Pilot-Scale Base Hydrolysis Processing of HMX-Based Plastic-Bonded Explosives

The degradation of HMX-based high explosives (HMX, PBX 9404, and PBX 9501) with sodium hydroxide solutions is described. To obtain practicable reaction rates, the reaction was carried out in a pressurized reactor at temperatures up to about 155 °C. Above about 70 °C, mass transfer rates significantly affect the observed reaction rate. Therefore, a solid−liquid mass transfer model, based on gas−liquid film theory, was developed to describe the reaction rate. This model successfully predicted the experimentally observed degradation of explosives. Similar work with sodium carbonate solutions was reported previously. Faster reaction rates were observed with sodium hydroxide, a stronger base. Sodium hydroxide is preferred when the explosive contains a base-resistant binder, such as the binder used in PBX 9501, or when large, pressed pieces of explosives are used. Sodium carbonate hydrolysis and sodium hydroxide hydrolysis yielded the same degradation products.

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Base Hydrolysis of HMX and HMX-Based Plastic-Bonded Explosives with Sodium Hydroxide between 100 and 155 °C

Bishop

Flesner

Dell`Orco

et al. 1999

“…Base hydrolysis followed by hydrothermal oxidation (BH/HTO) has been proposed as a treatment method for waste high explosives resulting from post-Cold War demilitarization. − Currently, such materials are disposed of primarily through open burning/open detonation (OB/OD), which may be disallowed in the future because of environmental regulation. Unlike OB/OD, BH/HTO produces no NO x gases.…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Treatment of C−N−O−H Wastes: Reaction Kinetics and Pathways for Hydrolysis Products of High Explosives

Dell`Orco¹,

Eaton²,

McInroy³

et al. 1999

Bench-scale studies demonstrated the efficacy of hydrothermal oxidation for the treatment of wastes derived from the alkaline hydrolysis of the high explosive PBX 9404 (94% HMX, 3% nitrocellulose, and 3% chloroethyl phosphate). Specifically, chemical kinetics studies were used to deduce major global reaction pathways, and to develop a kinetic model. Although the hydrolysis liquor is a complicated waste matrix, a three-parameter kinetic model captured major reaction paths. The kinetic model used total organic carbon (TOC) as a bulk parameter for dissolved organic materials, while NO x - was used to represent the oxidized nitrogen species in solution (NO2 - and NO3 -). With the use of the kinetic model, an optimal treatment strategy using two oxidation stages was derived. The first stage involved balancing NO x - and O2 redox chemistry to minimize aqueous nitrogen in the effluent, while the second stage mineralized the remaining TOC.

Hydrothermal Treatment of C−N−O−H Wastes: Model-Based Reactor Effluent Control

and¹,

Littell²,

Dell`Orco³

et al. 2001

In this work, we present model-based control and estimation algorithms developed to control the effluent composition for a hydrothermal oxidation reactor. The reactor is used to oxidize the organic compounds present in the hydrolysate solutions obtained from the destruction of HMXbased high explosives by base hydrolysis. The objective of the model-based control is to minimize the total amount of aqueous nitrogen compounds in the effluent of the reactor while maintaining the desired excess oxygen concentration in the reactor to ensure the complete destruction of the organic carbon compounds. A novel aspect of the controller design for this reactor is that the total aqueous nitrogen effluent concentration is locally uncontrollable at the desired optimal operating conditions. The controller uses a plug-flow reactor model with a reduced kinetic model describing the oxidation-reduction reactions in the hydrothermal oxidation reactor. Simulation and reactor implementation results are used to verify the closed-loop control algorithm.