Sodium carbonate (Na2CO3) is identified as a hydrolysis reagent for decomposing HMX and HMX-based explosives to water-soluble, nonenergetic products. The reaction kinetics of Na2CO3 hydrolysis are examined, and a reaction rate model is developed. Greater than 99% of the explosive at an initial concentration of 10 wt % PBX 9404 was destroyed in less than 5 min at 150 °C. The primary products from Na2CO3 hydrolysis were nitrite (NO2), formate (HCOO-), nitrate (NO3 -), and acetate (CH3COO-) ions, hexamethylenetetramine, (hexamine:  C6H12N4), nitrogen gas (N2), nitrous oxide (N2O), and ammonia (NH3). The rate of hydrolysis was characterized for HMX powder and PBX 9404 molding powder from 110 to 150 °C. The rate was found to be dependent on both the chemical kinetics and the mass transfer resistance. Since the HMX particles are nonporous and external mass transfer dominates, gas−liquid film theory for fast chemical kinetics was used to model the reaction rate.

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.

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.

and Technology (DX-2), M/S C920, Los Alamos, NM 87545 (USA) Charakterisierung eines Slurry-Prozesses fu È r die Herstellung eines kunststoffgebundenen SprengstoffsDie Wirkung der Ru Èhrgeschwindigkeit, der Luftstromgeschwindigkeit und der Reaktionsgefa Èûtemperatur bei der Herstellung von PBX 9501, einem kunststoffgebundenen thermoplastischen Sprengstoff, wurde untersucht. Diese Variablen beein¯ussen die Agglomeratla Ènge, die Agglomeratgestalt und die Schu Èttdichte des Preûgranulats, haben aber geringen Ein¯uû auf die Eigenschaften der Preûstu Ècke, die aus dem Granulat hergestellt wurden.Caracte Ârisation d'un processus slurry pour la synthe Áse d'un explosif a Á liant plastiqueOn a e Âtudie  l'effet de la vitesse d'agitation, de la vitesse de l'e Âcoulement d'air et de la tempe Ârature de la cuve de re Âaction lors de la synthe Áse de PBX 9501, explosif thermoplastique a Á liant synthe Âtique. Ces variables in¯uencent la longueur de l'agglome Âre Â, sa structure et la masse volumique apparente du granule  comprime Â, mais n'in¯uencent gue Áre les proprie Âte Âs des comprime Âs fabrique Âs a Á partir du granule Â. SummaryThe effects of agitation rate, air sweep rate, and reactor temperature in the production of PBX 9501, a plastic-bonded explosive molding powder, were investigated. These variables affected the agglomerate length, the agglomerate shape, and the bulk density of the molding powder, but had very little effect on the properties of pressed pieces made from the molding powder.

Los Alamos Natlonal Laboratounder contrad W-7405-ENG-3z~By acceptance of thls artlcle, the publisher recognizes that the U.S. Government retains a nonexclushre roy publish or rqroduca the published form of thls contnbutlon, or to allow others to do so. for U.S. Government p u y e s . AbstractLos Alamos National Laboratory has demonstrated that many energetic materials can be rendered non-energetic via reaction with sodium hydroxide or ammonia. This process is known as base hydrolysis. A pilot scale reactor has been developed to process up to 20 kg of plastic bonded explosive in a single batch operation. In this report, we discuss the design and operation of the pilot scale reactor for the processing of PBX 9404, a standard Department of Energy plastic bonded explosive containing HMX and nitrocellulose. Products from base hydrolysis, although non-energetic, still require additional processing before release to the environment. Decomposition products, destruction efficiencies, and rates of reaction for base hydrolysis will be presented. Hydrothermal processing, previously known as supercritical water oxidation, has been proposed for converting organic products from hydrolysis to carbon dioxide, nitrogen, and nitrous oxide. Base hydrolysis in combination with hydrothermal processing may yield a viable alternative to open burning/open detonation for destruction of many energetic materials.