597. [Google Scholar] [CrossRef]
- Wan, Q.; Rao, F.; Song, S.; Morales-Estrella, R.; Xie, X.; Tong, X. Chemical forms of lead immobilization in alkali-activated binders based on mine tailings. Cem. Concr. Compos. 2018, 92, 198–204. [Google Scholar] [CrossRef]
- Shi, C.; Fernández-Jiménez, A. Stabilization/solidification of hazardous and radioactive wastes with alkali-activated cements. J. Hazard Mater. 2006, 137, 1656–1663. [Google Scholar] [CrossRef] [PubMed]
- Reeb, C.; Pierlot, C.; Davy, C.; Lambertin, D. Incorporation of organic liquids into geopolymer materials-A review of processing, properties and applications. Ceram. Int. 2021, 47, 7369–7385. [Google Scholar] [CrossRef]
- Cantarel, V.; Nouaille, F.; Rooses, A.; Lambertin, D.; Poulesquen, A.; Frizon, F. Solidification/stabilisation of liquid oil waste in metakaolin-based geopolymer. J. Nucl. Mater. 2015, 464, 16–19. [Google Scholar] [CrossRef]
- Al-Mashaqbeh, A.; El-Eswed, B.; Banat, R.; Khalili, F.I. Immobilization of organic dyes in geopolymeric cementing material. Environ. Nanotechnol. Monit. Manag. 2018, 10, 351–359. [Google Scholar] [CrossRef]
- Duxson, P.; Fernández-Jiménez, A.; Provis, J.L.; Lukey, G.C.; Palomo, A.; van Deventer, J.S. Geopolymer technology: The current state of the art. J. Mater. Sci. 2007, 42, 2917–2933. [Google Scholar] [CrossRef]
- Turner, L.K.; Collins, F.G. Carbon dioxide equivalent (CO2-e) emissions: A comparison between geopolymer and OPC cement concrete. Constr. Build. Mater. 2013, 43, 125–130. [Google Scholar] [CrossRef]
- McLellan, B.C.; Williams, R.P.; Lay, J.; Van Riessen, A.; Corder, G.D. Costs and carbon emissions for geopolymer pastes in comparison to ordinary portland cement. J. Clean. Prod. 2011, 19, 1080–1090. [Google Scholar] [CrossRef]
- Salas, D.A.; Ramirez, A.D.; Ulloa, N.; Baykara, H.; Boero, A.J. Life cycle assessment of geopolymer concrete. Constr. Build Mater. 2018, 190, 170–177. [Google Scholar] [CrossRef]
- Yuan, W.; Zhang, L.; Liu, Y.; Fu, P.; Huang, Y.; Wang, L.; Ma, H.; Wang, H. Sulfide removal and water recovery from ethylene plant spent caustic by suspension crystallization and its optimization via response surface methodology. J. Clean. Prod. 2020, 242, 118439. [Google Scholar] [CrossRef]
- Ellis, C.E. Wet air oxidation of refinery spent caustic. Environ. Prog. 1998, 17, 28–30. [Google Scholar] [CrossRef]
- Karamalidis, A.; Voudrias, E. Leaching of VOCs from cement-based stabilized/solidified refinery oily sludge using solid phase microextraction. Environ. Technol. 2007, 28, 1173–1185. [Google Scholar] [CrossRef]
- Zhang, Q.; Ji, T.; Yang, Z.; Wang, C.; Wu, H.-C. Influence of different activators on microstructure and strength of alkali-activated nickel slag cementitious materials. Constr. Build. Mater. 2020, 235, 117449. [Google Scholar] [CrossRef]
- Rożek, P.; Król, M.; Mozgawa, W. Geopolymer-zeolite composites: A review. J. Clean. Prod. 2019, 230, 557–579. [Google Scholar] [CrossRef]
- Lee, S.K.; Stebbins, J.F. The degree of aluminum avoidance in aluminosilicate glasses. Am. Mineral. 1999, 84, 937–945. [Google Scholar] [CrossRef]
- Engelhardt, G.; Michel, D. High-Resolution Solid-State NMR of Silicates and Zeolites; John Wiley & Sons: Hoboken, NJ, USA, 1987. [Google Scholar]
- Richardson, I.G. The nature of CSH in hardened cements. Cem. Concr. Res. 1999, 29, 1131–1147. [Google Scholar] [CrossRef]
- Peng, Z.; Vance, K.; Dakhane, A.; Marzke, R.; Neithalath, N. Microstructural and 29Si MAS NMR spectroscopic evaluations of alkali cationic effects on fly ash activation. Cem. Concr. Compos. 2015, 57, 34–43. [Google Scholar] [CrossRef]
- Criado, M.; Fernández-Jiménez, A.; Palomo, A.; Sobrados, I.; Sanz, J. Effect of the SiO2/Na2O ratio on the alkali activation of fly ash. Part II: 29Si MAS-NMR Survey. Microporous Mesoporous Mater. 2008, 109, 525–534. [Google Scholar] [CrossRef]
- Luo, H.; Cheng, Y.; He, D.; Yang, E.-H. Review of leaching behavior of municipal solid waste incineration (MSWI) ash. Sci. Total Environ. 2019, 668, 90–103. [Google Scholar] [CrossRef]
- Gokhale, C.; Lorenzen, L.; Van Deventer, T. The Immobilisation of Organic Waste by Geopolymerisation. Master’s Thesis, University of Stellenbosch, Stellenbosch, South Africa, 2001. [Google Scholar]
Component | SiO2 | Al2O3 | K2O | Fe2O3 | TiO2 | CaO | MgO | LOI |
---|---|---|---|---|---|---|---|---|
wt% | 49.18 | 33.80 | 2.28 | 4.89 | 0.73 | 4.84 | 0.81 | 3.47 |
Specimen No. | Fly Ash | NaOH | Spent Caustic | Water |
---|---|---|---|---|
1 | 100 g | 0 g | 25 mL | / |
2 | 2 g | |||
3 | 4 g | |||
4 | 6 g | |||
5 | 8 g | |||
6 | 10 g | |||
7 | 12 g | |||
8 | 2 g | / | 25 mL | |
9 | 4 g | |||
10 | 6 g | |||
11 | 8 g | |||
12 | 10 g | |||
13 | 12 g | |||
14 | 14 g |
Sample | No. 3 | No. 8 | No. 10 | No. 13 |
---|---|---|---|---|
Q4(0Al) | 26.96% | 1.42% | 30.07% | 10.44% |
Q4(1Al) | 28.18% | 2.59% | 27.01% | 19.02% |
Q4(2Al) | 3.14% | 26.96% | 0.45% | 19.81% |
Q4(3Al) | 30.73% | 31.20% | 33.13% | 22.93% |
Q4(4Al) | 5.66% | 24.47 | 1.35% | 17.98% |
Q2(0Al) | 1.03% | 13.36% | 1.14% | 9.82% |
Crystalline silica | 4.30% | / | 6.85% | / |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Zhang, R.; Wan, Q.; Zhang, Y.; Zhang, X. Synthesis and Characterization of Fly Ash-Based Geopolymers Activated with Spent Caustic. Gels 2022, 8, 562. https://doi.org/10.3390/gels8090562
Zhang R, Wan Q, Zhang Y, Zhang X. Synthesis and Characterization of Fly Ash-Based Geopolymers Activated with Spent Caustic. Gels. 2022; 8(9):562. https://doi.org/10.3390/gels8090562
Chicago/Turabian StyleZhang, Ruobing, Qian Wan, Yimin Zhang, and Xuemian Zhang. 2022. "Synthesis and Characterization of Fly Ash-Based Geopolymers Activated with Spent Caustic" Gels 8, no. 9: 562. https://doi.org/10.3390/gels8090562