Non-isothermal kinetics and characteristics of calcium carbide nitridation reaction with calcium-based additives

Abstract

The nitridation reaction of calcium carbide and N₂ at high temperatures is the key step in the production of lime-nitrogen. However, the challenges faced by this process, such as high energy consumption and poor product quality, are mainly attributed to the lack of profound understanding of the reaction. This study aimed to improve this process by investigating the non-isothermal kinetics and reaction characteristics of calcium carbide nitridation reaction at different heating rates (10, 15, 20, and 30 °C·min⁻¹) using thermogravimetric analysis. The kinetic equation for the nitridation reaction of additive-free calcium carbide sample was obtained by combining model-free methods and model-fitting method. The effect of different calcium-based additives (CaCl₂ and CaF₂) on the reaction was also investigated. The results showed that the calcium-based additives significantly reduced reaction temperature and activation energy E_a by about 40% with CaF₂ and by 55%–60% with CaCl₂. The reaction model f(α) was also changed from contracting volume (R3) to 3-D diffusion models with D3 for CaCl₂ and D4 for CaF₂. This study provides valuable information on the mechanism and kinetics of calcium carbide nitridation reaction and new insights into the improvement of the lime-nitrogen process using calcium-based additives.

Graphical abstract

Keywords

lime-nitrogen / calcium carbide / calcium-based additive / thermogravimetric analysis / non-isothermal kinetics

References

[1] Nagumo Y , Tanaka K , Tewari K , Thiraporn K , Tsuchida T , Honma T , Ohtake N , Sueyoshi K , Takahashi Y , Ohyama T . Rapid quantification of cyanamide by ultra-high-pressure liquid chromatography in fertilizer, soil or plant samples. Journal of Chromatography A, 2009, 1216(29): 5614–5618

[2] Rouwenhorst K H R , Travis A S , Lefferts L . 1921–2021: a century of renewable ammonia synthesis. Sustainable Chemistry, 2022, 3(2): 149–171

[3] Yamamoto A , Akiyama H , Naokawa T , Miyazaki Y , Honda Y , Sano Y , Nakajima Y , Yagi K . Lime-nitrogen application affects nitrification, denitrification, and N₂O emission in an acidic tea soil. Biology and Fertility of Soils, 2014, 50(1): 53–62

[4] Aono T . Studies on reaction between gas and solid. VI. Azotation of calcium carbide and the effect of catalysers on its velocity. Bulletin of the Chemical Society of Japan, 1932, 7(9): 287–297

[5] Aono T . Studies on reactions between gas and solid. VIII. The mechanism of nitrogenation of calcium carbide. Bulletin of the Chemical Society of Japan, 1941, 16(4): 106–114

[6] Hellinckx L J . A problem of discrimination between a diffusional or a flow mechanism. Chemical Engineering Science, 1962, 17(12): 997–1005

[7] Nagai S , Kanazawa T , Ishida H . (111–112) Influence of potassic ores on the nitrogenation of calcium carbide. VII. Effects of fluoride and phosphate. Journal of the Society of Chemical Industry, Japan, 1953, 56(4): 242–243

[8] Zhang L , Wu J , Yang H . Study on thermal analysis kinetics of copper slag reduction. Journal of Thermal Analysis and Calorimetry, 2023, 148(10): 4267–4280

[9] Zhang L , Yang H . Study on oxidation kinetics and mechanism of copper slag under non-isothermal conditions. Mining, Metallurgy & Exploration, 2022, 39(4): 1587–1596

[10] Lyu B , Wang G , Yang F , Zuo H , Xue Q , Wang J . Kinetic analysis of isothermal and non-isothermal reduction of iron ore fines in hydrogen atmosphere. Metals, 2022, 12(10): 1754

[11] Hessels C J M , Homan T A M , Deen N G , Tang Y . Reduction kinetics of combusted iron powder using hydrogen. Powder Technology, 2022, 407: 117540

[12] Wang R , Liu Z , Ji L , Guo X , Lin X , Wu J , Liu Q . Reaction kinetics of CaC₂ formation from powder and compressed feeds. Frontiers of Chemical Science and Engineering, 2016, 10(4): 517–525

[13] Cordova S , Estala-Rodriguez K , Shafirovich E . Oxidation kinetics of magnesium particles determined by isothermal and non-isothermal methods of thermogravimetric analysis. Combustion and Flame, 2022, 237: 111861

[14] Si F , Zhang H , Feng X , Dou J , Wu L , Li L , Wang L , Zhao L . Thermal analysis kinetics study of pulverized coal combustion under oxygen-rich atmosphere. ACS Omega, 2023, 8(37): 33975–33981

[15] Kök M V , Yildirim B . Gasification kinetics of Thrace region coal by thermogravimetry analysis. Journal of Petroleum Science Engineering, 2020, 188: 106869

[16] Mao R , Shao J , Wang G , Wang F , Wang C . Thermal behavior and kinetics analysis of co-combustion of petroleum coke and paper sludge-derived hydrochar. Waste Management, 2022, 153: 405–414

[17] Liu Y , Qu J , Wu X , Zhang K , Zhang Y . Reaction kinetics and internal diffusion of Zhundong char gasification with CO₂. Frontiers of Chemical Science and Engineering, 2021, 15(2): 373–383

[18] Singh A , Singh S , Soni P K , Mukherjee N . Non-isothermal thermogravimetric degradation kinetics, reaction models and thermodynamic parameters of vinylidene fluoride based fluorinated polymers. Journal of Macromolecular Science Part B: Physics, 2020, 59(1): 1–24

[19] Kaur R , Gera P , Jha M K , Bhaskar T . Pyrolysis kinetics and thermodynamic parameters of castor (Ricinus communis) residue using thermogravimetric analysis. Bioresource Technology, 2018, 250: 422–428

[20] Dilmaç N . Isothermal and non-isothermal reduction kinetics of iron ore oxygen carrier by CO: modelistic and model-free approaches. Fuel, 2021, 296: 120707

[21] Vyazovkin S , Burnham A K , Criado J M , Pérez-Maqueda L A , Popescu C , Sbirrazzuoli N . ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochimica Acta, 2011, 520(1–2): 1–19

[22] Singh R K , Patil T , Pandey D , Tekade S P , Sawarkar A N . Co-pyrolysis of petroleum coke and banana leaves biomass: kinetics, reaction mechanism, and thermodynamic analysis. Journal of Environmental Management, 2022, 301: 113854

[23] Flynn J H , Wall L A . A quick, direct method for the determination of activation energy from thermogravimetric data. Journal of Polymer Science Part B: Polymer Letters, 1966, 4(5): 323–328

[24] Doyle C D . Series approximations to the equation of thermogravimetric data. Nature, 1965, 207(4994): 290–291

[25] Akahira T , Sunose T . Method of determining activation deterioration constant of electrical insulating materials. Res Rep Chiba Inst Technol, 1971, 16: 22–31

[26] Starink M J . A new method for the derivation of activation energies from experiments performed at constant heating rate. Thermochimica Acta, 1996, 288(1–2): 97–104

[27] Müsellim E , Tahir M H , Ahmad M S , Ceylan S . Thermokinetic and TG/DSC-FTIR study of pea waste biomass pyrolysis. Applied Thermal Engineering, 2018, 137: 54–61

[28] Su D , Chen X , Wei X , Liang J , Tang L , Wang L . Comparison of thermal stability between dicyclopentadiene/hydrogenated dicyclopentadiene petroleum resin: thermal decomposition characteristics, kinetics and evolved gas analysis by TGA/TG-MS. Thermochimica Acta, 2021, 699: 178853

[29] Coats A W , Redfern J P . Kinetic parameters from thermogravimetric data. Nature, 1964, 201(4914): 68–69

[30] Poomsawat W , Poomsawat S . Pyrolysis kinetic behavior of composite polypropylene-biomass solid fuels derived via co-hydrothermal carbonization process. Thermal Science and Engineering Progress, 2023, 43: 101953

[31] Khachani M , Hamidi A E , Halim M , Arsalane S . Non-isothermal kinetic and thermodynamic studies of the dehydroxylation process of synthetic calcium hydroxide Ca(OH)₂. Journal of Materials & Environmental Sciences, 2014, 5(2): 615–624

[32] Kumar Trivedi M . Effect of biofield energy treatment on physical and structural properties of calcium carbide and praseodymium oxide. International Journal of Materials Science and Applications, 2015, 4(6): 390–395

[33] Trubyanov M M , Mochalov G M , Suvorov S S , Puzanov E S , Petukhov A N , Vorotyntsev I V , Vorotyntsev V M . Towards the interaction between calcium carbide and water during gas-chromatographic determination of trace moisture in ultra-high purity ammonia. Journal of Chromatography A, 2018, 1560: 71–77

[34] Huang R , Teng Z , Li S . Gaussian model analysis and thermal decomposition kinetics of nature fibers. Journal of Cleaner Production, 2022, 357: 131784

[35] Li Z . General rate equation theory for gas-solid reaction kinetics and its application to CaO carbonation. Chemical Engineering Science, 2020, 227: 115902

[36] Kastens M L , McBurney W G . Calcium cyanamide. Industrial & Engineering Chemistry, 1951, 43(5): 1020–1033

[37] Klimek A , Yount J , Wozniak D , Zeller M , Piercey D G . A laboratory preparation of high-purity calcium cyanamide. Inorganic Chemistry, 2023, 62(40): 16280–16282

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. U20A20151 and 21978210) and the Haihe Laboratory of Sustainable Chemical Transformations.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2401-9 and is accessible for authorized users.

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