BASE HYDROLYSIS AND HYDROTHERMAL PROCESSING
Base Hydrolysis and Hydrothermal Processing of PBX-9404 ExplosiveJ. A. Sanchez, RL. Flesner, T. Spontarelli, P.C.Dell'Orco, J.F. KramerLos Alamos National LaboratoryDX-16, MS C-920Los Alamos, NM 87544 USAABSTRACTBase hydrolysis in combination with hydrothermal processing has beenproposed as an environmentally acceptable alternative to open burnindopen detonation for degradation and destruction of high explosives. In this report, weexamine gaseous and aqueous products of base hydrolysis of the HMX-basedplastic bonded explosive, PBX-9404.We also examine products from the subsequent hydrothermal treatment of the base hydrolysate. The gases produced fromhydrolysis of PBX-9404 are ammonia, nitrous oxide, and nitrogen. Majoraqueous products are sodium formate, acetate, nitrate, and nitrite, but not allcarbon products have been identified. Hydrothermal processing of basehydrolysate destroyed up to 98% of the organic carbon in solution, and higherdestruction efficiencies are possible. Major gas products detected fromhydrothermal processing were nitrogen and nitrous oxide.
Base Hydrolysis and Hydrothermal Processing of PBX-9404IN'IXODUCTIONIn dismantling weapons fromstockpile reduction, suitable degradationof the associated high explosive (HE)waste to environmentally acceptable formsis a critical objective within the DOEcomplex. Currently, open burning is themethod of choice for HE disposal and separation of HE and uranium components.Revocation of burning licenses couldhinder HE disposal and impact thedismantlement process. Thus, alternatemethods are needed as back-ups and,eventually, as replacement techniques.Base hydrolysis is one proposedalternative method that involves chemicalreaction of the HE with sodium hydroxidesolution at temperatures of approximately85 to 90 C. The resulting product mixtureis no longer energetic and mostly watersoluble. Explosives such as nitrate esters,nitroaromatics, and nitramines are decomposed under basic conditions (1-5).Nitramine explosives RDX and HMXdecompose to form nitrates, nitrites,ammonia, nitrogen, organic acids,formaldehyde, and hexamethylenetetramine. In addition to this, RDX is morereadily hydrolyzed than HMX (3,6).The products' from the basehydrolysis of PBX-9404l have not yetbeen fully characterized. In Order toproperly dispose of the hydrolysis productmixture, it is desirable to obtain a massbalance for the reaction. The primaryfocus of this work is to identify andquantify the products from the basehydrolysis of PBX-9404.Secondary processing of basehydrolysis products is needed becausesome constituents of the process areconsidered hazardous. Hydrothermaltreatment has been proposed as asecondary process of base hydrolysate. Inhydrothermal treatment, the hydrolysate isThe formulation for PBX-9404is 94%HMX, 3%nitrocellulose, 3% chloroethylphosphate,and 0.1%diphenylamine,13/20/95heated to elevated temperatures and pressures ( 200OC, 100 bar) in the presence ofan oxidant. Above water's critical parameters (374OC, 221 bar), hydrothermaltreatment is known more formally assupercritical water oxidation. The transport properties of supercritical waterresemble those of gases, allowingchemical reactions to occur without diffusion limitations. Solution densities are alsoreasonably high in SCWO/hydrothermalsystems (0.1 to 0.9 g/cm3), allowingreasonably high waste throughputs (7).Because required organic oxidationtemperatures are below 60O0C, NO, gasesare not generated (8). In addition,hydrothermal processing/SCWO reactorsare totally enclosed treatment facilities, inwhich gaseous and liquid effluents can beanalyzed and retained, if necessary, beforetheir release to the environment. In thiswork, we will discuss destruction of PBX9404 hydrolysate in a hydrothermalprocess reactor. The general termhydrothermal treatment is applied to the9404 hydrolysate, because the criticalparameters of the solution are unknown;that is, even though treatment parametersare above the critical parameters for water,they may or may not be above the criticalparameters for the hydrolysate.EXPERIMENTAL, METHODSRase Hvdrolvsis Reaction Conditions.The amounts of materials typicallyused were 10 milliliters of 1.5 normalsodium hydroxide solution per gram ofexplosive. Base solutions were preparedwith reagent grade sodium hydroxide andin-house deionized water. Hydrolysisreactions were normally performed in around-bottom flask fitted with acondenser. A temperature controller wasused to obtain a constant 85 to 90 O Ctemperature. The temperature was heldbelow the solution boiling point to minimize foaming and to keep the explosive2
Base Hydrolysis and Hydrothermal Processing of PBX-9404hydrolysate originally treated with 1MNaOH in a molar ratio of 1 mole nitricacid per mole of organic carbon residing inthe sample. Hydrogen peroxide was addedto hydrolysate originally treated with 1.5MNaOH in a molar ratio of 1 mole hydrogenperoxide per mole of organic carbon.Hydrothermal Product Analysisfrom splashing onto the sides of thereaction vessel. For the on-line massspectral analysis of gaseous products, thegases were swept with helium into theinlet of the instrument.Base Hydrolysis Product AnalysisProducts from the hydrolysis reactionswere analyzed by a number of differentmethods. Nuclear magnetic resonance(nmr) spectrometry was used to identifythe major hydrolysis products. A E O LGSX-270 multi-nuclear spectrometer wasused to obtain proton and carbon nmrspectra. Analyses were performed on thehydrolysis solution with a small amount ofdeuterated water added to provide a locksignal. Mass spectrometry was used toanalyze gaseous hydrolysis products(Extrel residual gas analyzer) and for solidresidue analysis (Finnigan-Mat model8200). Some gas analysis was alsoperformed by Fourier transform infraredspectrometry using a Bio-Rad FTS 40instrument. Ammonia was analyzed bytrapping in dilute hydrochloric acid solution and using a gas sensing electrode forquantitation. Quantitative analysis forinorganic and organic anions wasperformed with a Dionex ion chromatograph using a conductivity detector. Solidresidues from dried hydrolysis solutionswere tested for thermal stability by differential thermal analysis (DTA) using aDupont model 910 thermal analyzer.Hydrothermal Reaction ConditionsReactions were carried out from960 to 1100 bar at 380 to 45OOC in a 0.478cm ID Inconel 625 reactor. A completedescription of this reactor and experimental procedures has been providedelsewhere (9,lO). The average residencetime of reaction was approximately 1min.Nitric acid and hydrogen peroxide wereused as oxidizers for the base hydrolysiseffluent. Nitric acid was added to3/20/95'Products from the hydrothermalreactions were analyzed by ion chromatography, gas chromatography, and totalorganic carbon. Quantitative analyses forinorganic and organic anions, and ammonium were performed with a Dionex ionchromatograph using a gradient eluent, anAS9 column, and a conductivity detector.Gas products were measured using a HP5890 series 11gas chromatograph, using aCarbPLOT column, helium carrier gas,and a thermal conductivity detector. Totalorganic and inorganic carbon weremeasured using a Rosemount-DohrmannDC-190 TOC analyzer.RESULTS AND DISCUSSIONDualitative Analvsis of Gaseous PBX9404 Hydrolvsis Products bv FrIRFourier transform infrared (FT'IR)spectroscopy was used to identify thegaseous products from the hydrolysis ofPBX-9404. Prior to and during thehydrolysis reaction, the mixture waspurged with argon to replace air in thevessel. When gas evolution was visiblefrom the mixture, a sample was takenusing a gas tight syringe. The gas wasinjected into an evacuated infrared gas cellfor analysis. The infrared spectrum,Figure 1, below, shows nitrous oxide andammonia as the major infrared-detectableproducts. Nitrogen is also known to be aproduct and was analyzed by massspectrometry (seediscussion below).3
Base Hydrolysis and Hydrothermal Processing of PBX-94043/20/95IImiFigure 1. FI?R Spectrum of Gaseous PBX-9404 Hydrolysis Products.Biotreatment in addition tohydrothermal processing has beenproposed as a secondary method fortreatment of base hydrolysis effluent.Because the biotreatment of hydrolysaterequires neutralization, the gases 'evolvedupon addition of acid to PBX-9404hydrolysate were also analyzed. Sulfuricacid was added to the hydrolysate and themixture was put in an ultrasonic bath todrive off the gases produced. The gaseswere sampled as described above andfound to contain the following: carbondioxide, formic acid, nitric oxide, andhydrogen cyanide. Although this gasmixture is highly toxic, the neutralization'conditions used were a worst case.Conceitrated acid was added quicklyallowing the mixture to become warm andacidic in pH. Solutions of nitrite, a majorhydrolysis product, are expected toproduce nitric oxide under these conditions. When neutralization is done byslow addition of dilute acid, very little gasis produced.Gases produced from pyrolysis ofdried PBX-9404 hydrolysate (describedbelow) were also analyzed. The pyrolysiswas found to produce nitrous oxide,carbon dioxide, ammonia, and carbonmonoxide as shown in Fig. 2.
105.NaDx100.1wTra5anSm90.ittan85Ce80-75-I-Figure 2. FTIR Spectrum of Gases Produced from Pyrolysis of PBX-9404 Hydrolysate.Quantitative Analvsis of Ammonia fromPBX-9404HydrolvsisThe gaseous hydrolysis productswere also analyzed for ammonia content.A dilute hydrochloric acid trap was used toconvert the ammonia to ammoniumchloride. A one gram sample df PBX9404 was hydrolyzed and the gases wereswept into the trap with argon. Ammoniaanalysis of the trap solution was thenperformed with a gas-sensing electrode. Itwas found that nine millimoles of ammonia were produced from one gram of HE.This represents 35 percent of the nitrogencontained in the PBX-9404.Analysis of Gaseous PBX-9404Hydrolysis Products bv MassSDectrometrvGases were analyzed on-lineduring a reaction by sweeping them withhelium into the instrument inlet as theyw e r ep r o d u c e d .Mass/intensity/time/temperature data werecollected for masses up to 100 amu over aperiod of approximately one hour. Thereaction was then stopped by cooling inice and the unreacted material (HMX) wasfdtered and weighed. A three-dimensionalplot of the data is shown in Figure 3,below. Because no masses above 50 amuwere detected, the mass range plotted is10-50 mu.
Gas Products50.0I0.01I20.0IITime (min)160.0110.0140.0Mass intensity (mv)10.0Figure 3. Three-dimensional Plot of Mass-Time-Mass Intensity Data of Gaseous PBX-9404Hydrolysis Products.Over the course of the reaction, theonly significant masses detected were 44,30, 28, and 18 through 14. The gasesidentified from these data are nitrousoxide, nitrogen, and water vapor.Although mass 44 matches carbon dioxideas well as nitrous oxide, the absence of apeak at 12 amu indicates C 0 2 is notpresent. The mass intensity data at 44 and28 amu were converted to amounts ofnitrous oxide and nitrogen. Calibrationdata were acquired by injecting knownamounts of pure N20 and N2 into theinstrument. The mass spectrum of N20includes fragments at 30 and 28 m u , andthe intensity due to nitrogen at 28 wascorrected for this. Figure 4 is a plot of therates of N20 and N2 evolution versus timeof reaction. Also plotted is the temperature profile for the reaction.Because of the time delay of thegases reaching the detector, the massspectral data lags the temperature data by2-3 minutes. As the final temperature of85 C is reached, the rate of N20 and N;!evolution peaks and then graduallydeclines. When the reaction is quenchedin ice, gas evolution ceases abruptly.Integration of the gas evolution curvesgives the total amounts of N20 and N2produced. This was found to be 1300pmoles and 290 pmoles, respectively.Based on the weight of material thatreacted, the total nitrogen (N not N2)consumed in the reaction was 20.9millimoles. The above amounts of N20and. N2 represent 12'and 3 percent of thereacted nitrogen, respectively.
t118IttI1'III0.0'0lo002000Time (sec)3Ooo4000Figure 4. Rates of Nitrous Oxide and Nitrogen Evolution versus Reaction TimePBX-9404 Hydrolysis Non-gaseousProduct AnalysisBecause no significant amount ofcarbon has been detected in the gaseousproducts, it can be assumed that nearly allof the carbon remains in solution as watersoluble products. The 13C nmr spectrumof PBX-9404 hydrolysate shows the2H2CO NaOH-An experiment was performed totrap and analyze methanol in the gaseousproducts. A purge of argon was used tosweep the gaseous hydrolysis productsthrough water that was cooled in ice. Thewater trap solution was then analyzed bygas chromatography for methanol content.The amount of methanol found represented only one percent of the carbon fromthe PBX-9404. This means that either theformate is produced by some othermechanism, or the methanol is consumedin a subsequent reaction.formate ion as the major carbon-containing product. One explanation for theproduction of formate is the reaction offormaldehyde, the initial product of HMXhydrolysis, with sodium hydroxide. Thisis known as the Cannizzaro reaction andmethanol should be produced in equimolaramount to the formate (11).NaOOCH CMOHIon chromatography and 13C nmrspectrometry have shown that approximately one-third of the carbon is convertedto sodium formate. The 13C nmr alsoshows at least fifteen peaks in addition tothe formate peak, most of them relativelysmall, as shown in Figure 5. Many of thepeaks are grouped between 50 and 80 ppmchemical shift, some are near 180 ppm,and a couple are near 20 ppm. A nmrexperiment called DEPT (DistortionlessEnhancement by Polarization Transfer)
Base Hydrolysis and Hydrothermal Processing of PBX-9404was performed to determine the carbontypes, i.e., methyl, methylene, methine, orquaternary. The unknown peaks near 20ppm were found to be methyl carbons,those between 50 and 80 ppm weremethylenes, and those near 180 ppm werequaternary carbons. One of the quaternary3/20/95and one of the methyl carbons may be dueto the acetate ion. A peak matching theretention time of acetate was found in thei o n chromatographic analysis.Quantitative analysis showed it to represent 13% of the total carbon from thePBX-9404.FormateCH2 CarbonsQuaternaryCarbonsI260do140140140do8h 040I20I 10Figure 5. Carbon NMR Spectrum of PBX-9404 Hydrolysate.LIn addition to the Cannizzaroreaction described above, formaldehydemay undergo condensation reactions inbase solution (11). Condensation reactionsof formaldehyde can form hydroxyaldehydes, hydroxy ketones, and sugars.The unidentified 13C nmr peaks of thePBX-9404 hydrolysate have chemicalshifts in the region expected for thesetypes of compounds. Some of thesematerials were obtained or synthesized,and evaluated by nmr as possible products.The following compounds were checked:dihydroxyacetone, 1,4-dioxane, formaldoxime trimer, formalin, formamide,glycolaldehyde, glyceraldehyde, glyoxal,methylene bis-f ormamide, andparaformaldehyde. Of all the materialschecked, dihydroxyacetone came closestin nmr chemical shift to the hydrolysisproduct unknowns, 64.6 ppm. It has notyet been verified that dihydroxyacetone is,in fact, among the hydrolysis products.PBX-9404 Material BalanceTable 1 shows all of the productsthat have been identified for PBX-9404hydrolysis. To date, 47 percent of thecarbon, 70 percent of the nitrogen, and 62percent of the chlorine have been8' I
Base Hydrolysis and Hydrothermal Processing of PBX-94043/20/95accounted for. Further work is required toachieve a better mass balance.Table 1. Products from the Hydrolysis of PBX-9404(Shown as percentage of starting C or N from explosive)Hydrothermal Processiw Results of PBX9404 H v d r o l v aNitric acid oxidationNitric-acid was initially used as anoxidant for two reasons. The nitrate ion isan effective oxidant for organic matter inhydrothermal systems (12), and the aciditself helps to neutralize the basic hydrolysis solution. In addition, nitrate has beendemonstrated to be a considerably moreeffective oxidant for ammonia thanmolecular oxygen in supercritical water(13);. ammonia removal frqm thehydrothermal reactor effluent may benecessary for the final disposal.Reaction conditions for theseexperiments are shown in Table 3.Oxidation kinetics were studied in threeexperiments at temperatures from 405OCto 453 C. Total organic and inorganiccarbon (TOC and TIC) were measured forthe feed solution and effluent samples todetermine a material balance on theeffluent and to determine organic carbondestruction efficiencies. Gas chromatography (GC) was used to identify gaseousnitrogen and carbon products. The basicpH of the effluent (pH between 9 and lo),compared with the feed solution (12.9)indicated hydroxide was consumed inproton transfer reactions with C02produced from carbon oxidation. Noplugging was observed at reactor operatingpressures near 1000 bar. Pluggingtypically occurs at lower pressures andhigher temperatures, which favors sodiumcarbonate precipitation from solution (14).Table 3. Reaction Conditions for Hydrothermal Processing of 1M Hydrolysate using NitricAcid as OxidizerReaction Temp ("C)4054294531Pressure (bar)1111j 110911113Ion chromatography (IC) andTOC/TIC results for these experiments arepresented in Table 4. Data in Table 4Residence Time (s)646057Effluent pH10.0 *9.89.8indicate that increases in reaction temperature resulted in increased TOC destruction.This fact is also illustrated by acetate and9
Base Hydrolysis and Hydrothermal Processing of PBX-9404formate concentrations, which monotonically decrease with increases in temperature. Acetate and formate also appear asthe majority of the organic carbonremaining after oxidation, representing93.6% to 114.0% of the measured effluentTOC values. Because TOC values resultfrom a subtraction of TIC from TC values,low TOC concentrations in the presence ofa high TIC background are difficult toaccurately quantify. This analyticaldifficulty, combined with the fact thatacetate and formate have long beenrecognized as refractory carbon reactionintermediates in hydrothermal systems(15), suggests that effluent TOC valuesmight better be derived from acetate andformate concentrations.As TOC values decrease withincreasing reaction temperature, inorganiccarbon concentrations increase. . The pH3/20/95of the effluent samples (Table 3) indicatethat TIC is present predominately asHCO;, with a significant amount COS .As discussed previously, these species areformed in rapid proton transfer reactionswith C 0 2 produced from organic carboncombustion. Ammonium values firstincrease from the feed solution, and thendrop slightly. The initial increase is likelyproduced from nitratehitrite reductionwith the organic matter. This behavior hasbeen observed in nitrate/methanol andnitrate/acetate hydrothermal systems(16,17). The subsequent decrease, albeitsmall, may result from subsequentammonia reactions with nitrate to form N2and N20. These reactions have beenobserved at similar temperature regimes inbasic N a N O m 3 solutions (13).Table 4. Total Organic Carbon and Ion Chromatography Results from Nitric AcidOxidized Hydrothermal Processing of Base Hydrolysate. (Allresults presented in m a )* - Includes HNO3 addition** - Below detection limitsGas products from the hydrothermal processing are reported in Table 5.No oxygen was detected in the gaseouseffluent. Significant amounts of hydrogenwere evolved at 405OC, but at highertemperatures, less hydrogen and moremolecular nitrogen were observed.Hydrogen appears to be produced in earlystages of carbon hydrolysidoxidation, onlyto be oxidized to water with nitratelnitriteat higher temperatures. This hydrogenproduction behavior has also been'observed in the hydrothermal treatment ofEDTA using nitratehitrite oxidizers (9).Nitrous oxide production remained near10% of the total gas production for allthree temperatures;its conversionappeared to reach a maximum at 429OC.Small amounts of hydrocarbon materials,notably methane and ethylene, were alsoproduced, with higher conversions evidentat lower temperatures. At 453OC, the onlyreduced gaseous product present was atrace amount of methane.10
Table 5. Gas Products from Nitric Acid Oxidized Hydrothermal Processing of BaseHydrolysate. (All results presented are percentage of total volume of gas produced per liter ofsohtion)Good mass balances were obtainedfrom the nitric acid oxidation experiments,as shown in Table 6. Also shown in Table6 are the observed TOC destructionefficiencies. The carbon mass balance isbased on the ratio of the known carbonconstituents in the effluent to the organiccarbon in the feed solution. These carbonconstituents include the difference ininorganic carbon between the feed and theeffluent. The total destruction efficiencyis based on the total organic carbon in thefeed compared to the total organic carbonin the effluent and carbon containing gasesevolved. As shown in Table 6, the carbonmass balances range from 94 to 114%.Some of these results are larger than 100%because of probable errors in inorganiccarbon measurements. As previouslydiscussed, at high inorganic carbonloadings the determination of small levelsof TOC is analytically difficult. As aresult of this potential error, for thereaction conditions at 429OC and 453OC,DRE's (Destruction Removal Efficiencies)were calculated using acetate/formateconcentrations rather than TOC measurements. This prevented the calculation of anartificially high DRE.IReactionTemp ("C)405429453WCarbon MassBalance*94%103%114%LDestruction efficiencies increasedwith increasing temperature. Nearly all ofthe organic carbon was converted tobenign products above a reaction temperature of 429OC at 1 minute residence time.Higher destruction efficiencies could beachieved by longer residence times orhigher operating temperatures.Hydrogen peroxide oxidationTotal Organic CarbonDestruction Efficiency*78.0%95.3%98.3%Hydrogen peroxide was also usedas an oxidant in the hydrothermal processing of base hydrolysate.A moreconcentrated sample of base hydrolysate(1.5 M NaOH) was used in thisexperiment, and has been describedpreviously in the experimental methodssection. Reactions were carried out at onetemperature because of experimentalproblems with H202. Hydrogen peroxidereacts with the base hydrolysate at roomtemperature to form small gaseous
Base Hydrolysis and Hydrothermal Processing of PBX-9404bubbles. These bubbles make it difficultto pump the solution at high pressure. Onerun at 419OC was made before the pumpwas unable to continue to pressurize thereaction to 1034 bar. Since the time of theinitial experiment, a revised experimentalsetup has been designed to allow the copumping of H 2 0 2 and hydrolysate atelevated pressures.The pH changedduring the reaction from 12.1 in the feed to9.5 in the effluent. The pressure of thereaction was 990 bar and the residencetime was 64 s.1'3/20/95Ion chromatography and totalcarbon results of feed and effluent ionconcentrations are shown in Table 7.Using hydrogen peroxide, nitrate andnitrite were completely reacted, but TOCdestruction removal efficiencies were notas effective as with nitric acid. Note thatonly one temperature was attempted;organic carbon destruction would be moreeffective at higher temperatures andincreased residence times.Table 7. Total Organic Carbon and Ion Chromatography Results from Hydrogen PeroxideOxidized Hydrothermal Treatment of Base Hydrolysate. (All results presented in m a Nitrite163830Ammonia. 6992482Formate1887910118Acetate133774212products. Significant amounts of hydrogen are evolved at 419 C. Small amountsof methane and ethylene were alsodetected, as observed also in the nitric acidoxidation experiments.Gas products from the H202oxidation experiment were, measured bygas chromatography and are presented inTable 8. In contrast to nitric acid oxidizedprocessing, no N 2 0 was detected, butoxygen was detected in the gaseousTable 8. Gas Products from Hydrogen Peroxide Oxidized Hydrothermal Treatment ofBase Hydrolysate. (All results presented are percentage of total volume of gas produced perliter of solution)Destruction efficiency, or organiccarbon conversion, for hydrogen peroxidewas not as good as when nitric acid wasused as the oxidizer. The destructionefficiency for the one peroxide run was58%. Since nitrate or nitrite were notpresent at the end of the reaction(oxidizers themselves), this indicates thatnot enough oxidizer was added to the feedsolution. It is possible that hydrogenperoxide decomposition to molecularoxygen in the feed container resulted in.these lower than stoichiometric values.One desirable feature of this reaction isthat the nitrogen species are completelyconverted to gaseous products; this mightsuggest that a step feed reactor is afavorable reaction scheme, withnitratehitrite carbon oxidation in the firstreactor segment and oxygen oxidation inthe second segment. In this experiment,92% of the carbon in the feed solution wasrecovered in the effluent. This mass12
Base Hydrolysis and Hydrothermal Processing of PBX-9404balance was calculated in the same way asfor the nitric acid experiments.CONCLUSIONSWe have shown base hydrolysis tobe a viable alternative to openburning/open detonation disposal of energetic materials. This low temperaturechemical treatment method results innonenergetic and water-soluble products.The gases produced from hydrolysis ofPBX-9404 are ammonia, nitrous oxide,and nitrogen. A mass balance of 70percent has been determined for nitrogenproducts, and 47 percent for carbonproducts. More work is needed to identifyadditional products. If a secondarytreatment step is required for the hydrolysis product stream, this can be achieved byhydrothermal processing, biotreatment, orpossibly low temperature pyrolysis.3/20/95We have also demonstrated that wecan process the aqueous effluent of basehydrolysis in a hydrothermal reactor.Destruction efficiencies up to 98% wereachieved using nitric acid as an oxidizer.Major gas products detected were N2 andN 2 0 at these temperatures, and H2 atlower reaction temperatures. Nitrate,nitrite, and ammonia were detected in theeffluent, and nitrate and nitrite productscan be minimized by using less oxidizer.Some acetate was detected in the effluentstream, and formate was detected at loweroperating temperatures. For hydrothermalprocessing using hydrogen peroxide as anoxidizer, lower destruction efficiencieswere observed than with nitric acid, but webelieve that these destruction efficienciescan be increased with larger amounts ofoxidizer and operation a t highertemperatures.I
Base Hydrolysis and Hydrothermal Processing of PBX-94043/20/95ACKNOWLEDGMENTSWe gratefully acknowledge the support of the Department of Energy.REFERENCESUrbanski, T. “Chemistry and Technology of Explosives”, Volume I, Pergamon Press:1.New York, (1964).2.Urbanski, T. “Chemistry and Technology of Explosives”, Volume II,Pergamon Press:New York, 1965.Urbanski, T. “Chemistry and Tecbology of Explosives”, Volume III, Pergamon Press:3.New York, 1967.Urbanski, T. “Chemistry and Technology of Explosives”, Volume IVYPergamon Press:4.New York, 1984.Miles, F.D. “Celiulose Nitrate”,Interscience Publishers: New York, 1955.5.Buntain, G.A., Sanchez, J.A., Spontarelli, T., and Benziger T.M., Los Alamos National6.Laboratory, “Destructionof Waste Energetic Materials Using Base Hydrolysis,” Proceedings ofthe 1993 Incineration Conference.7.Shaw, RW., Brill, T.B., Clifford, kk,Eckert, C.A., and Franck, E.U., Chem Eng. News69(51), 26 (1991).8.Tester, J.W., Holgate, H.R., Armellini, F.J., Webley, P.A., Killilea, W.R, Hong, G.T.,and Barner, H.E., ACS Symp. Ser. 518,35 (1993).9.Foy, B.R., Dell’Orco, P.C., Breshears, D., et al., “Hydrothermal Kinetics of Organic andNitratdNitrite Destruction for Hanford Waste Simulants”. Los Alamos Unclassified Report, LAUR-94:3174, September, 1994.10. Dell’ Orco, P.C., “Quality Assurance Project Plan for TWRS-Hanford Project,Hydrothermal Processing of Hanford Tank Wastes, CST-4”. Los Alamos Unclassified Report,LA-UR-94-1989, May, 1994.11.Walker, J.F., “Formaldehyde,” Second Edition, ACS Monogr. 120,16 (1953).12.Robinson, J., B. Foy, P. Dell’Orco, et al., “Destructionof Nitrates, Organics, andFerrocyanides by Hydrothermal Processing”, LA-UR-93-456, February (1993). Presented atWaste Management ‘93, Tuscon, Arizona.13.Dell’Orco, P.C. “ReactionS of Inorganic Nitrogen Species in Supercritical Water”. Ph.D.Thesis, Department of Civil Engineering, The University of Texas at Austin, May, 1994.14. Anderson, G.K., Allen, D., Butenhoff, T., Goemans, M., and Knutsen, IC, “PhysicalProperties of Hanford Tank Waste Simulants and Related Systems Under HydrothermalConditions’’. Los Alamos Unclassified Report, LA-UR-943352, September, 1994.Li, L.,P. Chen, and E.F. Gloyna. “Generalized Kinetic Model for Wet Oxidation of15.Organic Compounds.” AIChE J. 37(11), 1687 (1991).Dell’Orco, P.C., B.F. Foy, J.R Robinson, and S.J. Bueiow, “HydrothermalTreatment of16.Hanford Waste Constituents”,Hazardous Wastefiazardous Materials 10,221 (1993).Foy, B.R. et al., “Kinetics of Organic Oxidation by Nitrate in Hydrothermal Systems”,17.Los Alamos Unclassified Report, LA-UR-93-3147, September, 1993.14
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Base Hydrolysis and Hydrothermal Processing of PBX-9404 3/20/95 IN'IXODUCTION In dismantling weapons from stockpile reduction, suitable degradation of the associated high explosive (HE) waste to environmentally acceptable forms is a critical objecti
COFFEE BREWING WETTING, HYDROLYSIS & EXTRACTION REVISITED 2. COFFEE BREWING WETTING, HYDROLYSIS & EXTRACTION REVISITED HYDROLYSIS Hydrolysis is the name for a general chemical reaction that occurs when water reacts with another compound to alter it or break it down. Duri
formic acid oxidation before hydrolysis for the determination of the sulphur containing amino acids, hydrolysis methods for the determination of trypto-phan and recent developments in the hydrolysis) of the proteins. 3 Ion exchange chromatography of amino acids 3.1 Introduction After sample preparation, in most cases meaning hydrolysis of the .
Investigation: Life on a Hydrothermal Vent. EDUCATOR GUIDANCE. Some common misconceptions students may share as they experience this phenomenon include: algae are plants plants and algae can photosynthesize in the dark animals in the hydrothermal vent ecosystem survive by only eating dead things that sink to the sea floor
840 to 865 m. At “PP 10/F 11” sites hydrothermal precipitates cover an area of about 50 m in diameter. Anhydrite chimneys up to 2 m high are present at the summit of this low elevated hydrothermal mound. A few patches (500 cm2 each) of mussels were present. A few geryonid crabs (Chaceon affinis) were present in the vicinity.
Hydrolysis of salts The term salt hydrolysisdescribes the reaction of an anion or a cation of a salt, or both, with water.Salt hydrolysis usually affects the pH of a solution. (1) The salts composed of an alkali or alkaline earth metal ion and the residue of a strong aciddo not undergohydrolysis and their solutions are assumed to be neutral.
Figure 1. Historical overview of the net production, consumption and imports of petroleum products (U.S. Energy Information Administration, 2011). 3 Figure 2. Renewable Fuels standard targets (Schnepf & Yacobucci, 2010). . 4 Figure 3. Hydrothermal processing phase diagram of water.
Acid-Base Properties of Salt Solutions: Hydrolysis To learn about the concept of hydrolysis and gain familiarity with acid-base indicators. 500-mL Erlenmeyer flask Bunsen burner ring stand and iron ring wire gauze dropping bottles of methyl orange, methyl red, bromothymol blue, phenol red, phenolphthalein, and alizarin yellow-R 0.1 M solutions .
February 2019 State Current ASME A17.1 and A17.7 Code Versions Summary and Background Current Rule Development Status Upcoming Action Contact Agency Name Citation Regulatory ID AL ASME A17.1 (2016) ASME A17.7 (2007) Alabama auto-adopts the latest version of ASME codes six months after its publication date without the need for additional rulemaking. ASME A17.1 (2016) became effective 7/31/2017 .
