DMSO Recrystallization of HMX and RDX

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[AD

AD-E400 556

CONTRACTOR REPORT ARLCD-CR-80052

DMSO RECRYSTALLIZATION OF HMX AND RDX

MICHAEL D. ROTHROCKHOLSTON DEFENSE CORPORATION

vctl HOLSTON ARMY AMMUNITION PLANT

KINGSPORT, TN 37662

L. SILBERMANH. RICCI

R. GOLDSTEINARRADCOM

a ELEECTE•

•,%•.•.iF, 1981 •..

FEBRUARY 1981

US ARMY ARMAMENT RESEARCH AND DEVELOPMENT COMMAND

LARGE CALIBERWEAPON SYSTEMS LABORATORY

DOVER, NEW JERSEY

"APPROVED FOR PUBUC RELEASE; DISTRIBUTION UNLIMITED.

L-J

'81 ,

The views, opinions, and/or findings contained inthis report are those of the author(s) and shouldnot be construed as an official Department of theArmy position, policy or decision, unless sodesignated by rther documentation.

Destroy this report when no longer needed. Donot return it to the originator.

The citation in this report of the names ofcommercial firms or commercially availableproducts or services does not constitute officialendorsement or approval of such commercialfirms, products, or services by the United StatesGovernment.

I

-,m mw mm ! . mmmm

UNCLASSIFIEDSECURITY CLASSIFICATION OF THIS PAGE ("on Dat. Efntered)

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I REPORT NUMBER A2 GOVT ACCESSION NO. 3 RECIPIENT'S CATALOG NUMBER

CONTRACTOR REPORT ARLCD-CR-80052 _________04 TITLE (mnd Subtitle) 5 TYPE OF REPORT & PERIOD COVERED

DMSO RECRYSTALLIZATION OF HMX AND RDX Final

s PERFORMING ORG. REPORT NUMBER

7. AUTHOR(&) 5. CONTRACT OR GRANT NUMBER(@)

Michael D, Rothrock, Holston Defense CorporationL. Silberman, H. Ricci, and R. Goldstein, DAAA-09-73-C-0079ARRADCOM

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT. TASKHolston Defense Corporation AREA I WORK UNIT NUMBERS

Holston Aim), Ammunition Plant DARCOM MW Proj 57x4310Kingsport, TN 37662

1,. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATEARRADCOM, TSD FEBRUARY 1981STINFO (DRDAR-TSS) 13, NUM1ER OF PAGESDover, NJ 07801 17514. MONITORING AGENCY NAME I AODRESSQI different from Controlilnd Office) 15. SECURITY CLA.SS. (of this r"Port)

ARRADCOM, LCWSL UNCLASSIFIEDEnergetic Systems Process Div (DRDAR-LCM-E)Dover, NJ 07801 IS1. DECLASSIFICATION7OOWWGRAOING

SCHEDULE

16. DISTRIBUTION STATEMENT (of thl. Report)

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IS. SUPPLEMENTARY NOTESThis project was accomplished as part of the U.S. Army Manufacturing Methods andTechnology Program. The primary objective of this program is to develop, on atimely basis, manufacturing precesses, techniques, and equipment for use inproduction of Army materiel19. KEY WORDS (Continue an termse tide it nceeoawy mnd Identify by block numiber)

Recrystallization Pilot plantDMSO Continuous cooling crystallizationRDX Dilution crystallizationHMX MT-Process improvement

123, AIIIITN ACT (Condomt 40 ,evWSM S N nme'"006 wmu h"lIfV by block nu""w)A pilot-scale process for recrystallization of RDX and HMX from DM50 was designe,procured, installed, and evaluated at Holston AAP. Process design was based onprevious work which indicated cooling crystallization techniques using continu-ous nucleation and classified product removal to be most effective. Although alexpected classes of material were successfully recrystallized, operating diffi-culties forced departure from the original equipment design and required iaple-mentation of alternate operating strategies. As a result, five distinct modes

1 ,Continued .DoDo OANM 03 •• now of Iov 45ois omoLEVE UNCLASSIFIED

SEC'ImIY C%.*A3IrCATnW OF THIS PAGI (00k- D01e Entered)

. UNCLASSIFIED,SECURITY CLASSIFICATION OF THIS PAOE(WShan Data Entert*

20. ABSTRACT (cont)

of operation were established, dependent upon the particular class of materialbeing recrystallized. Two of these (for Class 5 RDX and Class 5 HMX) werebatch.

Although the pilot plant failed to demonstrate the design concept of asingle, multiclass recrystallization process using separation and recombinationto give desired class, the direct recrystallization techniques developed weresatisfactory and, in some cases, could be scaled-up based on the data generated.In other cases more piloting will be required in order to develop the data basenecessary for sound scale-up,

Material recrystallized in the pilot plant was shown to meet all existingspecifications, A variety of explosive fornulatiorns was produced for furthertesting which will include both interim qualification and end iten, tests.,

A preliminary economic analysis indicates DMSO to result in significantcost reductior. for recrystallization of HMX at production rates in excess of

150,000 pounds per morth, while little or no cost reduction is anticipated forRDX.

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UNCIASS I IED

SECURITY CLASSIFICATION OF THIS PAGEfWhef L- .n L10 '.d)

CONTENTS

Page

Introduction I

Experimental 3

Equipment 3Materials 12Product Requirements and Methods of Analysis 12

Experimental Procedure 17Results 28Discussion 33Economic Analysis 55

Conclusions 66

Recommendations 68

References 70

Appendixes

A - Tables 71H - Figures 121C - Mixing EquF.tions for RDX/HMX, Recycle Solvent

and DMSO 155D - Physical Properties of DMSO 158

Distribution List 167

FAccesson For

NTIS GRA&IDTIC TABUznenn~ouncedDT CJustification

lE!-EC T -

198

Di tr bz ,o. i-

INTRODUCTION

Laboratory work performed during the Phase I study of "R crystallizationand Growth of HMX/RDX, a Study of Methods and Equipment" indicated that

significant increases in explosives recrystallization rates with corres-ponding decreases in recrystallization costs could be achieved in existingbatch equipment using DMSO and cooling crystallization processes. Theimprovement was attributed primarily to the larger batch sizes possibledue to the higher solvent power of DMSO for RDX and HMX when compared withthe standard recrystallization solvents, acetone and cyclohexanone. Otherbenefits of recrystallization from DMSO included improved crystal charac-t eristics such as clarity and shape. Cooling processes were also shownto provide safer, more controllable recrystallization systems which couldprovide more consistent product particle size distributions (PSD).

The Phase II pilot plant study2 revealed that the predicted batch sizeincreases were obtainable in batch, stirred-tank cooling crystallizers.Also, the products from these recrystallizations compared favorably withsimilar products recrystallized by conventiondl methods. However, it wasalso discovered that production of the larger particle size distributionsin batch equipment was difficult. Therefore, the batch systems were judgedpractical only for producing the finer PSD's (Classes 1 and 5). Effectiveproduction of the coarser Class 3 and Class 4 distributions required thefines control capability of the draft-tube crystallizer which was alsoevaluated during this pilot plant. The draft-tube design had the disad-vantages of low production rates and high equipment cost,

A need for the simplicity of the batch stirred tank equipment plus thefines control capability required for production of coarse explosives ledto the investigation of a batch, controlled nucleation, classified productremoval (CNCPR) crystallization system during the later part of the Phase IIpilot plant. The high effective growth rates achieved in the batch CNCPRsystem as well as the high production rate potential of this system pro-vided the incentive for he more detailed investigation presented in thisreport.

The accomplishments of the Project 4310 pilot plant phase included thefollowing:

1. Process design of the CNCPR crystallization system and all auxiliarysupport systems.

2. Mechanical design of the pilot equipment and specification of instru-

ments ane control systems.

3. Procurement, modification, and installation of pilot plant equipment.

4. Development of a liquid chromatographic procedure for process controland pilot plant performance evaluation.

SHolston Defense Corporation I Kingsport, Tennessee

Technical Report No. HDC-58-80

5. Completion of a hazards analysis based on the final pilot plant design.

6. Evaluation of the pilot plant including debugging, calibration, opera-tor training, operatiun, and product manufacture.

7. Analysis of the data generated, the presentation of conclusions reached,and recommendations for future work based on the results achieved.

Holston Defense Corporation 2 Kingsport, Tennessee

R.-.'


EXPERIMENTAL

EQUIPMENT

The equipment and facilities used to perform the experiments during thepilot plant phase are located at Building C-6, Holston Army AmmunitionPlant. Most of the building equipment and the new process equipmentwere used to perform experiments as required.

Process and Instrumentation Diagram

The original process flow sheet (P&I) diagram for the Building C-6pilot plant recrystallization process is presented as Figure 1.The equipment, instruments, and connected piping required to performthe basic experiments and produce recrystallized RDX and HMX areindic3ted on this figure. Changes in process configuration are notindicated on this figure but are discussed in detail in Section IV.

Equipment Layout

The original equipment layout plan for the pilot plant is detailedby Figures 2, 3 and 4. Table 1 presents a listing of each piece ofequipment and its designated code number.

Process Equipment Description and Basic Functions

Slurry Mix Tank, CA-52 (Figure 5)

The slurry mix tank is a 50-gallon (0.189 mn3 ), agitated, 304Lstainless steel tank used to blend the input materials for therecrystallization processes. The tank is positioned on threehydraulic load cells which are calibrated to determine the netweight of the tank contents. A dial indicator is provided forreading the weight, (Note: Due to failure of the hydraulicload cells the weigh system could not be used. The slurry mixtank was instead volumetrically calibrated for liquid measure-ment. Solids and make-up DMSO were weighed prior to addition).

Charging of explosives is accomplished by shoveling from anutsche or charging from preweighed bags, Recycle solventis pumped from storage tanks while any virgin solvent requiredis pumped directly from a drum as needed. A hydraulic, variablespeed agitator is provided for mixing the ingredients, Slurryis transferred from the slurry mix tank to the evaporator feedtank by opening the air operated slurry mix tank drop valve andstarting Pump CA-IO.



Evaporator Feed Tank, CB-50 (Figure 6)

The evaporator feed tank is a 200-gallon (0.757 m3 ), agitated,304L stainless steel tank equipped with coils and jacket forheating or cooling. Material received from the slurry mix tankmay be heated in this tank to prepare it for feeding to theevaporator. Automatic temperature regulating instrumentationis provided. The feed solution is continuously circulatedthrough a low pressure steam-jacketed loop by Pump CB-10 witha feed take-off to the evaporator. The feed rate to the evap-orator is controlled by the evaporator level signal-and maifi-tains proper evaporator level.

Evaporator, CB-51 (Figure 7)

The evaporator is a 100-gallon (0.379 m3 ) 304L stainless steel,full vacuum rated tank equipped with coils and jacket for heat-ing or cooling. Automatic temperature regulating instrumenta-tion is provided to control the steam flow to the coils andjacket. Total system pressure is variable and automaticallycontrolled by an air bleed to the two stage vacuum jets mountedon the roof. The solution in the evaporator is continuouslycirculated through a steam jacketed loop by Pump CB-ll. Agita-tion of the tank contents is furnished by the returning fluidstream from this loop.

Feed to the dissolver is drawn from this loop via a control valveand magnetic flowmeter. The vapors from the boiling tank con-tents are fed directly into the rectifying column (CB-21) whichis integrally mounted on top of the evaporator.

Rectifying Column, CB-21 (Figure 8"

The rectifying column is a packed column consisting of a 12-inch(0.30 m) diameter, 304L stainless steel shell packed with one-inch (25.4 mm) sodium-etched, Exlon rings. k-tive packed heightis 18 feet (5.49 m) with liquid redistribution every 4.5 feet(1,.37 m) and gas redistribution in the center of the column.Liquid feed distributors are located at six feet (1.83 m) andat 15 feet (4.57 m) from the bottom of the column, Reflux rateis controlled by action of a timed three-way valve connectingthe distillate condenser to the distillate receiver and thereflux head. Vacuum is maintained by the two-stage vacuum jetslocated on the roof.

Dissolver, CB-52 (Figure 9)

The dissolver is a 100-gallon (0.379 m3 ) 304L stainless steel,agitated atmospheric tank equipped with coils and jacket for


-'-


heating or cooling. Feed entering this tank is diverted fromthe evaporator circulating loop by a three-way metering valve.A magnetic flowmeter is provided to measure the flow rate ofthe feed stream and instruments are provided to allow this rateto be controlled and varied. Temperature measuring and regula-ting instrumentation is provided to control steam flow to thecoils and jacket. The hot, DMSO/explosives solution in thedissolver is circulated to the crystallizers by Pump CB-12through two independently controlled flow loops. The overflowfrom each crystallizer combines at the crystallizer overflowand returns by gravity to the dissolver. Level control in thedissolver is provided by limit switches which allow the levelto fluctuate between two predetermined points. When the highlevel is reached, the air-actuated three-way valve in thecrystallizer overflow line diverts the flow from the dissolverto the mother liquor receiver and the level in the dissolverdrops. When the low level limit is reached, the three-wayvalve returns to its original position and the crystallizeroverflow continues back to the dissolver. Loss of air supplydiverts all flow to the dissolver.

Crystallizers, CC-50 and CC-51 (Figure 10)

Each crystallizer is a 9.5-gallon (0.036 m3 ), 304L stainlesssteel, agitated, atmospheric tank equipped with coils andjackets for cooling. The solvent/explosive solution from theaissolver is independently circulated to both crystallizers byPump CB-12. Feed rates to the crystallizers are individuallycontrolled by separate control valves and measured by magneticflowmeters. Instrumentation is provided to allow control andvariation of these rates. The combined overflows from thecrystallizers are returned to the dissolver or the motherliquor receiver as determined by the level in the dissolver.

Temperature is measured and regulated in each crystallizer byinstrumentation which controls the automatic valve in thecooling water supply line. Product is removed through ram-typedrain valves centered in the bottom of each crystallizer. Therate of product removal is controlled by manually setting thesupply pressure to the valve operators to control the percentageof full open required. Signals to the valve operators are pro-duced by electric, interval timers which control both the fre-quency of product removal and the volume of slurry removed.Separate timers are provided for each crystallizer with twoset points to control the frequency and duration of the open/closed cycles. (Note: During experimentation, capacitanceprobes were added to each crystallizer timer circuit to allowmore precise volumetric product removal).

Holston Defense Corporation Kingsport, Tennessee


Mother Liquor Receiver, CD-50 (Figure 11)

The mother liquor receiver is a 50-gallon (0.189 m3 ), 304Lstainless steel, agitated, atmospheric tank equipped with atempered water jacket. The tank functions as a receiver forthe recycle solvent stream from the decant system, The re-cycle solvent is held at ambient temperature or can be heatedusing the tempered water jacket. A high level alarm soundswhen the level in the tank reaches approximately 85% of totaltank volume. The tank contents are manually transferred period-ically for recycle solvent processing or direct recycle.

Product/Mother Liquor Decant System (Figure 11)

The original product mother liquor screen equipped with a 270mesh (53 um) screen was replaced with the product/motherliquor decant system. The function of the screener was toreceive the product stream from the crystallizers and to per-form the initial solids/liquid separation. During initialtrial runs constant plugging of the 270 mesh screen forcedelimination of the screener altogether. The separation wasdone, instead, using the decant system. The crude decant systemconsists of several 2.5 gallon (0.0095 m3 ) buckets for receivingthe product slurry from the crystallizers, After settling, theliquid is manually decanted to the mother liquor receiver, theproduct solids are reslurried with water, and the slurry ismanually transferred to the first wash screen.

First Wash Screen, CD-02 (Figure 11)

The first wash screen is a single-deck, 18-inch (0.46 m),electrically driven, Sweco vibrating screener of 304L stainlesssteel construction equipped with one 325 mesh (44 ,m) screen anda self-cleaning kit. This screener receives the reslurriedsolids from the initial solids/liquid separation describedabove. A spray nozzle is used to provide a water wash to removeresidual solvent from the product crystals. Washed solids over-flow to the second wash screen (CD-03) and the wash liquor alongwith any precipitated fines underflows to Filter No. 2 (CD-52).

Second Wash Screen, CD-03 (Figure 11)

The second wash screen was originally a multi-deck, 18-inch(0.46 m), electrically driven, Sweco vibrating screener of 304Lstainless steel construction equipped with 8, 50, 120 and 325mesh (2380, 297, 125 and 44dm, respectively) screens in a con-tinuous stack. A self-cleaning kit was included on the bottom

Holston Defense Corporation Kiigsport, Tennessee

Techoical Report No. HDC-58-80

screen and a m~etered filtered water wash was provided via aspray nozzle. The function of this screener was to performa final water wash and physical separation of individual screenfractions which could later be blended in various ratios toproduce different intermediate explosives products. Duringtrial runs constant plugging occurred on all the screens forcingabandonment of the size separation idea. All the screens exceptthe 325 mesh were removed. The product from CD-02 was simplywashed a second time on CD-03 and then discharged into a 2.5gallon (0.0095 m3 ) polyethylene bucket. This material was thenmanually charged into Vacuum Filter No. 3 (CD-53) for finaiwash and dewatering.

Vacuum Filters; CD-51, CD-52 and CD-53 (Figure 11)

The three small vacuum filters are 20-inch (0.51 m) diameter,304L stainless steel, tank-type filters with removable, poly-ethylene cloth support grids, Each filter has a 38-gallon(0.144 m3 ) filtrate capacity and an 18-gallon (0.068 m3) solidscapacity. CD-51 and CD-52 are equipped with tempered waterjackets. Removable cloth filter bags are used to collect thesolids. Each filter has an independent vacuum supply controlvalve and level indicator,

Vacuum Filter No. 1 (CD-51) was designed to remove productfines from slurry received from the mother liquor receiver.Because of growth of crystals on and subsequent blinding ofthe filter cloth, this filter was bypassed and this procesringstep eliminated.

Vacuum Filter No. 2 (CD-52) receives the first wash waterunderflow from the first wash screen which contains the finesprecipitated during the first wash. The cake required somewashing to remove the residual solvent present.

Vacuum Filter No. 3 (CD-53) receives the washed underflow andoverflow streams from the second wash screen. The materialaccumulated in this filter provides the bulk of the productand the filtrate provides the bulk of the first wash water.

Recycle DMSO Receiver, CF-51 (Figure 12)

The recycle DMSO receiver is a 150-gallon (0.568 m3 ), 304Lstainless steel, agitated, tank equipped with both coolingwater and tempered water supplies to the jacket along withtemperature indicating instruments. The tank contents aremaintained at a predetermined temperature depending on theexplosive product present and the solvent content. Mother


Technical Report No. H'C-58-80

liquor received from vacuum filter No. 1 fCD-51) or directlyfrom the mother liquor receiver (CO-50) -s cooled to precipi-tate excess dissolved explosives which are allowed to settlein the tank. The cooled solution overflows from the tankthrough the overflow nozzle provided to the recycle DMSO stor-age tank (CF-53). Accumulated impure solids are periodicallydropped to vacuum filter No. 4 (CF-52) where the solids arecollected for disposal or use depending upon the composition.

Product Line Wash Reservoir, CF-54 (Figure 12)

The product line wash reservoir is a 2.5- gallon (0.0095 m3 ),inline holding tank used to store recycle DMSO overflowing therecycle DMSO receiver. A manually controlled, air-operated,drop valve is provided to allow the intermittent flushing ofthe product discharge line from the crystallizers (CC-50 andCC-51) to the decant system.Vacuum Filter No. 4, CF-52 (Figure 12)

Vacuum Filter No. 4 is a 304L stainless steel filter with a25-gallon (0.095 m3 ) solids capacity and a 75-gallon (0.284 m3 )filtrate capacity. A removable cloth filter bag is used tocollect solids from various recycle DMSO streams prior tofurther processing or disposal, Collected solids material isrecycled or handled as waste explosives depending on its purity.

Recycle DMSO Storage Tanks; CF-53, CA-50 and CA-51 (Figures 12and 13)

The recycle DMSO holding tank (CF-53) is a 150-gallon (0.568 m3 ),polyethylene tank which is used to co,lect the recycle DMSOfrom either the recycle DMSO receiver or Vacuum Filter No. 4.The tank contains only the working invenitory of recycled DMSO.Excess recycle DMSO may be pumped to either DMSO Storage TankCA-50 or CA-51 or directly to the wast5 solvent storage tank.CA-50 and CA-51 are 350-gallon (1,32 m ) agitated, 304L stain-less steel tanks which are used for storing various solutionsfor start-up or shutdown operations. Dilution operations werealso performed in these tanks to precipitate excess dissolvedexplosives prior to pumping to the waste solvent recovery equip-ment.

Condensate Holding Tank, CE-5i (Figure 14)

The condensate hold tank is a 100-gallon (0.379 m3 ), polyethylene,atmospheric tank which is used to collect and store both therectifying column overhead (distillate) stream and the second



wash water from vacuum filter CD-53, The combined materialis then pumped to the first wash screen and used as firstwash water.

Waste Solvent Recycle Tank, CB-53 (Figure 15)

The waste solvent recycle tank is a 75-gallon (0.284 m3 ),

316 stainless steel, unagitated tank equipped with a heatingcoil and temperature indicating and control instrumentation.Filtered wiste solvent is pumped as required to this tank andpreheated to the appropriate temperature. The waste solventis fed to the rectifying column during recovery operations.

Waste Solvent Storage Tank, CG-50 (Figure 16)

The waste solvent storage tank is a 5,000 gallon (18.9 m3 ),316 stainless steel, agitated tank which is used to store allwaste solvent containing less than 30% DMSO. Water is addedas required to correct the DMSO content to 10-20%. This materialis held for recovery of DMSO or for disposal.

Waste Solvent Filter, CG-51 (Figure 16)

The waste solvent filter is a 304L stainless steel, vacuumfilter with a 175-gallon (0.662 m3 ) solids capacity and 300-gallon (1.13 mi) filtrate capacity. A removable cloth filterbag is used to collect solids which will be discarded as wasteexplosives. The filtrate contains 10-20% DMSO which is pumpedeither to the waste solvent recycle tank for recovery or to asolvent wagon for processing and/or disposal.

Vacuum Systems (Figures 17 and 18)

Vacuum is maintained on the five vacuum filters via two vacuumreceivers (CJ-50 ana CJ-51) using a set of two, single-stage,steam ejectors (CJ-10 and CU-11). Filters 1, 2 and 3 connectto a common header while filters 4 and 5 share a second header.Piping is arranged so that either or both receivers can be usedas the vacuum source. Vacuum is maintained on the rectifyingcolumn (CB-21) and the evaporator (CB-51) using a separate two-stage, intercondensed, steam ejector (CB-13). The pressure ofthis vacuum supply system is controlled by an air bleed just aheadof the main jet inlet. Steam flow to the first and second stagejet and the water flow to the intercondenser are monitored.



Exhaust System (Figure 19)

Exhaust hoods are provided at all locations where the possibilityof operator contact with solvent fumes exists, The hoods arelocated over the slurry mix tank (CA-52), the decant andscreener positions (CD-Ol, CD-02 and CD-03), Filter No. 1,Filter No. 2, Filter No. 3 and Filter No. 4. The overflowheader from the crystallizers (CC-50 and CC-51) has a smallcrossflow vent located behind the sampling Cort. The airmover for the ventilation system is an exhaust fan (CH-IO)located on the building roof.

Pumps

All the pumps used in this process are 304 stainless steel,centrifugal, slurry pumps equipped with water flushed, stuffing-box type seals. High temperature shut-off as well as an inter-lock for seal water failure protection is provided.

Waste Water Holding Tank, CG-52 (Figure 20)

The waste water holding tank is a 10' x 15' (3.0 m x 4.6 m)stainless steel 8,000-gallon (30.3 m3 ) storage tank which isused to collect the excess water generated during the pilotplant evaluations. This waste water overflows by gravity fromthe condensate holding tank (CE-51) and accumulates duringthe pilot operation. Disposal of this water depends upon theconcentration of DMSO as monitored by LC analysis. Most ofthis stream was discharged during this evaluation.

Hydraulic System (Figure 21)

Two hydraulic oil drive units are u3ed to furnish power to thehydraulic drive motors for each agitated tank used in theprocess. Each agitator has its own variable speed control.One hydraulic power unit supplies the motors on the crystallizers(CC-50 and CC-51). The other unit supplies motors on theslurry mix tank (CA-52), the recycle DMSO receiver tank (CF-51),the dissolver (CB-52), and the mother liquor receiver (CD-50).

Tempered Water 3ystem (Figure 22)

A Pick water heater is used to furnish the 40-50oC (313-323 K)tempered water for the mother liquor receiver (CD-50), FilterNo. 1 (CD-51) and Filter No. 2 (CD-52), This water heater isa thermostatically controlled steam/water mixer which suppliesconstant temperature water over a variable range of demand con-ditions dictated by the recrystallization process. Used



tempered water is not recirculated but is discarded afterone pass.

Safety and Emergency Systems

Fire Protection

A sprinkler system of the wet-pipe design is provided for all

operating areas of Building C-6. Activation of this system isby heat only. No manual activation is currently available.When the sprinkler system is activated, the fire bell is auto-matically engaged by the flow of water.

Emergency Alarm and Interlock

Paddle switches located at all the Building C-6 exits activatethe building emergency alarm as well as the automatic buildingemergency shutdown sequence. The alarm switch is activated bypersonnel as they exit the building as soon as they realizethat an emergency or uncontrolled dangerous situation exists.Activation of the emergency alarm automatically shuts downcritical process equipment including all process pumps, thescreeners, the vent fan, and the steam supply to all processtanks. The tank agitators continue to run.

Safety Showers and Eye Wash Stations

Safety showers are located as close to potential sites ofpersonal contact with solvent and explosive solutions asphysically possible. Eye wash units are located near the filter-ing area on the first floor, near the Sweco separators on thelower mezzanine, and near the slurry mix tank. Safety showersare located with the eye wash stations as well as at otherstrategic locations throughout the building.

Personnel Protective Equipment

Due to the potential for the existence of hazards associatedwith operator contact with DMSO/explosives solutions whichmight contain unknown contaminants from the crude explosives,care was taken to contain all DMSO/explosives solutions withinthe process equipment and to minimize operator exposure as muchas possible. In those situations where potential operatorexposure could not be avoided, the following additional per-sonnel protective equipment was provided:


LAi


'-. Face shields (clear plastic, full coverage)2. Aprons (-ubber, covering chest and upper legs)3. Galoshes (rubber, worn over safety shoes)4. Gloves (rubber, solvent resistent)

MATEPiALS

Process Materials

Dimethyl Sulfoxide (DMSO - See Appendix D for physicalproperties)

Crude RDX (Filtered, washed, nutsched)

Crude HMX (Filtered, washed, nutsched)

Analytical Materials

HexaneAcetonitrileDimethyl Formamide (DMF)MethanolChloroform

PRODUCT REQUIREMENTS AND METHODS OF ANALYSIS

RDXHDC Analytical

AttriDutes Reutremernts Standard Metnod

Purity, % RDX 1-26+, i-153++IHMX, % 0.01* Microscope

Acidity, % as Acetic Acid 0.02 Mlax. C-9Melting Point, OC 190 Min. P-12Acetone Insoluble3, 0.0". Max. C-6Inorganic Insolubles, 0.03 Max, C-6Insoluble Particles

Retained on USSS No. 40 None C-460 5 ax.

Impact cm 33+ P-4Color White VisualResidual DMSO, GC Procedure #33Granulation F-5

Internal Contr-1+ Irformaticn Analysts+4 Drocess C.ontrol (,C-6)

Fiolston Defente Corporatiomt 12 )irspoL't, TeInssee

I'i

Techn,cal Report No. HDC-58-80

U.S. Standard Weight % PassingSieve No. CLASS

_-- _ _ 3 5 6 7 , 8

8 1001212 99-10020 96-100

S35 98-100 0-40 100

50 80-100 90-100 30-50 96-100 98-10060 96-10080 91-100

100 30-90 50-80 10-30 1 82-98 90-100120 :67-93170 43-80200 5-45 20-46 0-20 31-61 55-80230 122 - 50

325 1 97 -100{ 8-36 . 40-60

HMXHDOC AnalyticalAttributes Requirements Standard Method

Purity, % HMX Grade A - 93 Min. 1-4, 1-151+, 1-153++Grade B - 98 Min.

% a HMX < 0.10* 1-4% SEX - 1-151+, 1-153++

Polymorphic Form Beta 1-4

Melting Point, °C 277 Min. P-12

Acidity, % Acetic Acid 0.02 Max. C-9

Color White*

Insolubles: Acetone, % 0.05 Max. C-6Inorganic, % 0.03 Max. C-6

Insoluble ParticlesOn USSS No. ho 0 C-4

60 5 Max. C-4

Impact, cm 30 Min.* P-4

Residual DMSO, % GC Procedure #33

*Internai Control

+Irformaclon Analysis++Process Control (C-6)

Hn1ston Defense Corporation 13 Kingsport, Tennessee


Particle Size, P-5

% Passing for Class

USSS No. 1 2 3 4 5 6

8 10012 99-100 85-100 99-10035 10-4050 84-96 100 25-55 90-100

100 40-60 10-30 0-15 50-80120 98-100200 14-26 0-20 15-45325 3-13 75-100 98-100 5-25

Composition A-3Requirements HDC Analytical

Attributes Minimum Maximum Standard Method

% RDO, 90.3 91.7 C-36% Wax 8.3 9.7 C-36% Moisture - 0.1 1-7% Acidity 0.02 C-37Insoluble Particles on C-4

USSS40 - 060- 5

Granulation, % PassingUSSS 6 100 -

100 - 5 P-9

Bulk Density (gm/cc) P-172Army Procurement 0.77Navy Procurement 0.81

Foreign Matter - None P-60

Composition A-5 Requirements HDC AnalyticalAttributes Type I Type 1I Standard Method

RDX % 98.5 - 99.0 98.5 - 99.0 C-29Stearic Acid % 1.0 - 1.5 1.0 - 1.5 C-29Moisture % 0,10 Max. 0.10 Max. 1-7Bulk Densityg/ml 0.95 Min. 1.00 Min. P-8Insoluble Particles

on USSS No. 40 None None C-460 5 Max, 5 Max.



Comp A-5 (cont'd)HOC Analytical

Attributes Type I Iype II Standard Method

Granulation, % PassingUSSS No. 12 99.0 Min. 99.0 Min. P-9

200 2.4 Max, 2.4 Max.

Composition C-4Requirements HDC Analytical

Attributes Minimum Maximum Standard Method

RDX, % Class 1 and 2 99.0 92.0 C-48

Class 3 89.8 91.2

Class 4 88.9 90.9

Binder, % Class 1 and 2 8.0 10.0 C-48

Class 3 8,8 10.2Class 4 9,0 11.0

Moisture, % 0.25 1-7

Plasticity, Class 1 and 4 0.030 P-29

Class 2 - 0.080Class 3 0,018 -

Specific GravityClass 2 only 1.50 - P-30

Insoluble Particles C-4

on USSS No. 40 - 060 5

Composition B RequirementsType I Type II HDC Analytical

Attributes Min. Max. Min. Max.. Standard Method

% RDX 57.5 61.5 57.5 61.5 C-7

% TNT 37.2 41.8 37.2 41.8 C-7

% Wax 0.7 1.3 0.7 1.3 C-8

%H- 0.20 - 0.20 C-3

BuNl Density,gm!cc - - - 0.90 P-172

Insoluble Part.Ret'd. on USSS 60 - 5 - 5 C-4

Efflux Vis.,Sec.:Grade A - 7,0 - - P-l

Grade B - 17.0 -

Granulation; P-9

% Pass. USSS No.10- - 100 -

200- - - 1.0



lotol

HDC Analytical

Attributes Requirements Standard Method

Type I II IIClass - A B

Min. Max. Min. Max. Min. Max.

% RDX 73.0 77,0 68.0 72.0 67.6 71.6 C-2C-7

% TNT 23,0 27.0 28.0 32,0 by Difference

% CalciumSilicate .35 .65 C-l

ViscosityEfflux Sec. 15.0 - 10.0 - 10.0 P-l

% Moisture 0.25 0.25 0.25 C-3

InsolublesParticlesRetained onUSSS No. 60 5 5 5 C-4

Octol

Attributes Requirements

Type I II II

Class 1 2HDC Analytical

Mi. Max. Mi. Max Mi. Max. Standard Method

% HMX 73.0 77.0 68,0 72.0 68.0 72,0 C-7

% TNT 23.0 27.0 28.0 32.0 28.0 32.0 C-7

ViscosityEfflux Sec. - 15.0 12.0 - 8.0 P-1

Moisture - 0.25 0.25 0.25 C-3

PolymorphicForm Beta Beta Beta 1-4

ForeignMatter None None None Visual


* .*'.

Technical Report No. HDC-58-80HDC Analytical

Min. Max. Min. Max.. Min. Max. Standard MethodInsolublesParticlesRetained onUSSS No. 60 5 5 5 C-4

% Acetone Insoluble 0.1') 0.10 0.10 C-6

EXPERIMENTAL PROCEDURE

The DMSO-recrystallization process as originally designed underwentmany physical changes throughout the evaluation phase of the project.This evaluation was primarily due to problems which arose and weresolved using the most practical and available means possible. Theresulting modified processes are described in general terms in SectionIV. A. and in more detail in Section IV. B. A more detailed comparisonof the modified pricesses with original processes may be accomplishedusing Standing Operating Procedure No. 1800-6702 at HSAAP.

General Process Description (Reference Figures 26 and 27)

Feed was prepared in the slurry mix tank by mixing crude explosives,recycle solutions of varying composition, and make-up DMSO. Themixture was pumped to the evaporator feed tank and then meteredinto the evaporator/rectifier system. DMSO was concentrated inthe evaporator by removing water as an overhead stream from the topof the rectifying column. Concentrated DMSO/explosives solution inthe evaporator became the feed for the CNCPR crystallization system.The ratio of explosives to DMSO as well as the evaporator conditionswere controlled so that the feed solution was maintained at 85-90%DMSO by weight on a solids free basis and contained no undissolvedexplosives. This feed material could be introduced to the CNCPRsystem at several points depending on the particular product to beproduced. Generally it was metered directly into the crystallizersor tne dissolver. Conditions within the CNCPR system were controlledto cause precipitation of explosive crystals. This was accomplishedby water quenching to produce fine PSD's or by simply cooling thefeed solution to produce the coarser PSD's. The conditions chosendetermined both the particle size dictribution and throughput ratesobtainable.

Coarse explosives (Classes 1, 3, and 4) produced by cooling techniqueswere removed from the crystallizers at timed intervals in a thickenedslurry containing approximately 40% solids and 60% spent solvent.The liquid was decanted into the mother liquor receiver and held atambient temperature until transferred for recycle solvent processingor reused directly for making new feed solution. After decanting,the solids were diluted with water to reduce the solvent concentra-tion and to precipitate the remaining dissolved material. Reslurried


F;4


product was then fed to the first wash screener and spray washedwith a weak (0.5 - 2%) DMSO solution. The underflow fines ob-tained from the screening operation were collected, filtered, andwashed with clean water in a vacuum filter. Filtrate was trans-ferred to the waste solvent storage tank. The bulk of the productcrystals overflowed onto the second wash screener and were washedagain with clear water. The combined overflow and underflow werecollected in another vacuum filter, dewatered and then placed inproduct containers. The filtrate was combined with the fractiona-ting column distillate in the condensate receiver and used for firstwash water. The excess was discarded.

Fine explosives (Class 5) produced by water quenching techniques wereremoved from the crystallizers in a slurry containing 10 to 20%solids by weight and liquid which contained approximately 20 - 50%DMSO by weight. This slurry was metered directly onto two vibra-ting screeners equipped with water sprays and 325 mesh (44 pm)screens for scalping oversized particles, The product solids inthe underflow were collected in vacuum filters- ashed, dewatered,and placed in product containers. The combini filtrate and washýwater were transferred to the waste solvent storage tank.

Recycle DMSO collected in the mother liquor receiver was useddirectly to make new feed solution or processed as recycle solvent.Material transferred to the recycle DMSO receiver was cooled to20 - 250 C (293 - 298 K) to precipitate the remaining explosives.The solids were allowed to settle out in the receiver and tne liquidoverflowed to the recycle DMSO holding tank. The settld solids inthe receiver eventually required filtration in filter #4. The filtratewas combined with the receiver overflow in the holding tank whereit was stored until required for making new feed. The sclids infilter #4 were water washed and stored as waste explosive's, Thewash water was transferred to the waste solvent storage tank.

Waste solvent generated from the various product washing operationsplus the solvent purge generally contained 10 - 30% DMSO and 1 - 2%explosives by weight. Recovery of the DMSO involved filtering theslurry in the waste solvent filter to remove explosives and othersolid impurities, fractionating the resulting solution to remove waterand other volatile impurities and to concentrate the DMSO, and evap-orating the concentrated DMSO as an overhead distillate to freethe DMSO of dissolved impurities. The evaporator temperature, thecolumn pressure, and the reflux ratio were controlled to obtainthe desired concentration of DMSO in the evaporator an' distillate.In general the DMSO was concentrated to 95 - 98% while -he distillatecontained less than 0.01% DMSO. The concentrated DMSO was collectedin storage tanks and then later fed to the evaporator where it wasevaporated as an overhead product and collected as 85 - 86% DMSO.(Note: The remaining 14% of this distillate is water which enters thesystem through the evaporator circulation pump packing gland.)



Detailed Procedure (Reference Figures 26 and 27)

Receiving Explosives

Crude RDX and H14X were individually received at the BuildingC-6 pilot plant in nutsches. The explosives had been filtered,washed, and dewatered prior to receipt. Upon receipt eachnutsche was sampled and analyzed by liquid chromatography (L.C.)for composition and moisture content, This information wasused for determining the amounts of explosives to be addedto feed batches. The crude explosives were stored in thenutsches until used.

Receiving and Storing DMSO

DMSO was received at the pilot plant in 55-gallon (.208 m3 )drums as packaged at the supplier. Since the drums receivedfrom the solvent storage building (Quonset Hut 133) normallycontained frozen DMSO, enough was kept at the pilot plantto allow time for thawing. Normally, 5 - 10 drums werereceived at a time.

Preparing Evaporator Feed

Feed batches were prepared in the slurry mix tank. Crudeexplosives, a recycle solvent stream, and make-up DMSO wereall charged to this tank to produce a desired ratio of ex-plosives to DMSO in the final mixture. The calculationsrequired to determine the ratios of the various streams toeach other involved the use of the temperature/solubilityrelationships presented in graphical form as Figure 23 andFigure 24. Equations were developed based on these relation-ships and programmed into a Texas Instruments (TI-59) cal-culator to facilitate the calculations performed at the pilotplant. The equations derived and a typical calculation arepresented in Appendix C. In general the steps followed inmaking a typical feed batch are as follows:

1. Charge 30 - 45 gallons (0.11 - 0.17 m3 ) of recycle solventto the slurry mix tank. While agitating, sample therecycle solvent and analyze for percent explosives,percent DMSO, and % water.

2. Using the analysis of the recycle solvent and the crudeexplosives moisture content derived previously, performthe mixing calculation to determine the weights of wetexplosives and make-up DMSO to be charged.



3. Using a shovel or scoop, transfer wet explosives froma nutsche into a plastic bag or bucket. Using theweigh scales provided, weigh out the proper amount andthen charge the explosives to the slurry mix tank.

4. Weigh the make-up DMSO into plastic buckets and chargethis to the slurry mix tank.

j. Agitate the mixture until homogeneous.6. Transfer the mixture to the evaporator feed tank.

The evaporator feed tank was used only for hold-up of thefeed mixture prior to feeding to the evaporator. (Althoughthe evaporator feed tank has provisions for heating the feedmaterial, this ptocedure was discontinued after initialplugging problems were experienced in the evaporator feedsystem caused by the circulation of the hot, 90 - lO0OC(363 - 373 K) material.) The cold feed material was cir-culated in a continuous pump loop to the evaporator. Atake-off for feeding the material to the evaporator was pro-vided at the evaporator.

Concentrating the Solvent in the Feed Solution

Due to the decreasing solvent power of DMSO for ooth RDXand HMX with increasing water content, the extra waterwhich enters the system with the explosives must be removed.Solvent is co,;centrated to 85 - 95% DMSO (solids free basis)which is high enough to dissolve all the explosives and toincrease the efficiency of the process. Solvent concentra-tion was accomplished using the evaporator/rectifying columnsystem. The evaporator feed material was metered to theevaporator which was operated at 100 - 150 mm Hg (13.33 kPa)and 80 - 90 0C (353 - 363 K), The water-rich vapor fromthe evaporator passed through the rectifying column andbecame richer in water as it approached the top of the column.The condensed liquid exited the top of the column with onlya trace (less than 0.01%) of DMSO detectable. A reflux ratio(L/D) of 1/3 was required to achieve this result.

Crystallizing in the CNCPR System

Many experiments using the CNCPR system and several modifi--cations of the CNCPR system were performed for the purposeof identifying the basic process conditions which would allowproduction of the required classes of explosives intermediates.After these basic conditions were discovered, system variables


._-4 lJ -


were manipulated in order to optimize the production rateof the particular product within the physical constraintsof the equipment. During the initial experimentation, theCNCPR system required several modifications to allow effi-cient production of the various explosives intermediates.These different systems are presented graphically in Figure25 and are briefly described as follows:

Basic CNCPR System- The basic CNCPR system, as designed,uses two independent crystallizers and a common dissolver.Saturated or sigjhtly unsaturated 80 - 900 C (353 - 363 K)feed material irom the evaporator, which consists of asolution of explosives, DMSO, and water containing no un-dissolved material, is fed at a controlled rate to the65 - 750C (338 - 348 K) dissolver, The dissolver materialis continuously circulated to each crystallizer at indepen-dently controlled rates. Nucleation and growth takes placein the crystallizers due to the increase in supersaturationwhich occurs as the warm dissolver solution cools in thecrystallizers which are maintained at 35 - 450 C (308 - 318 K).Cooled, saturated solution, containing excess nuclei and fines,overflows from the crystallizers back to the dissolver whereit is reheated to the dissolver temperature causing dissolu-tion of the nuclei and fines. The feed rate to the dissolveris controlled to maintain an explosives concentration suchthat the solution is unsaturated by at least 50C (5 K).Product crystals are periodically removed from the crystallizersat variable timed inter-als. The length of the inteyvaldetermines the average residence time of crystals in thecrystallization environment and thus helps control particlesize distribution of the product. The variables besidesthe particle residence time which most affect the productPSD and throughput rate are the dissolver/crystallizer cir-culation rate and the dissolver explosives composition.

CNCPR-MOD-I - The first modification of the basic CNCPRsystem attempted was CNCPR-MOD-I. The difference from thebasic configuration is that instead of feeding evaporatorsolution to the dissolver, feed material is introduceddirectly to the crystallizers with the feed point in thecrystal bed. This produces a much higher localized super-saturation in the crystallizer and therefore a highercrystal growth rate is potentially possible.

CNCPR-MOD-2 - This modification is similar to CNCPR-MOD-lin that feed is introduced directly to the crystallizers.However, the dissolver/crystdllizer circulation loop is



not used. In this system the production of fines and nucleiis not controlled and therefore the PSD of the product isaffected mostly by the feed rate and the crystal residencetime.

CNCPR-MOD-3 - The distinctive feature of this modificationis the purposeful addition of water to the crystallizer.Otherwise, CNCPR-MOD-3 is the same as CNCPR-MOD-2. The addi-

tion of the water dilutes the DMSO and reduces its solventpower with a r...t~nt precipitation of many very smallparticles. The a•2'+ic2 of water is controlled to producea desired final concenL,, **;n of DMSO in the diluted solvent.The water addition exerts ti. zingle highest effect on theproduct PSD with the feed rate , imarily affecting onlyproduction rate.

Crystallizing by Dilution

The dilution crystallization experiments performed in thepilot plant basically involved quenching hot DMSO/explosivessolutions with cold water to precipitate fine PSD's ofexplosive crystals. The procedures attempted with RDX areas follows:

1. Hot feed material was added to an agitated crystallizerinitially containing a heel of cold water. Feed wascontinued with agitation until the DMSO concentrationin the crystallizer was 40 - 60%. When this point wasreached, water addition was begun so that the ratio ofwater to feed would maintain the 40 - 60% DMSO concen-tration in the crystallizer. When the level in thecrystallizer reached the operating level, continuousproduct removal was begun at a rate which would maintainthe operating level. The temperature in the crystallizerwas not controlled for these experiments.

2. Same as "a" except the water heel was initially 700C(343 K),

3. Hot feed material and cold water were mixed in thecrystallizer feed line in a ratio which produced a45 - 65% DMSO concentration and then the mixture waspiped directly to an agitated crystallizer. The batchwas then heated to 700C (343 K) and aged for 10 - 30minutes (0.600 - 1.800 ks) prior to filtration.

4. Same as "c" except that the batch was not heated to 700C(343 K) prior to the age.



5. Hot feed material and cold water were mixed in thecrystallizer feed line in a ratio whicn produced aninitial DMSO concentration of 65%. The batch wasaccumulated in an agitated crystallizer and aged for10 - 30 minutes (0.600 - 1.800 ks). Additional waterwas then added to the crystallizer so that the finalconcentration of DMSO in the liquid was 45 - 50%.The batch was then dropped to the filtration equipment.

The procedures attempted with HMX are as follows:

1. Hot feed material and cold water were mixed in thecrystallizer feed line in ratios which produced aninitial liquid concentration of 65 - 80% DMSO. Themixture was accumulated in a crystallizer and agitatedfor ten minutes., A second addition of water reducedthe DMSO concentration to 45 - 55% before filtrationof the product fines.

2. Hot feed material was metered into an agitated heelof 95 - 1000C (368 - 373 K) water until the DMSO con-centration was 20 - 25%. After a 20 minute (1.200 ks)age at 950 C (368 K), feed material and water wereadded separately to the crystallizer at a ratio whichproduced 20 - 25% DMSO in the mixture, The productslurry was continuously removed at a rate which heldthe crystallizer volume constant. Crystallizer tem-perature was maintained at 950 C (368 K) throughout therun.

3. Same as "b" except the heel contained beta-HMX seedmaterial.

4. Hot feed material was metered into an agitated heel of95 - 980C (368 - 371 K) water containing beta-HMX seedmaterial. Thr resulting mixture containing 15 - 20%DMSO was 3ged for thirty minutes at 950C (368 K) andthen cooled rapidly to 500C (323 K). The batch wasthen dropped at 50°C (323 K) to filtration equipment.

5. Hot feed material and cold water were simultaneouslymetered into a agitated heel of cold water containingbeta-HMX seed material. The final mixture containingapproximately 25% DMSO was heated to 970C (370 K), agedfor 30 minutes (1.800 ks), cooled to 500 C (323 K), andthen dropped to the filtration equipment.



6. Hot feed material and cold water were simultaneouslymetered into an agitated heel of cold water contain-ing beta-HMX seed material. The feed was continu•eduntil the fini! mixture DMSO concentration was approxi-mately 30%. At th'! point the feeds were stopped andthe mixture was heated to 950C (368 K) and aged for30 minutes (1.800 ks). After the age period, the feedand water were restarted in a ratio which produced aDMSO concentration of appruximately 45%. ProductK slurry was continuously removed at a rate which heldtthe crystallizer volume constant.

7. Sane as "e" except a heel of the material was retainediin the crystallizer as seed for the next batch. Up toeight consecutive batches were run and the remainingproduct was filtered. New series were started by addingnew seed material.

8. Same as "e" except no seed material was used,

Decanting Coarse Product Slurry

Coarse explosives were periodicilly removed from the crystal-lizer into 2.5 gallon (0.0095 mj) plastic buckets. Approxi-mately 1.5 - 2 gallons (0.0057 - 0.0076 m3 ) of product slurrywere removed during each cycle. The slurry ideally contained40 - 50% solids by volume and 50 - 60% spent mother liquor.After a brief settling period of 3 - 10 minutes (180 - 600 s)was allowed, the liquor was carefully decanted by pouring itinto the mother liquor receiver., The heavier solids whichremained in the bucket along with the remaining liquid werediluted and reslurried with enough water so that the slurrycould be poured, The material was then manually poured ontothe first wash screener.

Washing Coarse Explosives Products

Reslurried, coarse product explosives from the decant werepoured onto the first wash screener. The water spray (0.5 -2% DMSO) used with this screener removed most of the remain-ing DMSO from the product crystals. Precipitated fines,reslurry water, and wash water which passed through thescreen were collected in filter #2. Fines were washed withadditional clear water and stored as an impure fines fraction.The filtrate was transferred to the waste solvent storage tank.Coarse product overflow from the first wash screen passedto the second wash screen equipped with another 325 mesh



screen where it was exposed to a cledn water spray washfor removal of most of the remaining DMSO. The combinedoverflow and underflow from this screener was collectedin filter #3, given a fi'nal clean water wash, dewatered,sampled and stored as final product. The filtrate con-tairing the wash water (0.5 - 5% DMSO) was transferred tothe condensate holding tank, combined with fractionatingcolumn distillate, and used for first wash water.

Screening, Washing, and Filtering Fine Explosives Products

Fine explosives from either batch or continuous processeswere fed at controlled rates directly to the first washscreener. A water spray was used to promote efficientwet screening of the fines through the 325 mesh screen andto provide a product wash. The overflow from the firstwash screener (if any) passed to the second wash screeneralso equipped with a 325 mesh screen and a water spray.The underflow from each screener was collected in filter#2 and filter #3, washed again with water, dewatered, andcombined as the final fines product. "Overs" (if any) fromthe second wash screen were sampled and then placed in wasteexplosive containers for burning. Filtrate from both filterswas transferred to the waste solvent storage tank.

Processing Recycle Solvent

Liquid from the decant process along with excess dissolvermaterial was collected as mother liquor in the mother liquorreceiver. This material was transferred to the recycle DMSOreceiver for processing or reused directly for making newfeed batches as will be explained later. Processing in therecycle DMSO receiver involved cooling the liquid as much aspossible to precipitate some of the remaining dissolvedexplosives. The precipitated solids were allowed to settleout in this tank while the bulk of the cold, saturated liquidoverflowed to the recycle DMSO holding tank. This processedrecycle solvent was then reused from the holding tank asrequired. The solids which precipitated in the recycle DMSOreceiver were accumulated until removal was required, Thesolids were filterea and washed in filter #4.

Purging of solvent to remove impurities other than explosiveswas accomplished by transferring part of the processedrecycle DMSO to the waste solvent storage tank where theremaining explosives were precipitated by dilution and theweak DMSO solution held for recovery. The purge was automa-tic since all feed batches made included a percentage of new,make-up DMSO.


* - ---- "4 -. '77 -7.


Initially, all the spent solvent which was to be recycledwas processed before reuse. The idea for the processingwas to remove sc,.e of the remaining explosives by additional

Scooling of the spent crystallizer solvent. Tne explosivesremoved would be 3 relatively impure fines product since theminor explosive component would concentrate in this stream.Because the solubility of both RDX and HMX %n DMSO is similar,the resulting concentration of the minor explosive componentwould be approximately 5Q%. For example, crude RDX containsapproximately 10.% HMX a; an impurity. During recrystalliza-tion in D14S0, this HMX remairs in solution until its satura-

spent solvent stream by cooiing and decanting (ano/or filtra-

tion) removec the HMX component before recycle and thus doesnot allow it to build up. Tnerefore, the RDX product can beobtained 98 i-OM' pure.

Experimental results 'indicated that the R1.X impurity incrude HMX was normally only present at levels below 31.Calculations led to the corclusion thaL the 15% solvent purgerate was high ernough tc keep the level of RDX in the productwell below the desired limits and that processing the recyclesolvent wojld only lower the overall efficiency of the 'e-crystallization process. In the case of RDX, HMX impuritiesare not considered detrimental to the perforiiance of thefinal products. The only good reason for removing it is ifthere is interference with the crystallization process. Noevidence of such interference , was discovered; theretore,most recycle solvent processing was eliminated and the spentcrystallization solvent containing dissolved and precipitatedexplosives was reused directly. Processing of material removedas purge was continued to reduce the loss of explosives aswaste.

Recovering Solvent

Due to cost considerations, separate solvent recovery equip-ment was not purchased for the pilot plant. instead, theevaporator/rectifying column systenm was designed so that itcould be usea on a limiied basis to reconcentrate the DMSOcontained in the w',ste solvent so that it could be reusedfor recrystallizat:0r1.

Weak DMSO soIutiofl collected in the waste solvent storagetark was generated as a result of the solvent purge and theaCcumulation of the filtrate from the product wash. Theliqu;d po.-tion of this material usually contained 10 20%DMSO, 20 - 901 water, and traces of other accumulated

Hclston Defense Corporation Kingsport, Tennessee

t - - . -


impurities such as acetic acid, soluble nitramines, flyash and oil. The solids (1 - 2% of the total) were mostlyexplosives contaminated with fly ash and other insolubleimpurlties, The waste solvent was filtered to remove thesolids and the clear liquid collected as feed for the re-concentration. The DMSO in this stream was concentratedby feeding the weak DMSO solution to the rectifying columnusing the evaporator as the i-eboiler. The evaporator wasinitially filled with feed solution and then the operatingpressure, 75 mm Hg (10 kPa), was established in the system.Evaporator temperature was increased to the boiling pointof the weak DMSO/water solution and the column was allowedto reach its equilibrium temperature. The reflux controlwas activated and water and other volatile impurities wereremoved from the top of the column as distillate. The set-point temperature for the reboiler, 90 0 C (363 K), corres-ponded to the boiling point of 98 - 99% DMSO. Until theset-point temperature was reached, the reboiler level washeld constant by adjusting the feed rate to the column.When equilibrium was established, i.e., the reboiler set-point temperature was reached, the column feed rate wasmaximized by adjusting it so that the reboiler temperatureremained constant. A draw-off of reboiler material was be-gun at a rate which maintained a constant reboiler level.The draw-off material was stored as reconcentrated DMSO.Feed to the column was continued until exhausted. The dis-tillate and bottom draw-off were periodically sampled andanalyzed for percent DMSO by liquid chromatography. The1/3 reflux ratio was the same as that used for feed pre-paration and resulted in a distillate concentration of 0.01%DMSO or less.

Since the reconcentrated DMSO from the fractionation alsocontained the non-volatile impurities which could not beremoved by filtration, the decision was made to recoverthe DMSO from this stream a% a distillate leaving thesenon-volatile impurities in the still as a sludge. Theevaporator/rectifying column system was also used to accom-plish this final distillation. Distillation was begun usingthe heel of reconcentrated DMSO left from the fractionation.The reflux control was adjusted for "no reflux" so that allthe condensate was removed at the top of the column. Theconditions used allowed the system to operate at maximumoutput, i.e., the steam supply to the evaporator was maximumand the pressure was minimum. The feed material was intro-duced to the evaporator at a rate controlled to hold thelevel constant. Distillate was collected from the top ofthe column and placed in used DMSO drums. After completingthe distillation the sludge left in the evaporator was trans-ferred to the waste solvent storage tank.


,. * . .l .ey

it Technical Report No. HDC-58-80

RESULTS

Recrystallization of RDX in the CNCPR Systems

The information presented in Table 2 describes the experimentalconditions and procedures followed during the evaluation ofvarious CNCPR processes for recrystallizing RDX, Table 3presents the calculated results of each experiment.

Recrystllization of RDX in the Dilution Crystallizer System

Table 4 describes the experimental conditions and proceduresattempted during RDX/dilution crystallization experiments.Table 5 presents the calculated results of these experiments.

Analytical Results of Recrystallized RDX Samples

Tables 6, 7. 8, 9 and 10 present analytical results of testsperformed on samples of the recrystallized RDX from the variousrecrystallization processes. Table 11 presents the results ofadditional analytical tests performed on selected representativesamples from various experiments.

Recrystallization of HMX in the CNCPR Systems

Table 12 describes the experimental conditions and proceduresused during the evaluation of various CNCPR processes used torecrystallize HMX. Table 13 presents the calculated resultsof each experiment.

Recrystallization of HMX in the Dilution Crystallizer System

Table 14 describes the experimental conditions or proceduresattempted during HMX/dilution crystallization experiments.Table 15 presents the calculated results of these experiments.

Analytical Results of Recryastallized HMX Samples

Tables 16, 17, 18 and 19 present analytical results of testsperformed on samples of the recrystallized HMX from the variousrecrystallization processes. Table 20 presents the results ofadditional analytical tests performed on selected representativesamples from various experiments.

HMX Recrystallization Process Material Balances

Tables 21 and 22 present material balance information for15 lb/hr (1.89 g/s) and 30 lb/hr (3.76 g/s) HMX/CNCPR systems,


Technical RepQrt No. HDC-58,8Q

respectively. Table 23 presents the material balance for a7 lb/hr (0.88 g/s) HMX/dilution crystallization system. Flowstream numbers refer to Figure 26.

RDX Recrystallization Process Material Balances

Tables 24 and 25 present material balance information for20 lb/hr (2.52 g/s) and 35 lb/hr (4.41 g/s) RDX/CNCPRsystems, respectively. Table 26 presents the materialbalance for a 28 lb/hr (3.53 g/s) RDX/dilution crystallizationsystem. Table 27 is a material balance for a 45 lb/hr (5.67 g/s)RDX/CNCPR-MOD-3 crystallization system. Flow stream numbersrefer to Figure 26.

Solvent Recovery Material Balances

Figure 27 presents the material balance for the pilot plantsolvent recovery system.

Process Capability Estimates

Feed Preparation System

Feed for explosives crystallization systems using DMSO can

be produced efficiently in a feed preparation system similarto the pilot plant system. The pilot system consists of amixing tank, an evaporator feed tank, a vacuum evaporatorequipped with a rectifying column, condenser and refluxcontrols. The water entering the process in the crudeexplosives as well as the pump packing gland water can beeffectively removed with very low solvent losses by evap-oration and rectification of the vapor with reflux. Waterremoved from the top of the column can be expected to contain0.01% (or less) DMSO.

CNCPR Crystallization System

Both RDX and HMX can be crystallized from DMSO using the CNCPRconfiguration. This system is most effective for producingClasses 3 and 4 explosives PSD's with through-put efficienciesof 65 - 80% and 60 - 80% of theoretical yield for RDX ard HMXrespectively. Production rate of 15 - 18 lb/hr (1.89 - 2.27 g/s)can be 'xpected for both RDX and HMX produced in a CNCPR systemusing ;, single 9.5-gallon (0.036 m ) crystallizer.

CNCPR-MOD-l Crystallization System

RDX PSD's ranging'from nominal Class 1 RDX (too large foractual Class 1 RDX) to a nominal Class 3 RDX (too large for



actual Class 3 RDX) can be crystallized from DMSO using theCNCPR-MOD-l configuration. Production ra es of 14 - 18 lb/hr(1.76 - 2.27 g/s) per 9.5-gallon (0.036 in) crystallizer andefficiencies of 46 - 56% of the theoretical yield can beexpected with this .ystem.

HMX PSD's ranging from Class 1 HMX to nominal Class 3 HMX(too large for actuai Class 3 HMX) can be crystallized fromDMSO using the CNCPR-MOD-l configuration. Low productionrates in the range of oily 5 - 10 lb/hr (0.63 - 1.26 g/s)per 9.5-gallon (0.036 m ) crystallizer and efficienciesaveraging 60% of the theoretical yield can be expected.

CNCPR-MOD-2 Crystallization System

RDX PSD's ranging from nominal Class 1 RDX (too large foractual Class 1 RDX) to actual Class 3 RDX can be efficientlycrystallized from DMSO using the CNCPR-MOD-2 configuration.Producti n rates averaging 21 lb/hr (2.65 g/s) per 9.5-gallon(0.036 m3) crystallizer and efficiencies averaging 52% ofthe theoretical yield can be expected.

Although HMX was not recrystallized using this system, itis expected that results would show that the same generalclasses of HMX could be produced as with RDX, However,slightly lower production rates and efficiencies shouldbe expected with HMX compared to RDX.

CNCPR-MOD-3 Crystallization System

RDX Class 1 can be efficiently cry'tallized from DMSO usingthe CNCPR-MOD-3 configuration. Production rates f~om 45 -50 lb/hr (5.67 - 6.30 g/s) per 9.5-gallon (0.036 m ) crystal-lizer and efficiencies of 75 - 80% can be expected.

Although HMX was not crystallized using this system, it isexpected that the same general results would be obtained aswith RDX.

RDX Dilution Procedure "a"

RDX Class 7 can be efficiently crystallized from DMSO usingRDX Dilution Procedure "a". Production rites of 40 - 50 lb/hr(5.04 - 6.30 g/s) per 9.5-gallon (0.03C m ) crystallizer andeffic~tncies of 90 - 95% can be expected.


Technical Repvrt No. HDC-58-80

RDX Dilution Crystallization Procedure

Class 5 RDX can be crystallized from DMSO by precipitationfrom an RDX/DMSO solution using water as the diluent. Abatch procedure similar to "RDX Dilution CrystallizationProcedure 'e'" can be expected to yield a 95% efficiency(95% of theoretical yield). Production rates oý 14 lb/hr(1.76 g/s) of Class 5 RDX per 6-gallon (0.023 m ) (workingvolume) crystallizer can be expected.

HMX Dilution Crystallization Procedure

Class 5 HMX can be crystallized from DMSO by precipitationfrom an HMX/DMSO solution using water as the diluent, Abatch procedure similar to "HMX Dilution CrystallizationProcedure 'g'" can be expected to yield 70 - 95% efFiciencyas a percent of theoretical yield). Production rates of5.1 - 7.0 lb/hr (0.64 - 0.88 g/s) of Class 5 HMX per 7gallon (0.026 mi) (working volume) crystallizer can beexpected.

Recrystallized Intermediate Product Quality

All RDX crystallized in "cooling - only" systems, i.e.CNCPR, CNCPR-MOD-l, and CNCPR-MOD-2, can be expected toexhibit an improvement in purity over the crude RDX charged.Purities for RDX crystallized this way generally rangedfrom 97 - 99% RDX compared to the 90 - 93% crude RDX input.The HMX impurity is concentrated in the fines and wasteexplosives streams. Classes 5 and 7 RDX produced bydilution procedures can be expected to exhibit puritieswhich, in general, are approximately the same as thestarting RDX purity. Class I RDX 9roduced in the CNCPR-MOD-3system shows a slight purity enhancement to the 95 - 96%RDX range.

Particle size distributions of all RDX crystallized in anyof the CNCPR systems can be expected to be narrower andcontain fewer fines than the usual distributions obtainedfrom the evaporative crystallization processes used atHSAAP. Other physical properties of the RDX produced inthese systems are comparable to RDX produced by currentmethods.

All HMX crystallized in "cooling-only" systems can be expectedto exhibit purities of 99.5 - 100% HMX compared to the 98 + %crude HMX charged. HMX crystallized by dilution, like theRDX produced this way, can be expected to yield purities which



are approximately the same as the purity of the startingmaterial.

Particle size distributions of HMX crystallized in any ofthe CNCPR systems are narrower than HMX crystallized usingcurrent methods. Other physical properties of HMX crystal-lized from OMSO are comparable to HMX produced by currentmethods.

Recrystallized Product Retrieval Techniques

Retrieval of product from the crystallizers can be accomplishedby concentrating thecrystals in the bottoms of the crystal-lizers using agitation control followed by the removal ofa controlled volume of this thickened slurry on timed intervals.Coarse products can be removed with a high degree of efficiencywith very little or no loss of product by way of the crystal-lizer overflow. The finer PSD's are much harder to concentratein the crystallizer resulting in lower process efficienciescompared with the coarser product processes. It is expectedthat agitation improvements and a physically larger crystal-lizer will improve the effectiveness and efficiency of thisproduct removal technique for all explosives PSD's,

Product Decant, Washing, and Filtration Systems

Decantation of the spent liquor from the solids removed fromthe crystallizers can be used to provide a very efficientand effective initial solids/liquid separation. Reductionof the solvent content of the solids to an acceptable levelcan be accomplished by reslurrying the solids wich water,feeding the thick slurry to screening equipment, washingthe material on the screen using water sprays, and collectingthe product solids in filtration equipment for a final waterwash. It is expected that use of continuous filtrationequipment will improve the solids handling capability ofthis system apd reduce the overall residual solvent content.However, reductior, of the solvent content of the product belowthe levels obtained in the pilot plant using only the same orsimilar screening and filtration equipment is doubtful.

Solvent Recycle System

Spent solvent from the crystallization can be recovered andrecycled directly to the feed preparation system withoutprocessing. The buildup of the minor explosive componentin this recycle stream does not adversly affect the productpurity partly because of the 15 - 20% purge of the recyclestream.



Accumulation of other impurities in the system detrimentalto explosives crystallization was not observed during thepilot operation. It is expected that large scale systemswill require a purge rate no greater than that used in thepilot plant to achieve purity comparable to the pilot plantlevels. Control of the buildup of detrimental impuritieswill be accomplished as a side benefit of the solvent purge.

Solvent Recovery System

!. is expected that a solvent recovery system can be developedbased on the recovery procedure carried out in the pilotplant. The first step of the procedure includes, after aninitial filtration, an evaporative, vacuum distillation whichremoves the water as a relatively solvent-free distillateand concentrates the DMSO to 95 - 99%. The distillate fromthis step also contains trace amounts of other volatile impurities.Non-condensible, volatile impurities are scrubbed out inthe vacuum system. The concentrated bottoms stream contains,besides DMSO, all the solids, including explosives. Thesecond step includes as a minimum, the evaporation of theconcentrated DMSO from the bottoms stream as an overheaddistillate to obtain a purity level as high as 90 - 95% DMSO.This recovered solvent stream can then be used directly asmake-up solvent for the recrystallization processes. Theevaporator bottoms contain all non-volatile impurities,including explosives. Some of these impurities can befiltered from the stream after precipitation by water dilution.

DISCUSSION

Equipment Performance

With only a few exceptions, most of the mechanical pilot plantequipment performed satisfactorily throughout the evaluation.Some equipment changes were actually made and evaluated duringthe pilot effort. Other potential improvements in mechanicalequipment were simply noted as requiring changes to be evaluatedlater. Process control instruments also performed well. The processcontrol liquid chromatograph performance was poor. Table 28 providesa listing of items which performed unsatisfactorily or requiredmechanical or process changes to make them usable or satisfactory.Further discussion of some of the mechanical problems is includedin the Process Performance Section.

Process Performance

The basic pilot plant processes, with a few exceptions as noted,


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performed very much as designed. Some changes were required,however, because of mechanical problems which could not beovercome or because of system interactions as changes madein one sub-system affected another sub-system. For example,early experiments with the particle size separation screenerrevealed that with the equipment available, product particlesize separation was an impractical approach. Thus, processmodifications were required so that all the product particlesize distributions could be produced by direct crystallizationtechniques. This change in the basic project philosophy willnot be discussed since it cannot be evaluated until the originalidea itself is evaluated and compared to the results of thepilot work actually accomplished. However, the followingdiscussion will attempt to provide some insight as to the logicbehind the changes made as those processes actually evaluatedin the pilot plant evolved from the original process designs.

Feed Preparation Process

The feed preparation process did not suffer from any majorprocess design problems. Most of the changes required inthis system were mechanical in nature and are listed inTable 28. The only process change actually made involvedthe feeding of cold rather than hot feed to the evaporatorfeed circulating line. Initially, the switch to cold feedincreased the heat load on the evaporator and severelyreduced its capacity. However, reduction of the pumppacking gland water flow was sufficient to allow theevaporator to function with the capacity required tosupport crystallization.

The point must be made that although the feed preparationfunctioned well and was able to remove the unneeded extrawater from the process feed stream, there is one major flawin the process which will require refinement through furtherinvestigation and experimentation. Because of the "on/off"nature of the crystallization systems fed by the evaporator,the evaporator and column were constantly under variableload (usually either "no-load" or "full-load"). Besidesinefficiency in the column, this caused some fluctuationsin the feed composition which were not detected until thecrystallization system reacted to the particular change.A possible solution would require the preparation of feed"batches" while operating the evaporator system batchwiseat maximum efficiency. This would require intermediatestorage of the prepared feed for later use in the crystal-lization system.



CNCPR Crystallization Process

The crystallization systems themselves as expected, providedthe greatest challenge of all the areas of the pilot evaluation.The physical limitations of the crystallizers, i~e., relativelylow cooling capacities and poor agitation, combined with theother mechanical problems discovered, produced situations whichcould only be partially overcome by manipulating the otherprocess variables. The CNCPR system in principle performedvery much as expected. However, there were several unanticipatedfactors which complicated the system and made it difficultto control.

One such factor which was recoqnized during the early experimenta-tion was the dilution of dissolver material by water enteringthrough the dissolver/crystallizer circulation pump packinggland. At first glance this does not appear to present a majorobstacle to the success of the CNCPR crystallization system.It was, however, the root problem which interacted with otherminor difficulties and situations to create a very complicatedcontrul problem that was never satisfactorily resolved. Thisinteraction will be explained later. The obvious adjustmentneeded to counteract the constant dilution of the DMSO in thedissolver by the gland water is to increase the DMSO concentrationin the feed solution by raising the evaporator temperature.This was done in the pilot plant but, as will be shown, didnot provide a complete solution to the problem.

Another unanticipated factor was the inability to obtain reliabledissolver composition analyses capable of providing the necessaryfeedback for controlling the dissolver saturation. The lag-timebetween sampling and receiving the analyses was partly responsible.But, mechanical and procedural weaknesses in the liquid chromato-graph and the LC procedure itself also contributed to the overallprocess limitations. Because of this "limited-capability"situation, alternate process control techniques had to be usedwhich relied heavily on calculated material balance informationplus visual observations of the dissolver and crystallizer materialitself.

The successful production of coarse PSD's in the CNCPR crystal-lization process as well as the control of the process is depend-ent on the ma-itenance of an unsaturated condition in the dissolver.The unsaturated condition ensures that fines and nuclei returningfrom the crystallizer are dissolved and are not fed back to thecrystallizers. Also, the unsaturated feed entering the crystal-lizer environment ensures that minimum nucleation and maximumgrowth rates will result. Control of the CNCPR was usually lostas the explosives concentration in the dissolver approached

Holston Defense orpora~ion 35 Kingsport, Tennessee


the saturation point at the existing dissolver tempera-ture and DMSO concentration. The rise in saturation pointwas not readily detectable by the operators and usuallyoccurred due to a combination of product removal variationsin the crystallizers and high feed rate to the dissolver. Theusual response of the operators when this situation was dis-covered was to reduce or stop the feed to the dissolver orcrystallizers in order to force tie dissolver saturation backinto an unsaturated condition. Because of the interaction ofthe pump packing cland water, this response proved to be toolate to prevent upsetting the crystallizers. Because theinflow of packing gland water to the system was constant,the DMSO concentration began to fall when the feed was shutoff. This caused precipitation of more fines in thedissolver and a general worsenfng of the condition. Theresponse of the crystallizers included very fast depletionof the crystal bed and a very marked decrease in the averageparticle size of the decreasing amount of product removed.Eventually, though, enough material was removed from thecrystallizers as product so that the dissolver saturationdid drift back into an unsaturated condition. This becameapparent to the operators when the crystallizer overflowbegan to show fewer fines and the dissolver material was freeof solids. Also, the quantity and quality of the productremoved from the crystallizers began to improve.

When improving conditions were observed, the feed to thedissolver was restarted to regain ncrmal operating conditions.However, as soon as the feed was restarted, the DMSO concentra-tion in the dissolver began to rihe resulting in an increasingsolubility for exDlosives and thus a continued decreasingdissolver saturation point. The resulting effect on thecrystallizers was again a very fas: depletion of the crystalbed although for a different reason. After feed was maintainedto the dissolver for a sufficient period of time to allowthe DMSO concentration to stabilize, the explosives saturationclimbed to a level sufficient to allow the crystal bed torebuild. Eventually control of the system was reestablishedresulting in continued production of good quantities of highquality products.

Detection of the approaching critical dissolver saturationcondition by the operators was almost impossible. The firstindicator was the presence of a greater than usual number offines and nuclei in the crystallizers which produced a milkyappearance. A decreasing percentage of solids in the product



stream was observed shortly thereafter suggesting depletionof the crystal bed. As stated previously, if the CNCPRconditions deteriorated to this point, it was already toolate to reverse the process and save the experiment. Theorder of the events described above could not then bealtered and there was no choice but to follow the outlinedprocedure to reestablish control.

Reasoning applied to this problem led to the deduction thatthere existed only two possibilities for improving thissituation. First, eliminating the circulating pump glandwater altogether would allow quick recovery if control waslost since no dilution of the dissolver contents wouidoccur. Second, improving the capability to detect saturationcondition changes in the dissolver would help prevent over-saturation in the dissolver and thus eliminate loss ofcontrol itself. Because the existing HDC safety regulationsrequire the use of packing giand flush Water for all explosivesprocessing pu,,gs, the first possibility was eliminated. Thus,changes in tho' proce•,s were made to allow dissolver saturationcondition changes to be detected before the critical saturationcondition was reached. This was accomplished as follows:

1. Only one of the crystallizers at a time was used forcrystallizing in the CNCPR system.

2. The second crystallizer was held in idle status withthe cooling water off and dissolver material circulatingthrough it.

3. The "saturated" or "unsaturated" condition of the dissolverwas monitored visually by the operators by simply notingthe presence or absence of cloudy solution or fine crystalsin the idle crystallizer.

The processing change described above greatly reduced theincidence of complete loss of control due to oversaturationin the dissolver and allowed much longer runs without thesame types of major process upsets. However, refinementsof the overall process to provide an even greater degree ofprocess control or to eliminate the control problems will berequired before the continuous CNCPR system can be investigatedin enough detail to fully characterize or exploit its potentialas a coarse explosives crystallization system.

Modified CNCPR Crystallization Processes

Because of the basic control problems with the CNCPR system,various changes in the process configuration were evaluated



in order to simplify the system and thus improve the controlover product PSD. CNCPR-MOD-1 provides introduction of feedsolution directly to the crystallizers instead of the dissolver.This system experienced the same basic control problems duringevaluation as the CNCPR system and the introduction of feeddirectly to the crystallizers actually produced a detrimentaleffect on particle growth rates. The quick cooling of thehot saturated feed in the crystallizer environment producedmany fines and the resulting median crystal size was relativelysmall. The extra heat load on the crystallizers reduced thesystem potential since the resulting crystallizer temperatureswere higher than the CNCPR system. The calculated efficiencyof this system was high but this is misleading since the effi-ciency is simply a measure of the fraction of "system" potentialobtained. The CNCPR-MOD-I system offers no real or potentialtheoretical advantage over the CNCPR system.

CNCPR-MOD-2'is not actually a CNCPR system at all. Insteadit is a mixed suspension crystallizer with intermittentproduct removal. CNCPR-MOD-2 was evaluated primarily forClass 1 RDX explosives production but was also successfulin producing Class 3 RDX. The control problems of CNCPRand CNCPR-MOD-I were entirely eliminated because the dissolver/crystallizer circulation loop was not used. However, theability to produce the larger Class 4 particle size was alsosacrificed. Crystallizer temperature could be maintainedlower than either CNCPR or CNCPR-MOD-I which increased theproduct rate potential over either system, Good systemthrough-put efficiencies were attained of about the samemagnitude as the CNCPR system. Like the CNCPR-MOD-I system,hot, saturated feed solution introduced directly to thecrystallizer environment favors the production of relativelyfine crystals. But, because of the absence of fines controlcapability, more of the smaller crystals are retained in theCNCPR-MOD-2 crystallizer resulting in lower effective growthrates. The simplicity of this system, the high rate potential,and the good system efficiency makes it attractive as a nominalClass 1 or actual Class 3 explosives crystallization system.

CNCPR-MOD-3 is actually a variation of CNCPR-MOD-2. Water ismetered into the crystallizer with the feed solution resultingin dilution of the solution and lowering of the DMSO con.:en'ra-tion. The dilution effect precipitates additional fines in thecrystallizer and causes an effective growth rate even lowerthan CNCPR-MOD-.2. Product is removed intermittently. Thissystem was evaluated for production of actual Class 1 explosivesdistributions since these could not be achieved by "cooling-only" methods as in CNCPR-MOD-2. This system had a very highproduction rate, high system potential, and high efficiency forproducing Class 1 explosives, As in the CNCPR-MOD-2 system,the simplicity of the CNCPR-MOD-3 system along with the high


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Technical Report No. HDC-58-8O

rate potential and high system efficiency make it attractiveas an actual Class 1 explosives crystallization system,

Another variation of CNCPR-MOD-3 (RDX Dilution Procedure "a")was originally intended for Class 5 RDX production. Insteadof reducing the DMSO concentration in the crystallizer by5 - 10% using a small amount of dilution water as in CNCPR-MOD-3,enough water is added to the crystallizer to reduce the DMS0concentration by 30 - 40'. The product is removed continuouslyby maintaining a constant level in the crystallizer, Evaluationof this process indicatea that it is incapable of producingClass 5 RDX but is effective for producing the Class 7 RDXdistribution, A higher system potential than the CNCPR-MOD-3system and an efficiency comparable to CNCPR-MOD-3 was achieved.The primary disadvantage of this system, a3 evaluated in thepilot plant, was the relatively high solvent usage rate comparedto the other CNCPR systems. However, the solvent usage rateof this process compared to other dilution crystallizationsystems was significantly lower. Like the CNCPR-MOD-3 system,RDX Dilution Procedure "a" is an attractive process due to itssimplicity, high system potential, and high efficiency.

RDX Dilution Processes

The original processes evaluated for production of Class 5RDX (including RDX Dilution Procedure "a") failed to yieldparticle size distributions containing enough sub-325 meshmaterial to be practical. These systems included mixing hot,saturated feed solution and water in ar agitated crystallizervessel and removing the product either continuously or as abatch. Dilution of the feed material to DMSO levels of 30 - 50%produced product PSD's with a very low percentage of sub-325mesh material. Additionally, dilution below the 50% DMSOlevel proauced large quantities of alpha HMX and very impactsensitive product. A change in the process to allow instantaneousdilution of the feed solution to the desired final DMSO concentra-tion solved the particle size problem and increased the percentageof sub-325 mesh particles to 90 + %. However, the alpha HMXcontent of the product remained high and the product was veryimpact sensitive (4 10 cm long impact).

Experimentation with the instantaneous dilution process indicatedthat dilution of the feed solution to the 65 + % DMSO levelfollowed by a brief age of the precipitated material collectedas a batch would convert the alpha HMX to the beta form. Furtherdilution of this material to aiy lower DMSO level did not yieldany more alpha HMX. Because a significant quantity of RDX wasstill in solution at the 65% DMSO level, yield improvement was



realized by further dilution of the batch to the 45-50%DMSO level. The final process (RDX Dilution Procedure "e")proved to be a very simple process with both high systempotential and high system efficiency.

The primary process limitation with the pilot plant systemwas caused by the lack of good agitation in the crystallizationvessels. Because of this problem, the entire volume of thecrystallizers could not be fully utilized. Refinement ofthis process and equipment improvements could provide asystem which would have a production rate limited only bythe physical constraints of the equipment, i.e., crystallizerstze, degree of agitation possible, maximum feed rates avail-able, and product slurry processing method and rate. The pilotplart process used vibrating screeners to scalp over-sizedT1aterial from the product stream. The quantity of this over-sized material averaged only 2 - 5 % of the batch. Therefore,screening should not be considered as a necessary part of theprocess. Separation of spent solvent and product and thefinal product wash can be accomplished with equal or higherefficiency using simple batch or continuous filtration equip-ment.

HMX Dilution Processes

A two-step dilution procedure similar to the successful RDXprocedure was attempted using hot, concentrated DMSO/HMXsolutions. This procedure produced impact sensitive HMXcontaining large quantities of both the alpha and gammapolymorphs. Subsequent batch and continuous experimentscarried out in the laboratory3 and the pilot plant revealedthat dilution of the HMX feed solution in a crystallizationvessel in the presence of fine beta HMX seed material (Class 5pump-ground HMX, HGF) produced fine beta HMX with 90-100%of the batch in the sub-325 mesh size range. However, theimpact values of this material were low (19-22 cm) comparedto standard values (30-32 cm). Further experimentationrevealed that the impact values of material produced thisway could ba improved by heating the batch to 950C (378 K)and aging for 30 minutes (1.800 ks). Impact values of materialtreated in this manner showed increases into the normal rangeof 28-33 cm.

Other experiments performed without the HGF seed materialalways produced mixtures of alpha and gamma HMX during theinitial dilution. Batches produced without seed at anytemperature followed by a heating cycle resulted in conversionof the gamma HMX in the mixture to alpha HMX. All the batchesproduced without beta HGF seed were impact sensitive. Thequantity and size of beta-HMX seed particles used determined



the rate of conversion of the ganmna HMX formed during thedilution to the beta polymorph. The heating cycle andage period allowed stress relief of the "beta-strain" in

the converted beta crystals and thus reduced the sensitivity.

The successful batch process used to produce most of theClass 5 HMX was HMX Dilution Procedure "g". The processbegan by diluting hot, saturated HMX solution in a crystal-lization vessel containing a 1,7% slurry heel of water andF beta HGF seed material. After the heating and age cycles,

most of thf' product material was removed from the crystallizer.Part of the product slurry, however, was left as the heeland to provide seed material for the next batch, Severalconsecutive batches were produced using this procedure untilthe sub-325 mesh fraction was reduced to a level less than50% of the batch. The crystallizer was then emptied and anew series started with new beta HGF seed.

As in the Class 5 RDX process, the Class 5 HMX productionrate was limited by the physical constaints of the crystal-lizers themselves, i.e., poor agitation prevented utilizationof the entire volume of the crystallizer. During the consecutiveproduction method employed, the observation was made thateach batch of Class 5 HMX contained an increasing quantity ofmaterial larger than 325 mesh. These "overs" decreased theyield of each consecutive batch until eventually most ofthe batch was too large. In general, the percentage ofmaterial from each consecutive batch that was too large(> 325 mesh) and had to be screened out as "overs" is asfollows:

Batch No. % Overs

1 0-42 0-153 20-254 28-485 30-606 40-707 > 508 > 70

The Class 5 HMX process also used vibrating screeners to scalpover-sized material from the product stream, Since initialbatches and the first consecutive batch yielded a high percentageof sub-325 mesh material, screening should also not be considereda necessary part of this process. Refinements of this processusing more suitable equipment could be made to provide a veryhigh yield, efficient Class 5 HMX process,


Technical Report No. ,HPC-58-80

Product/Solvent Separation, Screening, Washing and FiltrationProcesses and Recycle Solvent Processing

The overall performance of the original process for separatinrthe product from spent solvent followed by washing andseparating the product into size fractions was poor, Thepoor process performance was primarily due to poor equipmentperformance. The initial separation of spent solvent fromproduct was to be accomplished using a vibrating screener.Severe blinding of the original 270 mesh screen used and the120 mesh screen used later forced early abondonment of thisidea. A crude decanting process was substituted which provedto be very efficient.

Following the product/solvent separation, another screener wasused to provide a primary wash. Blinding of the first screenercaused overflow of spent solvent with the product to the Istwash screener and eventual blinding of the screen in this unit,also. Use of the decant procedure eliminated this problem,

The final screener in the series was originally equipped witha stack of four screens for separating the product into fourdistinct size groups. The separation process was to haveprovided a broad capability with several advantages. Thecrystallization systems would not be required to provideexact particle size distributions of explosives meeting existingspecifications for the various classes of explosives. Theparticular size fractions chosen could be recombined in ratiosto produce these exact distributions if required. This wouldallow optimization of a system of multiple, independent crystal-lizers for the most efficient production of recrystallizedexplosives without regard to the production of specificdistributions. Process variables would be manipulated toproduce specific ratios of coarse to fines which could beseparated and then recombined to meet the total plant demandfor those individual products. Additionally, the system wouldhave the ability to produce biinodel distributions directlyinstead of requiring the blending of other products. A muchmore consistent and repeatable PSD of the final products producedby blending specific particle size fractions would also berealized.

The screener intended to perform the separation and allowevaluation of this idea did not function. Each screen inthe stack became clogged with explosives in such a way thatretained product would not discharge. This was attributedto a poor screen-to-screen flow pattern and insufficientwater flow to each screen. A better design of the screeningequipment or a different arrangement of the same type of


A - "


equipment could possibly salvage the basic elements of thisidea. However, it could not be evaluated during this pilotplant effort.

The performance of th-e screeners in providing product washingcapability was satisfactory. Water spray nozzles distributedwash water over the product during its retention on the screen.Removal of a sufficient percentage of the fine particles(sub-325 mesh), whicn were precipitated during the reslurry ofthe product after decanting, was accomplished in the firstwash screener. Since in most cases these precipitated finescontained a high percentage of the minor explosive componentas an impurity, removal of this material improved the purityof the final product.

Filtration equipment used to filter explosives from relativelyconcentrated DMSO/explosives mixtures containing dissolvedexplosives produced severe filter cloth blinding and extremelylong filtration times. The mother liquor filter, which wasthe first step in recycle solvent processing, was unable tomaintain a filtration rate high enough to filter all themother liqLor produced. Therefore, this initial recyclesolvent processing step was eliminated after only a fewinitial experiments. Mother liquor was transferred, instead,directly to the recycle DMSO receiver and held until filteredin the recycle DMSO filter. Although very slow filtrationrates were experienced in this filter, also due to filtercloth blinding, the larger filter size provided enough capacityto process all the recycle solvent. Analyses of the filtercake, however, r-ovealed that the purity level of the solidsremoved was as high in most instances as the input crudeexplosives. Therefore, recycle solvent processing waseventually discontinued altogether in favor of direct recycleof mother liquor. Direct recycle proved to greatly simplifythe solvent recycle and purge and decreased the percentageof explosives lost as waste.

The modified processes used to handle the recrystallizedproduct and recycle solvent, although different from theoriginal processes, performed satisfactorily. Design of aneffective decanting system for DMSO/explosives slurries willbe required but should provide an efficient, dependable initialseparation technique, Improvement of the screening process willbe required if the original product PSD separation idea is tobe incorporated into overall recrystallized explosive productscheme. If direct crystallization processes are to be used,continuous filters such as the Bird-Pannevis or Eimco designswould offer advantages over screening equipment to performproduct washing functions.

Holston Defense Corpordtion 43 Kingsport, Tennessee


Solvent Recovery Process

The solvent recovery process was not part of the originalpilot plant design, The original intention was to usethe evaporator/rectifier system to demonstrate that a simpleprocess could be used to reconcentrate the DMSO from thewaste solvent streams to a level which would allow itsreuse for crystallization. The reconcentration was alsoto demonstrate that this procedure could be performed witha minimum of solvent loss and that no problems would resultdue to the presence of small quantities of explosives. Becauseof the ease with which the reconcentration was accomplished andthe absence of any major problems, the decision was made tocarry the process one more step to recover the DMSO from theconcentrate by vacuum distillation to free the DMSO from theexplosives and any other non-volatile impurities. The resultingdistillate contained most of the DMSO and was free of anydetectable impurities other than water.

The apparent relative simplicity and efficiency of thisprocedure carried out in equipment not designed for this purposeimplies that a system based on this procedure could be easilydesigned to perform this function on a larger scale. Use ofthe pilot plant data thus far obtained would facilitate thisdesign effort.

Process Material Balances

Crystallization Processes

Figure 26 is the flow diagram for the basic crystallizationprocesses evaluated in the pilot plant. Tables 21 through27 present the material balance information correspondingto Figure 26 for several of the recrystallization processespreviously discussed. The values used for flow rates andcompositions are average values based on analyses of samplestaken from the different process streams during the evaluationphase. Internal streams in some cases bear calculated valueswhich may or may not represent actual situations observedduring evaluations. Instead, these values represent thosewhich would be expected using the results actually observedin the product output streams with known input streams. Sincethese values represent ideal situationscare should beexercised if this information is to be used to design alarger facility. More rigorous evaluation of the overallsystem should be considered after the refinements are madeIn the various sub-systems as discussed in the previoussection. Economic considerations expressed in this report,however, are based on the material balances presented.



Solvent Recovery Process

Figure 27 is the flow diagram/material balance for thepilot plant solvent recovery process. Rates and compositionsagain reflect the average values observed through repeatedexperimental runs. Intercal stream rates and compositionsin some cases were calculated and represent those valueswhich would produce the output results actually observedgiven the input rate and composition.

Experimental Results

RDX/CNCPR Experiments

The experiments conducted with the RDX/CNCPR systems areV described in Table 2. calculated results of these experimentsare presented in Table 4, and analytical results of samplestested are presented in Tables 6, 7, 8, and 11. Brief analysesof these experiments are as follows:

1. CNCPR-MOD-l (Experiments 1 - 7) - Seven experiments wereconducted using the two-crystallizer, CNCPR-MOD-I flowconfiguration. Feed was introduced near the bottoms ofboth crystallizers in an attempt to provide high, localizedsupersaturation levels in the crystal bed where the largestcrystals were. Most of these experiments were plagued byproblems associated with poor dissolver saturation controldescribed previously. Loss of control occurred frequently,as exhibited in Table 2, when the dissolver saturationtemperature, Ts, exceeded the dissolver operating temperature,TD. The particle size distribution of the product showeda great deal of variation corresponding to these upsets.

The product removal cycle time provided very little controlover product PSD except during the "in control" situations.The products from these experiments were for the most partnominal Class 3 RDX PSD. However, some actual Class 3 RDXwas produced as well as actual Class 4 RDX. The Class 4RDX was all produced during experiment #4. O)issolvercontrol had been lost and was being reestablished byallowing the system to drift without feed. Due to this"no-feed" situation, the system was actually a CNCPRsystem rather than a CNCPR-MOD-I system. After control

was regained and the feed was restarted, the product PSDdrifted back into the Class 3 domain. This result demon-strates that the introduction of a highly saturated feeddirectly to the crystallizer produces a negative particlegrowth effect compared to normal CNCPR dynamics. There isalso evidence that periods of increasing dissolver saturation



produce higher growth rates than periods of decreasinedissolver saturation.

The effect of dissolver saturation on product particlesize is shown graphically in Figure 28, Figure 28 alsoshows the extremely erratic nature of the dissolversaturation and emphasizes the difficult control problemthat existed, Note that the dissolver saturation seemedto have critical limits which if exceeded had detrimentaleffects on the product particle size. When the value of(TD-Ts) approached zeto or drifted into the negativeregion, the dissolver solution became saturated and thedissolver lost its ability to control the fines returningfrom the crystallizers. If (TD-T ) was highly negative,the dissolver itself even became • fines producer., Also,if (TD-T ) increased above 150 C (288 K), the averageproduct PSD decreased suggesting that growth rates werelow and that nucleation effects dominated the production.

Also shown in Fiqure 28 is the effect of crystallizer feedsupersaturation on the resulting product PSD. The crystal-lizer supersaturation is the difference between thedissolver saturation temperature, TS, and the crystallizeroperating temperature, T (. T -T ) values as high as 400 C(313 K) and as low as 106C (283 K) were experienced.Flunctuations in (Ts-T ) contributed to the fluctuationsnoted in the product PSD but did not have as large acontrolling effect as (T0 -Ts). However, when very low(Ts-T ) values are experienced, as shown at the 32 -36hour I115.2 - 129.6 ks) and the 52 - 56 hour (187.2 -201.6 ks) periods in Figure 28, (Ts-Tc) becomes thecontrolling factor and greatly depresses the apparentparticle growth while nucleation and fines productionremain fairly constant. Thus, a much smaller product PSOresults.

The results of CNCPR-MOD-I experiments, presented inTable 3, show that system production rates of 11.86 -35.17 lb/hr (".494 - 4.431 g/s) were achieved withcorresponding system efficiencies of 45.8 - 67.7% oftheoretical yield, The solvent usage rates ranged from1.19 to 1.94 lb of DMSO/lb of product (1.19 to 1.94 kgof DMSO/kg of procict), Note that the highest efficiencywas achieved during the production of the Class 4 productduring experiment Number 4. This can be attributed tolower loss of solids dnd dissolved material in thecrystallizer overflow. Better settling of the larger,heavier particles in the crystallizers combined with alower average dissolver saturation produced this effect.



2. CNCPR-MOD-2 (Experiments 8 - 13) - Six experiments wereperformed using the single-crystallizer, CNCPR-MOD-2flow configuration, These experiments, which were designedprimarily to produce Class 1 RDX PSD's, used severalcombinations of feed composition (28.4 to 32% RDX), feedrate (0.3 to 0.5 GPM (19 to 32 cm /s)) feed point (4 to12 inches (0.1 to 0.3 m) from the crystallizer bottom)and product removal cycles (7, 10, and 20 minutes (0.420,0.600, and 1.200 ks)). However, most of the productwas nominal Class 1 too large for the actual Class 1 PSD.None of the controlled variables had any major effecton product PSD although there were several treids notedas follows:

a. Raising the feed tube from the bottom of the crystal-lizer toward the crystallizer overflow reduced theproduct particle size.

b. Increasing the feed rate reduced the product particlesize.

c. Changes in feed composition had no measurable effect.

d. Increasing the product removal cycle time increasedthe product particle size. (The 20-minute (1.200 ks)cycles produced actual Class 3 RDX.)

The results of the CNCPR-MOD-2 experiments, presented inTable 3, show that system production rates of 8.88 - 33.82lb/hr (1.119 - 4.261 g/s) were achieved with correspondingsystem efficiencies from 32.1 - 79.8% of theoretical yield.The solvent usage rates ranged from 1.84 to 3.96 lb ofDMSO/lb of product (1.84 to 3.96 kg of DMSO/kg of product).Due to the presence of the very many small particles, agita-tion was very critical. Too high agitation rates causeddestruction of the crystal bed resulting in a homogeneousslurry in the crystallizer. During occasional upsets ofthis nature, a large amount of product was lost by way ofthe crystallizer overflow thus reducing both the productionrate and the system efficiency. Constant readjustment ofthe agitator speed was required to properly maintain thecrystal bed.

3. CNCPR-MOD-3 (Experiment 14) - One experiment using theCNCPR-MOD-3 flow configuration was performed. The conditionswhich resulted in the minimum PSD's in the CNCPR-MOD-2experiments plus water dilution were used to produce theactual Class 1 PSD. The results of this experiment, presentedin Table 3, show that a very high production rate of 48.72 lb/hr



(6.139 g/s), a system efficiency of 78.6%, and a solventusage rate of only 1.18 lb of DMSO/lb of product (1.18 kgof DMSO/kg of product) were achieved. Careful controlof agitatirn was maintained throughout the run and wasthe major factor responsible for the high production rateand efficiency.

4. CNCPR Experiment Number 15 - One experiment was performedusing the basic CNCPR flow configuration using only onecrystallitzer. The idle crystallizer was used to visuallymonitor dissolver solution as previously discussed. Thepurpose of this experiment was to produce Class 4 RDX.Experience gained during the earlier CNCPR-MOD-l experimentswas used in attempts to provide greater control overdissolver saturation and thus prevent :he negative valuesof (T -TD) which contributed to the Pcir particle growthresults obtained previously. The reslits of this experiment,presented in Figure 29, again show the effect of dissolversaturation on the product particle size. Although dissolversaturation control was successful and the kTD-Ts) valueswere positive throughout most of the run, the product particlesize was small indicating that the particle growth rateswere again fairly low. However, Figure 29 indicates thatthe (Ts-Tc) values fell during the ititial part of theexperiment and remained low during most of the run. Thedepressing effect of these low values on crystal growthrates is believed responsible for the small size of theproduct obtained.

The results of the CNCPR experiment are presented in Table 3,These results show a production rate of 15.38 lb/hr (1.938 g/s)at 80% efficiency as li! as a solvent usage rate of only1.08 lb of DMSO/lb of product (1.08 kg of DMSO/kg of product).

5. CNCPR Products - No unusual qualities were discovered inany of the RDX intermediate products recrystallized fromDMSO using the CNCPR process. Alpha HMX content was monitoredby infra red and microscopic analysis. The analytical datapresented in Tables 6, 7, and 8 show that occasional tracesof alpha HMX were detected in some samples; but, these amountswere in all cases judged by microscopic analysis to be withinacceptable limits less than 0.01% by weight. There werenever, however, any impact sensitivity problems. Sincethis would not have been the case if alpha HMX contaminationhad been substantial, it is believed accurate to assume thatno polymorph problems were experienced.



RDX/Dilution Experiments.

The experimental conditions used to produce fine RDX bydilution are described in Table 4, calculated results ofthese experiments are presented in Table 5 and analyticalresults of samples tested are shown in Tables, 9, 10, and 11.

A total of two continuous and twelve batch experiments wereperformed in attempts to produce Class 5 RDX. The alpha HMXcontamination problem, which occurred during the initialcontinuous experiments, as well as the discovery that growthrates were too high in the continuous system to allow productionof the Class 5 PSO, led to the adoption of the successful batchprocess. The successful conditions used included an initialwater dilution of the hot, DMSO/RDX solution by plug flowmixing in the crystallizer feed lire, aging the mixture withagitation at ambient mixture temperatures, a second waterdilution in the crystallizer, anc filtration and washing torecover the product. The continuous product removal versionof this proc.•ss was successful in producing only Class 7 RDX.

The results o• the RDX/Dilution experiments presented in Table 5show that the final RDX Class 5 procedure using the pilot plantequipment was capable of producing 14 lb/hr (1.76 g/s) ofproduct per crystallizer at efficiencies of 95%. Most of theproduct losses occurred during the filtration and washing steps.Impact sensitivity problems due to alpha HMX contaminationwere eliminated due to the aging step following the initialdilution. This is evident by observing the consistently highimpact sensitivity values obtained on products from Experiments9 through 14. Analytical results presented in Tables 9, 10,and 11 show that the Class 5 RDX produced meets all specificationsfor recrystallized RDX. No unusual properties were discovered asa result of any of the tests performed.

HMX/CNCPR Experiments

Experiments performed in the HMX/CNCPR systems are describedin Table 12, calculated results of these experiments arepresented in Table 13, and analytical results of samples testedare presented in Tables 16, 17, 18, and 20. Brief analysesof the experiments are as follows:

1. CNCPR-MOD-I (Experiments 1 - 6) - Six experiments wereperformed using the two-crystallizer, CNCPR-MOD-l flowconfiguration. Feed was introduced near the bottom ofeach crystallizer to provide high localized supersaturation



and high growth rates in the vicinity of the largestcrystals. Better control of the dissolver supersaturationlevel was maintained during these experiments than duringthe corresponding RDX experiments. However, as shown inFigure 30, the saturation level was actually maintainedtoo low to produce the desired high growth rates requiredto produce Class 4 HMX using the 20-minute C1,200 ks)product removal cycle. Also, the direct introduction offeed to the crystallizers, as was noted during the earlierRDX experiments, appears to increase the production ofnuclei and fines resulting in depressed effective growthrates in the crystallizers.

Figure 30 alsu shows less erratic dissolver saturationvariations than in the RDX experiments and therefore tnecorresponding changes in the product particle sizedistributions were not as drastic. However, the lowdissolver saturation values resulted in low (Ts-TC)values which depressed the growth rates and contributedto the failure to produce the desired larger particlesize distributions.

The results of the CNCPR-MOD-l experiments, presented inTable 13, show that system production rates of 6.75 -20.85 lb/hr (0.851 - 2.627 g/s) were achieved withcorresponding system efficiencies of 28.8 - 86.8% oftheoretical yield. The solvent usage rates ranged fromonly 0.55 to 2.18 lb DMSO/lb of product (0.55 to 2.18 kgDMSO/kg of product). The most favorable conditionsoccurred at the beginning of the run when the values ofdissolver saturation and (Ts-Tc) were high while (TD-Ts)values were positive.

2. CNCPR (Experiments 7 - 11) - Five experiments were performedusing the CNCPR flow configuration with only one operatingcrystallizer. The idle crystallizer was used as a visualreference of the dissolver saturation condition as in theHMX/CNCPR-MOD-l experiments previously described. Figures31, 32 and 33 show that the same general results wereobtained during these experiments as with the otherexperiments, i.e., the use of the idle crystallizer wassufficient to keep the (T -Ts) values positive but thevariations in both (TD -TS? and (Ts-Tc) caused correspondingvariations in the product particle size distribution.However, the proper conditions were established and heldlong enough during part of the experiments to provide thegrowth and fines control necessary to produce the Class 4PSD. These conditions included a combination of sustainedhigh (Ts-Tc) values, sustained positive (TD-Ts) values,



and 30-minute (1,800 ks) product vithdrawal cycles.

Table 13 shows that system production rates of 14.69 - 17.13lb/hr (1.851 - 2.158 g/s) were achieved with correspondingsystem efficiencies of 36.6 - 80.8% of theoretical yield.The solvent usage rates ranged rom 0.65 to 1.40 lb DMSO/lbof product (0.65 to 1.40 kg DMSO/kg of product),

3, CNCPR Products - Analytical data presented in Tables 16,17, 18 and 20 show that all the DMSO-recrystallized HMXfrom the CNCPR process meet the specifications forrecrystallized HMX. One of the samples tested forvacuum thermal stability (VTS) at 100 0C (373.15 K) for48 hours (172.8 ks) showed an atypical result of 0.10 cc/g.Moisture content of the test sample could be responsiblefor this result. All other test results were normal. Noother unusual properties or qualities which would suggestchemical or physical interactions between DMSO and HMX werediscovered during the performance of the tests.

HMX/Dilution Experiments

The experimental conditions used to produce Class 5 HMX bydilution are described in Table 14,calculated results ofthese experiments are presented in Table 15, and analyticalresults are shown in Table 19 and 20.

Sixteen batch experiments were performed in attempts to produceClass 5 HMX. Initial HMX experiments were based on thesuccessful RDX procedures. Plug flow mixing to achieve thedesired particle size and two-step dilution for polymorphcontrol were attempted. These batches, however, were allimpact sensi*ive and the material was predominantly gammaHMX. Seeding the dilution water with beta HMX seed fromthe regular Holston HGF production (pump-ground) process,even at very low concentrations, provided the needed polymorphcontrol. The very small particle size required was easilyobtained without plug flow mixing because of the very lowgrowth rates of the HMX in the diluted solutions. This resultcould possibly be due to the relatively slow polyntorph conversionobserved. Leaving a heel of fine beta HMX seed for the nextbatch reduced the overall requirement for initial HGF seed.However, after a few consecutive batches, an obvious growthof material took place and reduction in process efficiencyresulted.

The results of the HMX/Dilution experiments, presented inTable 15, show that the batch pilot Class 5 HMX procedurewas capable of producing 5.1 - 7.0 lb/hr (0.64 - 0.88 g/s)



of product per crystallizer at total efficiencies of70 - 95%. Reductions in production rate were experiencedas a result of the heel seeding method since a greaterpercentage of product was lost as uovers" from the screeningprocess. 95 - 1(10% efficiency could be achieved if onlyone or two consecutive batches were produced this way.Other small product losses were attributed to the filtrationand washing steps. Alpha contamination and impact problemswere encountered prnimarily during the first 12 experiments.However, definite improvement was shown during the final 4experiments with most of products exhibiting impact valuesabove 30 cm. The 30-minute, 950 C heating cycle used toobtain the impact value improvement is believed to relieve"beta strain" whi'ch occurs during solid phase conversion ofgamma HMX crystals to beta. Aging at 950 C (368 K) allowsenough molecular mobility for realignment of the HMX moleculesinto a more stable crystal structure.

Analytical results of Class 5 HMX samples tested at Holstonare presented in Tables 19 and 20. The samples representingthe pilot production process are Hll19i300.CD52/3S throughH11200500.CD52/3S. All specifications for Class 5 HMX weremet on each of these samples. Additional tests revealed thatone sample when tested for vacuum thermal stability (lO0OC for 48hr), showed an atypical value of 0.33 cc/g. High sample moisturedue to incomplete drying of the test sample is suspected to havecaused this result, No other unusual physical or chemicalproperties were observed.

Residual Solvent in DMSO-Recrystallized Explosives

Previous concern was expressed that the quantities of residualDMSO that remain with the intermediate explosives after recrystal-lization and final washing could cause potentiai problem,- whenusing these materials in final products. Subsequent liwitedtesting by other agencies has indicated tnat thete might be somecompatibility problems, but, these must be dealt with individually.Due to concerns of this nature, care was taken during the designof the DMSO-recrystallization pilot equipment to provide sufficientwashing to reduce the total residual levels of DMSO in the productsas low as practical. The solvent levels 3btained are, therefore,representative of what would generally be expected for most OMSOprocesses.

Residual DMSO test results presented in Tables 11 and 20 weredetermined by gas chromatography. Two analyses were performedon each sample. One analysis determined the total residual DMSOcontent of the wet sample just as it left the washing step ofthe recrystallization process. Another analysis determined theoccluded DMSO content after the sample was oven dried to remove



the surface moisture. Occluded DMSO averaged 0,03% and 0.08%by weight in tests of all the RDX and HMX samples, tespectively.Total residual DMSO in the same senples averaged 0.35ý and 0.41%.These values are not entirely rep.esentative since in all cases thefiner intermediates (actual Classes 1, 5, and 7) were haraer towash and dewater than the coarser intermediates (nominal Class Iand Classes 3 and 4). Thus, the finer material contained highertotal residual moisture with higher levels ot DMSO than thecoarser material. The total residual solvent in the coarse RDXalone averaged only 0.16% while in the fines it averaged 0.64%.Comparable values for HMX were 0.25% DMSO in the coarse and0.75% in the fines.

Final Incorporated Products from DMSO-Recrystallized Explosives

Tables 29 and 30 present analytical results of the final productsmade using DMSO-recrystallized intermediate explosives. Theseproducts, which include Compositions A-3, A-5, C-4, B, 70/30Cyclotol, and 70/30 and 75/25 Octul, meet all applicable militaryspecifications and will be used for qualification tests. Nomanufacturing problems were encountered which could be attributedto the chemical properties of the residual DMS0 or the recrystallizedexplosives themselves. Viscosity specifications on the 70/30Cyclotol and 75/25 Octol could not be achieved using standardincorporation techniques. The difficulties encountered were atleast partly attributed to the narrow particle size distributionand relatively small average size of the coarse explosives (Class 4)compared to regular HSAAW Production material. However, a modifiedincorporation procedure, which was developed during the 1973 DMSOpilot effort, was successfully applied to the problem and therequired amounts of "in-specification" test products were produced.

Solvent Recovery Capability

Since the development or evaluation of a solvent recovery processwas not included in the project scope oF work, no formal investigationwas performed in this area. However, due to the accumulation ofrelatively large quantities of 10-30% DMSO/water solutions, reclaimingthe DMSO in a form suitable for reuse was necessary. The availablepilot plant equipment, i.e., the evaporator/rectifier system, wasused for this purpose. During this crude recovery operation severalobservations were made which may prove helpful for designing a DMSOrecevery process. These observations include the following:

1. No explosives migratior by entrainment was detected byvistial inspection of the intern3ls of the rectifyingcoltmn or condensor,

Holston Defense COrporation 33 Kingsport, Tennessee

iechnical Report No. HDC-58-80

2. Concentration of the 10 - 30% DMSO to 95 - 99% DMSOis possible by single step fractionation,

3. The concentration of DMSO in the distillate from theconcentration step can be maintained at less than 0.01%DMSO by weight using a reflux ratio ([/D)of 1/3.

4. DMSO free of solid or liquid impurities other than waterand possible trace quantities of acetic acid can beobtained by vacuum distillation of the concentratedDMS0. A sludge draw-off from the distillation containsall the non-volatile impurities present in the wastesclvent feed.

Since the objective of the solvent recovery operation was not

to perform a detailed solvent recovery study, but simply torecover solvent from the waste stream, no efforts were made tooptimize the system through process variable manipulations orto determine what the system limitations were. Thus, additionalwork will be required to determine the most efficient conditionsfor solvent recovery with respect to minimum reflux ratio, optimumtemperature and pressure conditions, the number of fractionatorsrequired (two are used in the Crown Zellerbach process), andthe operating limits of the system. Another study shouldcharacterize the sludge from the evaporation step and determinethe sludge draw-off rate required to control potential chemicalinteractions between the various impurity components and therequirements for disposition of this material.

Particle Size Separation/Recombination

The particle size separation/recombination idea could not beevaluated during this pilot plant evaluation because of theunsatisfactory performance of the size separation equipment.The direct recrystallization of the individual classes ofexplosives, which was not in the original scope of the project,became the new project objective after the separation systemfailed. This new project objective was met. Because thetheoretical advantages of size separation/recombination have notyet been evaluated, the idea cannot be completely dismissed.However, the following facts should be considered before afinal decision is made:

1. Individual processes are now available which can provide allthe desired products without the additional processingrequired for separation and recombination.

2. Individual recrystallization processes are more efficientsince the demand For particular products is relatively


1-..• • • . ...... .. .. .. . .. .. ... .. .... T T T B 7 • • - .. ... •T • • . . . • ' • • . .. .. .


independent of the demand for other products. (Sizeseparation/recombination would produce variable mi'xesof all products).

3. Redesign and evaluation of separation equipment for performingthe size separation would be required before the actual capa-bility and benefits of size separation/recombination could bedetermined.

CNICPR Improvement

The lack of control over product particle size which was experienced

during the evaluation of the continuous pilot CNCPR system was dueto interactions between several controlled variables within thesystem. Due to the complexity of these interactions, it is feltthat changes in the existing system controls will not result insufficient improvement to provide a reliable process. Therefore,an alternate process configuration designed to eliminate thesecontrol problems should be considered for production of coarseexplosives, particularly Class 4. The modified configurationwill incorporate the best features of the previously demonstratedbatch CNCPR technology with the successful features of the continuousCNCPR system to produce a semi-continuously fed, intermittent productremoval CNCPR system.

ECONOMIC ANALYSIS

Recrystallized HMX

The approximate incurred costs for recrystallizing HMX by conven-tional methods to produce Classes 1 and 4 HMX and for recrystal-li'zing, pump grinding, and classifying Class 5 HMX are shown inAttachment 1. Actual "out-of-pocket" unit costs of utilities usedduring the first quarter 1980, the 1980 HDC labor estimating rates,and the labor, material, and overhead values charged against variousRDX and HMX products during June, 1980 are presented in Attachment 2.Assumptions made for estimating the costs of conventional HMX re-crystallization include the following:

1. Utilities usages were calculated by performing energy balanceson existing processes using current operating procedures andoperating logs as bases. Costs were calculated by applyingthe "out-of-pocket" unit costs from Attachment 2.

2. Steam usage includes a 10% additional for miscellaneous butdoes not include building heat or ventilation.

3. Electrical usage does not include lighting or other miscellaneoususage.



4. The total of direct labor, materials, and overhead costsapplied to recrystallization is the difference between thecost accumulated through the recrystallization step minusthe cost accumulated through the filtration/washing step(represented by the value of crude explosives) at currentproduction rates.

The estimated incurred costs for recrystallizing Classes 1, 4,and 5 HMX from DMSO in a hypothetical 864,000 lb/month (0.151 kg/s)recrystallization facility are presented in Attachments 3, 4, and 5,respectively. The assumptions used for these estimates includethe following:

1. The hypothetical facility produces a maximum of 432,000lb/month (0.076 kg/s) of nominal Class 1 HMX, 216,000 lb/month(0.038 kg/s) of Classes 3 or 4 HMX and, 216,000 lb/month (0.038kg/s) of Class 5 HMX. These maximum rates are the bases forthe calculated operating costs.

2. Solvent recovery facilities are included in the overall facility.

3. Utilities and materials usages are based on material andenergy balances performed using the flowsheet presented inAppendix B, Figures 26 and 27.

4. Utilities costs were calculated by applying the "out-of-pocket"unit costs from Attachment 2.

5. Labor requirements are based on a total facility requirementof 5 men/shift, 3 shifts/day, and 7 days/week,

6. Labor rates are 1980 estimating rates for HMX recrystalliza-tion from Attachment 2.

7. Steam usage includes a 10% additional for miscellaneous butdoes not include building heat or ventilation.

8. Electrical usage does not include lighting or other miscellaneoususage.

Comparison of the calculated unit recrystallization costs of theselected products at the production rates chosen shows that DMSOrecrystallization is less expensive than conventional processing.Because of physical and operational differences between the twosystems being compared, ie, batch versus continuous systems, theunit operating cost differences depend to a great extent upon theproduction rates chosen for the comparison. In general, the unitcosts of utilities and materials are independent of the productionrates in either system and remain fairly constant. However, theunit labor cost is much more sensitive to production rate, especially



for the hypothetical DMSO facility. In order to provide a moremeaningful comparison, the effect of production rate on the unitrecrystallization costs must be analyzed and taken into account.

Because of the continuous nature of the DMSO facility, most of thesystem equipment must be operated at all times regardless of theproduction rate. For most operating rates a full operator crewis required and the total operator requirement at half rate isessentially the same as at full rate. Consequently, the unitoperating labor cost will double at half the 864,000 lb/monthmaximum production rate. At very low rates, however, the laborrequirement can be reduced by at least one operator since severalof the operating phases such as solvent recovery and Class 5recrystallization can be run intermittently instead of simply turningdown to a lower rate. By contrast, the unit labor cost of conven-tionally recrystallized products is less sensitive to productionrate changes since each recrystallization system is independent. Atlow production rates, only those systems actually needed areoperated and thus operating labor iF reduced accordingly. Forpurposes of this analysis, the production rate sensitivity ofconventional processes is estimated to be approximately 15% (unitlabor cost is 15% higher at 76,500 lb/month than at 612,000 lb/month).

The effects of production rate changes on the total operating costsof both the conventional arid the hypothetical DMSO facilitiesdescribed above are illustrated in Attachment 6. Note that thedifference in the unit recrystallization costs of the two systemsdecreases rapidly as the production rate decreases. At approx-imately the 150,000 lb/month (0.026 kg/s) level, the DMSO facilityloses its operating cost advantage. However, at very high ratesa large advantage is apparent. Over the current normal operatingrange, the recrystallization cost advantage varies from $0.12 to$0.18 per pound. (Note: The costs compared to determine this costadvantage include only the direct charges incurred during recrystal-lization and are not total product costs.)

In considering other advantages of the DMSO facility over conventionalfacilities, it should be noted that three separate conventionalfacilities would be required to recrystallize the quantity possiblein the hypothetical DMSO facility. Also, a 2 to 3 million poundper month (0.350 to 0.525 kg/s) DMSO facility is just as feasibleas the 864,000 lb/month (0.151 kg/s) because of the relativelysmall size of the equipment required. Thus, a DMSO facilitywould provide a very high mobilization potential not presentlypossible with existing systems.

Recrystallized RL.X

Actual calculations fur comparing recrystallization costs for RDXby conventional versus D1SO methods were not undertaken for thefollowing reasons:

Holston Defense Corporation 57 Kingspo•-t, Tennessee


1. Large scale RDX recrystallization from DMSO such as nominalClass 1 RDX for Composition B, is not considered practical dueto the quantity, size, and cost of the equipment required andbuilding load limit problems anticipated.

2. Large scale production of coarse RDX for coated compositions,such as nominal Class 3 RDX for Composition A-5, is not consideredeconomical because of the extra processing steps required andthus the higher operating costs implied.

3. Previous estimates 2 comparing DMSO-recrystallization with con-ventional recrystallization projected only a "break-even" com-parison for coarse RDX products. This projection is stillconsidered valid.

4. Since the DMSO-recrystallized Class 5 RDX process is similar tothe Class 5 HMX process, the same relative operating expenseis anticipated for equivalent production rates. Thus, the costof DMSO-recrystallized Class 5 RDX can be projected using theClass 5 HMX cost calculations as a basis.

In considering DMSO based facilities for production of nominalClasses 1 or 3 RDX for Compositions B, A-3, and A-5, it was notedthat mobilization rate quantities of each of these products wouldhave to be considered for comparison with facilities using conven-tional processes. A 7.5 million pound per month (1.313 kg/s)Composition B line would require a 4.5 million pound per month(0.787 kg/s) nominal Class 1 recrystallization facility. A 4.1million pound per month (0.717 kg/s) A-Products line would requireapproximately a 3.8 million pound per month (0.665 kg/s) recrystal-lization facility. There are several problems associated withusing DMSO technology for systems requiring rates of this magnitude.With cyclohexanone systems, approximately eig;,t, 5,000-gallon (22.7 m3 )crystallizer-stills are required to recrystallize 4.5 million poundsper month (0.787 kg/s) of nominal Class 1 RDX. Since the recrystal-lization cycle ends with the recrystallized RDX in a hot water slurry,coating to produce any of the A-Products is easily accomplished.Also, pumps can be used to transfer the recrystallized RDX slurry toother buildings for any other end use. The load limits in such afacility could be maintained within acceptable limits by staging thebatches.

DMSO facilities would require only three 5,000-gallon (22.7 m3 )crystallizers to recrystallize the 4.5 million pounds per month(0.787 kg/s) of RDX. However, the recrystallized product doesnot end up in a water slurry but must be reslurried if it is tobe pumped or coated. This creates a minimum of one additionalprocessing step which implies higher cost, at least for A-Products.In addition to the three crystallizers, two continuous filters

Holston Defense Corporation 58 Kingsportq Tennessee


(one for dewatering incoming crude RDX and one for removing solventfrom and washing the recrystallized product), an evaporator system,a product decant/recycle solvent handling system, a solvent recoverysystem (most likely a separate facility), and miscellaneous feedsystems and controls would be required.

Preliminary building layout of a DMSO-recrystallization processof the magnitude required within the existing recrystallizationbuilding floor plan results in an extremely overcrowded situation.The quantity of equipment needed demands a high personnel require-ment. With only a "break-even" cost projection for DMSO-recrystal-lized RDX compared with conventional RDX, the additional capitalexpense would not be recoverable. As previously discussed, loweredproduction rates would not necessarily reduce the personnel require-ments and would, therefore, additionally increase the unit cost ofthe product. In the case of the A-Products, where additional pro-cessing steps are required, it is doubtful that even a "break-even"cost situation would actually exist.

The load limits of the DMSO/RDX facility would also present someproblems in that explosives involved in several of the processingsteps, such as filtering and decanting, would have to be classifiedas Class 1.1. Also, due to the continuous nature of the feed pre-paration and product washing processes, even at reduced rates mostof the equipment would be full most of the time and the explosivesload could not be staged to reduce the explosives quantity for loadlimit purposes. In summary, for all production situations con-sidered, DMSO processes for manufacturing the high volume RDXproducts mentioned appear neither practical nor economical comparedwith conventional processes.

Conventional methods for producing Class 5 RDX involve water quenchingRDX/acetone solutions to precipitate the fine RDX crystals. DMSOprocedures are similar but the batch sizes could be increased usingthe same crystallizer vessels by a factor of approximately four. Thecost of recrystallizing Class 5 RDX using a DMSO process is expectedto be approximately the same as Class 5 HMX (approximately $0.24/lbproduct). The cost of labor, materials, and overhead alone for theconventional Class 5 RDX is $0.4693/lb product (see Attachment 2).Thus, a favorable cost advantage with a factor of approximately twois expected for Class 5 RDX recrystallized using the DMSO process.


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Attachment 2

Utilities: Ist Quarter 1980 (Out-of-Pocket)

City Water - $0.4523/1000 galFiltered Water - $0.0849/1000 galRiver Water - $0.0163/1000 galSteam - $2.2139/1000 lbElectricity - $25.5800/1000 kw hrAir - $0.1056/1000 ft 3

Labor Rates for 1980:

Dept. 223 (HMX Recrystallization) - $20.04/hr; Labor and Benefits

Dept. 207 (RDX Manufacturing) - $22.12/hr; Labor and Benefits

Labor and Materials Costs:

DMSO - $0.62/lb (Crown Zellerbach)

*RDX ($/lb) Labor Materials Overhead Total

Crude 0.1197 0.1713 0.1272 0.4182Class 1 0.1758 0.1764 0.1593 0.5115

**Class 3 0.3101 0.1458 0.1578 0.6137Class 4 0.2448 0.1831 0.1995 0.6274Class 5 0.3765 0.2277 0.2833 0.8875

*HX_ ($/lb)

Crude 0.4479 0.4331 0.6109 1.4919Class 1 0.6701 0.5024 0.7077 1.8802Class 4-2 0.7472 0.5094 0.7329 1.9895Class 5 1.1715 0.4796 0.9291 2.5802

*Data from Contract Pricing Proposal No. 1585 for January - December, 1980.**Actual for May 1980

61

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Attachment 6: Recrys~allization Cost Comparison for ExistingVersus DMSO Recrystallization of H14X

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65

Technical Report No, HDC-58-80

CONCLUSIONS

1. Feed solutions for RDX or H14X crystallization systems using DMSO asthe crystallization solvent can be efficiently generated usirg a feedpreparation system similar to the pilot plant system. The preparedfeed solution, containing no undissolved solids, can be used directlyas feed for crystallization systems.

2. The continuous CNCPR crystallization system can be used to crystallizeboth RDX and HMX from DMSO. Although the production of the coarseexplosiv2s distributions, Classes 3 and 4, was demonstrated, the capa-bility of the continuous CNCPR system te consistentiy and repeatablyproduce the coarse distributions was limited by poor dissolver satura-tion control. The CNCPR-MOD-l systm, a variation of the CNCPR system,caused increased fines production and thus additionally reduced theeffectiveness of this system to produce the coarse distributions.

3. The continuous CNCPR-MOD-2 crystallization system can be used tocrystallize explosives particle size distributions ranging frominominal Class I to actual Class 3. Pilot plant datd are consideredsufficient for sizing a prototype :rystallization unit for this ptirpose.

4. The continuous CNCPR-MOD-3 crystallization system can be used tocrystallize actual Class 1 RDX and HMX particle size distributions fromDMSO. Direct scale-up of this system to prototype scale is consideredpossible using tVie pilot plant data generated. A modification of theCNCPR-MOD-3 process which allows more dilution and continuous ratherthan intermittent product removal can be used to produce Class 7 RDX.

5. A batch, RDX dilution crystallization procedure is required for pro-ducing Class 5 RDX containing the stable beta polymorph of HMX. Sizingof equipment for a prototype Class 5 RDX production unit is consideredpossible using the existing pilot plant data. Good agitation duringthe aging period and a good product wash are considered of primaryimportance to a successful future design.

6. A batch, HMX dilution crystallization procedure is required for producingClass 5 HMX. The dilution must take place in the presence of fine betaHMX (HGF) and a thermal age period must follow to obtain the stable, betaHMX polymorph. Sizing of larger scale equioment for production ofClass 5 HMX with this procedure is considered possible using existingpilot plant data. Good agitation and product washing are essential toa successful future design.

7. The RDX and HMX crystallized from DMSO meet all existing specificationsfor these products. Standard test results were comparable to ROX andHMX recrystallized by conventional methods.

KHolston Defense Corporation 6o Kingsports Tennessee

Technic&' Report No. HDC-58-80

8. A det.ant system is considereo a desirable alternative to the originalproduct/solvent separation technique which used a vibrating screener.lite crude decant system used during the pilot evaluation performed theinitial separation with good efficiency.

9. Screening equipment can be usea to provide satisfactory initial and finalproduct wash of the coarser products from the CNCPR systems.

10. Purity analyses of the various recrystallized RDX and HMX productsindicate that processing the spent crystallization solvent by coolingand filtration to remove an impure explosives stream prior to recycleis Pot necessary. The build-up of the minor explosive component inthe ROX or HMX processes can be effectively controlled by selection ofan appropriate solvent purge rate. The present pilot plant data areconsidered adequate for sizing a recycle solvent handling system fora prototype production unit.

11. DMSO can be recovered from dilute water solutions which contain dissolvedand undissolved solid and liqu;d impurities to obtain high purity sol-vent suitable for reuse. Although the present pilot plant data wouldbe useful in designing a DMSO recovery system, it is not consideredadequate for scale-up.

12. The direct recrystallization techniques developed in the pilot plant forrecrystallization of individual classes of explosives are consideredacceptable alternatives to the "multiclass explosives" idea using thesize s3eparation/recombination technique which failed due to unsatisfactoryequipment performance.

13. lhe DMSO-recrystallized RDX from the pilot plant can be used as inputmaterials for the manufacture of Composition A-3, Composition A-5,

Composition C-4, Composition B and 70/30 Cyclotol. The resulting finalproducts meet all specifications for these products.

14. The DMSO-recrystallized HMX from the pilot pldnt can be used as inputmaterials for the manufacture of 70/30 and 75/25 Octol. The resultingincorporated products meet all specifications for these products.

15. Economic evaluation of hypothetical DMSO-recrystallization facilitiesindicate that DMSO processes can reduce the recrystallization cost ofall HMX products at production rates higher than 150,000 pounds per month.The DMSO-recrystallization costs of the relatively large quantities of nominalClasses 1 and 3 RDX required for Composition B and A-Products are projectedto be approximately the same as conventional processes. Class 5 RDX costscan also be reduced using the DMSO process. A lower recrystallization costadvantage results for both DMSO-recrystallized RDX and HMX compared withconventional methods if the DMSO facilities are operated at reducedcapacity.

Holston Defense Corporation 67 Kinsport, Tennessee


RECOMMENDATIONS1. The following minimum efforts should be accomplished in support of any

further DMSO recrystallization project work:

a. All mechanical and general process improvements cited in this reportrelative to the existing pilot plant, including the design andinstallation of a product decant system, should be implemented.Individual and collective evaluation of the improvements should becompleted before additional products are manufactured, Since mostof these improvements will require redesign, modification, orpurchase of additional capital items, additional project fundingshould be provided.

b. Efforts should be made at HSAAP concurrent with Recommendation No. l.a.to further evaluate the present analytical capabilities with respectto liquid chromatographic characterization of solutions containingRDX, HMX, DMSO, and water. If the present capabilities are deter-mined to be unacceptable, improvements in the LC techniques orinstruments should be pursued or alternate methods proposed whichwill provide the acceptable analytical capabilities required tomore accurately evaluate the DMSO-recrystallization systems.

c. Qualification tests of products from the current pilot plant evalua-tion should be completed as soon as possible. Results should bemade available for review by HDC and HSAAP personnel as soon as thetests are completed in order to determine if additional improve-ments in the DMSO-recrystallization processes will be adequate toprovide acceptable products.

d. A study should be initiated to identify any accumulated impuritiesin the recycle and waste solvent streams generated during thepilot evaluations. Edgewood Arsenal should perform the appropriatetoxicity studies of the impurities identified so that the potentialhazards associated with the proposed recrystallization processescan be determined and evaluated.

2. After successful completion of Recommendation l.a. and initiation ofRecommendations l.b. - l.d., the pilot plant should be operated as asemi-works facility to provide additional test quantities of DMSO-recrystallized explosives as needed. These products could be providedas test material in the support of the development of new products orapplications. Efforts should be made to solicit customer ideas andorders for these products.

3. Design and evaluation of a pilot DMSO recovery process should beaccomplished to provide sufficient information for design and scale-up to prototype.


[e.'hrIL dl Relpu t No. II)C-',8-]()

4. If future ID)X ind llMX production requirements justify prototype •rproduction facilities, the following processes are recommrended:

(a) Batch coolinq with dilution capdbility for producing actual andnominal Class I RDX and IIMX, actual Class 5 RDX and HMX, andactual Class 7 RDX.

(b) Batch CNCPR for producing actual and nominal Class 3 RDX and HMXand actual Class 4 RDX and IIMX.

(c) Continuous coolinc with dilution capability for oroducina actualand nominal Classes 1 and 3 POX and IIMX and actual Class 7RDX.

5. Since demonstrated DMSO crystallization technology is available forefficient preparation of most individual classes of RDX and HMX, itis recommended that additional evaluation or use of the originalcontinuous CNCPR concept (which includes particle size separation/recombination) for simultaneous production of all classes of explo-sives be abandoned unless justified by specific production need and/oreconomics.

6. Due to the complexity of parameter interactions within the continuousCNCPR system, it is recommended that no additional effort be expendedto improve the existing continuous CNCPR process for production ofcoarse explosives.

7. If justified by economics and specific production needs for productsrequiring coarse explosives, is recommended that a semi-continuousCNCPR system, which is based on the combined successful features ofthe batch and continuous CNCPR systems, be evaluated in the existingpilot plant. The relatively minor modification recommended, whichshould eliminate the need for strict control of dissolver saturation,involves batch feeding of the dissolver to produce a semi-continuouslyfed, intermittent product removal system,

8. Based on the present economics and pending qualification of DMSO-recrystallized products from the pilot plant, it is recommended thatdecisions regarding future facilities projects for recrystallizaticnof all classes of HMX or Class 5 RDX include consideration of DMSOprocesses as alternatives to conventional recrystallization process.

Holston Defense Corporation b Kingsport, Tennessee


REFERENCES

I. HDC Technical Report, HDC-PE-15, Phase I, 'Recrystallization and Growthof HMX-RDX, A Study of Methods and Equipment", D, M. Mahaffey, 1972.

2. HDC Engineering RepQrt, HDC-19¶74, "Recrystallizatiton and Growth ofHMX-RDX, A Study of Methods and Equipment, Phase II%, M, D. Rothrock,1974.

3. HDC Technical Report, 79-0088, "Precipitation of HMX Fines from DMS0",B. A. Hunter and F. D. Pilgrim, 1980.

4. HDC Progress Report, 20-P-26, "Physical and Chemical Properties ofRDX and HMX", J. T. Rogers, 1962.

5. Treybal, R. E., "Mass Transfer Operations", 2nd Edition, McGraw-HillBook Co., New YorK, 1968.

6. Crown Zellerback, Chemical Products Division Publications, "DimethylSulfoxide, Recovery from Aqueous Solutions", Dimethyl Sulfoxide as aReaction Solvent" and "Dtmethyl Sulfoxide, Summary of Toxicologicaland Safety Information".

7. Military Specificatons, RDX, MIL-R-398C.8. Military Specifications, HMX, MIL-H-45444A.9. HDC Development Report, "rncorporations of DMSO-Recrystallized RDX

and HMX to Make Cyclotols and Octols", R. E. Dawson, 1974.10. McCabe, W. L. and J. C. Smith, "Unit Operations of Chemical Engineering",

2nd Edition, McGraw-Hill Book Co., New York, 1967.11. Perry, R. H., C. H. Chilton, and S. D. Kirkpatrick, "Chemical Engineers'

Handbook". 4th Edition, McGraw-Hill Book Co., New York, 1963.12. HDC Technical Report,77-0057, "Hazards Analysis of the DMSO RecrystallizationPilot Plant at Building C-6", S. A. Carmack, 1977.


APPENDIX A

TABLES

71

Table 1: Equipment List

Equipment Name Code Number

Slurry Mix Tank CA-52

Evaporator Feed Tank CB-50

Evaporator CB-51

Rectifying Column CB-21

Condenser CB-22

Dissolver CB-52

Crystallizers CC-50, CC-51

Mother Liquor Receiver CD-50

Product/Mother Liquor Screen CD-01First Wash Screen CD-02

Second Wash Screen CD-03

Vacuum Filter No. 1 CD-51Vacuum Filter No. 2 CD-52

Vacuum Filter No. 3 CD-53

Recycle DMSO Receiver CF-51Product Line Wash Reservoir CF-53

Vacuum Filter No. 4 CF-52

Recycle DMSO Storage Tanks CA-50, CA-51

Recycle DMSO Holding Tank CF-53

Condensate Receiver CE-50Condensate Holding Tank CE-51

Waste Solvent Recycle Tank CB-53

Waste Solvent Storage Tank CG-50

Waste Solvent Filter CG-51Primary Steam Jets CJ-lO, CJ-ll

Vacuum Receivers CF-50, CJ-51

Evaporator Vacuum System CB-13

Exhaust Fan CH-10

Waste Water Holding Tank CG-52

Feed Slurry Transfer Pump CA-1OEvaporator Feed Pump CB-10

Dissolver Feed Pump CB-11

Crystallizer Circulating Pump CB-12

Mother Liquor Transfer Pump CD-1O

Filter No. 2 Filtrate Pump CD-i1

Filter No. 3 Filtrate Pump CD-12

Waste Solvent Pump CG-10Recycle Solvent Pump CF-10

Condensate Pump CE-1OWash Water Pump CE-11

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Table 29: Analytical Results of DMSO-Recrystallized RDX Test Products

CompositionsA-5 A-3 C-4

% RDX 98.84 91.11 89.94

% Stearic Acid 1.16 -

% H20 0.01 0.01 0.014

Bulk Density 1.03 0.82 -

% Binder - - 10.06

Plasticity - - 0.054

% Wax - 8.89 -

Acidity - 0

Foreign Matter None None

Insoluble Particles None None None

Granulation:

% Passing USSS No. 6 - 100 10012 100 - -

100 - 0.1 0.3200 0.2 - -

Composition B 70/30 Cyclotol

% RDX 59.91 70.58

% TNT 38.91 29.42

% Wax 1.18 -

% Water 0.06 0.11

Viscosity, See. 4.4 9.5

Insolubles None None


119

i -~-' - -'- *5 j-~5.5*. ,

Table 30: Analytical Results of DMSO-RecrystallizedEHX Test Products

70/30 Octol 75/25 Octol

% HMX 69.38 73,34

% TNT 30.62 26.6

% Water 0.10 0.13

Viscosity, sec. 11.12 14.1

Insoluble Particles, USSS No. 60 None None

% Insolubles 0.00 0.00


1

r 120

APPENDIX B

FICURES

121

-I . -, I i -'--. •. , •:

L -- - *' - - "-' -" & - - i

122:

U.4.

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123

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C G-50

- 2 nd Floor Layout

F I G U R E a JIM

124

- t

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20

w MI

(AC

4L-

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125

DMSO FROM DRUMS RDX/HMX From NIITSCIIES

IR

¢:*:•-~ .C ,52

To Evap. Feed TkCB-50

From H4

Recycle DIMSO

HOLDING Tk. CF-53C A•- 10

Slurry Mix Tk.

F FIGURE 5

JRC

S1 2$

C., - ,-.

TIO

CB-51.

F erNo4

- Evap orator Feed TkE-

F IG U RE ED.JAC

127

ToRect if ier

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Feed

* (CB-50)

FromEvap.FeedTank

EvaporatorFeed Tank

FW "'Shutdown)

DrainWahu

- Evyap orator3ZI

F IG UR E 7

128

_ Vacuum'4aste

Solvent

VirginDMSO FW

CondensateHolding

2I Tank

Sample/Drain

CE-10

From.Evaporator

- Recti fi er -

FIGURE .8129

Vent

From FiIater

F OverIowv FromA

-- •.•To oMother Liq. Rec.

Dr~i n on Aio CB-52. Level

•"• "• I C B-52

To Evaporoamic"

IA A

F EFIGUE T

Feed T Slurry Mix Tk.-I• I F14 -.Cry s tallie

Fro°m Evap Sa m' S Tp I e Fee, '•Pd

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F IG U RE 9

130

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131

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Recei ver

V OC.

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D SMSO _,I n Waste

System

SFIGURE IJAC133

-. 4

Fro0mACF-51

D~rum- off Station

Recycle DMSO

StorageJRC

FIGURE 13

134

FRomFILTER it. 3

i___ _.,WASTE

INUSTRIALCOMOENSAý SEWEFROM CE-_ CE-51

FIRSTWASHSCREEN

CE-fl

CONDENSATE

HOLDING TANK

rr' FIGURE 14

135

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IT

1•5 PSIGSnm

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TOCB-21

OR CF-52

- Waste Solvent -

- Recycle TankSFI

G U R E 1 5

136

From Filter #1 • Recycled DMSO

(CD-Si)

From Filter #2(CD-52) Wosk $ote-

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Vacuum

"-1 CG-51. Drum-Off

Station

W aste SolventRecycle Tank

(CB-53)

SolventWagon

Washout to

Industrial Waste 4

C-O10

Waste Solvent -

Storage & Filtering

FIGURE 16137 JRC

~~***'j -. 5 1

co-52 CF-57-a CO-53

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F IG URE 17

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For

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F FIGURE 18 JAC

139

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Roof

CC-50 CC-51

CA-52

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MezzmnineZ~

CF-52 CD-01 CD-02 CD-03

lt FloorCD-51 CD-50 CD-52 CD-53

- Exhaust Syste m

FIGURE 13 JKc

140

*4 - - .

- .4 ,4 4.'4i4

Cond. Holding Tk.

(CE- 51)

CG-52

"1--6D i t c h

_-.Waste Water-

-Holding T k.

FIGURE 20

JAC

141

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STlow Control Valve

nze

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cProduct

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isle Dissolvez

CNCPR-MOD-2 CNCPR-MOD-3

Feed Feed Water

Zxyst, ~rystCy .

Cryst. -Li-t.Product Product

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Recycle RecycleSolvent( 5 lv t

Figure 25: CNCPR Systems

146

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153

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'I 154

APPENDIX C

MIXING EQUATIONS FOR RDX/lMX,

RECYCLE SOLVENT AND DMSO

155

Mixing Equations for RDX/HMX, Recycle Solvent, and DMSO:

Ib dry explosives

R = Operating Line Ratio = lb dry explosives + lb DMSO (100% Basis)

WR - Operating Line

M Make-up Solvent Rate = lb DMSO (100% Basis) in Make-up DMSO

lb DMSO (100% Basis) in Recycle Solvent

A Lb of Wet Explosives Component A

B Lb of Make-up Solvent Component B

C = Lb of Recycle Solvent = Component C

W= Mass Fraction of Water in Component i.

D; Mass Fraction of DMSO in Component i.

EE - Mass Fraction of Explosive in Component i.

r - Density of Component i (lb/gal)

Equations: (1) Ct = 1

Wc + Dc + Ec *SPGE RDX = 1.8

8.34 9.17 *SpGE(8.34) HMX = 1.9

(2) C = Cc X (gals. of C) Measured in Mix Tank

(3) B - MCD.DB

(4) A - R(CD, + BDR) - CEc (l-R)(1-WA) X (l-R)

Calculation Procedure:

1. Measure gallons of recycle solvent (Component C) in the slurry mix tank.

2. Sample and analyze Component C using LC for explosites (Ec), water (We),

and DMSO (DO).

156

3. Determine moisture content of wet, crude explosives (Component A)as WA.

4. Calculate the density of Component C (•) using equation (1).

5. Calculate C using equation (2).

6. Given M and DB, calculate B using equation (3).

7. Given R, calculate A using equation (4).

Example Calculation for HMX System:

Given - R - 0.335, DB = 0.86, M - 0.20

Determined -gallons of C in mix tank - 42WA by LC analysis f 0.400Dc by LC analysis - 0.729Ec by LC analysis - 0.142Wc by LC analysis - 0.129

Calculated- ec - 1 f 9.622 lb/gal0.129 + 0.729 + 0.1428.34 9.17 (1.9X8.34)

C - 9.622 X 42 = 404.1 lb recycle solvent

B (0.2)(40&.1)(0.729) - 68.51 lb. make-up solvent0.86

A 0.335 [(404.1)(0.729)+(68.51)(O.86)] - C(404.1)(0.142)(1-0.335)1(1-0.4) (1-0.335)

201.2 lb wet HMKX

157

APPENDIX D

PHYSICAL PROPERTIES OF DMSO

J

! 158

PHYSICAL PROPERTIES

TABLE 1 PROPERTIESOFDMSO

Molecular Weight. ... ....... 78.,13Boiling Point at 760 mm Hg .. -. .. . 189 0 C (3720F)Melting Point ............................ 18.55 OC (65.4 OF)Specific Gravity at 25 0 C (77 OF) .. ....... .. 1.096 (9.,15 lb per gal)*Refractive Index at 25 0 C ..... ............. 1.477Vapor Pressure at 25 0 C .... ........... ... 0.62 mm Hg*Surface Tension at 25°C ............ 42.85 dynes per cmViscosity at 251C ..... ............... .. 2.00 Centipoise*Specific Heat at 29.4°.C .... ........... ... 0.47 ± 0.015 cal/(gm)(OC)*Heat of Vaporization at 250C ............ .. 12.64 Kcal/mole (291 Btu/lb)

at 189 0 C ... ....... .. .10.31 Kcal/mole 1237 Btu/lb)Heat of Solution in Water at 20"C ......... ... 60 cal/gmHeat of Fusion ........... .............. .. 44 cal/qmHeat of Combustion at 250 C .... ........... 6050 cal/gmFlash Point (TOC) ..... ............... .. 95 0 C (2030F)Ignition Temperature in Air ........ 300-3020 C (570-5750F)Flammability Limits in Air Lower ......... ... 3-3.5 vol %

Upper ......... ... 42-63 vol %Thermal Coefficient of Expansion.... . . . 0. 00088 cc per degree CElectrical Conductivity 20 0 C ...... .. 3 x 10 -8ohm- 1 cm-1

80 0 C . . ... ....... .7 x 10- 8ohm-lcm-iWater Solubility. ... ................. Completely Miscible

*Additional data are found in the following tables and figures

FIGURE 1VAPOR PRESSURES OF DM,0

*,00ý -

400 .. i 'IS,~~oo ,

"I-Oo40

o.

o.

to, o o 'o .o o - o

2.0O ---- 1

}-- -159

FREEZING POINT CURVES FOR DMSO-WATER SOLUTIONS

FIGURE 2a FIGURE 2b25 .

0

-50 7.

* U*

a -.

M 2-cu I I4

fU>I

t

u2060- >

Q20- 0-0 40 80 120 160 20o 0 25 50 75 100

TEMPERATURE C WT. DM90

160

TABLE 2 HEAT CAPACITY OF DMSO

Temp, °C Cp (liquid), cai/(g)(OC)

30 0.47

60 0.47100 0.48150 0.52

TABLE 3 DENSITY OF DMSO

Temp, °C Density, grams/cc

25 1.09660 1.062

100 1.023150 0.974

161

TABLE 4 VAPOR-LIQUID EQUILIBRIUM DMSO-WATER

(3DNE ATMOSP"EHE PRESSUREI-----

OLFATON MCI. F4ArTION

TEMPERATLME 1. WATER IN LIQUID WATER IN VAPER

100.0 1.000 0.0008

100,6 0.988 0.9997

iU1.0 ~0.975 o99

I a -0 0.945 0.9994102.00,9090.9989

103.3 0.909 o.9983

105.0 0.860 0.997

138. 0 0.740o.9

113.0 0.6750 0.990

11c.0 0.645 o.986120.0 0,651 0.964

1430.0 0.378 0.921

149.0 0.313 0.890

165.0 0).176 0.773

174.5 0.100 0.573

177.0 0.081 0.3573

183.0 0.048025

184.6 0.034 0.282187.7 ~0.0110.0

189.7 0.000 0.000

FIGURE 6

BOILING TEMPERATURE CURVE

FOR DM80 - WATEFI SOLUTIONS0(ONE ATWSPWRE P"E"M 7

200

Ito

190

1162

f 1GR

VAPOR LIQUID CQUILIBRIUM CURVEDMSO WATER AT ONE ATMOSPHERE

10

00

016

FIGURE 8

THEORETICAL PLATE REQUIREMENT

DMSO/WATER SYSTEM

CONDITIONS:

REFLUX RATIO I:1OVERHEAD 50O PPM DMS50BOTTOMS 500PPMPRESSURE IH ATMOSPHERE

U)0'

00 20 40 60 80 000

[ ~DMS0 IN FEED, WTZ.

FIGURE 9

REFLUX REQUIREMENTS -DMSOIWATER SYSTEM

"CONDITIONS:THEORETICAL PLATES 12

t -=RumA 500 PPM DM50

BOTTOMS 500 PPM HWIM PRESSURE 1 ATMOSPHERE

IZO IC - - - --oILF IC I

" 164

o.0---- -

IL QOI - 0d~(Fh~ 9010

I DM9 0 IN FEED, WT. Z

164

FIGURE 10

THERMAL DECOMPOSITION OF DMSO

1000

2w

uI

OU _.o___oo10.0 .001

2

0

IA

00

0.10 - - - - - - -- -_ _ _ _

300 260 220 IS0 140 100 s0 60 40

TEMPERATURE OC

165

Distribution List

CommanderU.S. Army Armament Research and

Development CommandATTN: DRDAR-CG

DRDAR-LC

DRDAR-TDADRDAR-LCM

DRDAR-LCM-E (5)DRDAR-TSS (5)DRDAR-LCE-D

Dover, NJ 07801

CommanderU.S. Army Materiel Development and

Readiness CommandATTN: DRCDE

DRCMTDRCPADRCPP-IDRCPIDRCSG

5001 Eisenhower AvenueAlexandria, VA 22333

CommanderU.S. Army Armament Materiel

Readiness CommandATTN: DRSAR-IR (2)

DRSAR-IRC

DRSAR-IRM (2)DRSAR-PDMDRSAR-LCDRSAR-ASF (2)DRDAR-SF (2)

Rock Island, IL 61299

DirectorU.S. Army Industrial Base

Engineering ActivityATTN-: DrXIB-MTRock Island, IL 61299

,P16O

I

AdministratorDefense Technical Information CenterATTN: Accessions Division (12)Cameron StationAlexandria, VA 22314

DirectorU.S. Army Materiel Sytems

Analysis ActivityATTN: DRXSY-MPAberdeen Proving Ground, MD 21005

Commander

U.S. Army Armament Research andDevelopment Command

Weapons Systems Concepts TeamATTN: DRDAR-ACWAPG, Edgewood Area, MD 21010

Commander/DirectorChemical Systems LaboratoryU.S. Army Armament Research and

Development CommandATTN: DRDAR-CLJ-LAPG, Edgewood Area, MD 21010

DirectorBallistics Research LaboratoryU.S. Army Armament Research and

Development CommandATTN: DRDAR-TSB-SAberdeen Proving Ground, MD 21005

CommanderU.S. Army Munitions Production Base

Modernization AgencyATTN: SARPM-PBM-LA

SARPM-PBM-T-SFSARPM-PBM-EE (3)

Dover, NJ 07801

CommanderHolston Army Aumunition PlantATTN: SARHO-COKingsport, TN 37662

168

CommanderJoliet Army Ammunition PlantATTN: SARJO-COJoliet, IL 60436

CommanderLonghorn Army Anmunition PlantATTN: SARLO-XCMarshall, TX 75670

CommanderLouisiana Army Ammunition PlantATTN: SARLA-XCShreveport, LA 71130

CommanderNewport Army Anmunition PlantATTN: SARNE-CONewport, IN 47966

CommanderPine Bluff Arsenal"ATTN: SARPB-XOPine Bluff, AR 71601

Commander's RepresentativeSunflower Army Ammunition PlantBox 640DeSoto, KS 66018

CommanderVolunteer Army Ammunition PlantATTN: SARVO-XCChattanooga, TN 34701

CommanderIndiana Army Ammunition PlantATTN: SARIN-ORCharlestown, IN 47111

CommanderKansas Army Ammunition PlantATTN: SARKA-CEParsons, KS 67537

169

CommanderLone Star Army Ammunition PlantATTN: SARLS-COTexarkana, TX 57701

CommanderMilan Army Ammunition PlantATTN: SARMI-COMilan, TN 38358

CommanderRadford Army Ammunition PlantATTN: SARRA-ENRadford, VA 24141

CommanderBadger Army Ammunition Plant

ATTN: SARBA-CEBaraboo, WI 53913

Commander

Iowa Army Ammunition PlantATTN: SARIO-AMiddletown, IA 52638

CommanderU.S. Naval Ordnance StationIndianhead, MD 20640

CommanderU.S. Naval Ordnance Test StationChina Lake, CA 93557

ChiefBenet Weapons Laboratory, LCWSLU.S. Army Armament Research and

Development CommandATTN: DRDAR-LCB-TLWatervliet, NY 12189

CommanderU.S. Army Armament Materiel

Readiness CommandATTN: DRSAR-LEP-LRock Island, IL 61299

170

DirectorU.S. Army TRADOC Systems

Analysis ActivityATTN: ATAA-SLWhite Sand Missile Range, NM 88002

CommanderAeronautical Systems DivisionWright-Patterson Air Force BaseDayton, OR 45433

DirectorU.S. Army Materials and Mechanics

Research CenterATTN: DRXMR-FR, Technical

Informrtion SectionWatertown, MA 02171

CommanderU.S. Army Missile Research and

Development CommandATTN: Redstone Info Center (2)Redstone Arsenal, AL 34809

171

Documents

DMSO Recrystallization of HMX and RDX