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Title: Safe operating temperatures for pressurized alkaline hydrolysis of HMX-based explosives

Abstract

Alkaline hydrolysis is used to convert high explosives to nonenergetic, aqueous compounds. Base hydrolysis of high explosives is exothermic ({Delta}H{sub 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 PBX9501 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 PBX9501 with 0.75, 1.5, and 3.0 M NaOH and water and both pressed and nonpressed PBX9404 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.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Los Alamos National Lab., NM (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20076073
DOE Contract Number:  
W-7405-ENG-48
Resource Type:
Journal Article
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 39; Journal Issue: 5; Other Information: PBD: May 2000; Journal ID: ISSN 0888-5885
Country of Publication:
United States
Language:
English
Subject:
45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE; CHEMICAL EXPLOSIVES; ALKALINE HYDROLYSIS; SAFETY ENGINEERING; TEMPERATURE CONTROL; DETONATION LIMITS; WASTE PROCESSING

Citation Formats

Bishop, R.L., Harradine, D.M., Flesner, R.L., Larson, S.A., and Bell, D.A. Safe operating temperatures for pressurized alkaline hydrolysis of HMX-based explosives. United States: N. p., 2000. Web. doi:10.1021/ie9904448.
Bishop, R.L., Harradine, D.M., Flesner, R.L., Larson, S.A., & Bell, D.A. Safe operating temperatures for pressurized alkaline hydrolysis of HMX-based explosives. United States. doi:10.1021/ie9904448.
Bishop, R.L., Harradine, D.M., Flesner, R.L., Larson, S.A., and Bell, D.A. Mon . "Safe operating temperatures for pressurized alkaline hydrolysis of HMX-based explosives". United States. doi:10.1021/ie9904448.
@article{osti_20076073,
title = {Safe operating temperatures for pressurized alkaline hydrolysis of HMX-based explosives},
author = {Bishop, R.L. and Harradine, D.M. and Flesner, R.L. and Larson, S.A. and Bell, D.A.},
abstractNote = {Alkaline hydrolysis is used to convert high explosives to nonenergetic, aqueous compounds. Base hydrolysis of high explosives is exothermic ({Delta}H{sub 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 PBX9501 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 PBX9501 with 0.75, 1.5, and 3.0 M NaOH and water and both pressed and nonpressed PBX9404 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.},
doi = {10.1021/ie9904448},
journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 5,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}