The depletion of ores, a rise in the cost of their extraction, enrichment and processing led in the last 10‒15 years to a sharp rise in prices for tungsten products. Therefore, the processing began to involve technogenic waste ‒ dumps of enrichment factories and metallurgical industries, which previously did not represent the commercial interest on this case, we present the information on the results of the thermodynamic modeling of tungsten and bismuth chloride distillation in the processing of industrial waste using NaCl as a chlorinating agent. To calculate thermodynamic models for the associated extraction of tungsten and bismuth from industrial wastes, the ASTRA-4 software complex was used which created on basis of the maximum entropy of all possible reactions occurring during the retrieval of refractory metals from waste. Thus, the calculations carried out and experimental studies of the main provisions of thermodynamic calculation have shown the possibility of using NaCl salts for bismuth chlorination. At the same time, the maximum degree of sublimation of bismuth not be lower than 98% and can be achieved even at a temperature of 1200 K and a pressure of 0.01–0.1 MPa. At the same time, NaCl is not an effective chlorinating agent for retrieving of tungsten during high-temperature processing of industrial wastes.