Novel Sampling and Sample Preparation Systems with Industrial Validation for Biomass–Coal Co-Combustion Ratios Based on 14 C Determination

Focusing on enhancing the performance of the 14 C method in determining biomass–coal co-combustion ratios, this study developed two novel sample preparation systems: a direct flue gas injection benzene synthesis system based on Liquid Scintillation Counting (LSC) and a direct flue gas sealing graphitization system based on Accelerator Mass Spectrometry (AMS). These systems reduced sample preparation time from 20–24 h to 6–8 h. Experimental validation showed relative errors in biomass blending ratios (1–40%) below ±4% for LSC and ±3% for AMS, except at the 1% blending condition. Compared with conventional methods, both accuracy and efficiency were significantly improved. An enhanced 14 C-based industrial measurement scheme was established and successfully applied for monitoring biomass blending ratios (15–50%) in industrial facilities. Deviations between AMS and LSC were within ±3%, confirming the method’s accuracy, despite discrepancies with the Distributed Control System (DCS) estimates. Additionally, predictive formulas for 14 C activity in biomass and air CO 2 reduced economic investment, with relative errors from ±0.04% to ±3.25%. Overall, the new scheme improved accuracy by 50%, efficiency by 60%, and reduced detection costs by 60–80%, demonstrating feasibility and practical value for industrial applications.