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This report contairs test results defining the operating chsractcristics of lithin peroxide to the extcnt required to quantify system level ponalties. The effects of chemical caulysts, bed cooling, che.,ical Panufacturing tech uiques, opera ing conditions, and cheaica) handling jroc Curea are evaluated.

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TAlBLE OF CO_&E!PS

Section me No.

1.0 SUMM4ARY 1

2 .0 INTRODUCTION 3

3.0 PROGRAM DEFINITION

3.1 Program Objectives 4 3.2 Test Objectives 4 3.3 Program Description 5 3.4 Test Conitions T 3.5 Test Facility 7 3.6 - Test Hardware 12 3.7 Planned Test Sequence 18 3.8 Test.Results 21

ho TEST DATA PRESENTATION 22

4.1 Performance Data 22 4.2 Chemical Analysis Data 1o6

5.0 PERFOrd4ICE ANALYSIS 109

5.1 Catalyst Evaluation 109 5.2 Bed Cooling Evaluation 134 5.3 Procedural Test Evaluation 0h5 5.4 Off Design Test Evaluation 153 5.5 End Item Canister Evaluation 157 5.6 Li 2O2 System Penalty Evaluation 163

6.0 RECOM ENDED FUTURE EFFORT 165 7.0 APPENDIX 167

7.1 Specification for Lithium Peroxide 167 Manufacturing 7.2 Specification for Lithium Peroxide Storage a68 7.3 Specification for Lithium Peroxide 170 Cartridge Loading

iv Standard 5712

LIST OP TABLFS

Table No. Ps, No.

4-1 Test Data Summary 104

4-2 Chemical Analysis of Post Mortem Test 107 Bed Samples

5-1-1 Performance Analysis Siumnary 110

5-1-2 Catalyst Investigation Summary 128

5-2-1 Passive Cooling Data Summary 137

5-2-2 Passive/Dynamic Cooling Data Summary 138

5-2-3 Dynamic Cooling Data Summary 140 5-2-4 Cooling Techniques Data Comparison 141

5-3-1 Comparison of Catalyst Loading Technique 147 vs. Test Performance

5-3-2 Comparison of Catalyst Granular Size vs. 148 Test Performance

5-5-1 Canister Evaluation Test Summary 162 Hamilton , 5

'LIST OF FIGURES

Figre o. itl Paeeo.

3-1 Lithium Peroxide Test Rig Schematic 8

3-2 View of Flovt Meter Panel and Canister in Big 9

3-3 View of Inlet and Outlet Instrument Panels 10

3-4 Li 2O2 Test Canister Mounted In The Test Rig 11

3-5 Canister #1 (no internal heat conduction rods) 13 3-6 Canister #2 (with internal heat conduction rods) 14

3-7 Li202 Test Canister #3 25

3-8 Prototype Cooling Cartridge (Canister #4) AG

3-9 Prototype Cooling Canister (Canister #4) 17

4-1 thru Plots of carbon dioxide removal, oxygen generation, 23-103 4-81 maximum bed temperature and heat removal rate

4-82 Chemical Test Apparatus 106

5-1-1 Catalyst Evaluation Data 112

5-1-2 Catalyst Evaluation Data 113

5-1-3 Catalyst Evaluation Data 114

5-1-h Catalyst Evaluation Data 115 5-1-5 Catalyst Evaluation Data 116

5-1-6 Catalyst Evaluation Data 117

5-1-7 Catalyst Evaluation Data 118

5-1-8 02 Generation vs. Bed Temperature 122

5-1-9 CO2 Partial Pressure vs. Bed Temperature 123

5-1-10 Percent Theoretical 02 Evolution vs. Bed 129 Temperature 5-1-11 Percent Theoretical 02 Evolution vs. Bed 130 Temperature

vi Hamilton U Standard p SESR 5Y12

LIST OF FIGURES (Continued)

Figure No. Tite Q~u~o 5-1-12 Percent Theoretical 02 Evolution vs. Bed I1N Temperature 5-1-13 Percent Theoretical 02 Evolution vs. Bed 132 Temperature

5-]-11, Lithina Peroxide Expcrimental Catal:yt Test FI 33

5-2-1 Canister #1 (without conductive members) 135

5-2-2 Canister #2 (with conductive members) 136' 5-2-3 Average Values of Maximum Bed Temperature 12 vs. Cooling Techniques

5-2-4 Average Values of Maximum Reat Removal Rate vs. 143 Cooling Techniques

5-2-5 Average Values of Penalty Factor vs. Cooling lh4 Technique

5-3-1 Comparison of Canister Loading Process on Test h9 Performance

5-3-2 Comparison of Granule Size (Binder X) on Test 150 Performance 5-3-3 Comparison of Granule Size (Binder Y) on Test 152 Performance

5-4-1 Effect of Inlet Water Vapor Variation on Test 15h Performance

5-4-2 Effect of Inlet CO2 Variation on Test Performance 155 5-4-3 Effect of Total Flow Rate Variation on Test 158 Performance

5-5-1 Prototype Cooling Canister (Canister #h) 159

5-5-2 Prototype Cooling Cartridge (Canister #) 160 Hamilton U Standard

1.0 SIRVARY During Phase II of the lithium peroxide development program, the effect of chemical catalysts, bed cooling, chemical manufacturing techniques, operating conditions, and chemical handling procedures were evaluated.

The main objective of the catalyst evaluation tests was to identify a catalyst material which would promote oxygen evolution at chemi cal bed temperatures which are conducive to good carbon dioxide removal performance.

Initial catalyst testing consisted of twenty-two (22) full scale tests which evaluated MnO, FeS0k, Nz0 2 , Ti0 2 , nO + silver/copper, AgNO 3 , and CaO as catalyst materials. Additionally, small scale tests were performed on twenty-four catalyst materials. The results of the catalyst tests indicated that MnO catalyst tended to stabi lize test performance and allow for more even oxygen generation, but none of the catalysts evaluated truly promoted low temperature oxygen evolution to the degree necessary to achieve efficient use of the available oxygen.

Red cooling tests were conducted using passive, passive/dynamic, and dynamic cooling in test canisters both with and without inter nel heat conduction rods. Passive tests consisted of cooling one face of the test bed to simulate direct sublinator cooling. Passive/dynamic cooling consisted of cooling all four sides of the chemical bed and dynamic cooling utilized liquid cooling coils running through the chemizal bed.

Results of thermal control testing showed that low bed temperature (310 0F) could be maintained using any of the three cooling con figurations if the canister had internal heat conduction rods, but temperatures ran as high as 755OF for the same cooling config uration without internal conducting rods during passive and passave/ dynamic testing. This was due to the low thermal conductivity of the lithium peroxide chemical. The low conductivity caused very high temperature gradients between heat removal points and indi cated that heat removal paths must be distributed through the chemical bed. In addition to the thermal control tests, a new lithaum peroxide test canister (similar in size to the Portable Life Support System LiOH canister) which employed passive/dynamic cooling and could be recharged without the making or breaklng of liquid lines was fab ricated and tested. Results of testing showed that this cooling configuration could maintain the chemical bed temperature it!the desired operating range. Hamilton U Stanoard.. .

1.0 SURVARY (Continued)

Off-design tests were conducted to evaluate the effect of irl dew point variation, inlet flow rate variation, and inlet cnrl,,r dioxide concentration variation. These tests dermonstratMd, 1, general,'that carbon dioxide removal performa:ce and oxy-en =- duction increase with increased inlet dew point while thte acti, effect of mass flow rate and carbon dioxide concentration varition appears to be small.

Procedural testing consisted of eight manufacturing process testr and six canister loadin process tests. 7ot resuflz provi,, the information required to write manufacturing process, chealca storage, and canister loading specifications for lithium peroxid. These specifications are presented in Section 7.0 as an appendix to this report.

The results of this test program indicae that optimum overrl performance is obtained with bed temneratures fron 390"F lo 7"F. Within this range, the higher bed temperatures deter the earbon dioxide removal performance but enhance the oxygen evolution per formance due to thermal decomposition of the lithium peroxide. In addition, the MnO catalyst proved to be the most effective catalyst because it tended to stabilize parformance and provide maximum oxygen generation (up to 60 per cent of required 02 for metabolic consumption and leakage). In order to obtain optimum performance from the MnO catalyst, the crewman's metabolic rate must be above 1300 BTU/hr., so as to provide a C02 flow rate sufficient to attain abed temperature above 3900F. A maxinun. heat removal rate of 600 BTU/hr. is required to maintain optiur bed temperatures.

A comparison between a lithium peroxide system and a lithium hydroxide system using the same canister and test conditions reveals that the Li2O2/O2system is approximately 16 per cent lighter and occupies about the same volume as the LiOH/0O syste for the 0.5 mm Hg CO2 limit; it is about 25 per cent lighter a'd about 10 per cent smaller for the 4.0 mm Hg condition. Hamilton U StandardSTE IQ

.2.0 INTRODUCTION

In an attempt to reduce weight and volume of expendables roqnureKi for environmental control systems, a numcer of chemicals h-7, been evaluated to determine their suicability as an oxygen penCrat lon/ carbon dioxide rerjval material. Chemicals such as at3, KOj, 0 Li02, Ca(02)2, a02, K02 , L2 2, Na202, and K202 have been irvesti gated for this application with varying degrees of success. The most promising of these materiels has been lithium peroxide (Li02). Testing has shown that the chemrical is stable in vr:t tion and has high carbon dioxide removal capability (0.96 lb-C02 / lb-L1202 ) and acceptable oxygen generation potential (0.35 lb-C2 ! lb-Li2 O0). With these capabilities, a lithium peroxide oxygen generation/carbon dioxide removal system offers substantial reduc tions in system weight and volume for expendables.

During the previous phase 'Phase i) of the lithium peroxide development program, the effect of varying certain parameters such as test bed geometry, operating temperature, chemical bulk density, inlet dew point, and addition of catalysts was evaluated. it vas found during Phase I that chemical performance was a function of bed geometry, bed temperature, bulk density, and inlet dew point. Also, the addition of catalyst materials such as NiS04 seemed to improve chemical performance. Phase II of the lithium peroxide test program extended the resuits of the Phase I study. Catalyst addition was studied in greater detail with the final objective of isolating an optimum catalyst material. Means of controlling bed temperature were also evaluated. The effect of chemical manufacturing and handling techniques, as well as the effect of off-design operating co:ndi tions also were investigated during the Phase II study.

The results of the Phase II study are presented in the following sections. Test data results are presented in Section 4. and the analysis of these results is presented in Section 5.0. Conclusions and recommendations resulting from the Phase II study are prosented in Section 6.0. Specifications for lithium peroxide manufaciule, storage, and cartridge loading are presented in Section 7.0 as an aprendix to this report, Hamnhton - U Standard ""C.h. -:1

3.0 rRrGcAt DTFFINTTTO7

This section defines the program objectives, test obj tiv, ,, program detcription, test conditions, test fltcility, re. , hardware and plined test sequence. 3.1 Proara: Objectives

The ovevall program objective was to define the operating charac teristics of lithium peroxide to the extent required to quant i.t system level penlties incu-rrcd Uith a lithi'r p('r'xi'dT ranoval/O2 supply system. The specific objectives were:

To advance the state-of-the-art in life support system technology.

To develop specific components and subsystems for incorporation into an advancedportable life support system.

3.2 Test Objectives

The following objectives were established for the test program:

Determine an optimum catalyzing agent, considering An0, FeSOh, Mn0 2 , and NISCh, to promote oxygen evolution. Establish an optimmn method of heat transfer to maintain the bed within the desired operating range, utilizing the techniques described herein.

Conduct an analysis via gas chromatography, of the effluent gas to determine if either noxious or toxic gas constituents are present.

Generate procedural documents which specIW chenical handling requirements, canister loading procedure, and the granule manufacturing process requirements.

Evaluate off-design performance of the optimum r.aterial.

Generate data to quantify all system level penalties feed accrued by the Li02 02 subsystem (eg.- establish the vater requirement due to the heat of reaction of the chemical). Evaluate the feasibility of a bed cooling vehnq' hich will allow chemical recharge without .oluir~j, disconnect on or connection of fluid coolivy; lf.a. Hamilton U Standard p. ",:

3.3 Progrm Description

The test prograli, which had a sum total of 69 tests, war .'r'posed of the following set of test series.

1. Catalyit F.aluat2on 2. Bed Cooling :Ialuation 3. Procedural Tests L4. ff-Design Evaluation 5. End Item Canister Evaluation

A test sumary is given in Section 3.7.

Catalyst Rvluntion

Catalyst evaluation tests were conducted to evaluate the effect of the addition of certain materials to iithir peroxide in order to promota low temperature oxygen evolution. She ohen.!cals evaluated as catalyst :,ateriels Iurinz full scale zesii., wer mangarese oxide (MnrC), iron sulfate (FeFOj), r.s--nanese aicxde (oo), titanium dioxide (Ti0,), nanranese oxide plus silv:r coated cooper, silver nitrate (Agno 3 ), and calcium oxide (CaO). Approximately fifty catalyst substances were evaluated Tricr to selecting the above materials for full scale testing.

Catalyst testing was conducted at a metabolic rate of 2000 BTh/hr. with the final three tests run using a variable metabolic profile. Various bed operating temperatures were utilized for each catalyst material in order to determine an optimum temperature range asso ciated with each catalyst.

Bed Cooling Evaluation

A thermal control evaluation was conducted to determine the roost effective way to cool the chemical bed. Three different means of bed thermal control were evaluated. These were passive cooling, passive/dynamic cooling, and dynamic cooling. For passive and passive/dynamic cooling, test canisters both with and without internal heat conduction rods were evaluated. Passive cooling consisted of cooling one face of the test canister to simulate the use of a sublimator. Fassive/dynamic cooling consisted of cooling all four sides of the test canister, while dynamic cooling utilized internal cooling coils through the chemical bed.

Procedural Tests

Tests v'ere conducted to establish the criteria for and verify the alidity of specifications which were formalized for material storage, material manufacture, and cartridge loading, The sum total for this test series was 14 tests, all at baseline conditions, and was made up of the following tests.

5 Hamilton , U Standard . sWC. 5112

3.3 Program Descriion (Continued)

1. Manufacturing process - The granule manufacturing process was closely monitored to accumulate the information needed to generate a formal procedure. Two distinct granule sizes, each made with an appropriate percentage of two different binders, were tested tWice for each comboination of granule size and binder for a total of eight tests. These tests were to verify the performance repeatability of granules manufactured per the process specification.

2. Canister loading process - Canisters were loaded, one third of a bed at a time, and vibrated at three distinct vibration levels. Two tests were run for canisters loaded at each distinct vibration level to deternine the optimum loading technique. A total of six tests were performed and a formal loading procedure was generated based on these results.

Off-Design Evaluation

The following off-design tests were conducted to obtain additional operational information. A total of nine tests were run during this series,

1. Inlet water vapor variation - A total of three tests at baseline conditions were conducted with the following levels of water vapor flow rate: no water vapor present, 50OF and 850F dew points.

2. Inlet C02 variation - A total of four tests at baseline conditions were run for the following levels of C02 flow rate: No C02, CO2 corresponding to metabolic rates of 500, 1000 and 3000 BTU/hr.

3. Total flow rate variation - A total of two tests were run, using the variable metabolic profile, with the system flow rate at five efm for one test and nine cfm for the other.

End Item Canister Evaluation

A new Li202 test canister design which allowed recharging of the liquid cooled cartridge without the making or breaking of liquid lines was fabricated and tested. A total of seven tests were run to demonstrate the feasibility of the new canister design. This test canister was delivered as a contract end item upon completion of testing.

6 HamiltonU Standard • q \m$F$v ,1

3.1; Test Conditions

This section defines the test conditions employed for both1 th constant and variable metabolic profiles employed during tlit test program.

Constant Metabolic Profile TFLf3ls,,.

Total Gas Flow Rate (lb/hr) 8.11 + 0.: Inlet Gas Temperature (OF) 85 472 Inlet Pressure (3.7 psia nom.) 191 + 2 Inlet Dew Point (OF) 70 + 1 C02 Flow Rate (lb/hr) (0.39 + 0.02) (0-.3 + o,. , Variable Metabolic Profile

Metabolic Expenaiture (BTU/hr) - Mission Duratinn (min)

2000 h5 2500 30 500 15 2000 45 2500 30. 500 15 2500 6o

For the variable profile tests, the total rate, inlet temperaturo and pressure are the same as for the constant metabolic profile. The carbon dioxide flow rate and the dew point are as defined below:

Metabolic Rate (BTU/hr) Dew Point (OF) C02 Flow Rate (lh/hl-)

500 55. 0.98 + 0.005 2000 70. O.39 + 0.02 2500 80. 0.188+ 0.02

3.5 Test Facility

The testing was performed using the Li2 02 test ri; lig 21) which is shown schematically in Figure 3-1 and is depic - frn Figurex3 3-2 and 3-3. A close-up of a canister mounted in .h rig i_ shown in Figure 3-b. This test facility is a clo, i loop szteg having a total volume of about 1.5 ft3 to simulate tor internal volume of a space suit and portable life support sytt,:m. The metabolic )rccesses of the crewman are simulated by fgridinr carrot-. dioxide an. Mater vapor into the system at the desired retnhrdi,. level and simultaneously oleeding gas from the syst. to accr,.ct for the crewmen's metabolic oxygen consumption. All g.as Cndt,I

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3.5 Test Facility (Continued)

into the lithium peroxide canister are identical to thos which would be the effluent from a space suit for the metabnllc conditions being tested. Included in the rig instrument,:tion are the following:

Instrument Accurac v 1. 02 Bleed Flowmeter + 2% F.S. 2. CO2 Make-up Flowmeter + 2% F.S. 3. Diluent Make-up Flowmeter (N2 , He) + 2% .S. h. Loop Sample Flowmeter + 2% F.S. 5. Loop Sample Flowmeter 7 2% F.S. 6. Loop Flow Flowmeter + 2% F.S. 7. Pressure Gage (Delta PI- 2 ) + 5 m-m g 8. Pressure Gage (P3) + 0.15 psi 9. Pressure Gage (P) 4 0.15 psi 10. Pressure Gage (P6) + 0.15 Psi 11. Pressure Gage (p7) + 0.15 psi 12. Pressure Gage (Qg) + 0.15 psi 13. Pressure Gage (P9) + 0.15 psi i4. Pressure Gage (PI) + 0.15 psi 15. Pressure Gage (PI) ± 0.15 psi 16. Temperature Indicator + lop 17. Thermocouples (All) 41 0 F 18. Dewpointer (Cambridge) + 5% 19. CO9 Analyzer (VISA Lira) + 5% 20. C6 Analyzer (MSA Lira) + 5% 21. Beckman 02 Analyzer + 0.5% 22. Beckman 02 Analyzer + 0.5% 23. Scale + 1/16 lb. 24. Speedmax Temperature Indicator 2°F 25. Cooling Water Floinneter + 2% F.S.

3.6 Test Hardware

A total of h test canisters were used during the program. They are shown in Figures 3-5 through 3-9. Test canisters number 1 and 2 were fabricated from aluminum while canister number 3 and the prototype cooling canister were fabricated from stainless steel. Canister number 2 contained internal heat conduction rods. The dimensions of these canisters are defined as follows:

Canister No. 1

Flow area = 50 in2 (5 in x l0 in) M'aximum Length = 10 i/i in. No internal heat conduction rods

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3.6 Test Hardware (C'ntinued) Canister Nc 2

Flow area = 50 In2 (5 in x 10 in) Maximum Lenr:'h = 10 i/h in. With inter',l heat conduction rods

Canister N:. 3

Flow area ir 92.5 in2 (6.6 in x lh.0 in) Maximum Length = 4 in. No internal heat conduction rods

Canister No. 4

Diameter = 4.6 in. Length = 10.0 in. Radial flow: configuration - Prototype cooling configuration 3.7 Planned Test Sequence

This section defines the test sequence as originally pAnned.

The following designations are defined to simplify the descrir tion of each test.

a. Baseline Condftion - The metabolic profile for the test is constant at 2000 BTU/hr. (conditions per Section 3.h). (Metabolic rate is 1600 BTU/hr. for testing performed after January 15, 1970) b. Variable Profile - The variable metabolic profile is defined per Section 34. c. Canisters 1, 2, 3 aud I (defined in Section 3.6) are designated as Cl, C2, C3 and C respectively.

d. BT - Lithium peroxide bed temperature.

e. Subscripts a, b, c, etc. are used to define repetitive testing to'the same test description.

f. TBD - To be determined after more information is availab:,.

18 Hamilton . U SHS R ,712 Standard IN

3.7 Planned Test Seauence (Continued)

Test Seouence

Catalyst Evaluation Test No. No. of Tests Description

MSC2-1 2 Baseline conditions - MnO catalyst-low cooling MSC2-2 2 Repeat MSC2-1, except high cooling MSC2-3 2 Repeat MSC2-1, except FeS04, catalyst, NSC2-s 2 Repeat MSC2-3, except high coolin, MSC2-5 2 Repeat 14SC2-1, except MO cstaly .t MSC2-6 2 Repeat 10SC2-5, except . ich Poc in 1M002-7 2 *Bseline conditions - composite - low cooling I-SC2-3 2 *Repeat NSC2-7, except high coon m, ms -2 *ep-at best test of MSC -7 or !90 -J N--10 3 Varnable metabolic profil"-beoz n.,ta"iql "'I sample effluent for con'amriants

* Or evaluate other vooling levels with the ',osf promisi.g catalyst bed Cooling Evaluation

Test N~o. No. of MO'sst Descrittion Passive Cooling MSC2-1l 2 Blaseline condit joi - pa-; ivo cool in- - without conductive mnmblrs - MSC2-12 2 Repeat MSC2-11, except with conducive =embers Passive/Dynamic Cooling MS02-13 2 Baseline conditions passive/dynamic cooling without conductive members MSC2-T4 2 Repeat 14502-13, except with conductive members

Dynamic Cooling 14S02-15 2 Baseline conditions - cools perpendicular to gas flow - low temperature coolant MSC2-16 2 Repeat 1, 2-l5, except high temperature coolant MSC2-17 2 Repeat MSC2-15, except cools parallel to gas flow 14SC2-18 2 Repeat M4SC2-17, except high temperature coolant SC2-19 I Repeat best cooling test MSC2-20 3 Variable metabolic profile - best cooling 20 technique

19 Hamilton _s.nu Standard sI:SFR 5..

3.7 Planned Test Sequence (continued)

Test No. No. of Tsts Description

Manufacturing Process

MSC2-21 2 Baseline conditions - granule size A - binder X 14C2-22 2 Repeat 14SC2-21, except with binder Y 14C2-23 2 Repeat NOC2-21, except granule size B MSC2-24 2 Repeat MSC2-23, except with binder Y

Canister Loading Process

14SC2-25 2 Baseline conditions - vibration level 1 MSC2-26 2 Repeat ?SC 2-25, except with vibration level 2 MSC2-27 2 Repeat 14SC2-25, except with vibration level 3

Off-Design Evaluation

Test No. No. of Tests Description Inlet Water VaDor Variation

14C2-28 1 Baseline conditions - no water vapor present MSC2-29 1 Baseline conditions - 500 F dew point 1C42-30 1 Baseline conditions - 850F dew point

Inlet C02 Variation

3SC2-31 I Baseline conditions -no C02 present 14SC2-32 1 Baseline conditions - C02 flow rate for 500 BTU/hr. MSC2-33 1 Baseline conditions - C02 flow rate for 1000 BTU/hr. MSC2-34* I Baseline conditions - C2 flow rate for 3000 BTU/hr.

Total Flow Rate Variation

1.0C2-35 1 Baseline conditions - 5 efm flow rate SC2-36 1 Baseline conditions - 9 eft flow rate

End Ttem Canister Evaluation

MSC2-3T 2 Baseline Conditions MSC2-38 2 Variable Profile MSC2-39 1 To be determined 69 Tests Total

20 Ha ritonfl . U " . ,,,. Standard

3.8 Test Results

Data Reduction

Reduction of the test data was accomplished using th- Li20 data reduction computer program, H-137. This program, ran on the UNIVAC 1io8, performed the analytical reduction of the data and the performance results are provided in both tabular and gsarbinal form as a function of tine. The performance curves included the following for each test;

1. Li2 02 Canister Outlet C02 Partial Pressure vs. Time 2. Li2O 2 Canister 02 Generator Rate vs. Time 3. Li2 02 H20 Removal Rate vs. Time 1, Total CO2 Removed vs. Time 5. Total 02 Generated vs. Time 6. CO2 Utilization Efficiency vs. Time 7. 02 Utilization Efficiency vs. Time 8. CO2 Removal Efficiency vs. Time 9. C02 Removal Rate vs. Time 10. Li2 02 Canister Inlet Temperature vs. Tire 11. Li2 02 Canister Outlet Temperature vs. Time 12. L 2 02 Canister Inlet Pressure vs. Tine 13. Li0 2 Canister Inlet Flow Rate vs. Tine . Li0 2 Canister Inlet B20 Vapor Flow Pate vs. Ti.e 15. Li202 Canister Inlet 002 Flow Ease vs. Tine 16, Li2O2 Canister Inlet CO2 Partial Pressure vs. Time '17. Li2 02 Canister Heat Removal Rate vs. Time 18. Li20 2 Bed Temperature vs. Time

Chemical Analysis

Gas Sample Analysis

Periodic gas samples were taken from the test rig loop and stored for chemical analysis after the test was completed. These were analyzed for NZ, 02, C02, CO, H20 and trace constituents with a gas chromatograph.

Li202 Chemical Analysis

Samples of the test beds were collected before and after testing and analyzed for chemical composition. The results of these chemical analyses were correlated with the measured test results to assure the validity of the performance results,

21 Hamilton U .'V.!.Jn YW Standard P&

oO TEST DATA PRESETATION

This section presents the data for the 81 actual tests which were completed during this program. The data for carbon dioxide renoval, oxygen generation, Iaxisiau bed temperature, and heat removal rate is shown in Figures 4-} through 4-81 for all tests.

4.i Performance Data

Table 4-i is a tabulation of the major parameters for each test and the columns of this tabulation are defined as follow's:

(i) Test number

(2) Canister number

(3) Time in the test that the canister outlet partial pressure of carbon dioxide reached 0.5, 1.0 and 4.O mmHg. (minutes) (4) Chemical weight (Ib)

(5) Average useable oxygen generation rate (lb/r). This excludes all oxygen that was vented overboard during peak generation rates.

(6) Test duration that the oxygen supply requirement (0.36 Ib/hr) was exceeded (minutes).

(7) Total quantity of usable oxygen produced during 4 hours, or at test termination if earlier (ib).

(8) Total quantity of oxygen generated during 4 hours, or at test termination if earlier (Ib).

(9) Oxygen utilization efficiency at 4 hours, or at test termination if earlier (Percent of theoretical capacity - 0.35 lb. of 02 per lb. of 020). (10) Total quantity of carbon dioxide removed during 4 hours, or at test termination if earlier (lb).

(11) Carbon dioxide utilization efficiency at 4 hours, or at test termination if earlier (Percent of theoretica) capacity - 0.9r lb. of CO2 per lb. of L12 02 ). (W2) Chemical type

(33) Maximum bed temperature (OF)

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I Total 02 Total 02 Evidence Of Total Test 02 2 . C02O f. Chemical Max. Bed Thermal Diration (Lb.) () (Lb.) (%) Type Temp- oF e-omposition (fin.)

'7.91 72.7 1.561 44.28 lnO 647 Yes 276 1.013 75.0 1.56 42,60 MnO 640 Yes 250 0.515 39.0 1.5o 43-.05 IMO 350 No 230 3 0.916 72.7 1.561 45.13 MnO 630 Yes 245 -0.402 48.58 1.559 42.63 FMO 185 No 243 .U14- 30.46 1.539 41,24 MnO 196 No 237 5 0.335 26.25 1.56 14h4.48 FeS% 260 No 25.3 0.,01 63.0 1.30 38.81 FeSO;l 625 Y s 200 L 0.524 65.66 1.561 45.38 FeSO14 270 No 290 ) 0.570 72.83 1.561 46.12 Fe304 325 No 280 0.65 78.30 1.561 5264 FeS0 4 230 No 300 0.545 53.83 1.562 41.41 FeS% 190 No 300 0.531 62.72 1.561 46.20 1th092 515 No 270 0.58S 65.03 1.559 46.43 10 2 270 No 260 0.211 26.93 1.106 31.42 M 231 0No 170 0.373 b2.91 1.559 45.61 1nOf9 No 240 0.543 67.9 1.559 43.86 TiO2 325 No 240 ,0.466 34.85 1.561 42.53 MnO + Ag!Ou 190 No 277 0.356 27.35 1.561 43.72 No Cat. 210 No 244 0.417 34.71 1.562 47.36 AgNO3 200 No 303 0.5414 43.87 1.561 42.75 CaO 325 No 316 0.683 52.39 1.561 43.61 mnO 175 No 330 0.701 50.19 1.561 40.72 KnO 481 No 330 0.634 48.66 1.561 43.63 FeS% 478 No 275 . 0.887 69.11 1.561 44.31 FeSO-4 667 Yes 245 0.476 37.17 0.588 16.72 MnO 730 Yes 95 0.516 40.61 1.531 43.89 MnO 355 No 296 0.587 42.88 1.596 42.44 M O 364 No 315 0.814 55.42 1.022 27.67 MO 762 Yes 158 0.797 514.67 0.996 27.16 MnO 733 Yes 154 0.369 26.50 1.559 44.51 0 280 No 258 0.340 24.47 1.561 44.66 FMO 305 No 250 0.706 45.U1 1.556 38.75 FAO 520 No 260 O.h5l 28.80 1.559 39.63 MnO 376 No 289 0.295 20.34 1.561 42.74 MnO 275 No 266 0.391 24.54 1.561 3-.94 MnO 290 No 298

Test .ta Summa'7 TABL,. 14-1

lo'. Total Test S- t.l Total 02 Total 002 Evidence Of 1'? 02 tf. O2 Sf - 3herical Max. Bea Thermal Duration :t..) m) (Lb.) (5) Type Tem-p OF? D omosiion- (Min.) .0o,9L. L1.51 1.559 U3.27 MaO 653 No 270 1T.50.5.6214 1.556 42.14 Mio 703 Yes 240 0.549 35.86, 1.559 40.47 MnO 760 No 268 .58a 0.598 45.4,2 1.562 47.15 tO 170 No 323 .3)41 0.3,1 25.42 1.561 46.32 MaO 163 No 287 .56)4 0.633 h3.22 1.447 39.27 1-hO 615 Yes 223 *5 1 0.531 35.38 1 560 41.31 HnO 700 No 306 . 0,..490 35.7e 1.560 44.75 :nO 330 110 2 .1s6 0.296 20.05 1.560 42.05 KnO 175 No 255 J435 0.435 25.18 1.562 35.91 MnO 210 No 37h .bO11 0.401 23.76 1.562 36.84 Mao 210 No 380 0.453 24.31 1.513 h5.57 nO 235 No 230 0.1488 36.94 1.596 48.06 ViO 249 No 260 S0.453 34.35 1.596 48,07 hnO 226 No 285 0.331 24.45 1.231 36.37 Mio 410 No 287 1.122 0.322 24.15 1.230 36.67 KnO 332 No 250 ).0?5 ,254 19.LO 1.065 32.41 MnO 290 No 205 ).271 0.271 20.53 1.073 32.31 MnO 290 No 210 ).207 0.207 18.25 0.964 33.75 MiO 255 No 188 ).181 0.181 15.95 0.845 29.70 MiO 240 No 165 ).356 0.356 27.06 1.228 37.08 V4O 295 No 250 ).363 0.363 28.93 1.229 38.97 I.In: 250 No 280 ).i,25 04±25 27.99 1.558 40.80 Mno 277 N4o 250 ).1l 0.-12 28.35 1.559 I12.68 IsO 312 No 2140 ).385 0.385 29.06 1.475 44.20 MnO 245 No 227 ).371 0.371 28.41 1.481 45.06 IMaO 250 No 228 3.255 0.255 18.72 1.059 35.06 -nO 300 No 163 3.208 0.208 17.70 1.O66 36.08 MnO 290 No 164 3.033 0.033 2.73 .307 10.11 MnO 100 No 60 3.04 0.L94 40.91 1.226 4,.37 MnO 500 No 257 o.514 0.511 41.22 1.226 39.06 MnO 505 No 270 0.483 0.483 36.83 1.231 37.35 MnO 170 No 415 0,066 0.066 4.91 0.333 9,93 VMO 512 No 360 3.149 0.149 1!.20 0.365 11.35 MnO 165 No 740 0.247 0.247 18.17 0.767 23.63 !1nO 270 No 680 O.415 0.833 62.92 1.699 51.04 MnO 528 Yes 178 0.6241 0.624 47.38 1.229 37.10 MnO 505 No 332 u.b64 0.,464 37.30 1.230 39.11 MnO 350 No 335 0.059 0.059 5.82 0.520 20.28 MnO 225 No 80 1.119 0.119 11.56 0.518 20.07 MnO 182 No iOO o.026 0.028 2.88 0.290 12.02 MnO 150 No - 0.028 0.028 3.31 0.129 6.06 InO 115 Io 20 3.034 0.034 2.76 0.322 10.28 MnO 175 110- 50 I.], 0.144 16.99 0.579 27.16 MnO 390 No 90 2f<- 0.025 3.42 0.258 14.24 I-mo 110 No 40 Test Data Su-mary (Con' td) TABL I-I l0 ) Hamilton U Standard--

Time To Chemical Ave. Useable Time 02 < Total : Test Canister .5-1.0-4.0 1t. " ,02 3.36 lb/hr. 1"'Y-,' !Iuzber No. (min.) (Lb.) (Lb./!Ir,) (Mln.) . - H3202-LA 3 196-214-265 4.05 .2 56 . ". S-IB 3 174-190-222 h.10 .23 60 072 .M$J2-!0 3 155-IB0-255 4.00 .128 0 I. tr N&-'2-1D 3 186-200-235 3.82 .192 60 0. C. MSC2-2A 3 145-182-227 4.12 .167 0 O.12 OV1 NSC2-2B 3 137-160-217 h.12 .105 0 0.t11 9._

SC2-3A 3 146-169-235 3.87 .0837 0 0.335 0. - 3 132-.49-189 3.85 .175 l" 3 17D-215-277 3.95 .13 0 F0C2-3f 3 180-210-265 3.92 .1h 0 0.570 0. MSC2-hA 3 195-220-284 3.38 .165 0 0.65 0." V.P.2-hB 3 200-238-295 b.02 .133 0 o.5h)5 . YN3Z2-5A 3 170-200-265 3.80 .135 0 0.541 ':. C 2-5B 133-162-2L5 3.81 .15 0 0.*2 -. :tS2-tA. 3.82 0 0.2. 3 140-167-232138-45N-1:6 3.78 .095.08 0 O.37j N'&S2-7A 3 13S-170-250 4.06 .131 0 0.5 3 R302-7B 3 170-189-265 h.05 .12 0 046-5 C.L ,-CY2-70 3 165-185-235 3.9-6 .089 0 0.35 Y.3C2-70 3 180-240-29g 3.61 0 o.117 0.. 1302-7E 3 151-205-298 .03 :3 0 0. h C.. MSC2-A 3 185-223-314 3.95 .17 0 0.683 C. MSC2-_B 3 165-211-320 4.23 .175 0 0.701 0. R3C2-9A 3 174-202-263 3.45 .16 0 0.634 3." M1$02-9B 3 170-185-227 3.89 .178 69 0.712 0.-- 1$C2-10A 3 45- 70- 91 3.88 .192 30 0.303 0.11 "[32-lOB 3 98-181-293 3.85 .125 0 0.516 .: M1302-100 3 180-182-3D3 h.15 .146 0 0.587 0./' NSC2-11A 1 53- 59-135 h4,A45 .192 5.7 02.I? .' Y.02-IIB 1 58- 68-138 4.142 .159 52 0.407 0.2 Mtr32-12A 2 '35-165-235 4.22 .092 0 0.369 0.. M302-12B 2 180-205-235 4.21 085 0 0.3j0 0. MS12-13A 1 1l0-160-240 h1,64 .177 0 0.7o6 0.7 j Y1C2-13B 1 135-160-255 4.74 .113 0 OL51 3. : M30S2-Thl A 2 145-185-245 4.10 .074 0 0.225 0., t lSC2-l4B 2 175-205-275 4.83 .098 0 0.391 0. -j I Hamilton ,,_1R7U Standard Ap sWIS®571

Continued

(14) Evidence of the occurrence of thermal decomposition.

(15) Total test duration (minutes).

4.2 Chemical Analysis Dats

In order to confirm the validity of the measured test re-uits, chemical analyses were made of post-mortem samples of the test t- ,* These samples were analyzed to determine the amount of carbon dioxide removed and the quantity of oxygen evolved. The results of the chemical analysis and a comparison of these with the measured test results is shown in Table 4-2. These results show excellent agreement for carbon dioxide removal and good agreement with th9 oxygen evolution test results. It is believed thlt the diser . . in the oxygen -evolution results was due to post test o ygen evolu tion during the period that the canister was cooling prior to beilg unloaded.

The chemical analysis data was measured using the .r-aratus ckn in Figure 4-82

FLASK FOR ADD)MON oF POTASSIUM PERMAN4GANATE AND SULFURfC ACID TO CHEMICAL SAMPLE

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Chemical Teat Apparatus

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ic6 Hamilton U Standard f,

Time To Ohenical Ave. Useable Time 02 Tht1 r Test Canister .5-1.0-l.0 . 02 0.36 lb/hr. "-2'Q'1s C, n, 1 fuber NO. (in.) (Lb.) (Lb./Hr.) (Nin.) - YSC2-15A 1 110-20-250 04.344O.t80 0.1,

VS02-153 1 85- 95-210 .1445 0.156 26 0.62, C.t 2 ISC2-15~i 1 90-120-245 /64 0.137 0 0.519 Ol. E502-16A 3 200-2140-315 .99 O.1149 0 0.5F ) YSC2-16B 3 150-195-275 4.06 0.085 0 O.,41 0.3±1 MC2-17A 1 80-100-205 4.44 O.246 30 0.5144 0.633 VS02-17 1 125-150-285 4.55 0.133 . 0 0.531 '-.531 10C2-170 1 115-180-265 4.20 0.124 0 0.49A O. 0 1432-1CA 1 155-170-233 4.47 0.07c 0 0.256 : Z2,--18B 1 225-260-350 5.24 0.109 0 0.435 0.> y5C2-!9 1 239-281-359 5.11 O.1O 0 0.401 0.Lo 11302-2OA 1 15-160-215 4.00 0.113 0 O.h53 0.452 YSC2-20B 1 165-195-225 4.00 0.122 0 0.486 O.,18 M'$02-200 1 217-181-265 4.00 0.113 0 'O.L53 .C2-23. 3 16h-204-271 14.10 0.0S3 0 0.131 9. IL021-21D 3 124-170-2414 4.OL O.O81 0 0.?22 L302-22A 3 iOO-14o-192 3.9t 0.073 0 0.1 .2 1.302-22B 3 110-1b5-207 4.00 0.077 0 0.271 C. :302-23A 3 102-161-169 34, 0.067 0 0.207 .... 4332-?3B 3 84- 97-158 3.43 0.o66 O 0.151 0.121 MSC32-24A 3 98-129-227 3.99 0.089 0 0.356 0,350 MSC2-24B 3 116-159-264 3.80 0.091 0 0.363 0.363 lSC2-25A 1 94-135-228 4.60 0O.06 0 0.1425 O.h2c !S02-25B 3 125-158-232 4.40 O.1O3 0 .11-. 0.- IK502-26A 3 127-155-2114 4.02 0.102 0 0,385 0.3c.4 502-26B 3 121-156-213 3.96 0.098 0 0.371 0.371 SC2-27A 3 90-108-3.53 3.64 0.094 0 0.255 0.2z MS02-278 3 103-116-154 3-56 0.076 0 0.208 0.2S MS02-28 3 1- 2- 8 3.66 0.033 0 0.033 0.333 MSC2-29A 3 100-134-242 3.66 0.123 O 0.49 4 .L MS02-29B 3 0-127-218 3.78 0.128 0 o.514 0.51 MS302-30 3 178-229-394 3.97 0.121 0 0.433 03 1102-31 3 335------4.04 0.0165 0 0.06 0.0& 11502-32 3 ------4.04 0.037 0 0.Th9 0.1V3 14S02-33 3 ------3.92 0.062 0 O.247 0. M3C2-34 3 63- 78-167 b.01 O.140 50 O.h!5 0.633 12C2-35 3 13h-182-33h 3.99 0.156 0 o.62L4 0.62L MSC2-36 3 181-223-318 3.79 0.116 - 0 I.146h 0.J4 ZC 2-37A 8- 13- 73 3.09 0.044 0 0.059 0.594 '(1- 47- 89 32.I 0.071 0 1.1]3 0.i? 1t3C2-38A 12- 18- 42 2.91 0.0375 0 0.026 0.026 P32-383 18------2.57 0.085 0 0.028 O.026 • 302-380 7- 12- 40 3.78 O.041 0 0.034 0.13! ,,!SC2-39A 3- 8- 82 2.57 0.096 0 0. 1h),4 0.311. M-Y2-393 21- 23- 37 2.185 0.037 0 0.025 0.12. Chemical Analysis of Post Mortem Test Bed Samples 0

Total CO2 Removed Total 02 Generated Final Bed Weight q Test Initial Final Final Lbs Lbs Lbs No. 02 Ccn. 02 Con. C02 Con. Chew. Test Wca/ Chem. Test Wca/ MSC2- cc/g cc/g / Anal. Data Wtd Anai. Data Wtd Measured Calculated WmI/We I

1A 242 42 197 1.8 2.8 1.0 2.01 1.0 1.03 5 09 1.61 1.1 33 242 33 186 1.67 1.62 1.03 1.08 1.02 1.06 5.00 4.52 1.1 iC 224 99 192 1.77 1.82 .99 .50 .61 .82 5.13 5.70 .90 2A 242 127 165 1.56 1-57 .99 .433 .405 1.07 5.26 5.60 .94 2B 242 i14 162 1.51 1.54 .98 .53 .42 1.26 5.17 4.75 1.09 3A 198 74 206 1.73 1.64 1.05 .55 .37 1.48 4.66 4.73 .98 313 198 29 173 1.38 2.28 1.08 .83 .78 1.06 4.44 4.40 1.01 3C 198 62 205 1.79 3.88 .95 .63 .63 1.0 4.85 L.60 i.O6 33 198 57 210 1.78 1.8o .99 .67 .65 1.03 4.71 4.6o 1.02 LA 221 48 226 1.94 1.95 .99 .68 .8o .85 4.80 4.42 1.09 4B 198 56 209 1.94 1.94 1.0 .68 .66 1.03 5.16 5.87 .88 5A 228 10 193 1.77 1.75 1.0. .43 .595 .725 5.08 5.36 .95 5B 228 17 185 1.67 1.69 .99 .44 .64 .6c 5.02 5.08 ..99 6A 228 135 131 1.07 1.1 .97 .34 .21 1.63 4.52 4.54 .99 6B 228 109 173 1-57 1.57 1.0 .41 .37 2.33 5.C6 4.77 a.oG 7A 233 134 164 1.43 1.54 .93 .39 .535 -73 4.84 5.70 .85 7D 230 92 185 1-75 1.80 .97 .555 .55 1.o6 5.27 4.63 1.13 8A 224 52 221 2.12 2.14 .99 .8o .81 .9p 5.32 4.85 1.10 8B 224 65 213 2.08 2.14 .07 .78 .82 .95 5.42 5.57 .97 PA 210 54 212 !.R4 1.78 1.03 .75 .70 1.07 4.83 4.63 1.04 933 210 2P 192 1.61 :.6o 1.00 ,3 .89 3.01 4.65 4.84 .96 ---

To Tabl~e 4-2 Hamilton U Standard p"

L.2 Conti nued

A fifty gram, homogeneous chemical sample is placed in the flask. Any oxygen in the chemical is released heu a saturatej potssrlun permanganate solution is added and is measured Ty the vet test a-, r. The carbon dioxide in the chemical is.re]esed by ad4Thv a "C' sufl furic acid solution in i03 ililfter iflcraxnts. jes evc-nt:n is complete Wmen the adi!tica of e 100 milliliter increen of s'-]furje acid increases the meter reading by only that volume.

108 Hanilton svHSE 573 Standard VS 1

5.0 PERFOPMZfC? ANALYSIS This section presents the performance analysis results for the test data of Section h.0. 5.1 Catalyst Evaluation

Various catalyzing agents were evaluated during this phase of the program in an effort to determine the most favorable activator for promoting oxygen evoluation from lithium peroxide. Although the primary purpose of catalyst addition is the enhancement of oxygen evolution, CO2 absorption performance was also considered in the catalyst selection.

Those catalysts which were subjected to the most extensive testing included ferrous sulfate (Fe0 4 ),manganese oxide (MaO)l, and manganese dioxide (Man 2 ). Other catalysts evaluated on a limited testing basis included titanium dioxide Ti02 ), manganese oxide with silver coated copper wire, silver nitrate (AgN03 ), and calcium oxide (CO). Nickel sulfate (KiO 4) was considered on the basis of testing conducted during Phase I.

The test item utilized for this phase was canister No. 3,shown in Figure 3-7. The canister face measures 6.6 in. x ].0 in., giving a flow area of 92.5 in 2 . The bed length for all tests was 2.87 in. A continuous 370 inch length of le inch diameter copper tubing was used for bed cooling. The cooling coil provides flow in a plane perpendicular to the direction of flow. Cooling water enters the coil on the downstream face of the bed and exits after passing through the row of coils along the upstream face,

Catalysts were evaluated at various cooling rates to determine the bed teirperature range providing optimum performance. The maximum rather than the average bed temperature vas used as a basis for establishing the-optimum performance temperature range since it is this temperature which is Indicative of the reaction taking place. Mnitoring of thermocouples located throughout the bed shows the maximum temperature proceeding from the inlet to the outlet side of the bed coincident with the location of the reaction as the test proceeds to completion.

Table 5-1-1 presents a summary of the results for those tests conducted during this phase. The columns of tabulation are defined as follows:

(1) Test Number

(2) Catalyst (Chemical Formula Shown)

l09 Hamilton U Standard p.SVHSR 57V

Performance Analysis Sumary Chemical Time To Ave Useable Cooling Water Test Wt. .5-i.0-4.0 02 Max. T Flow 'ate Nlumber Catalyst (Lbs.) (M~in.) (Lb./Hr.) F (LlI.IHr.)

3SC2-IA MnO 1,05 196-214-265 0.2 647 None MSC2-lB MmO .10 174-190-222 0.23 640 Nose MSC2-1C Mn0 t0 155-280-255 0.128 350 3 V3SO2-ID WMO 3.82 186-200-235 0.192 630 None MS02-2A Mn0 4.12 145-182-227 0.167 185 30 14SC2-2B MnO h.12 137-160-217 0.105 196 30 SC2-3A FeSOh 3.87 Ih6-169-235 0.0837 260 5 MSC2-3B FeSO 3.85 132-349-189 0.275 625 llone V502-3C FeSOO 3.95 170-215-277 0.13 270 3 !v5s32-30 FeS04 3.92 180-210-265 o.1, 325 2 MSC2-4A FeS04 3.38 195-220-284 0.165 230 30 3SC2-tB FeSOj h.02 200-238-295 0.138 190 30 ?SC2-5A MmOp 3.80 170-200-265 0.135 515 0, 10 C 00 VSC2-5B 4nO2 3.81 133-162-245 0.15 270 5 12S-2-6A mnO. 3.82 138-151-166 o.08 214 30 .MSC2-6B MnmO 3.78 140-167-232 0.095 196 ,0 143C2-TA Tio 11.06 138-170-230 0.13L -325 3, 5 80 NSC2-7B Mn0 + Ag/Cu 4.05 170-189-265 0.12 190 30 ,0SC2-70 No Cat 3.94 165-1i5-235 0.089 210 30 MSC2-TD !g NO- 3.64 180-240-295 O.101, 200 30 F0SC2-7E CaO b.03 151-205-298 0.136 325 2 MSC2-8A MinO 3.95 185-223-314 0.17 475 T2 350 - h50 MSC2-8B Mn0 4.23 165-211-320 0.175 481 TB b25 - 475 1SC2-9A FeSO4 3.45 174-202-263 0.16 473 TE 400 - 500 IASC2-9B FeSOh 3.89 170-185-227 0.178 667 1/2 MSC2-10A MnO 3.88 45- 70- 91 0.292 730 None HSC2-10B IMnO 3.85 98-181-213 0.125 355 2 14S2-10C MnO 4.15 380-182-303 .146 364 2 I/3C -1h NiSD4 3.38 0- 8-202 0.11 309 30 14SC -15 NiS0 4 3.18 0- 90-210 0.14 542 30 14SC -16 NiSO h 3.26 25-110-240 0.14 560 30 iMC -16b NJSO4 3.13 20-100-205 0.15 552 30 msc -16c NiSO 3.30 67- 86-1ho 0.25 59? 30 msc -16d 5i04 3.70 1h5-185-280 0.12 360 30 MSC -20 NiSO4 3.23 70- 95-195 0.13 563 30

TABLE 5-1-1

110 Hamiltoi U Standard ...... 5712

5.1 Continued

(3) Chemical Weight (lbs) (4) The elapsed time at which the canister outlet partial pressure of carbon dioxide is 0.5, 1.0, and 4.0 nm Hg (minutes).

(5) Average usable oxygen generation rate (lb/br) to an elapsed time of 240 minutes. This excludes all oxygen which would be vented overboard during those periods where generation is in excess of 0.36 lb/hr,

(6) Maximum bed tenmerature ( 0 ?)

(7) Cooling water flow rate (lb/hr)

Dta from Phase T testing of nickel sulfate catalyst is also pre sented for selected tests wher, the chemical weight and canister geometry are the same as those of the Phase II tests.

From the results tabulated in Table 5-1-1 and a study of the per formance curves shown in Figures 5-1-1 through 5-1-7, lithium peroxide catalyzed with manganese oxide is shown to provide the best COa absorption and 02 generation performance. The following discussion provides a Justification for the observed performance of those catalysts tested. This explnnation of results has been made in terms of their agreement with previously published literature concerning the nature of Li2 02 reactions. General Observations

Before proceeding to evaluate the catalyst performance, the following general observations are presented which constitute the basis on which explanation of the test results can be made.

Based on tests Conducted durin, this phase and on previous test experience, it is apparent that optimum 0 0 2 absorption and 0 generation performance must necessarily occur at a bed temperature range below that of rapid lithium peroxide thermal decomposition. Rapid decomposition results in an undesirably short period of high 02 evolution and subsequent degraded 002 performance resulting from poor utilization of the lithium oxide (Li 2 0) product, As shown by Boryta in Reference 1, good C02 absorption by lithiuu peroxide, requires the existence of the intermediate product lithium hydroxide monohydrate. This can be explained in terms of molar volume ratios where it is desired that the reaction product be of smaller volume than the substrate. This condition decreases 8tansdanmHamlltoni . [ g 1 _. --

no SVIiSEP 5712

Cata~yst Evaluation Data

6co '~ -' ~ ~ ~ ,~ 2 'Mno ,

2._00 _____

., ---.-.- ___. - I ..

L.- -. ..

20.- -

.0 80 1 0 160 200 240 .so

Elapsrd Tim - Kin. HI3nmIton,-_ _LU Siandard ,-.

- "T----_. - Catalyst L-a3uatio, Data? h------ ,...... -,--U----

7 ZZ.... Ztctz t...... j t-ue -- "" '--- -.- - ....------'-.4 -- *1

r---- . . Li...... - - -r-.. . -. .- .---- '----./ i-U_-- '

I ...... T -...... i ...- jz=7 ......

- ---. -, . 1-. 4. , .O. : ,. .

-7- .. - ,,~z> 2 .~:wz{:1

Z;-:~-tr-. 42t .4 -.. 4,----4s..,.. ,tJZLl

- --- -C -l StandardP® 571

-- - ...... Ct yst Evaluat io Datai

~ - .' ; ' ' ' !..

0. . .- 0 -&b -- z - ' - - . .- '. .

i, dO 2020 260 ?00 To

Elapsed i ...... T "

Figur < ) ill. Ham lt on....._, ..... Standard SVIISER 5712

600[- ._ "- 22 Catalysz -Evaluation_..Feh-Data------..

> 200 =T.

...... Y 2

.~ Ii

.2 ...... I - ._

--- rT-- -- -.- -

ho 60 120 160 200 2hO 2:i0

Elapsed Ti-e - Min. Figure 5 ];' Siandzru4L Uyt -7= Ca,,-o .21

...... oo...... - 4 z..... L_.r ------

...... C h---;-- - .=-., . .. - , -- . .... ;.. . . .

.2.4

. . . - .00. - ...... - - ,... ~-7,

. 10.60.. M n. . 4.4 Elapsed Tim-, _ . o-

.5-I-.== . . _ _, .L.- .. -4,- ._ ... . .4..-......

------. --- i-----~------.------... . .-...... - ... . .-. lO 0 l1.O 160o0 i

Elapsed Tint Mill. - Firar,- e.-.1 ,

-'C Stendard AVSP n 220 ...... _-, Catlyst Evaluation Data]

°-- I

0 ko bo 120 100 PO ;L0 ;1,0 Elapsed ine_.Mi. Figure 5-2-6 117 Hamilton etar Jard ¢4

.. ~s-zz-z 4EES~ '~Catalyst Fvalnet ion Data ,oo...... ----- ...... i..- ,......

-- "------_ -

______,tts,. , , ! ,i r 200

IC) ,20,0I..... __ ___ '-'.q.___-- ,>kt _.. .

- 4- -_

--A- + - -- 1 --- .."----zsr.....srn-4

I'.l'J,.;I ,, ..-t-- ...... ------.--....--- ..... t

"::t--,'- - -b ,-. . ... I , .-- -7. - .. .-.-- ,- -- =- - . . /'--- :-- ;,

-- ~ ~'VtILI

O 60 120 16o

Flapsed Time Min. .Figure 5-1-7 Hamilton., U Standard SVHSIR 572

51. Continued

- any diffusion resistance to C02, which may be created by a reaction product coating over the unreacted substrate.

.The poor C02 utilization, typical of those tests where rapid lithium peroxide deomposition occurs, is then the result of the atsence of monohydrate as an intermediate product. The lithium oxide reacting with C2 becomes coated with a lithium carbonate (Li 2 C03 ) product of higher molar volume. Performance decreases as a result of the diffusion resistance created by the particle coating. The following tabulation shows the C02 utilization efficiency to be noticeably higher for those tests where no significant decomposi tion has occurred.

CO2 Utilization Weight Max. T Efficiency (%) Test No. Catalyst Pounds OF at 4.0 mmHgnDti ecompcsi Lon

3B FeSO4 3.85 630 35 Yes 9B FeS04 3.89 667 42 Yes 3D FeSO4 3.92 325 h No 9A FeSO4 395 078 48 No IA MnO 4.05 6o 47 Yes lB Rao h.10 68o 39 Yes 8A M4O 3.95 475 57 No 8B MnO 4.23 481 54 No

It is desirable to operate at some temperature below that point where rapid decomposition occurs. Favorable C02 absorption and 02 generation performance have been observed at two temperature ranges; one range existing at low temperature, up to 2250 and the other at high temperature, 400 to 5000F.

At the low bed temperature range good C02 performance is possible through the existance of lithium hydroxide monohydrate. The mono hydrate, as explained previously with relation to lithium oxide, serves as an intermediate which provides a good molar volume ratio. From tests conducted by Selezneva, Reference 2, the percent of theoretical CO2 absorbed directly by lithium peroxide at low temperature is very small.

L1 2 02 , C02 Li2C0 3 + 0 (1) With water vapor only, however, a reaction resulting in 02 genera tion begins at much lower temperatures.

LI2 02 r H20 -P- 2Li0H 102 (2)

119 Hamilton U2 Standard

Continued

The net reaction above can also be represented by the follosin equations which are described by Markowitz in Reference 3 and 2ach in Reference 4.

U!202 + 21{pO - 2LiOH + 202 _(2a)

H2 02 -s- H20 + 2, (2b) As shown in Figure 5-4-1, 002 absorbtion is greater in the presence of water vapor. The presence of water vapor shows no direct re lationship to imoroved CO2 performance if the mechanism of absorb tion involves equation, 1. &o lithium hydroxide is formed by this reaction and there is no explanation as to why low temperature sLould result in imiproved CO? performance. Equation , referred to as the hydrolysis of lithium peroxide, is the more likely reaction. The presence of CO2 would improve performance since CO2 reacting with lithium hydroxide would create additiona] water to increase the hydrolysis of the peroxide.

The favorable performance shonm at the low temerature ranae can then be explained in terms of C02 absorition by lithium nydroxtde and lithium hydroxide monohydrate and the resultant effect of the monohydrate on this performance. Tests conducted at Hamilton Stan dard with water cooled lithium hydroxide have substantiated the desirability of operation at low bed temperatures.

It has been specifed that this low temperature range should be below 2250F. The temperature referred to is the maximum bed tem perature or temperature of the reaction zone where equation 2 is occurring. Most of the chemical bed, however, is below 150F there lithium hydroxide monohydrate can exist and the absorption of C02 can take place readily.

As the bed temperature rises above this range an attendant deteri oration in COs performance results due to increasing instability of the mnnohydrate. This trend continues until vigorus C02 absorption can take place by direct reaction with lithium peroxide; equation 1. This is shown to occur at Ppproximately 3OOF. Good C02 performance exists between this temperature and that poins vhere repid lithium peroxide decomposition begins, approximately 5000F. Above the point of rapid decomposition, C02 performance deteriorates due to poor utilization of the lithium oxide product as described previously.

With respect to 02 production, the general observation made fror. phase I testing showed that increased bed temperature 2esulted in

120 H-amilton .... U Standard

5.] Continued

higher 02 evolution. This is substantlatd by the phase TI t-st results shon in Figure 5 -1-8- Oxyaen evolution at )oy -p,, inra tures is provided through thermal decomposition of the }ydret-en peroxide created by hydrolysis of lithium p-rcxi6d. As IL - temperature increases hydrolysIg increaesps, as shown in Firsr-r 5-1-9, end hydrozen peroxide decomposition i, ncr, ce-?>.tr,. ',

result is increased 02 generation. As thu tooerature a1 prz-xches 3900F, more of the 02 evolved is due to direct reaction of C%2 with the lithium peroxide. This continues until the temperature is reached where rapid thermal decomposition of lithium peroxide accounts for virtually all of the 02 prodUced.

Catalyst Performance

Having established the general characteristics described in the previous section, application of these observations can be made In explaining the results of the catalyst evaluation tcsts.

Those catalysts subjected to a sufficient '-mberof vests to is tablish performance tiends with respect to bed temperature appear to fall into the following two categories:

(1) Catalysts ;hich show good CO2 and 02 performance at the low bed temperature range, below 225 0 F.

(2) Catalysts which show good C2 and Cy perforance at the high bed temperature range, 400 to 500OF.

The high and low temperature ranges referred to here are those previously discussed as showing good CO2 performance. The more active catalysts, as indicated by the heat generated during the manufacturing process when the catalyst and lithium peroxide powder are mixed, fall into the first category. They would include ferrous sulfate and nickel sulfate. Their perfonnence trends are shown in Figures 5-1-3, 5-1-4, and 5-1-6. The less aczlve cat alysts, manganese oxide and manganese dioxide, are included in the second catagory; their genera3 performance trends being shown in Figures 5-1-1, 5-1-2, 5-1-5.

Other catalysts were tested on a limited basis, but their evaluation is restricted to the observed performance at only one temperature level. In no case was exceptional performance indicated. Tn evaluation is therefore limited to those four catalysts :renticned which have undergone sufficient testing to demonstrate their performance capabilities.

321 .,N.+-irn-h.. . +....o---n,......

s -4. r . r -._4- 44. - _ -. + _- .4 * r .- ' --- +--. .. + t . .. . .

.... + ...... ,......

- -+, - -+ . . tjct-t+.+...... -I.. ..

- A-.-+,-+--+ T -- +_+z. . ,...... , ......

* - - .- - - -

Figu'" 5-1 U 7 717;I::i

U. F...... 4,4 - n.zrtzxittr.tt- ~-'-- - U,

* . .Ar <1......

- ~-'-' -. .. *-*,-:--.. - .~-.*---.--'-.-t-..'"-. -l-'-t- -1 2.L....4~..,...... WZr2ZZZS7A24 2Z$.ZZ *......

- .---- ... ,...... i.....-1. -v-4-~"--'"-"-- -- -.

,.4....~ 4 .ZZZZ 't4:::: -. .4L;2sz12.&2s2 p. c... V A- .. r' ... ± ---- r.~'-..,, r~ 1 '2 a -

S~.* C

-4- ..... A -..-.-...... 'C. ____ -- ,1~..A'.t>- 0 *~**** C) tz4~i3 -ttzr'' C) - .. ,zzrzt. zz~r± fl-- '...~.... -, ~sz1s. tz. t~- -zz 1 7 'nrtl-ztzm --- t ~ -t C zl±z~ ~ 1+ ~4

-- -4- - -.-.--- tZ~ZtPtttTh tt4.

___ -. ~1

~J24WZ -- n---'--. ~z --t-~-r-~- dZ '~ZW.2Z -

....-tzz . H ....~..zdzzr: ~~I2 ~..~SSEESEBVUi ::zJ _____ f -. r---- -~ -~

-1- 4 - ..

____ I K ~ .ujj; ~a '4U.J1115X4 1 N H Hamilton U Standard P,

The better ovcralJ petfor nc 0L04n by flrrxus ar I W:ce-l• VW. at lower tem.peratures can be e:n In FJ,pr- "-1-i an1 -" 4 These compounds, being active percxid- raflt.,r 0, *. fr" low temperatures in deeoiposin: hydrocn proIY , crcatnt t n%. lithium peroxide hydrolysi " . Good O? ,voj;ticn t 3 , tures is a result of the eff'ctlveiss In dMerpcst, 11" n " . peroxide into its water fenor and cxy,'er prcturs. '-c-, r'• rvalle lv ' thin rtaction servs tO pro:.Ar fy'Iro'sy . : , lithium purcxide creating addItional lithium nydr>Ud- Sad rtn hydrate. The result is increased C02 absorption. At the higir temperature range, however, C02 absorption decreases. It in tie apparent result of lithium peroxide decomposition ocerrin,' -.! rr below the 300OF point shovz by Se)eznpvi as OW tfrr, ri:. " WrWOcFar for activ, O, - ,trn. in...... ,., - wv.-r' ture for active C2 abs&-ption directly by lithium porcxide cann': be attained by the active catalysts without Incurring rnpid d- composition. It should be noted the' he catalysts were s-lct.d on the basis of being activators for decornosing hydrovrn p-roxKd. Their effect, however, is also to lower tOe dcc'rpsitI: n t-eTr-f.'a ture of lithium peroxide. In decompositicn tests carried ,ut a% Familton Standard, it was observed that the additirn f F .-ren nickel sulfate low.ered the beginning of the decompcsiticn ran," from 531°F to 4670F. Ferrous sulfate, being more actie, wool! tend to lower this temperature even further; thas narrcvinx the range of desirable high temperature ope~ioa which must exist above 390 0 F.

In the case of the weaker catalysts, manCanese oxide and dtoxide, low temperature operation is poor. The catalyst is not active enough to effectively decompose the hydrogen peroxide. A low 02 generation rate results and Co performance is poor since the water needed to promote lithium peroxide hydrolysis is mqde unavailable as undecomposed hydrogen peroxide. At hiher temperture, however, a sufficient range exists which allows active C02 abscrpTlcn directly by lithium peroxide without incurring rapid decctpoafttn.

At low temperature, nickel sulfate and ferrous sulfate sLow nooJ overall performance. Ferrous sulfate, however, benp thn nor active of the two catalysts provides the best perfcrnRncI,. $s shown in Figures 5-1-8 and 5-1-9 by tests Ic2-A and Lp. Me higher activity of ferrous sulfate provides the most efioctlve l(w temperature decomposition of hydrogen peroxide of any cutnvst tested.

At hirh tenperatures, 400 to 5 0 0F,all 0',catlysts sicV ,-,.d 0' evolution, but only the less active catolysts, .annatm cxdt n: dioxIde, are accompanied by rood CO2 asorpticn. nzr.,nes' Wde

3.e, Hamilton U Standard p

In thp on3y ni.- of th-a. two catOysts -r-: I r1 "' - t-' zni(ista n' hi,'q'r Wryrtures to fir'A. *...--! atrnfii'ty of its perforsmaneo in thin nt"",. 1hy-r[ . t chcnm by th weakr eatalysto at 11,,-h erktV re !r-nvec, q istlcvn as it vhether any c'alyst In r-.,! r. ht, Q!-r,.. a Iva %t t his rAnn- * L'f.react ona Invlv--,d I, tI,-. b.!,,. , r!t !.. , Q,. *sat'ra'In prycrc s Lt 1.1.': tc'n raruxtv, hadeaktp- vicusly, involve direct absorbtion of C02 by the iMt=u rf "x'MY with 0, as the resultant reaction product; no catalyst trIuj actively involved. The test data available for uncatnalyzwd] peroxide at this temperature range, howevcr, is insufficen, Ir " Patc ]I sL any d-lfinit ccne2rsins rrirdi, 4q.o r. eiJng: c(;,np.rable to 4. nanec oxiut c-,cn&..

The best performance of ferrous sulfate and manganese oxUo i'm shown by tests MSC2-hA and 4B and tests V.3C2-IA, A$ az3 IT. n spectively. For these tests, FiMures 5-3- nl 5-I-& n.. parabe CO, perforrance for the to eonzalyatr but : . hiter usaole 02 preluction for the r.angansse oxid&; t:, t r ternerature of the Inanrnteue oxide tests beir,- no.r- I ,o-• 2f releasing 02 than the catalyzing effect of ferrous suli,.tr %t lea temperature, On an overa]l performance basis, thertfore, m'mran.-se oxide provides tne best results of those catalysts evaiuatei, tut it does not achieve the desired result of proroting low temperature exygen evolution.

Smll-Scale Catalyst Testing

Twenty four additional tests, using 6 gram samples, were run to evaluate various catalysts to promote oxygen generation for LI202 via the water vapor reaction.

L12 02 If20 -,- 2LiOH +4-2 The objectiye was to identify a catalyst which would prcnte this reaction at low temperatures (4 150OF) so that maxitmm benefit could be obtained from the LiOH for C02 control.

The results of the program showed that the catalysts fell Into two categories:

(3) They reacted so rapidly with the LI2 02 that it Was impossible to manufacture graz.ues, or reacted violently at el..vat-d temperatures.

12" Hamiflton _U I Standard .

5.1 Continued

(2) M.ey ehowed little er no inraase.l 0 'vA'tiu, ,-.r '. alyzd LIPS below abcat 350P1. AbOle tI is -'r,*atr soma of the precious metulp ;whe'd cvldw'r ' 4 r'anennior. r.,ten Ino 0, eVC1utjon 4s A fly cttcx b' peraturr fOr*these rtoriala is gLov'i of Fl,mr;. -I : thrcurhi --13.

Table 5-1-2 lists the catalysts investigated and lists part.Wn' conents for those which could not be mixed with Li2 02 .

A t't rn, Ano-pa seh'-. aically I: Yl r .,'-- ', '.' - ".-,!. in t:,. 13fl Product Research Laboratofy. Small Iithum pprCxi IcV samples (approximately 6 grams) were placed in the glass 1-tub,. through which was passed a constant flow of humidifItd nitr,v, at a 650F dew point, and I atmosphere total pr-ssure. A" t'-tuPY, was placed in an electrically heated sand bWd p:il t"T-rolr.. measured by a ther.ocouple Pl ,ced In centPet .tL t:.Q ' surface of the U-tube at the lower portion cf tUs" - " . " effluent ,as from the U-tube was passed throuqh a 6a crc::atorap'. to detect oxygen. The dew point of the effluent ,raz was I ,_-4 ccn stant at 650 F. The test conditions were scaled to b- r,.r-'ontI, of the conditions existing for a 4 lb. 1.202 bed at OLN.4 ccnditic:'s. These conditions were:

Carrier gas - N2 Inlet flow rate - 800 cc/min (O.015 sc/m) Pressure - 14.7 paid Inlet dew point - 650F Bed temperature rise - 40F/min

The first two tests were run over a temperaturc ran;e of i0, to 2500 F. uxygen liberation at these temperatures prov-d to b- in significant, and in order to expedite testing, it was d'cide tG screen the samples over a higher temperature ran'e (250-000") end retest, starting at a lower temperature, with those candidates which showed promise at elevated temperatures. Unfortunately, none of the catalysts tested provided high 0 yields beiv cbcut 350F. The data is presented in Figures 5-1-10 through ;-i-23 and shows the silver nitrate catalyst provided the hi.hest 02 ,d (85% of the available 02) but not until the bed temperature' reached 4000 F.

The tabulation below shows the percent of the available -,-vclyyl as a function of temperature for the varlois catalysts.

W01b NOW i, I

Pt an n wvtcw. 1 3 l4 Bu tn carbon _ 'i ' A cn CON jL Lun:,

RU On aluminum 0" 6 2] Vu on Cao 0 5 21 (

It C&fn - 5-I1 th± MItt: Cr MV trrf! L 1,'&V ' n 0, emAlyt utV ±1-! - j ...... rf tj' jmr-' c; A It rv Further, t . wrnecW-(OWK - -- pr-ic- rfc c P 1exF.: (.>.-O) Fc;i3 A I r!V.np1 tesa, provded inferior perfcflance. i. I'i1at il oi usbestob 2. Iho!t4 on carbon

4. F,!rrouis l;Ifat r.

r. Pal!ladium on crbton 8. Platc.di on sbeotos 9. iutheniu on caeu carbonate

10. . h,lan on ai.in - povier 12. F veornitrato 13. V. &tut£su] cs IL. ickel sulfnae 15. C tpper oxide - beoI osed ai 200-2(OF vlh a 16. Sout Fhionaldehyde sulfonylate - Deccmposed at 3C0-j-,f violent reaction 1T. Sodiunhydrosulphite - Decoposed at 2QF with a 18. Zinc for dehyde sulnrtlate - Deo=posed ti LC w 1 1. -1 reaction 19. Zinc oxide - Decomposed at 400-50 0 OF with a vilent 20. Cobalt Napthanae - Reacted durn mixing, grnu2esC-tbr±,, be made 21. Magnesium - Violent reaction during mixing 22. Titanium dioxide 23. Calcium,oxide 2as. Alumina powder

IatIe *-1 - -7

*...... : ......

...... -...... p...... '...... L...... -.. . .

30 o4"--io7 t------*-r----..- I-- . .

......

20 -----.

0 ~e 2-w 100p

FtgFuru 5-1-10

-. 4I Swn Jar------

- ho - '14r. 7 ~

30~ - .;ij,1 ......

bora SVHSFR 57L

'-7

....+ JTF~ f l"-- . .. . t c t ? -.:t 2'...... Q;......

...... •. . . .. * . -.L

r f,-f ---f-h---t--,i------

.. 7 0 , + - t P.tr r t_'_ _

- ,. -,------ 3.o _._ _.._ _ . :-- - ,

0 1oo 3-: Bed Temp - OF

Figure 5-1-19 130 Flan|Ilton- U Standard pih

90 Zzdt2+ - 9

~s- "-- - -'--'-=------'" - ......

....F-...... l

-'-44' I .

.A. X---

703

0050 0 -

303 CC

Chroratograph ---

TePst C .rpl e

Lithiu lrei.q !lO Vac o

Lihu eroxid e Experirvntal :atalyst Test ,,. Hamilton U Standard AA

5.2 Bed Cooling Yvaluat .m

Test Canister Description

The initial phase of the Li2 02 cooling study concistel cfOh fabrication of two test canisters. both canisters wr- :inilqr in construction, both being rectangular in cross scetlon and having water jackets on four sides with gas inlet and or-let,on opposite ends. Canister 2 had internal conductin rod to aet 4,, heat transfer paths through the bed while canister 1 vas dHolrn-. to allow for installation of internal cooling cMOds. R Ph,'s.' rf the Li202 test canisters are given in Figures 5-2-1 and

Passive Cooling

Passive cooling tests were run to sinulate sublirabor , Ki.c'v flowing 0 0 F water through the lo;er colin-: fwa ,a,a rLt, w' approximately 270 lbs/hr. Test results for this cooling technique showed that low bed temperatures in the 300OF range ccfln4 be maintained by passive cooling if the canister had intrn1 conduc ting rods. In the canister without internal conductir: r,ds Wmd temperatures reached 755 0 F. Heat renoval rates cr";...v cooli: with internal conducting rods vere approximately 3,5?1 A iWr. while the rate for passive coolirg without interral r' L*.s approximately 1330 BTU/hr. A summary of test data for pssive cooling is given in Table 5-2-1.

Passive/Dynamic Cooling

Passive/dynamic cooling tests consisted of flowing water through all four sides of the test canister. The water temperature for these tests was 50OF and the flow rates were 20 lb/hr. through each side and Q0 lb/hr. through both the top and bottom face. Passive/dynamic cooling with internal heat conduction rods main tained the bed temperature below 300°F with a maximum heat removal rate of 1100 BTU/hr. Passive/dynamic cooling without internal rods allowed bed temperatures to reach 520 0 F with a heat removal rate of 1160 BTU/hr. A summary of passive/dynamic cooling test data is presented in Table 5-2-2.

Dynamic Cooling

Dynamic cooling tests consisted of cooling the chenical Led by circulating water through copper coils in the bed. Various configuration coils, water flow rates, and water inlet temperatures were evaluated. Initial testing of coil configurations runninf parallel and perpendicular to the gas flow showed no difference in performance between parallel and perpendicular coils.

IS1 Water Jacket

outt

Wate ,at__ e-er-i nn (1)r n

((Plce ) To1(i)Wt

- 'a

Tests Without Conductive Members Thst. WithTaternal Coils TfA2Sl\"S-Righ flow rate into top water jacket only (water in (2 ), 35'F wr.ter 2 1?ASIZIfl/YIIA.iC Water flow into all four water Jackets (water in (!) & (71 LYhA1C ''-Water through internal coilW (Z'ter ip (3)) Canister Yl Water Jacket 4 Sides5

Flow Fo

In W rW t r D C Water

" out Water ~Out

Waterer

In ut

C tcdu'torae. .

"*' ","lh ,*""-r~t, imc.o top " .ter Ja' tonl, , 2 o.."''r Passive Cooling Data Stumarn

Wt. Time (Min) To Ave 02 Max. T Heat+ " Removal Test No. Lbs. 5 .1o - 4.0 mm Hg Lb./r. F Re MTU/Hr. Internal Fod*

IIA 4.45 53 - 59 - 135 0.192 762 1339 No

l1B 4.42 58 - 68 - 138 0.159 733 1381 1o

12, 4.22 135 - 165 - 235 0.092 280 1056 Yes

12B 4.21 18o - 205 - 235 0.0o85 35 901 Yen

T1ABLL 3-2 Passive/Dynmic Cooling Data Sumarf 3

Wt. Time (Min) To Ave 0 Max. Test No. 2 T Heat R-noval Lbs. .5 - 1.0 - h.0 m Hg Lb./Hr. OF Rate N/Hr. Internal Rois -D'C 13B 4.64 14o - 160 - 24o .177 520 u16o e n c 13B 4.74 135 - 160 - 255 .113 376 957o 14A 4.4o 145 - 185 - 2L5 .074 275 1105 Yes IhB 4.83 175 - 205 - 275 .o98 290 1068 Yes cT

TABLE3 5. S;tarndard p.

ly thg .:,'lrs:so , in h. .t rV q v -flq 1, !1 ,- thtvhL f.C Ih .i O oil. vhi resuter- ltw'u !I-,r.%' a' eatqrof ihaseh troughe P nL rlA. SalotA; ip ,y oi tdonnAie atortol ' Q.:td 'Ia alo= ill", ; os z. r- alts rl, 'wed Lei aemperttt ,r.s inI tb" 7' .r=;,LIL r ';. 'vII r nt *n "f I5CM 11'flI . W-.t I h " 1 ±,. in. Wh . 01 rarr.:A Wtart ierroVad r'o a;trx tr. BTU/hr. for the 1/8" coil. Thuse results uupporteJ the er r. n thht the most important consideration in bed cooling in tP WIIPr hate beat removal paths through the chemical bed. A bsnary of dynam~ic cooling test data is presentet in TRYl~ 5-'-?.

Test Data I-Vjluaticn

The final conclusions reached in the thermal control stuly ,",. based on the desirability to maintain low bd i-nperat'res vilt. a 5nir..uYst. e nalty. that is, L low hear rr,ovra r . yi rsity f'istcr crn:.2 tr 4 heo~ir bCLIkdt'. T' t~rc : maxiun heat removal rate divided by 105 'isevaluatel for ni tv:zt. A l.w pt.nalty factor rpr,,ents a sAp.-rior c;cirg.: Ph.ai 4 Tenialty factors for each test are given in Table 5-2-4. MVrar' valueS of naxirum, be tenperature, naxinurm h'at re0v2, rate, I-1.1 penaliy factor verwis cooling technique are Siver in Figures 5-2-3, 5-Z-i and 5-2-5 respectively.

Teat data from the L 202 cooling evaluation indicates that for any cooling technique employed, a means of heat transfer thr ugh. the bed must be provided. Of the cooling techniques evaluated, dynamic cooling showed the best performance by maintaining a low bed temperature with the lowest heat removal rate penalty. Dyv,l-.c Cocllnp rrtnrIk mr 3eoval Wt. Tim,: (MZiz To Ave O0 Z X. EAt 5 3 Test Yc. Lbs. .5 - 1.0 - to0 mnHg Lb./Hr. OF Pate BTUI/Hm. rslnin 0

15A 4.3 110 110 - 250 b.148 653 997 Baseline Conditions - Cools terpendicular to gas flow 15B -.45 85 - 95 - 210 0.156 703 1079 loW temrerature coolant - I/14" coilsnc DIci 15 h.6h 90 120 - 2h5 0.137 760 1050

16A 3.99 200 240 7 315 0.1lL9 ito 1200 Sne as 15 except high temperature coolant 16B 4.06 150 195 - 275' 0.085 163 687 1/8" coils

- 17A 4.b4 80 100 205 0.146 615 1010 Saze as 15 etccpt cools parallel to sas flow 1iB L,55 125 - 150 - 285 0.133 700 767 1/" coils

17c h.20 115 - 180 265 0.124 330 685

IhA L.47 155 170 238 0.075 175 871 -ame as 17 ezce;t -h± Temperature coolpnt $41 leb 5.2L ?-25 - 260 350 0.109 210 773 Z1/" coil,

'CA L.0 215 260 - 215 0.113 235 078 Viriable ict'ho1lcprttle - '61"coils with UAgh LB.0 165 95 - P05 0.222 , tn.-peratu-= rcraIt -' " !hr. ccdlrs rne .. - .u11 '1' 1a6m6-

TA C'- -* Hamilton U Standard

E,'

PaL.ssive Cooling 11A 755 1339 30.1I 1No ~Pos1 ~ ~ P73O-1~ IT"lna ], .0 tn.roopl ' Passive Cooling 12A 280 1056 2.96 With Internal Pods 12B 305 901 2.75

Pas~sive/5Donarnic Cooling 13A 520 1360 6.05 N~o Internal Rods 13B 376 933 3.52 'I'!"cul Kro

Passive/Pyna.ic Cooling 1hA 275 1105 3.1 With Internal Rods 14B 29L 168 3.1

Dynamic Cooling 15A 653 997 6.5 Dewpoint Variation i/4" Coil 15B 703 1079 7.55 15C 76o 1050 8.0 17A 615 1010 6.2 17B 700 767 5.4 17C 330 685 2.26 V

Dynanic Cooling 36A 170 1200 2.04 Dewpoint Errcr 1/8" Coil 16B 163 687 1.12 18A 1"5 871 1.52 18B 210 773 1.62 19 210 738 1.55 20A 235 978 2.29 Variable Metabolic Rate 20, 219 898 2.24 20C 226 1016 2.29

TABLE 5-2-h Hln-nIton I . ..- ,

...

...... i .

- -..-. - -, .

...- I- , . 'indard P

CV~E 34

-4 1UT1000) DtIBUAQ[

-- stI tOJ D MS 7 ~ 3

8 3 003 0 1, 0V

di '0 - 0 0 U 0 A CV

21/fitl - I2Z TVAOUWIl WI1 UT1XV~ OVW4,AV Figure 5-2-4 143 Standard i i~an'...... tton .. - • ",.. ° ,r.-

...... + ......

...... r-I_-- t=q__ -- - -4 ------.--

~ ~ ~ -4--21~- ~ . EP-..~ , .....-4 ......

C77 . .... -- . .-zz' -- -. . .. --.... - .. . . . 'I... . .

-4 - - ...... - --.--. C -_ U -,O

4aI, Hamiton. U Standard"

5.3 Procedural Tests

Canister Loading Process

A series of six tests was conducted to establish the optirm. technique for loading a lithium peroxide canister. These tete also provided the information necessary for the developuent of the canister loading specification which is presented in SeeTion 7.0.

Two tests were conducted on beds loaded at each of three distinct vibration levels. Vibration was applied in a transverse mode using a pneumatic ball vibration which was attached to the canis ter flange. The vibration levels were controlled by cdj,'tmnz the supply pressure of the dry nitrogen used to operate the vibra tor. Although the vibrator supply pressure was monitored and used as a relative indicator of vibration frequency, it was found that the desired packing could be best obtained by direct observation of the relative particle motions.

The catalyst used in all tests was manganese oxide. The selected cooling flow rate resulted in bed temperatures below the or im.e range of operation for manganese oxide. Although the rerforrance is not representative of the best available using manganese oxide, the same cooling rate was maintained for all loading tests. This was done in the interest of preserving constant test conditions so a relative comparison of loading techniques could be made. Tests 14SC2-25A and 25B used a canister bed length of 2 7/8". The bed length for the remaining loading tests was reduced to 2 1/2 inches to provide a chemical bed weight below four pounds..

Test results show that insufficient or excessive vibration decreases the packing density of the bed with subsequent degraded C02 performance. The best performance was obtained for densely packed beds.

It was observed that desirable packing is attained when the lith ium peroxide granules tumble uniformly and slide slowly to occupy voids in the bed. If the vibration frequency is too high a boil 4ng effect of the particles is observed where voids are maintained due to the rapid particle motion. Insufficient vibration results in a failure of the particles to move adequately to occupy existing voids. The evaluation of loading teehniques can be made by observing the differences in C02 performance, better performance being the result of higher packing density where the particle diffusia. characteristics are improved and the chemical weight per unit volune is increased. The other performance paroneter, oxygen generation, is essentially the same for each of the six tests.

31,5 Hamilton U Standard ,-

5.3 Canister Loading Process (Continued) Test performance results for this test series i ttztar1!eu In Table 5-3-1.

Tests MS2-27A, 27B and 26A, 26B represent chmical bIuds oS IIh, same volme. The noticeably lower bed veights of tes.s .'TA atj] 27B indicate a poorer racking density resulting from a vlbrat~rn level which is too low. Figure 5-3-1 shows the degraded CC; performance which results. Tests 25A and 255-were loaded at high vibration frequency. The bed weights are higher and the CO2 performance is better than the other canister loading tests. The chemical bed volume, however, was also higher eand on an equivalent volune basis, the performance is less desirable thr. that rh- , for tests 26A and 26B.

The following conclusions were drawn from the test series cornduc ted to evaluate canister loading techniques. The optinun loadin vibration frequency is that frequency which corresponds to a state, obser ed visually, where the lithium peroxide granuiec tumble uniformly and slide slowly to occupy voids in the bed. Excessive vibration, observed as a boiling effect of the ;nrticle, or insufficient vibration, indicated by failure of the particles to move to occupy voids, were found to result in lower yacking. densities and degraded performance, Although the optimum loading vibration frequency may change with the canister and cooling configuration employed, a good packing density may be obtained for any configuration by observation of the granules and adjust ment of the vibration frequency to produce the desired particle motion.

Manufacturing Process

A series of eight tests was conducted using lithium peroxide manufactured in accordr.ice with the process specification presented in Section 7.0. These tests provided a performance evaluation of lithium peroxide made in two distinct granule sizes and with two different inert binders. Two tests were conducted for each com bination of granule size and binder material.

The maintenance of constant cooling conditions for these tests as explained in relation to the canister loading series, results in a similarity of oxygen generation performance. Carbon dioxide removal performance is therefore used as the parameter for ,'val uating the effects of granule size and binder. The results of the test series are given in Table 5-3-2. Figure 5-3-2 presvnts test data for tests 21A, 218, 23A, 238, 26A and 26B. Tests 36A and 26B were conducted under baseline conditions usin. Ine origi nal binder material and are presented for comparison.

146 Comtarison of Catalyst Loading vs. T&2t Pcfltaz:zg-

Wt. Time (Mn.) To Avg 0, Vax. T Vibrator Sapply Test :10. Lbs. .5- 1.0 - 4.o n_ H Lb./lHr. F Press. psi

25A 4.60 96 - 135 - 229 .108 277 20 253 4.b0 125 - 156 - 231 .i03 312 20

A h.02 126 - 156 - 214 .102 245 10

26B 3.96 121 - 156 - 213 .098 250 10

27A 3.0 90 - 109 - 153 .083 300 5 27B 3.56 02 - 116 - 156 .316 290 5

TAELE 5-3-1, 53 Coznarison of Catalyst Granular Size vs. Test Performance -

Wt. Time (Min.) To Ave 02 Max. T Granule Size Test No. Lbs. .5 - 1.o - 4.0 m Hs Lb./Hr. O & Binder Material F D:C 21A 4.10 164 - 204 - 271 0,083 410 Baseline conditions Granule Size A Binder X

21B 4.04 124 - 170 - 244 0.081 332 Baseline conditions Granule Size A Binder X

23A 3.44 102 - i61 - 169 0.067 255 Repeat 21 except :ranule B

23B 3.43 84 - 97 - 158 066 240 Bepeat 21 except Granule B 26A 4.02 127 - 155 - 214 0.102 245 Faseline Conditions except original tinder

26B 3.96 121 - 156 - 213 0.098 250 Baseline Condition cxcept original binder

TABLE 5-3-2 - -......

1 -4

. , ...... ~rt j- - 7

..*" . .... T: . : :2 :"-I. ...t......

...... - h.-- -.. - .-.- - _..L _: : _-.. _ ......

. . ,- - -.---- -

f-- , $.n,,......

l'o 80 120 1(3Go" , 0

Figure 1--3-1 Mamnifton

[ f7.

:------..- ....-......

.4. .. - ...-- ...... : ......

F.-... :::.l.I-4- ,- .. ...: rr ....._......

• : ---- - !:----a ::u ::1 ---: .. . _ ......

------

...... .- .

--.... - * - -,...... t'3alz,... -..- ". *f%jc

------

- . -...... Smndarsi

!-,inufactgrin Irocess (Cont inuedi)

Th binder raterial used for test series P1 and 23 provid1 t best performance of the two new materials evaluate." 0I, , r,.',iv Lt.is wit, re.Lect to metal-alic rate, h',wver, tue .riazlAm!t. matrial exhibits better CO2 adsorptinn characteristie with lrpr. l perforyance repeatability. In addition to letter perfcrri.-e. grcnulus Made from the orlizinal binder material were Parder ,nn ad s-s tendency to pulveriz4 during ha .dliig and while einp .uI,, d to ]ading vibration.

The granule sizes evaluated were i and 8 mesh; the latter being the mesh size of the granules used for all previous testing. Figure 5-3-2 Gives a comparison of the two granule sizes rqd.' with the first binder material and Fipaue 5-3-3 niva-s the a--..-n -;, so, for granules made with the second binder materia. Ine apparent bulk density for both granule sizes, based on the loaded bed w-ght, is essentially the seme (25 Ib/ft 3 ). It should be noted that tie lower bed weight of tests 23A and 23B is the result of the shorter bed length.

From these tests it is apparent that the smaller granule size pro vides th- best COp adsorption capabilities. The improved perfor rnarnce of tne smaller granules can be explained in terms of the larger active surface area exposed. The effect is somewhat anala gous to the results obtained in the Phase I testing where low bull, density, higher surface area granules were found to result in increased COP adsorption. The advantages of high surface area have been explained previously with relation to the catalyst evaluation tests. The use of smaller granules can therefore be considered a desirable step toward increasing the performance characteristics of lithium peroxide.

;YI ...... 4,,..- ...... " _ .. :.o

,...o _~~~~~...... --__= ...,. .. . I......

------. ---- ...... --- . . . .

I---- ......

-- - - ., ';'t t .....

...... Hamilton ... St.ndard p..

't. .CAT r'tsl-gn W''aiuai 1o'

The follravnej series of tests Va conducted to vval'u!p tr, .-fff r of gnt%'r vap-r, cr c. dtcxid.-, aid to' "tlo"r' rtv!.' . ! the perfr.Tce of luh,, peroxid, Addtioutdl, tf,ee 1, t, providei a botter ut.lerstsr.dlng of the cnnzu!eal nt ,hystc l ji-ocet.os oecurlnxg dur .c b,d o;'oraton.

iI rpt Wit or Vat r Var irti

Tests were conducted under three water inlet conditior.s. lhcr included Inle't conditions where the gat stream water content wnr zero, 50CF dew point, and 850F dew point. The results are r;h graphically in Figure ,-h-1. 't 2?. which hnr] v-ro i'..',r 1 r-u,"1r ,r oie hcur d ghichwn th. th f -, " " pressure Ifrediately exceeded the maximum scale of the analyrer; be5 tmperature remained constant with little 02 producti,-n. A 500Y dev point test, 29A, was run using the same ho"enicl. The drying effect on the chemical bed from the zero vr ,ttr t,. caused the effluent COp prartinl ;ressure, to 1rzxiihteyv'.- h, meaxyi-ur scal,. After a short perlol of crrat-Lin a water concentration was reached within the bed to allow !' adsorption to take place. A second 50OF dew point test* .' , w, run to provide performance results for a "fresh" chioiral ,-. Similar results were observed indicating that at low inlet watr conditiors a period of time is required for sufficient water to enter the bed to allow C02 adsorption to occur. The performance advantages and the Importance of water in promoting those reactions which result in Improved performance are apparent from the results of the 850F dewpoint test, The higher water concen tration increases the direct reaction of lithiwm peroxide with water vapor resulting in increased production of lithium hydroxide.

Li202 + 1120 2 MOH + I/2 02

The more favorable molar volume ratio created by the hydroxide intermediate results in better C02 adsorption. Since the ,axlrux, bed temperature profiles are similer, there is no significant -difference in the oxygen generation for the 50 and 850 F dewpointn. It Is lirportant to note that although decreasing the dewroint dt rades CO, performance, it does not Impair the ablity of the be4 to reac temperatures nigh enough to provide favorable oxygen generation. It Is preferable from an overall perforcance stand point, however, to operate at high dewapoint conditions. Inlet C3p Variation

Pour tests, the results of which are chown in Figur( ,-.:< wr conducted to evnluate the, effects of !net Cflp variation oei litnium peroxide performance. Test 31 was run wltr, z'r-A TC until fn ,"lapsed time of 16U mni"tes. At thio T Irt -t. . flow I't e van set et a rate roa.paratb]e to Pf".r. Wl.f

the~ ij:! t yua containinig -water way-or at s, 7,^F Orvpelr'I ftrd

ira ...--......

300 .,f ..... i- ...... 1 - :,z rto2.-:......

It -...... -----. .'- - ......

...... fz...... L7...... ; .-...... ' . :......

-1: : - .. . .$::= .Wate Vapor.. , * ,-J.t.,...--.4...... T. .... , :";,,+ ....

" -t{"t_-----4------...... -- .. ..

,;,";. - .-'" ......

-.- :-".• M - ...... * _ . ... :::.z:......

......

..d TIM.. "2Z ,

Fie r, ' ---" - ... , fInlet CO, Varlatior,

-- --.------1 31 - Zero COC -1600 bqU/r 150 ,in. f 32 - >o00 BTIJ/hr

-r 3 -100 BTU/hr * . ' . ,z ,. : . : t - .4 - FU/hr

300 ------

200 - -- , , ; ' ! < _ _, _

-d mT,,,i i I.. . - .-4

-- .-.,. I . - -. -. . --

4I 4- , [ ' --- -

- ~IL 2 Z I u ± 3.i*,,- .----. L ,- -.....

ii +,i i ,1 300 i,, 50, ft] i

Elapsed Tijnle i. in,

155 Hamilton U A Standard .

5., Off Design Evaluation (Continued)

C02, no reaetion was observed between the water vapor ai.1 it .i' peroxide. The bed tezperature remained constant at alout 't,% hud no oxygen generation occurred.

For this series of tests the results clearly show the expete, decrease in C2 performance with increasing metntbolic rat . .n, important performance results of the C02 variations, howevtr, are shown by the oxygen generation and maximum bed temperature curves; these curves being directly related to the amount of influent C02 . The effect of increasing the C02 flow rate is to increase the direct reaction of C02 with lithium peroxide.

Li2 02 + C02 1 Li 2 C03 + 1/2 02

Higher oxygen generation and bed temperatures result.

The high sensitivity of bed temperature and oxygen gncr:tf-, the inlet C02 concentration or metabolic rate is a churan erU'i which demands prime consideration in effecting the sysLte cox$.Rurt tion design. For lithium peroxide catalyzed with manganese -side it has been shown that operation at bed temperatures above L:OF is essential for good overall performance. The C02 inlet variation seriesi however, indicates that the crewman's metabolic rate ust be above 12 or 1300 BTU/hr. in ozder to provide a C02 flow rate sufficient to attain the temperature required. The sensitivity of bed temperature on retabolic rate indicates that optimum performance must employ a variable cooling configuration. A con stant cooling configuration may be used at the cost of some off design operation. It is with respect to this problem that the use of ferrous sulfate as a caralyst appears desirable. Ferrou: sulfate, an active catalyst with optimum performance at high cooling rate, low bed temperature conditions would provide o -erdl performance almost equivalent to manganese oxide. The high coing rate employed would result in a decrease in bed temperature .-ensi tivity to metabolic conditions. A constant cooling configur ion could be used. The final catalyst selection should therefor- b. made with respect to the complexity of conforming the system -o the imposition made by the individual catalyst characteristics.

Total Flow Rate Variation

Two tests, MSCO-35 and 36, were eonduetcd to evaluate the eff.c' of total gas flow rate on lithium peroxide performance. Mes number MSC2-35 was run at a flow rate of 5 ACFM while test VO,-3t was run at 9 ACEN. The nominal gas flow rate for lithium perxi t testing is 7 ACFM.

156 Hamilton U Standard fR

,,.h Off Design Evraluation (Continued)

Results for this test series are presented in Figure 5-4-3. As seen from the CO2 partial pressure curves, 'the CO2 perforrance 'nfl not, vary appreciably with total flow raze; the total amount of 7,2 removed and test duration being approximately the sane for both tests.

The most pronounced effect of total flow rate variation is on tLe thermal operating characteristics of the chemical bed. Both tests were run with no internal cooling. Bed temperatures reached during low flow rate test l'2C2-35 were over 500OF while the maxi mum bed temperature obtained during the high flow rate te;t was 350OF. This indicates that the hieh flow raze stabilizes th- bed operating characteristics ly transferring heat through the bed and eliminating local hot spots. It appears desirable then to operate at as high a flow rate as possible to obtain the maximum convective heat transfer through the chemical bed,

End Item Canister Evaluation

A new lithium peroxide canister was fabricated and tested to demonstrate the feasibility of a cooling technique for a lithium peroxide canister which would allow recharing of the canister assembly without the making or breaking of liquid cooling lines. This test canister was delivered as a contract end item at the completion of testing.

The canister assembly, shown in Figure 5-5-1, has internal dimensions equivalent to the present PLSS canister reservoir. Cooling of the reservoir is accomplished by coolant flow through the external coil assembly which in turn cools the canister wall. A coolant flow rate of 200 lb/hr. was maintained during testing with a coolant temperature of 500 F.

The cartridge assembly, shown in Figure 5-5-2, consists of a modified PLSS cartridge assembly. The end flange was modified to provide a new internal seal configuration and allow thp use of a stronger handle. Twelve radial beryllium copper fins which run the length of the cartridge and extend from the center of the cartridge out through the cartridge wall were added. The outer ends of the radial fins were spring tempered so they would main tain contact with the canister wall when the cartridge was in stalled in the canister. Heat is transferred from the bed through the internal fins and is then transferred through the canister wall to the coolant flow loop.

The test objective for this configuration was to remove enough heat to maintain the chemical bed in the desired operating rane. This operating range extends from 290OF to 430 0F depending on the catalyst material and the desired operating characteristics of the chemical.

157 4 { ' .-00,-_j ---oL- ...... - .. L. ... AjA.4C* -1..4 ...... ~4 -

.,-i-,-A--.- -. - Tp ------......

T ' -' ' - - . (..--,--,--,-,A---4.- -,......

---- "------ . ------

- -' -4-t<-...... -- " ...... "- -"...... /......

W- 0

(, ~ ~~~~~~~~~~___ _.- . ... V-Z-.---- .....------ 2 - = - -. FSp 4 Z2"t l t 1 Z--z"-' ...... z 1 4 .....

-zz -- j

60 1?0 180 110 "VOju w C - 1C-t4- . ,s T ,-- .n .

zt, u r . . v -- -~ StandardHamilton ~ U sin

-C------i//i

---

-- A' -

'/7 -6---- .4 -V -x--~-- - -' 4, A C. *4r <---- d 0-~

-- ~.-~-t= 0 4-~ 0) - .. ' 0 - U,-t .4 . '- -.- 1.- - - - ~ 4,ts - - *t-*t-~* ~>~- - 0 - e-~ - ,- - * - 4) 9 -. -. 0 '1 4-, - n

~~0%l~ * £

e "0.

f !! 7,7/,I• if 4

)IN

A :,::,: ':o, /

Prototype Cooling Cartride (Canister fAt) Hamilton u Standard As

End Item Canister Evaluation (Continued,

A total of seven tests was run during this series. It was i.-.m'n atrated that at a maximqum coolant flow rate of 200 It /r. fte bed temperature could be maintained below 225"F with a 1.Wht rn,-rl rate of 600 BTU/hr. The test cartridge was also rwn in a Kix fin configuration. The maximum bed temperature was 3900 F with a h-,t removal rate of 600 ITUJ/hr. at maximumi cooling flow for this 'n figuration. Test data for this tes't seric s in pr-set.d ir, Table 5-5-4. The data verifies that the cooling (o00ct1Iirt. was tested is capable of removing sufficient beat to maintain the chemical bed at the desired operating temperature.

Very poor chemical bed utilization was encountered during testIng. At first it was assmned shat the poor bed ut!liz-ticn r-.otf, 1 from flow channeling along the radial fins. Several different loading techniques were tried to improve bed utilization but these were unsuccessful. In a further attempt to isolate the problem, spoilers were placed along each fin so that flow could not ch.nne) along the fin surface. Since this did not improve perforn,.c channeling along the fins was eliminated as the caus-e of poer ted utilization.

During testing it was observed that the pressure drop through the canistei was only 2 mm Hg. This 3cw pressure drop is not believej sufficient To provide adequate floy distribution through the chemical bed. It results from the running of lithium peroxide in a canister originally designed for lithium hydroxide with its inherently lower pressure drop requirement. This poor flow distri bution is believed to be the main cause of the poor bed utiliza tion noted during these tests.

A second related deficiency associated with using a modified PIZS canister results from the short bed length I and small flow area of the radial flow configuration. Previous Li2 02 testing has shown that poor bed utilization has resulted when bed lengths less than 2.5 inches are used, This probably results from the poor flow distribution associated with low pressure drop. In the PLS, cartridge used for these tests the bed length was 2.0 inches. Better ted utilization could be obtained using the same cooling configuration by running flow thru the cartridge axially rather than radially,

.:.g~ h used here refers to the lengtl of gas -! v,. through the granul.- packed bed. 1D1

Canister !valuation Test S rnarv 10

. Time (Min.) To Ave. 02 Max. T Heat he.mC-vnl Test No. Lbs. .5- !.0 - 4.0 mm Hg (Lb/l:r) OF Rate 2:/Hr.

37A 3.09 8-13-73 0mO44 225 C77 37E 3-11 30-47-89 0.071 182 603 32A P.91 12-18-42 0.0375 150 551

385 2.57 18 O.O85 115 47t

3rC 3.78 7-12-40 0,041 175 537 tgA 2.57 3- 8-82 0.096 390 £3

395 2.185 21-23-37 0.037 n10o ~i Standard

Lf.,rp, .yutey Penalty Evalution

In order to evaluate the total system penalty a'.ocia'ed A using a lilt iu peroxide ystem, a comp'rtson was made wtcni. a Li-0 2 /0p and iO1/0 2 system. Test data used for c-XMtrP'" o' the two systems was generated using the a-v tvt ,'U..trnol test rig (Big 21). The comparison is for a cooled 1-JU tr 1 .'ystem and assumes the use of high pressure 01500 ps:a) oxyn',

.he comparison in made for a four hour, 2030 Pl/hr. minnir,. This correslonds to a required oxygen supply rate pf ..V 3i/hr. and a CO renoval rate of 0.39 lb/hr. Aor a four hour ,hsm it total of'1.hh lbs. of oxygen must be supplied and 1.56 Jb. of carbon dioxide must be removed.

The present development status of LIOH shows that for cooled WKMI the followi,: utilization can be obtained: For a .<,.i-:z, . , C02 outlet partial pressure of .5 mm Hg the utilization is .40 lb wo. It LIN~ and for a maximum allowable C02 outlet partial pressure of 4.0 Imn Q the utilization is .6 lbs C0p This data is for the rectanruflr, lb 11GH axial flow canister with a maximum bed temperature maintai',-d below 3800F. The present developwent status for Li202 cooled at the rate of 350 BTU/hr. gives the following utilizations: For a maxitum.

allowable C02 outlet partial pressure of .5 mn Hg the utilization

is .325 Jb CO2 and for a maximum allowable CO2 outlet partill lb LiM2 2 - 02 pressure of 4.0 mm Hg the utilization is .55 b Cr a lb IiO2 Li 20 2 system sized for CO9 removal, an average usable oxyt":. generation rate of .18 lb/hr. can be obtained.

Using the above design parameters and considering only tot. components which will vary between a LIOH and Li202 sysvem re"'flta in the following system comparison:

Outlet CO partial pressure - 0.5 in Fg

LJOH/Op LIC; I4' W.(a) Vj(Ho W14fit.) pi.i)

Chemical 3.9 -- I,d - Charcoal 0.36 -- 0.36 -- Cani ster P.20 390 2. . HPO (Cooling) 1.90 -- J.ir 11,O Tark . t I. 1.

Q., T';nk 3.6, 70 1. 515 11.82 ",

Outlet CO2 partial pressure 4.0 H

TAOH/O Lipo 0, U. (ib) x" (An3 v (it)

Chemical 2.60 -- 3.0, -- Charcoal 0.36 -- 0.3 6 - Canister 1.50 290 1.70 H-.0 (0noling 1.90 -- 1.1, 0 Tank 0.76 55 .L44 02 1.44 -- .72 - 02 Tank 3.62, 70 i.;,D

12.16 415 9.12

This data shows that the LiP2 O0 2 system Is approxi.'ately lbs. lighter and occupies the.,same volume as the LIOH/O. ;yt ,-n for the 0.5 un Hg C02 limit and is 3.0 lbs. lig"ter ar"d X.{ In' sma~lr for the 4.0 tn Hg limit. Hamllton - U-. .. Stnnldard

t_1 lhree major areas requiring~ furthevr 4: tloxzr!; hav'r,e to U am k r sult of the present lithium peroxide test prcprr. Thi: fire furth~r etalyst study the evaluation of the uvr. Ci yter vulor noa catalyst to oxygen production, tu'i (ertA r n, -eui.,' too3t canister configuration.

.11 nt alyr~t valfuatson

arnet catalyst testing has not Isolated a ratori'fl ', ,' -, otes oxygen evaluation at low bed temperatures. These cataly.,' should promote oxygen generation through the water vapor rcaoene ":

Li202 4 2H20 - 2 MI11 + HlpO + 1/ 0 ,

To determine this catalyst material, testing should I. w,.t.-. similar to the small scale testing which was initiated d4urn; this phase of the lithium peroxide study. This test serzi'; heuld isolate a catalyst material which initiates th, re],i: z: oxygen in the presence of water vapor at a temperature !-lo': j.1.2 XVater Vapor Catalyst Approach

Present test results show a direct relation between lithium. peroxide performance and inlet dewpoint condition. This sur-U:.tr that chemical performance could be improved greatly by golrg to a very high inlet dew point condition. For a high dew point inl,-t condition it appears that the water vapor acts as a catalyst to oxygen generation through the reactions:

0 2 02(s) + 2112 O()------2 Li0H(s) + H2 02(1) 0 H2 2 (1) ------11 2 0 (V) + 1/2 02 (g)

2 LIOUi(s) + CO2 (Q)--- 2 C03(s) + H20(v)

The net result for this process is:

L12 02 + C02----Li2 C03 + 1/2 02

with no net loss of water to the system.

A system could be built where the inlet air stream is conditionAd to a very high dew point condition (1000 - 150F dew point) to increase the vtter vapor reaction. A condenser could then be used to reclaim the water vapor in the system for recv)y--Vr. This vould provide higher oxygen evolution and good CO2 ranoval In a way similar to catalyst addition.

Wr, Mi proyssd t. t etprogram n-f P KIM ban a ur ttl f.

composed of the following Oet of test reries.

6.2.1 Ctalyst Rvaution - Sa11 scale testa Vill ii'epr.&.dt..4 ,r fT.tv ( "f- - - b' TpAfY'>7 ur. riat'-I, r: - 't P1, catulyI t A. I A jn. , UY,bt ' FW-OfMENit, GP . reactions at low tcmperatures. A total of 100 tests, two per catalyst material, vil I to r, These te.,L Vill consist of flow g,.gconiiti-a" oyy e-n 'tr c'italy-cd AMthiur per'oxide. Osyron Wvo1tlW w .l !- P".r as a f-w,cton of ch,=ical bxld terr.ytnstur - for'-;.-h ,.",: .' nct.ri~al with tlhe objective of fiwj.ar-it n - %ir will proviae 1UD'. ccnversion of lithiurt peroxide to Bhi... . i.- at 2o temperature through the reaction:

Li 2 02 + If20 - -P 2 LIOH + Ifp + i/; 0,

6.2.2 High Dew Point Catalyst Evaluation - Nine (9) full al'- t.. will be run to determine it a high dev point system car, t designed to Increase lithim peroxide pertorrut ce.

Testing will consist of evaluating the performnce of l itnion peroxide run at ioO, 1250, and 1500 F dew point and wIh W.ti.n bed temperatures of 2000, 3500, and 6000 for eqch of tts O.r. dew points evaluated.

C-1.3 Coanter Configuration Evaluution - A total of rivo')( *r) r will be run during this series. The present cooling -valuntle* cartridge will be reworked to run in an axial flow . e ant! Ot cooling eva.uation tests conducted during the ,-nd tos ,'.v=! evaluations (Section 3.7) will be repeated'

I o. s.tandard A0SVISE4 5'712?

[.0" APPENDIX

L. Specification for Lithium Peroxide (L1202) Manufacture

"1,i.I Scope

This specification establishes the process requirements for the manufacture of catalyzed granular lithium peroxide for enviro, mental use as a carton dioxide adsorbent and oxygen source. Care must be exercised because of the toxicity of lithium peroxide as well as maintaining cleanliness and contaminant free conal.ions.

".I.2 Reouiremgnts

The manufacturing process shall takd place in an inert dry argon environment to minimize atmospheric contamination of the lithium peroxide. 7t.1.2.1 Eauinment

The following equi~ment shall be required:

A. Dry argon chamber (00 F dew point or less) B. Granulator C. Mixing container D. Drying oven (equipped with dry argon purge) E. Sifting screen (Standard No. 8 mesh)

7.1.2.2 Materials

The following materials shall be requireC:

A. Virgin lithium peroxide powder (minimum Li202 content of 97.0%) B. Inorganic inert binder C. Catalyst - manganese oxide (ime) D. Anhydrous methyl alcohol E. One gallon, screw top, wide mouth, polyethylene bottles F. Polyethylene bag liners G. One inch vinyl tape

7.1.3 Requi ei Procedures and Onerations

".3.3.1 The amourt of lithium peroxide granules to be made in each process batch shall be limited to approximately one (I) pound to preserve safe manufacturing conditions.

'.1.3.2 The granulator, mixing container, and specified materials shall be placed in the dry argon chamber. Hamilton U Standard p,.'. "

7.1.3.3 The lithi=m peroxide power, inert hinder and catalyst . Q, thoroughly mixed in the mixing container to provide a bnmogrne.us powder mixture of the following proportions by weight:

Lithium peroxide powder 93% min. Catalyst .0 +00% Inert binder 5.0 ± 0.2 ,

7.1.3.1; Anhydrous methyl alcohol shli be blended into the power rixtrn.'e until a thick slurry is formed.

7.1.3.5 The slurry shall be processed through the granulator which shall force the mixture through a Standard No. 8 nesh screen. Th granules are then formed by cutting the slurry extrsis!r fK S length of 3/16 of an inch.

7.1.3.6 When the entire slurry has been granulated, the particles shal be removed from the argon chamber and placed on dryin r-y in the argon purged oven. A maximum of ten (10) one (I) pzri batches may be processed and placed in the oven befc w i' ryir operation is begun.

7.1.3.7 The drying process is initiated by turning the oven on and maintaining 120OF to lNOWF to evaporate the methyl alcohol processing aid.

7.1.3.8 The drying process shall be maintained until the moisture content of the granules is lers than one (1) per cent by weight. (Approx imately 8 to 10 hours). The termination of drying shall be determined when a random 2 to 3 gram sample of particles taken from the drying trays exhibits less than a one (1) per cent weight change when subjected to a high temperature oven (180OF to 1900P).

7.1.3.9 On completion of drying, the granules shall be placed in the argon chamber where any fine particles or dust shall be sifted away. The liners shall be placed in the polyethylene bcttles and purged with argon 'before filling with lithium peroxide granules. When each bottle is filled the liner shall be sealed closed with vinyl tape. The bottle cap shall be screwed on tightly and sealed by wrapping circumferentially with vinyl tape.

7.2 Specification for Lithium Peroxide (Li202) Storage

7.2.1 Scoe

This specification establishes the requirements for th., stoiwgse of granular lithium peroxide to minimize chemical degraditic , over prolonged periods of time. Hamilton Standard svn,, 571?

7.2.2 Requirements

General Requirements

The chemical shall be packaged and stored, in an area which shall have a controlled environment suitable for maintaining to the fullest extent the original chemical properties.

7.2.2.1 Detail Requirements

Packaging

a. The chemical shall be packaged in a dry argon enviroranent in one (1) gallon, screw cap, wide mouth, polyethylene bottles.

b. The chemical in each bottle shall be contained in a polyethy lene bag liner which shall be purged with dry argon and sealed with one (1) inch vinyl tape.

c. The bottle screw cap shall be tightened and sealed to the container by circumferential wrapping with one (1) inch vinyl tape before removal from the dry argon atmosphere..

d. Weight of the chemical shall not exceed five (5) pounds per bottle.

.7.2.2.2 Storage Environment

a. The chemical storage area shall be maintained between 60-800F.

b. Relative humidity of the storage area shall not exceed ho percent.

c. The storage area shall have temperature and relative hunidity indicators which shall be monitored daily.

d. Exposure of the chemical to direct sunlight shall be prevented.

e. The chemiccl shall be kept remote from combustible materials, water and steam.

T.2.3 Handling

Exposure of the chemical to an uncontrolled environment, while being moved between controlled areas, shall not exceed twenty four (2h) hours in duration. Wnen exposed to an uncontrolled environment, the following limitations are in effect, a. The chemical bottles shall be packaged in cardboard containers sealed with masking tape with no more than four ()) bottles per carton.

169 Hamilton • U Standard"' .

7.2.3 Handling (Continued)

b. Vibration of the chemical shall be held to a miinu..

S2. h Shnrrent

The chemical shall be shipped in a tewperature contrtl, vehicle to maintain exposure within the specified 1nIzt-. nn .

7.2.5 Receiving

The chemical shall not be exposed to a receiving area whose environmental conditions do not satisfy the storage area speci fications for nere than eight (8) hoerr.

7.3 Specification for Canister Charging Lithium Peroxide (Lipc)

7.3.1 Scope

This specification establishes the requirenents and rrorsdi.ts to be followed when charging a lithium peroxide canister. ar should be exercised when charging the .anister bacause of IU. toxicity of lithium peroxide as well as maintaining cleanlins: and contaminant free conditions.

7.3.2 Requirements

7.3.2.1 Equipment

The following equipment shall be required:

A. Ditrogen chamber equipped with:

1. Purge system (using dry nitrogen gas 00 dew Point or less) 2. Vacuum cleaning system 3. Purge hose with adapters as required 4. Loading fixture with pneumatic vibrator B. Li202 canister

7.3.2.2 Naterials

Those irterials listed below shall be required:

A. Li 402 he'nica! B. lion-waxed paper cup

7.3.3 Required Procedures and .terations

7.3.3.1 Weigh and record the weipht of the unopet d Li -O , cc:.L.,-'r the nearust 0.01 1I.

"fu Hamilton . U ...... Standard .l.

7.3. 1.2 Place the equijq tnd materials of paragraph 2.3 and 2. in tb nitrogen chamber.

t..3 Attach nitrogen purge hose to pneumatic vibrator.

t.-. .h Close chamber door and initiate flow,of nitrogen through ch.nlr. Maintain flow for 10 ± 2 minutes before opening L 20p cont4incrs to allo chamber to approach dry nitrogen conditions.

T.-.s.5 Fill The canister approximately one third (1/3) full of Li2 02 by pouring granules directly from polyethylene container. Use steel rod to level particles assuring even distribution.

p -. Z..6 Turn on pneumatic vibrator end adjuet ritroren supm. yy-."r - * increase or decrease the vibration frequency as required to obtain good packing of Li 2 02 . Good packing may be attained wher the Li20 2 granules tumble uniformly and slide slowly to occury voids in the bed. Do not permit the i2 02 bed to assoe a boil-w effect during vibration loading.

7-[S.5.7 Allow canister to vibrate for 10 + 1 minutes.

7.3.3.8 Load remaining two one third (1/3) sections while the canister is vibrating; allowing 10 ± I minutes of vibration after each one third section is loaded.

7-3.3.9 Close canister and seal inlet and outlet flanges with tape. Hamflton .

1. C",rutrib' ic:v' itfMtr to t" I ,iL' Ir C,. A.crj.'s;.t rx.1.I ..

MirdeI co .pt cnter P2, 19s7.

2. IntenslIo of Litti.m Peroxide with Water Vatrr mw, .'ax ___1 -,_ K. I. Selezneva, Russian Journal of Inorganic Chemistry, - ) August, 1960.

Technioces in IWmned- Sealed Environcents, A-L-fl'&A 1. Mrkowitz and E. W. De)nmelyk, Foote Mineral Co., Felruarv, Ow,.

A11catIn of L~thu-, 1u.tir'ais Fur Air c=r'rq'r of aw °-22r ::, AZ-'-65-&u6, 3C. ,±., M.do. .r, W J. W. vobinson, Jr., Lithium Corp. of Aeri 's, J :i., 1Q.. A Reproduced Copy OF

Reproduced for NASA by the NASA Scientific and Technical Information Facility

FFNo 672 Aug 65