Анотація
The paper presents the results of pH, redox, and conductometric studies on the acid-base interaction during sulfur dioxide chemisorption by aqueous solutions containing 0.1 mol/L monoethanolammonium (MEA·1/3CA) and polyethylenepolyammonium (PEPA·1/3CA) citrates, as well as buffer solutions of monoethanolamine–monoethanolammonium citrate (MEA·1/6CA) and polyethylenepolyamine–polyethylenepolyammonium citrate (PEPA·1/6CA), in comparison with sodium citrate. The composition of the compounds formed during SO2 absorption by Na3Cit, MEA·1/3CA, PEPA·1/3CA, MEA·1/6CA, and PEPA·1/6CA solutions at 273–313 K was determined.For the same amount of absorbed sulfur dioxide, an increase in specific electrical conductivity (æ) with rising temperature was observed in SO2–Na3Cit–H2O and SO2–MEA×1/3CA–H2O solutions within the 273–313 K range. However, in the SO2–MEA×1/3CA–H2O, SO2–PEPA×1/3CA–H2O, SO2–MEA×1/6CA–H2O, and SO2–PEPA×1/6CA–H2O systems, a decrease in Δæ was noted upon heating to 303 K, which is attributed to their ion-molecular composition.
Based on developed mathematical models, the ion-molecular component composition of SO2–MEA×1/3CA–H2O and SO2–MEA×1/6CA–H2O solutions was determined at 283–313 K. The concentration and thermodynamic constants for the formation of ionic associates were calculated:(NH3CH2CH2OH)2SO3, {H3CH2CH2OH}{HOC3H4(COOH)2(COO-)} (Ia), {H3CH2CH2OH}2{HOC3H4(COOH)(COO-)2} (IIa), {H3CH2CH2OH}2{HOC3H4(COOH)2(COO-)} (IIb), {H3CH2CH2OH}3{HOC3H4(COO-)3} (IIIa), as well as ion-molecular associates:{H3CH2CH2OH}{HOC3H4(COOH)3} (Ib), {NH2CH2CH2OH}3{H3CH2CH2OH}3{HOC3H4(COO-)3} (IVa), {NH2CH2CH2OH}2{H3CH2CH2OH}4{HOC3H4(COO-)3} (IVb).
In SO2–MEA×1/3CA–H2O solutions, as the temperature increases, bond rearrangement occurs in ionic associates IIa and Ib, as indicated by the absence of a clear temperature dependence ofp, along with the strengthening of IIa and Ib. Conversely, in SO2–MEA×1/6CA–H2O solutions, increasing temperature leads to the weakening of the bonds in compounds Ia, IIIa, IVa, and IVb, while in compound Ib, the bonds strengthen.
Посилання
Hanif M.A., Ibrahim N., Abdul Jalil A. Sulfur dioxide removal: An overview of regenerative flue gas desulfurization and factors affecting desulfurization capacity and sorbent regeneration. Environ. Sci. Pollut. Res. 2020. 27: 27515–27540.
doi: 10.1007/s11356-020-09191-4
Hou Y., Chen Y., He X., Wang F., Cai Q., Shen B. Insights into the adsorption of CO2, SO2 and NOx in flue gas by carbon materials: A critical review. Chem. Eng. J. 2024. 490: 151424.
doi: 10.1016/j.cej.2024.151424
Khoma R.E. Acid-base interaction and sulfooxidation at chemosorption of sulfur dioxide by alkylamines aqueous solutions. Abstract of Doctor’s degree dissertation, 02.00.01. Kyiv, 2019, 50 p. (in Ukrainian).
Khoma R.E., Bienkovska T.S., Gelmboldt V.O., Klimov D.G., Horlichenko M.G. Composition and the relative stability of sulfur dioxide interaction products with potassium and monoethanolammonium taurates aqueous solutions. Prolonged-action chemosorbent. Visn. Odes. nac. univ., Him. 2023: 28(3): 35–51.
doi: 10.18524/2304-0947.2023.3(86).297810.
(in Ukrainian).
Ennan A. A.-A., Khoma R.E., Dlubovskii R.M., Zukharenko Yu.S., Benkovska T.S., Knysh I.M. Mono- and bifunctional impregnated fiber chemosorbents for respiratory purpose. Visn. Odes. nac. univ., Him. 2022. 27(1): 6–36.
doi: 10.18524/2304-0947.2021.4(80).248297.
(in Ukrainian).
Bekassy-Molnar E., Marki E., Majeed J.G. Sulphur dioxide absorption in air-lift-tube absorbers by sodium citrate buffer solution. Chem. Eng. Process. 2005. 44(9): 1039–1046.
DOI: 10.1016/j.cep.2005.02.001
Jiang X., Liu Y., Gu M. Absorption of Sulfur Dioxide with Sodium Citrate Buffer Solution in a Rotating Packed Bed. Chin. J. Chem. Eng. 2011: 19(4): 687–692.
doi: 10.1016/s1004-9541(11)60042-6
Sun Z., Zhou Y., Jia S., Wang Y., Jiang D., Zhang L. Enhanced SO2 Absorption Capacity of Sodium Citrate Using Sodium Humate. Catalysts. 2021: 11(7): 865.
doi: 10.3390/catal11070865
Khoma R.E., Bienkovska T.S., Tsyganenko K.V., Karych A.M., Kononchenko A.R. Acid-base and electrochemical behavior of monoethanolamine (polyethylenepolyamine) – citric acid – water solutions. J. Chem. Technol. 2024: 32(1): 30–42.
doi: 10.15421/jchemtech.v32i1.292412.
(in Ukrainian).
Khoma R.E., Bіenkovska T.S. Water vapor, sulfur dioxide and ammonia adsorption by fibrous material impregnated with citrate-monoethanolamine buffer solutions. Visn. Odes. nac. univ. Him. 2024: 29(2):101–116.
doi: 10.18524/2304-0947.2024.2(88).322135.
(in Ukrainian).
Apelblat A.Citric acid. Springer. 2014. 357 p.
doi: 10.1007/978-3-319-11233-6
Verhoff F.H., Bauweleers H. Citric acid. in Ullmann’s Encyclopedia Ind. Chem. 2014. 11 p.
doi: 10.1002/14356007.a07_103.pub3
Citric acid. Available at https://pubchem.ncbi.nlm.nih.gov/compound/Citric-Acid#section=Solubility
Apelblat A., Manzurola E. Extraction of Citric Acid by n-Octanol and n-Hexanol. Ber. Bunsenges Phys. Chem. 1988. 92(7): 793–796.
doi: 10.1002/bbpc.198800195
Sodium citrate. EHS Support. 2021. 8 p. Available at https://www.santos.com/wp-content/uploads/2021/04/Sodium-citrate-March-2021.pdf
Sodium Citrate, Dihydrate. LabChem. Safety Data Sheet. 2020. 6 p. Available at https://ehslegacy.unr.edu/msdsfiles/36924.pdf
Monoethanolamine. Available at https://pubchem.ncbi.nlm.nih.gov/compound/Monoethanolamine#section=Carcinogen-Classification
Polyamine B. SDS AkzoNobel. 2014. 125 p. Available at https://www.alliancechemicals.com/wp-content/uploads/2011/10/Polyamine BSDS.pdf
Polyethylene Polyamine. Chem BK. Available at https://www.chembk.com/en/chem/Polyethylene%20Polyamine
Khoma R.E., Shestaka A.A., Gelmboldt V.O. On interaction of sulfur(IV) oxide with aqueous solutions of ethanolamines. Russ. J. Appl. Chem. 2012: 85(11):1667–1675.
doi: 10.1134/S1070427212110067
Hartley F.R., Burgess C., Alcock R.M. Solution Equilibria. Ellis Horwood Limited: Chichester, West Sussex, England. 1980. 361 p.