Safe Operating Temperatures for Pressurized Alkaline Hydrolysis of HMX-Based Explosives

• Published in: Industrial & engineering chemistry research 2000-05, Vol.39 (5), p.1215-1220
• Main Authors: Bishop, Robert L, Harradine, David M, Flesner, Raymond L, Larson, Sheldon A, Bell, David A
• Format: Article
• Language: English
• Subjects: ALKALINE HYDROLYSIS; Applied sciences; CHEMICAL EXPLOSIVES; Chemical industry and chemicals; DETONATION LIMITS; Exact sciences and technology; Industrial chemicals; MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE; Other wastes and particular components of wastes; Pollution; Powders, propellants, explosives; SAFETY ENGINEERING; TEMPERATURE CONTROL; WASTE PROCESSING; Wastes
• ISSN: 0888-5885; 1520-5045
• DOI: 10.1021/ie9904448

Alkaline hydrolysis is used to convert high explosives to nonenergetic, aqueous compounds. Base hydrolysis of high explosives is exothermic (ΔH RXN = 2.3 kJ/g), and thermal runaway of the reaction is a possibility at elevated temperatures (>120 °C) where the rate of reaction is large. Thermal runaway could result in an accidental detonation of the energetic material being treated, so safe operating parameters for base hydrolysis need to be determined. To measure the safe operating temperature, base hydrolysis was performed at temperatures ramped from 20 to 300 °C. The results show that PBX 9501 molding powder detonates at a 185 °C bulk temperature in 1.5 M NaOH with a 4.5 °C/min linear temperature ramp and no agitation. The reaction of pressed PBX 9501 with 0.75, 1.5, and 3.0 M NaOH and water and both pressed and nonpressed PBX 9404 with 0.75, 1.5 M, and 3.0 M NaOH and water did not produce a detonation with a 4.5 °C/min linear temperature ramp. A previously developed reaction rate model was used to show that thermal runaway should occur when the base hydrolysis reaction rate reached a maximum at a bulk temperature between 185 and 225 °C.