A -,b

U. S. NAVY

MARINE ENGINEERING LABORATORY

FOB~~):

"':ii '""- Annapolis, Md.

Dedicated To PROGRESS IN MARINE ENGINEERING

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DEDICATED TO PROGRESS IN MARINE ENGINEERING

The Marine Engineering Laboratory is charged with

the discovery of fundamentai knowledge, the

development of new and unique equipment to meet

and anticipate new naval requirements, analysis

of Fleet machinery failures, and evaluation of

prototypes to insure high performance and relia-

bility in the Fleet. Dedicated to progress in

naval engineering, the Marine Engineering Lab-

oratory contributes co the technical excellence

and superiority of the Navy today - and tomorrow.

ANY MATTERS OF COMMERCIAL CONFIDENCE INCLUDED IN

THIS REPOPT MUST BE TREATED WITH DUE REGARD FOR

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THE INFORMATION CONTAINED HEREIN SHALL NOT BEUSED FOR ADVERTISIING PURPOSES.

THIS REPORT HAS BEEN MACHINE ASSEMBLED. IF

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Development of an ImrprovedSProcess- for the Catalytic Oxidation

of -Atmospheric Contaminantsin Submarines

Phase-II, -Assignment 73 107

MEL R&D Report 4419/65LS January -1966

By4' R. Calvert

W. R. CALVERT

Approved by

{ E. M. HERRMANNIMachinery Systems Division

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Distribution of this document is unlimited.

MEL Report 449/65

ABSTRACT

Studies in the development of an improvedcatalytic oxidation process reveal that pol.-luted air causes other problems along with thecorrosion which has been experienced in sub-marines.-

CO/He Darner troubles are explained bydata showing inhibition of Hopcalite due toadsorption of CO 2 and organic halides andshowing catalyst granules turning to dustbecause of thermal fracture.

Minimization of air pol2lutants is neces-sary, and preprocessing to remove certainmaterials before the catalytic oxidation is anecessary part of air purification.

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j MEL Report 449/65

ADMINISTRATIVE INFORMATION

The work reported herein was performed under MEL Assignment73 107, Sub-project S-F013 08 03, Task 4095. The project wasauthorized by Bureau of Ships letter Serial 649G-1264 of 9 July1963 and is based upon a proposal forwarded by MEL letter-NP/10330(833), Assignment 73 107 of 30 August 1963.

TECHNICAL REFERENCES I]1 - Calvert, W. R. , "Development of an Improved Process for the

Oxidation of Atmospheric Contaminants in Submarines," MELR6D Phase Rept 118/64, Nov 1964

2 -MEL Conf ltr NP/10330(733), Assigt 73 107, to Chief, BUSHIPS(Code 649G), Jan 1966 1

3 - MEL Itr NP/10370(833), Assigt 73 114, covering the work tobe performed to provide nuclear submarine forces withcriteria for selection of materials to be, used in originalconstruction and/or overhaul, 27 Feb 1964

14 - BUSHIPS ltr SSN/SSBN 9380 ser 649G2-961 of 28 May 1965"5 - Ross, P. H., Jr., "Examination of Return-from-Aft Ventila-

tion System in USS JAMES MADISON (SSBN 627) and USS SAM

RAYBURNw (SSBN 635),." MEL Tech Memo 3144/64, Jan 19656 - Temple, Wolfe, zisman, Borgstrom, and Van Keurmn, "A Method

for the Study of Hydrolysis of Organic Fluorine and ChlorineCompounds Submitted for Use as Non-Inflammable HydraulicOils," NRL Rept P-2009, 26 Feb 1943 I

7 - Fields, D. E., "Investigation of Sources of ChlorinatedEvdrocarbons on Nuclear Submarines and Inspection of CorrosionR-.3ulting from the Combustion of These Materials in CO-H 2 IBurners," NRL Trip Rept 6120-507:DEF:hlw, NRL Problem CO8-18,task group rept, BUSHIPS Project S-F013 08 03, 10 Sep 1964

8 - Calvert, W. R., "Report on Task Group Visitii to Three Ship- Iyards," MEL memo from Code 833 to Code 500, 214 3ep 1964

9 - Press release, American Aviation Publications, Inc., 1001Vermont Ave N.W., Washington, D.C., 20005, in "missiles and Irockets," 13 Sep 1965, p. 26

ERRATUM NOTE

In MEL Report 118/64, reference 1, page 5, paragraph 2.4.3,first line, please make the following change "The commercialcatalyst, No. 1, Table 1, was evaluated by the same procedure..."

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MEL Report 449/65

II TABLE OF CONTENTS

iI * Page

DISTRIBUTION LIST 7iII iABSTRACT iii

ADMINISTRATIVE INFORMATION ivi TECHNICAL REFERENCES ivi ERRATUM NOTE iv

THE AIR-PURIFICATION/CORROSION PROBLEM 1Corrective Measures 2

I Scope 2Background 2

APPARATUS 3DATA 4

Samples 4I CO/H2 Oxidation 4

Dust from Thermal Fracture 4Decomposition Products 4Adsorption Studies 4

DISCUSSION OF TESTS 6Hopcalite Alone 6Hopcalite with LiOH in It 7

• Thermal Fracture 7Decomposition Products 7Adsorption/Catalysis 8

SDISCUSSION OF SUBMARINE VENTILATION 8Corrosion 8Distribution of Pollutants 9

- Filtration of Dusts 9Regenerable Adsorpti.on 9i CONCLUSIONS FROM TESTING 9

I RECOMMENDATION 10FUTURE WORK 10LIST OF FIGURES

Figure 1 - Drawing, Flow Diagram of ExperimentalCatalytic and Adsorbent Processes

Figure 2 - Photograph, A Mixture of Hopcalite andI'. LiOH on a SieveFigure 3 - Curve, Hydrogen Oxidation Curves

I Figure 4 - Curve. Carbon !.Ionoxide Oxidation CurvesFigure 5 - Curve, Adsorption Curves (Catalysts and

Molecular Sieves)

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MELaor 44-9/65

TABLE OF CONTENTS (Cont.)

Appendix A - Examples of Chemical Reactions ProbablyApedi 0-Ocurring in CO/H 2 Burners and Other

Submarine Corrosion Sites

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-iito MEL Report 44J9/65

DEVELOPMENT OF AN IMPROVED PROCESS FOR THE

CATALYTIC OXIDATION OF ATMOSPHERIC CONTAMINANTS IN SUBMARINES

1.0 THE AIR-PURIFICATION/CORROSION PROBLEM

-- and The previous report1 describes air-purification equipmentand materials involved in corrosion, along with data from test-ing of oxidation catalysts. This report continues the assemblingof information and broadens the definition of the problem toinclude distribution of corrosion within the submarine's system.Organic halide reaction in the CO/Hs burner is strong evidenceof incompatability. This directs attention to similar reactionwhich may be involved in trouble found elsewhere within thesubmarine.

"Ventilation" distributes corrosion within nuclear sub--marines. Thi3 is not the "ventilation" of common definitionsince it circulates but does not replace foul air. The needswithin the enclosed atmosphere are better described by "air-maintenance." "Ventilation" employs the concept which permitsaccumulation of contaminants up to trace quantity levels,considered to be a more practical approach than to provide com-

Spletely purified air to replace foul air-4 The trace quantitiesbecome askew because of pollution not accounted for in thedesign of the system. Major pollution occurs as emissions fromI I materials of construction, maintenance, and normal operations.Some pollution causes severe corrosion, some is toxic, and somecan be tolerated.

An abrupt change of thinking comes with the realization that[ the enclosed air is used as the media through which pollutantsj are transferred from sources to the air purification equipment,and that is expected to keep this same media suitable for use bythe crew and by sensitive electronic (and other) submarine gear.Ii The main mass of air is being polluted while a fraction of it isprocessed to remove a few kinds of contaminants. "Ventilation"has sometimes made the enclosed air worse instead of better.

'Superscripts refer to similarll numbered entries in theTechnical References at the beginning of this report.

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•1 MEL Report 449/65

A high dilution (circulation) rate averages the pollutantsobscuring any correlation of test results with physiological orother effects due to exposure of crew or gear to higher concenItrations near sources. In addition, some pollutants have strangeeffects on the analytical instrumentation with resulting unresolvedtroubles and doubtful data.

1.1 Corrective Measures. This Laboratory is active in three pro-grams to provide corrective measures, with objectives as follows:

o The first is to eliminate the sources of pollutants. Asearch is under way -to find acceptable adhesives, etc for sub-.

marine construction.1

The second is to provide help needed to alleviate exist-ing corrosive effects. Alkali-impregnated paper filters wereprovided to three' submarines. This effort has been supercedeC by

the BUSHIPS program of installing filter beds made of granularlithium hydroxide. The possible benefit obtainable from neutraliz-ihg CiO/H Burner effluent, by combining it with effluent from CO2Scrubbers, is under study.'

e The third is to develop a process of catalytic oxidationof CO and H2 which avoids decomposition of organic halides intocorrosive materials. 1

1.2 Scc:)e. Progress in the second phase of the third programincludes details from the study of:

pr! es Catalytic oxidation of CO and H, while organic halides areS~ present.

Thermal fracture of Hopcalite and LiOH granules, producingS~dust.

o Adsorption by catalysts and by molecular sieves.

The discussion leads to recommendations for future air-maintenancesystems in submarines.

1.3 Background. This Laboratory's approaches to the problem andthe Bureau of Ship5 suggested modification of the catalytic pro,cess are now viewed in a different way as a result of previouswork.

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IMEL Report 449/65

1.3.1 "Use of a catalyst different from that now used." In! addition to ability to oxidize, the catalyst will not produceIdust and will be better to handle and to store. One or -morecatalysts are acceptable,.and if circumstances are right'duringtheir use, the organic. halide corrosion will be minor.

1.3.2 "Operation of the system at temperatures lower than nowII U~Iused." Least heat input is preferred. Minor decomposition of1 ifi organic halides limits temperatures to below 300 F,* an arbi-

trarily chosen valu,, based on testing expezience.

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It ~ 13.3 "Use of chemical reactants and adsorbents to preventundesired components from entering and/or leaving the system.'The Bureau of Ships suggested use of a preadsorber, such asInsilica-igel to remove moisture, row becomes a necessary pre-

Sprocessing to remove damaging species of pollutan ts, such as

Refrigerants 1of and 1i2, methyl- nchlord form, amines etc, whenpresent.

2.0v APPARATUS

The apparatus previously described1o has been modified. slightly to permit liquid vaporization so that catalytic.IH oxidation of CO and H2 can be studied inethe presence of vapors

Iefrom methyl achloroform,iRefrigerant 11, etc.

Iii A chamber was added in such a way that adsorption alone canSbe studied. This same apparatus, Figure 1, can be used to study

adsorption followed by catalytic oxidation. Organic halides were;ah measured employing hydrogen flame ionization. In earlier work a

Perkin-Elmer 213B hydrocarbon detector was used. In later workSgas chromatograph (Beckman GC-2) was used. Both hydrogen and

I organichalides were measured by gas chromatography using athermal conductivty cell in series with a hydrogen flame

I t ionization detector.

j *Abbreviations used in this text are from tba GPO Style Manual,g ]1959, unless otherwise noted.

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-- IZL Re"ort

The apparatus for studies of dusts from catalyst and LiOH Iwere: U. S. Standard Sieves and Tyler ROTAP sieve shaker, abalance, and a heat-treatment furnace. II3_-0 DATA j I-3.1 Samples. Samples of Hopcalite (with LiOH) were obtained Ifrom shipboard- CO/H 3 burners. One was a new mixture and anotherhad -beený in use for 250 hours. One other sample, Figure 2, wasItaken because of a complaint regarding persistently high backpressure across a catalyst chamber.6

3.2 CO/I%-Oxidation. Data and procedures have been described& I Ifor Hopcalite alone and in the absence of organic halides.Because LiOH was added to alleviate corrosion effects from air-borne halogen compounds carried into the catalytic oxidationreaction zone of the CO/H 3 burners, the oxidation studiesincluded it,with methyl chloroform and Refrigerant 12, in the I-itest stream of simulated submarine air. Hydrogen and CO con-tente of effluent after reaction were measured to show changesat various catalyst temperature levels. Data curves are shownin Figures 3 and 4.

3.3 Dust from Thermal Fracture. Sieve test data, Table 1, showthe particle size decrease after heat treatment of two catalysts i"and LiOH granules.

3.4 Decomposition Products. During catalysis and when measuringeffluent components, the products from decomposition of organichalides show as a CO signal in the LIRA analyzer. Some toxic11-materials (phosgene and other carbonyls) could be expected inthese products that are hydrolyzed to corrosive materials. Datafrom long path infrared analysis are shown in Table 2. Examples

S~of chemical reactions probably occurring in submarines are given

in Appendix A.

3.5 Adsorption Studies. Adsorption (and oxidation) curves fromtests with catalysts and molecular sieves are shown in Figure 5.Effluent changes were measured while processing a simulated sub-marine air stream through the adsorption chamber and apparatusof Figure 1.

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MEL Report 449/6

Table 1Thermal Fracture Data* " N

[From a study comparing Hopcalite, LiOH,and one of the platinum-alumina catalysts.]

Standard Sieves-S•square hole sizes, inches

Particles Passing ---- 0.132 0.094 0.066 0.056 0.028

Particles Retained on- 0.1321 0.09 0.066 0.056 0.028 PanGrams per 100 grams of sample

Hoscalite MnO2/CuO

granulesbefore heating 31.9 54.0 6.5 0 3.0 4.6after glowing 7.7 23.1 19.3 0 15.4 34.5(1•oo F)after 1100 F 7.8 15.5 14.6 3.8 12.4 45.9'heat treatment

No. I CatalstPt/Al,03 1/8 in.spheresbefore heating 0 42.2 54.2 0 1.6 2.0after glowing 0 41.8 53.5 0.4 1.7 2.6(1400 F)

after 1100 F 0 42.7 52.1 0.6 2.2 2.4heat treatment

LiOH H20 granulesbefore heating 30.0 41.6 23.4 0.8 0.4 3.8after 800 F heat 9.3 31.6 26.0 3.2 2.2 27.7treatment (meltsat 842 F, withfrothing)

*Samples were sieve tested (15 minute ROTAP), heated as shown,cooled, and sieve tested again.

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MEL Report 449/65

Table 2j Table Long-Path IR Analysis of Gas Samples II

[Collected after catalytic oxidation during periodsof product CO (LIRA) while there was no Co input.]

ganic Halide AnalysisII

Test LIRA P-E 213B Materials Found by Analysis withSStream CO ppx ppm (CH4 ) -. I Long -Path IR

250-HR Mix From SSBN 635 at 685 F

Input None 100 Refrigerant 12 (CClaFa) -a50 Methyl chloroform(CHaCCl8 ;O 0

sum =150

SEffluen t 9 90 Refrige rant 12 and viny liden e ch lo ride(Sum) (CH4:CCI2).COý%HO, with uncertain iden-* tification of minor components

•. ~~~N~ew. Mix From SSN, 595,. at 950. ,, FInput None -660 Methyl chloroform, COz, HaO N

Effluent 100+ 825 Vinylidene chloride (major) tri-(Sum) chloroethylene (CIICL:CCl 2 ) CO

(trace), COs, H.O, et-c

4.0 DISCUSSION OF TESTS

4.1 Hopcalite Alone. A higher temperature is needed to oxidizehydrogen in the presence of chloro- and fluoro-hydrocarbons(C-F-H), Figure 3(a). These materials are inhibitors exter.ing

"4- the effect of COa previously shown. 1

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i IL Report 44n/65

Adsorption of CO., CO, and Refrigerant 11 by Hopcalite is shownin Figure 5(b). This explains the low-temperature inhibition ofthe catalytic oxidaticn of CO in the presence of C-F-H, Figure4(a). Adsorption of endothermic materials inhibits exothermicoxidation.

4.2 Hopcalite with LiOH in It. The samples of new and used(250 hr} Hopcalite are shown to be alike, in Figure 3(b), forthe oxidation of hydrogen. These curves show incomplete oxida-tion of hydrogen, which was complete during a brief period whenthe C-F-H was absent. This same effect is shown in Figure 3(c),testing with lower hydrogen input concentration. The C-F-Heffect during CO oxidation is similar, Figure 4(b). In the COoxidation, three "blanks" were found. The third blank increaseswith heat input increase, cbscuring the measurement of COoxidation.

4.3 Thnermal Fracture. The thermal fracture of Hopcalite and LiOH,Table 1, explains the dust emission from the CO/Ha burner. Duringthe periods when the burner's heaters are on, the grmaules in the

T catalyst chamber are heated. When the heaters are off, thegranules fracture as they cool. The No. I catalyst is resistentto this thermal fracture and will not emit dust in large quan-tities.

The melting of LiOH at 842 F, with frothing, explains disappear-ance of this material from hot catalyst chambers and the loss ofcatalyat activity.

The LiOH gy:anulea fractlure easily, a fact that explains the largeamount of white material in the smaller-size fractions seen inFigure 2.

V 4.4 Decom2osit.on Products. Decompoaition products from theorganic halides (C-F-H) result in analytical problems because ofeffects on the instruments. The LIRA data, Figure 4, show three"blanks," Blank I is normal, being caused by water from Hg oxi-dation. Blank II is caused by decomposition product accumulation

- which changes infrared light transmission, and Blank III is caused'I by products•- carried in the sample stream. The amount of Blank IIIS increases as concentration of C-F-H increases when heat input to

these materials is sufficient. Such increase is shown in the LIRACO column of Table 2. Blank III may include product CO from

S partial oxidation of hydrocarbons which exhibit endothernictendency.

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- ÷ • • -•: - •. . .- - -- -• - - . - --- - --------- - • -_ -• •- •- - • • •• .-- •• • • • • •

_ 91MEL Rep'ort ~449/65i

4.4.1 The Perkin-Elmer 213B hydrocarbon detector was fouled in Iseveral ways by the decomposition products and by methyl chloroformsamples and standards tested at room temperature. During con- 1tinuous stream analysis with this instrument, the samples gavedrifting and fluctuating signals. Pressure regulators made ofaluminum alloy corroded, and white salts were found under theregulator diaphragm, in valves, and in capillary tubes. Itsflame ionization detector required frequent cleaning because ofaccumulations which altered its electronic circuitry. After Iabandonment of continuous stream analysis in favor of smallsamples (gas chromatography), the frequency of trouble becametolerable. I14.4.2 For the long-path infrared tests, the C-F-H concentrationin the sample was increased to enter within the field of sensi-1-tivity of this kind of instrumental analysis. Even so, resolutionand identity of products of decomposition was obscured. Conden-sation and hydrolysis in the high moisture content of thesesamples cause separation and changes during conveyance of samples Ito the instrument.

4.5 Adsorption/Catalysis. The organic halides in the submarine'sair make Hogdalite more adsorbent than catalytic, as shown inFigure 5. These curves also show. that the No. 2 (Pt/Al,10 3 ) cata- Ilyste is only briefly adsorbent and an excellent catalyst underthe circumstances of these tests. A further change in circum-stances may inhibit this catalyst too. For this reason the con- Jtemplated replacement of Hopcalite by a catalyst similar to No. 2 1

requires detailed consideration of circumstances in its use, toavoid improper performance. For example, Figure 5(c) shows oxi-Ildation of CO and H9 with no apparent effect on Refrigerants 12and 11 in this test apparatus. This result may be quite differ-ent in the operation of a Mark IV CO/H 3 burner.

5.0 DISCUSSION OF SUBMARINE VENTILATION

5.1 Corrosion. The corrosion from organic halides is not new.The U. S. Navy has recognized the fact for at least two decades,rejecting use of these materials in hydraulic fluids.' Extensiveuse of fire-retardant solvents in adhesives, etc, was probablynot expected when the ventilation system was designed. Refrigerat-ing gases are in hermetically sealed units and are therefore not[emitted as pollutants until leaks occur and when maintenance isnecessary. A search for materials of construction which mayresult in corrosion was made by a task group, 7 , in August 1964.

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SMEL Report 44.9/65 -I _________________________________

5.2 Distribution of Pollutants. Nuclear submarine patrol reportslist experiences related to distribution of dust and corrosive gases.It is obvious that toxic and damaging pollutants should not be dis-

tributed through the air which "blankets" the crew and sensitiveI-..- equipment. Distribution of purified air is preferred. The foul air

intake to purification equipment is preferably from space nearsources which emit pollutants. Minimized distribution of pollutantsshould lead to many improvements in problem areas wichin the sub-marine's system.

I ~ .5.3 Filtration of Dusts. Filtration to remove dusts is a requirementfor future air-purification processes, and it is preferred that anessentially dust-free filter will be found at scheduled cleaning time,

i rather than one loaded with difficult-to-handle-and-otherwise-objectionable particulates.

S5. 4 Regenerable Adsorption. Adsorption on inorganic solids, such asthe molecular sieves, is suggested as a means for removal of morekinds of contaminants. This can be viewed as a process which exposesprepared surfaces to the foul air for the purpose of attracting and

U retaining the contaminants, prior to controlled release and disposal[ to the sea during subsequent repreparation of the adsorbent surfaces.The adsorption of COa and refrigerant gases by 13X molecular sievesis shown in Figure 5.

I 6.0 COImCLUSIONS FROM TESTING

SSome of the troubles experienced in the operating of CO/HaBurners are explained by the inhibiting effects from CO and fromorganic halides which are adsorbed at low temperatures. Desorptionand oxidation occur as the Hopcalite is heated. To achieve completeoxidation of hydrogen, the required heat input increases as the con-

i L centration of inhibitors increase. CO oxidation is obscured by pro-ducts from the organic halides. Thermal fracture causes granules ofHopcalite E-nd LiOH to turn into dust. At least one of the known cata-lysts is resistant to thermal fracture. This permits elimination ofthe dust emission from the burners.

'With organi( .halide contaminants minimized and kept under con-trol trace quantities may be tolerable, if existing Mark IV CO/Ha

I Burners are modified to employ a platinum-alumina catalyst and areSoperated at low temperatures for the purpose of oxidizing CO and Ha.

Others9 favor a platinum metal. catalyst.

COg, hydrocarbons, organic halides, and other contaminants canbe removed to the sea by preprocessing the foul air employing regen-erable adsorption, in futura submarine air maintenance equipment.

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MEL Reprt JL0L/65 I

7.0 RECOM ioENDATI

Toxic and damaging airborne materials must be minimized insubmarines and kept under control. This applies to measuresthat can be taken during construction and repairs and includeschanges in COa Scrubbers to avoid amine emissions and in CO/Ha IBurners to avoid dust and corrosive gas emissions. Shipboardburners should be equipped with a different catalyst as soon aspossible. I

Capabilities of integrated air-maintenance equipment forfuture submarines should include removal of all contaminants andexcess heat to the sea, oxygen replenishment, pressure/volume @control, heating for comfort, and distribution of processed airto the crew and to sensitive equipment. To do this, fundamentalconcepts need revising.

8.0 FuTuRE WORKI

Future work described in the previous reporte will proceedafter a Mark IV CO/Ha burner beccmes available along with pro-visions needed for the modification and a realistic evaluationto assure proper performance under conditions which will existin submarines. I

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MEL Report 449/65

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USNMARINE ENGINEERING LABORATORY

$ Note the increased number of white LiOH particles as their sizedecreases.

Figure 2Sample: Mixture of Hopcalite and LiOHA Complaint Mixture from a CO/H 2 BurnerIt

MEL Report 449/65

MMIENGINEERING LABORATORY

--'4 Is I% HYDREN OXIDATION Si MOCAUTE ALONE INeU411

Legend (for Figures 3 and 4) 1Test Streama.-

maWITNOUT C43K ram CIH- Concentrations of CO and H2 as shown by

-- - - - curve: were included in the simulated sub-:" •0.6[ mairine air along with 50% MRi. 2% C092,00 PPMJ

Refrigerant 12, and 50 ppm methylyhloroform." ,0. -CFX through catalyst - 1.12 depth of bed 3.5

inch. FPX through catalyst - iO, volume ofbed 3.78 cu. inch. Heaters: air and cata-

-0.2- yst at 600 Ft pressure = 1 atmosphere.

0 100 200 300 400 500 600 700

CATALYST TEMPERATURE, F

(bI) 1% HYROOGEN OXIDATION BY SNIPSOARD SAPLS-WITH Cl-F-N

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CATALYST TEMPERATURE, F CATALYST TEMPERATURE, F

Figure 3Hydrogen Oxidation

Showing Need for High Temperaturesand the Incomplete. Hydrogen- Removal

When Chloro- and Fluoro-Hydrocarbons 1(C-F-H) Contaminants Pass Through the

Hopcalite + LiOH Mixtures

S rML Report 449/65

• • USN-'N7

MARINE ENGINEERING LABORATORY

~~( -I•- e CO OXIDATION..BY. HOPCAUITE ALONE

"'- -••-;) 0 "•'-'"t" C ¢'FH CO€ ADSORPTION |Foilv 51', •"

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-: C0 HEATING -C-F-H OFF,1' S LANK11N

CO-OFF -- A--f-a-] 10 "]- 1JiLL__LAffT-1 '½ IK

0 100 200 300 400 500 600 700CATALYST TEMPERATURE, F

(b) CO OXIDATION BY MIXTURE WITH LiOH[From -CO/!zBURMNER No2 SSN 5951

IC ---. I IITH C-F-H INPUT CO-O

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10 INCREASED LIRAI -I I BLANKU

0 100 200 300 400 500 600 700CATALYST TEMPERATURE, F

- Temporary LIRA Blanks

Blank I - The LIRA is sensitive to waterLI product from B2 oxidation.

Blank II - With CO input off, the blankis high after testing effluentcontaining C-F-H products.The LIRA signal returns tozero after overnight sweep-outwith air.L Blank III - With C-F-H input off and CO

input on, the CO signal decreasesThis blank increases as heatinput increases, and may beproduct CO.

Figure 4CO Oxidation

Showing Product CO WhenChloro- and Fluoro-Hydrocarbons (C-F-H)

Contaminants Pass Through Hopcalite AloneL and/or Hopcalite + LiOH Mixture

MEL Report 449/65

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MEL Report 449/65

Appendix AExamples of Chemical Reactions Probably Occurring

in CO/Ha Burners and Other Submarine Corrosion Sites,

11T Catalytic Oxidation/Decompositions

1. 2Ce ! CCla Air CH2 :CCla + CHCl:CCl 2I methyl chioroform Heat vinylidene trichlorethylenechloride

+ H2 0 + HCl + ? a miscellanyof partialoxidationproducts.

"2. CH 2 :CCla Air COCl (phosgene) + CO + H2 0 + ?

Hea1t

3. CHCl:CCl Air COCl 2 .COCla (oxalylchloride) + HCl + ? AHeat;-

4. Amine or NH3 Air Nitrogen oxides, amino- and•Heat' nitro-halides, etc

Hydrolysis on Moist Metals, with Salt Formation

S5. COF2 + Ha HaO -CO + 2HF Metal CO +-H2 + Metal fluorides

6. COCI-COCl + Fe HaO 2CO + FeCl2-2HaO

7. 2FeCl.-2h2O + COC12 HaO 2FeCl.-6E0o + co

8. Al + CHa-CC13 Air & H2O AlCl3-6HaO + CO + CO0room tempý

L Heat Decomposition on Steam Pipes and Other Hot Surfaces

9- CClF2 COG- COC12 + COF,Heatf-

Li

:1-

Secuuiti Classification Unclassif iedDOCUMENT CONTROL DATA - R&D

(Sasawlty clessitlation of el~e, body of abstraect and keind alnEmnotation must be entered whom the overall report is classified)t. ORIGINATING ACTIVITY (Corporate outhor) to. REPORT SECURITY C LASSIFICATION

U. S. Navy Marine Engineering Laboratory UcasfeAnnapolis, Maryland 21402 l RU

3. REPORT TITLE

Development of an Improved Process for the Catalytic Oxidation offAtmospheric Contaminants in Submarines4. DESCRIPTIVE NOTES (2ppe of ,reefr amei Inichaivs date.)

Phase IIS. ATHO(S)(Lost name. fint name. M11040)

Calvert, W. R.

6. REPORT DATE 7s. TOTAL NO. OF PAGES 7b. No. oF mapsJanuary 1966 139

Sa. CONTRACT OR GRANT No. 98. ORIOINATORIS REPORT NUMOSER(S)

6LPROJECT NO. S-F013 08 03 MEL Report 449/65

Tas 09 b T~ PONT NO(S) (Any odor numthere Met may be seal~wd

10. A VA IL ABILITY/LIMITA TION NOTICES$sinmn 0

LDistribution of this document is unlimited.

11. SUPPLEMENTARY NOTES IS. SPONSORINO LITARY ACTIVITY

NAVSHIP S

13. ABSTRACT

U Studies in the development of an improved catalytic oxida-L tion process reveal that polluted air causes other problems

along with the corrosion which has been experienced in sub-marines. CO/H8 burner troubles are explained by data showinginhibition of Hopcalite due to adsorption of CO2 and organichalides and showing catalyst granules turning to dust becauseof thermal fracture. Minimization of air pollutants isnecessary, and preprocessing to remove certain materialsbefore the catalytic oxidation is a necessary part of air13 purification.

U (Author)

0aDD I ON0447 Unclassified

Sscudty Classification

- A f

__ec__ OMS_'nUclssiie

I LINK A LIN;(S LINK~ aKEnO oLff WT f OLt Wi' ROL; w-

n UJL CU.LL ty.6- Slubtuar-Ines

Halgente Hyroaron

Air Pollution by IAir Contaminant RemovalCatalystsAdsorlbents

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D-D I JAN 3 1473 (BACK) Unclassif ied

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