Synthesis and Characterization of Potassium Bicarbonate and Urea-Modified Biochar from Rape Straw: Application in the Removal of Tetracycline from Aqueous Solution

Abstract

Using rapeseed straw as a raw material and potassium bicarbonate (KHCO3) and urea (CO(NH2)2) as modification reagents, the pyrolysis raw materials were mixed in a certain proportion, and the unmodified biochar GBC800, KHCO3-modified biochar KGBC800, and (KHCO3)/(CO(NH2)2) co-modified biochar N-KGBC800 were, respectively, prepared using the one-pot method at 800 °C. The physicochemical properties, such as surface morphology, pore characteristics, functional group distribution, and elemental composition of the three biochars, were characterized, and the adsorption performance and mechanism of the typical antibiotic tetracycline (TC) in water were studied. The results showed that the surface of GBC800 was smooth and dense, with no obvious pore structure, and both the specific surface area and total pore volume were small; the surface of KGBC800 showed an obvious coral-like three-dimensional carbon skeleton, the number of micropores and the specific surface area were significantly improved, and the degree of carbonization and aromatization was enhanced; N-KGBC800 had a coral-like three-dimensional carbon skeleton similar to KGBC800, and there were also many clustered carbon groups. The carbon layer changed significantly with interlayer gaps, presenting a multi-level porous structure. After N doping, the content of N increased, and new nitrogen-containing functional groups were formed. When the initial TC concentration was 100 mg/L, pH ≈ 3.4, the temperature was 25 °C, and the dosage of the three biochars was 0.15 g/L, the adsorption equilibrium was reached before 720 min. The adsorption capacities of GBC800, KGBC800, and N-KGBC800 for TC were 16.97 mg/g, 294.86 mg/g, and 604.71 mg/g, respectively. Fitting the kinetic model to the experimental data, the adsorption of TC by the three biochars was more in line with the pseudo-second-order adsorption kinetic model, and the adsorption isotherm was more in line with the Langmuir model. This adsorption process was a spontaneous endothermic reaction, mainly chemical adsorption, specifically involving multiple adsorption mechanisms such as pore filling, electrostatic attraction, hydrogen bonds, n−π interaction, Lewis acid–base interaction, π−π stacking, or cation −π interaction between the aromatic ring structure of the carbon itself and TC. A biochar-adsorption column was built to investigate the dynamic adsorption process of tetracycline using the three biochars against the background of laboratory pure water and salt water. The adsorption results show that the Thomas model and the Yoon–Nelson model both provide better predictions for dynamic adsorption processes. The modified biochars KGBC800 and N-KGBC800 can be used as preferred materials for the efficient adsorption of TC in water.

Keywords

• biochar
• potassium bicarbonate modification
• nitrogen doping
• tetracycline
• adsorption mechanism