to - dtic · test 8 5. cobalt based catalyst studies 11 5.1. catalyst preparation 11 5.2....

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AFRPL-TR-70-7

DEVELOPMENT OF A LOW COST CATALYST FOR HYDRAZINE (U)

O > ■• ••»

FINAL REPORT

JANUARY 15, 1968 - NOVEMBER 15, 1969

by

Martin Lieberman

William F. Taylor

Prtpared und«r Contract No. F04611-68-C-0044 for

Air Fore« Rock«! Propulsion Laboratory Edwards Air Fare« Bas«

Edwards, California 93523

•ru- ritt ennuini

, Sfrrnn» 79J a' I

i/cf prrs'if is pf

ilor i'drum |||e( ting 1 l"ilrH ''dies *ithin

■.ip.- Id*v Iillf 18,

7 M. il r t'd si'inMOn

' <)■ y ■•-di,''',f lo *n

H'1-ürH by U*

Esso Roport No. GR-7-DCH-70

In addition to security requirements which must be met, this document is subject to special export controls and each transmittal to foreign governments or foreign nationals may be made only with prior approval of AFRPL (RPPR/STINFO) Edwards, California 93523

jiji: ;- i970

Group 4

Downgroded at 3 Year Intervall;

Declamfied After 12 Yean

Esso Research and Engineering Company Government Research Division

Linden, New Jersey

CONFIDENTIAL (THIS PAGE UNCLASSIFIED)

JV.il.

A

UNCLASSIFIED

AKK1'L-TK-/U-/

DEVELOPMENT OF A LOW-COST CATALYST FOR HYÜRAZ1NE

By

Martin Lleberman William F. Taylor

Final Report January 15, 1968 - November 15, 1969

Contract No. F04611-68-C-0044

January 1970

For / / 7

Air Force Rocket Propulsion Laboratory Edwards Air Force Base

Edwards, California 93523

GR-7-DCH-70

In addition to security requirements which must be met, this document is subject to special export controls and each transmittal to foreign governments or foreign nationals may be made only with prior approval of AFRPL (RPPR/STINFO) Edwards, California 93523

UNCLASSIFIED bbHnyiüUtt d

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- i

KORKWORI)

(U) Tliis lotlmua 1 import was pt t'pai id tor lliu Air luiit- KiH'kot Propulsion Laboratory, Rcsoarch and Tt-flnuilogy Division, l.dwards Air Force Base, California by iho l.sso Kt'searcli and Knginet*ring Company, Government Research Laboratory, Linden, New UMSOV in completion of Contract FOAbll-b8-C-üü44. Under this Contract, Lsso Researcli has developed a thermally stable, non-strateglcally limited catalyst for the monoprope1lant decomposition of hyUrazlne fuel. Tliis final report covers all the work conducted on the contract over the period January 1 rj, 1908 - November lb, 1%'».

(.10 The Air Force Project Officer was l.l. I). Iluxtabie USAF/RPCL. The Lsso Research Program Manager was Or. M. S. Cohen from January 19b8 to June l%9, with l)r. I). Crafsteln assuming management after that date.

(U) This report has been assigned Lsso Research No. t;R-7-UCll-70.

(U) This report contains classified (CONFIDENTIAL) information generated In the program.

(U) This technical report has been reviewed and is approved.

W. H. Ebelke, Colonel, USAF Chief, Propellant Division

AFRPL-TR-70-7

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- ii -

TABLE OF CONTENTS

1. SUMMARY 1

2. INTRODUCTION 2

3. LITERATURE SURVEY 3

4. EXPERIMENTAL EQUIPMENT FOR CATALYST EVALUATION 7

4.1. Isothermal Rate Measurement Apparatus and Method 7

4.2. Five Pound Hydrazlne Monopropellant Thruster ... 7

4.3. Laboratory Adlabatlc Spontaneous Decomposition Test 8

5. COBALT BASED CATALYST STUDIES 11

5.1. Catalyst Preparation 11

5.2. Isothermal Rate Studies of Esso 101 11

5.3. Effect of Cobalt Concentration 12

5.4. Effect of Other Transition Metals 16

5.5. Effect of Catalyst Preparation Techniques 17

5.6. Screening of Other Non-Noble Metal Catalyst Material 18

6. HYBRID CATALYST STUDIES 20

6.1. Effect of Low Concentrations of Noble Metals ... 20

6.2. Effect of Higher Noble Metal Concentrations .... 21

6.3. Isothermal Rate Evaluation of Cobalt-Ruthenium Hybrid Catalysts 22

6.4. Five Pound Thruster Evaluation of Cobalt- Ruthenium Hybrid Catalysts 25

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TAIU.K OF CUNTKNTS (Cunt M)

/. RUTliENlUM BASI-.D CATALYST SILDIKS 2b

7.1. Isothermal Rate Studies uf Alumina Supported Ruthenium Catalysts 2ti

7.2, Five Puund Thruster Kvuluatlun ol Alumina Supported Kuthenlum Catalysts ii

7. J. Performance of Tungsten Carbide Supported Ruthenium Catalysts i'j

7.4. Performance of PTN Supported Ruthenium Catalysts 48

7.5. Performance of Refractory Üxlde Supported Ruthenium Catalysts AA

7.6. Preparation and Performance of Magnesia Supported Ruthenium Catalysts A6

7.7. High Temperature Stability of Various Hydrazine Decomposition Catalysts and Substrates A9

8. PtlOMOTED RUTHENIUM CATALYSTS - THE ESSO 500 SERIES ... 52

8.1. Characterization of Esso 500 Series Catalyst Properties 52

8.2. Performance of Esso 500 Series Catalysts in a Five Pound Thruster 53

8.3. Air Force Engine Firing Evaluation of Esso 500 . . 5A

8.4. High Stability of the Esso 500 Series Catalysts 54

9. BIBLIOGRAPHY 57

10. APPENDIX 58

A. Five Pound Thrust Motor Firing Data 58

B. Catalyst Preparation Processes 81

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LIST OF FIGURES

Figure

I

10

11

12

13

14

15

Pa^fc

Is.'tliermal Kali1 Study Apparatus y

Laboratory Adiabatic Spontaneous Decomposition Test 10

Effect of Cobalt Concentration on Activity of Co-Al 0 Catalysts ^

Effect of Cobalt Concentration on Isothermal Activity ^

Effect of Cobalt Concentration on Surface Area of Catalyst 15

Isothermal Hydrazine Decomposition Rate on Hybrid Cobalt-Ruthenium Catalysts 'l^

Performance of Cobalt-Ruthenium-Hybrid Catalysts in 5 Lb. Thrust Engine 27

Isothermal Hydrazine Decomposition Rate on Ruthenium Catalysts 29

Isothermal Performance of Alumina Supported Ruthenium-Platinum Catalysts 31

Performance of Ruthenium Catalysts in 5 Lb. Thrust Engine 34

Isothermal Performance of Tungsten Carbide Supported Ruthenium Catalysts 36

Isothermal Performance of PTN and MgO Supported Ruthenium Catalysts 40

Isothermal Performance of Scaled-Up Ruthenlum-PTN Catalyst 42

Isothermal Performance of Refractory Oxide Supported Ruthenium Catalysts 45

Surface Area Stability of Esso 500 50

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1

8

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10

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12

13

14

15

1.1 ST III' TAHI.KS

Materials Aotlvo t'ui liyiiraziiio IKHHHII^DSI t ii>ii . . .

I aw-lVmporaturo Acllvily ot Ksso lül l'owdiT . . .

Ktloi't of Cu-Proclpitat ing Nickel and lion with Cobalt

I'lie litfect ot Precipitation Proi-eUure on tin- Surface Area ot Cu-Preclpltated Cobalt- Alumina Catalysts

Screening ot Potential Non-Noble Metal Catalyst Materials

Isothermal Rate Measurements of Esso 101 Catalyst Powders Containing Small Quantities of Readily Reduced Transition Metals

Effect of Readily Reduced Transition Metals on the Low Temperature Hydrazine Decomposition Activity of Cobalt-Alumina Catalysts

Ignition Delay of Palladium Cobalt Hybrid Catalyst

Isothermal Decomposition Rate of Cobalt-Ruthenium Hybrid Catalysts

Ignition Delay of Cobalt-Ruthenium Hybrid Catalysts

Isothermal Hydrazine Decomposition Rate on Ruthenium Catalysts

Isothermal Performance of Alumina Supported Ruthenium-Platinum Catalysts

Ignition Delay of Alumina Supported Ruthenium Catalysts in a 5 Lb. Thrust Engine

Isothermal Activity of Ruthenium-Tungsten Carbide Catalysts

Thermal Stability of Esso PTN Support

16

17

19

21

22

23

26

28

32

33

37

38

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lt.

IS

19

JO

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25

26

27

v i -

1.1S1 DF lAlilLS (i cm M)

IsvUlu'iiikil Activity i>i I'lN Supjinrii'd Kut luMiiuiu Catalysts )'i

Kl'ti'i't i'l SinUT St i "iMij'.t lii-ni ii>', 0" Crush Stri'iiglti ot Ru-l'TN Catalyst IVlK'ts . 'i J

IVf t onnatu'i.' ot Ri'l'ractury tlxldo Suppurti'd Ruthoiiiuii! Catalysts ^4

Effect oi I'roccss Cotiililions on the Surface Area of Kcsulting MgO Substrates 4&

Performance of Magnesia Supported Ruthenium Catalysts 47

Effect of Phosphoric Acid Leaching on Magnesia Substrate Surface Area 48

Performance of Acid Leached Magnesia Supported Catalysts 49

High Temperature Stability of Hydrazine Decomposition Catalysts 51

High Temperature Stability of Hydrazine Decomposition Catalysts 51

Properties of Esso 500 Series Catalysts 52

Performance of Esso 500 Series Catalysts in a 5 Lb. Thrust Engine 53

Stability Characteristics of Esso 500 Series Catalysts 57

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CONFIDENTIAL

SUMMARY

(C) An active, highly stabK' Uydrazlnt- raonopropellant decomposition catalyst has been developud. This catalyst labeled Kssu 500, utilizes ruthenium for its active component and thus does not contain any costly and strategically limited iridium metal. Laboratory and 5 pound thruster studies conducted at Esso Research and Engineering Company and 5 and 25 pound thruster studies conducted at the Air Force Rocket Propulsion Laboratory indicate that Esso 500 is highly active at low ignition temperatures and shows unusually high resistance to loss of surface area during motor firing. Data obtained at both laboratories actually indicated that Esso 500 showed no loss of surface area after up to 24 minutes of pulse mode firing with hydrazlne.

(U) A cobalt containing catalyst, called Esso 101, was also developed. This catalyst has much lower activity than Esso 500 for hydrazlne decomposition at 50C. Esso 101. however, is active at higher temperatures and can be employed where short ignition delays at low temperature is not required and where extremely low cost is a desired property.

(U) Results of studies with various cobalt containing catalysts, cobalt-noble metal hybrid catalysts and ruthenium containing catalysts using several different substrate materials are also reported.

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2. LNTRÜDUC'L'ION

(Ü) The original objective oi tlic work conducted mitU-r this contract was to dwelop a low cost, ni-adily available, active cataly.si tor the decomposition ol bydrazine. At the present time, an active, low temperature spontaneous catalyst does exist ior the decomposition Of hydrazine--Sliel I 405. However, Shell 405 derives its activity frum the precious metal iridlum which is very costly and limited in availability

(C) in the early stages of this program, we investigated several alumina supported cobalt and cobalt-noble metal hybrid catalysts as hydrazine decomposition catalysts. Though cobalt appeared to be a very active hydrazine decomposition catalyst at high temperatures, it was not capable of affecting spontaneous hydrazine ignition at 50C. The use of about 10 wt. % of the metals platinum, palladium and ruthenium in hybrid combinations with cobalt Improved the low temperature activity. Kowevei, decomposition rates were still not great enough to cause spontaneous Ignition.

(C) A more detailed study with the metal ruthenium Indicated that a dramatic Increase In hydrazine decomposition rate could be obtained If the ruthenium was deposited on an alumina substrate containing no cobalt. Subsequent work with ruthenium on alumina showed that properly prepared catalysts at the 30 wt. % ruthenium level had activity approaching that of Shell 405. Ruthenium appeared to offer distinct advantages over Iridium as the active hydrazine decomposition catalyst. It Is much more widely available and is about one third the cost of iridlum. Additional studies with ruthenium based catalysts showed that active ruthenium catalysts with unusually high resistance to degradation in pulse mode hydrazine motor firing could be developed.

(Ü) This report discusses results of these studies with cobalt catalysts, cobalt-noble metal hybrid catalysts, and finally with supported ruthenium catalysts.

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-A. ,

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5. LlTEMTURt; SUKVKY

i.l. Active tlydraztne Catalysis

(C) Work couiiucted by Shell Development Company lor llie National Aeronautics and Space Administration (Contract No. NAS7-y7) indicated that the best possibility for obtaining high activity and stability, without a cost limitation lay in the platinum metals or their near neighbors in the periodic chartU). Shell workers found that ruthenium, iridium and platinum were more active toward hydrazine decomposition than any other metal with the binary of ruthenium and iridium being the most active of all. Other metals and mixture of metals that were found to be active are listed in Table 1 in descending order of activity.

Table I

(C) Materials Active for Hydrazine Decomposition (2,3)

Carbon Carrier Alumina Carrier

j Ru-Ir Ru-Ir Ru-Pt Ir 1 Ir Ru

| Ru-Rh Ru-Pt Ru-Pd Fe-Co-Ni-Rh Ru Ru-Os Ir-Os Pt-lr Fe.Co.Ni Pt-Os 1

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L

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(.(.') I,ill If I was iDtiijii KHI hy Slu-ll workfi.-. u-.iu,' lit|uiil pii.isi.' li'^ts. lUuh i MI lu>ii and aluniin.i wiir a.-u-il .i-. suiiputt-. l -i ihf various llstt'd iMl.llvlu- m.il rl i .1 1 ■. . L.iliuiH i-. i'iii lit llu nu.-.l tlu11111.11 Iv sl.ilili' malt-TUils kiuiwti. It lias .1 vi-iv lii^h suilai« aiiM .tiici IUML ol wetting pi'f ^1 am ot nulti'i ;al. lligli suil.ni' .111.f i;. .niv.ml ,i>'i vii'. in that it provivies an ox toudt'il support lur rat.ilvt ii prumut t-i .s. A high lu'at ol wi'ttiii).', helps tu attfft low tiMiiperature ignition. L'n- t ortuuate ly, Shell seieiilisls 1 omul that the earbou supjiort^ ir.utru with the hvdrogeu liberated in hydrazlue deiompos i t ion tu I orm im-tlMiie at high temperatures. Alumina was I outvd to hi- relatively stable .it high temperatures and was thus taken tu be .1 mure am/ptahle support, iluuigh alumina has a lower heat ot wetting than earbon, it is available in many lorms, is substantially Inert at high temperatures, and is used as a eatalyst support in many industrial processes. Alter considerable testing. Shell formed two catalyst I onmilations which were ,n : tve at l^C: A J8".. wt . metal catalyst with a Ku/Ir ratio ol .54 on Uarshaw Al-1404 alumina pellets and a K) wt . Z It catalyst on llarsliaw A1-1A04 pellets. The latter tormulation was found to be more stable and was later named "Shell 405". This catalyst has boen tested by many companies and has compiled an impressive record of stability and long lite. How- ever, It Is made from extremely costly Iridium which is limited in avallab 111ty.

(C) Other efforts have been made to develop an active hydrazine monopropellent catalyst using more readily available and less expensive transition metals. P. C. Marx, at ierospace Corporation, found that Girdier T-323 (silica gel treated w 50% pre-reduced cobalt on a KTeselguhr support) was found capable of initiating decomposition of hydrazine at 330C and restart at 530c(2.). However, this catalyst had poor life characteristics, presumably, according to Marx, because of the difficulty in degassing the silica gel at low temperatures.

(C) Hang and Ward found that the combustion of cobalt and copper on activated alumina showed the same catalytic behavior after a repeated number of testsO). Liengme and Tompkins at London Imperial College found that hydrazine could be decomposed on evaporated tungsten films at temperatures from -78 to 0oC^—■'. However, no rates were presented. Their efforts were aimed at examining the NH3/H2 ratio at different temperatures.

(C) Extensive work by A. F. Grant at the Jet Propulsion Laboratory in the early WSO's produced a series of catalysts using metallic iron, nickel, and cobalt deposited on an alumina carrier(5). They were active at high temperatures but were not capable of spon- taneously decomposing hydrazine at room temperature. Some of these catalysts are readily available from the Harshaw Chemical Co, Cleveland, Ohio, e.g., nickel catalysts Ni-1600S and Ni-1601T.

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J.2 Mtchauism ol llydia/. inc i)tc uuiposiLion on Catalytic Surtaccb

(C) Almost all ol thf liydraziiK' iii'te rugviK'uu.s di-tonipusi t iun reaction mt'chunlsms presoHtcU postulate an eK'ctruii donur scqunuf whereby liydrazlue donates electrons tu vacancies ur liules in the catalyst lattice. For example, überstein and tllassman postulate a nitrogen donor route whicli can account for liydrazine decumposit itui on platinum black at low temperatures and on silica at Intermediate and higli teinpera- tures M1 • 7 ' . in this mechanism, hydrazine is chemlsurbed un the catalyst by donating electrons from the nitrogen atoms to vacancies in the catalyst lattice (d-band lor platinum). Hydrogen atoms then migrate tu produce ammonia as well as 1N2 and U?. This is illustrated by tiie following schematic equation where M represents metal atoms and Ü metal d-band vacanc ies.

II II 2N„H, + 4M(0)—> 211N-NH

2 4 11 M M

2NH , 2M(0), 2M - Ml (1)

2M - NH -> N2 + ll2

The overall reaction is thus

2N,H. 2 4

2NH., + Nn + H,. J 2 ^

(2)

This has been shown to be the mechanism for catalytic decomposition on platinum black on acid supports^— . But this reaction does not account for some experimental results obtained with Raney Nickel. Eberstein and Classman found that the volume of gas obtained in the presence of Raney Nickel is always greater than that indicated by the above mechanism and more closely agrees with the following overall stoichiometric reaction;

3N2H4- •2NH, 2N„ + 3H. (3)

The additional hydrogen produced by the Raney Nickel at low temperatures is believed to be a result of a surface dehydrogenation of adsorbed hydrazine on the catalyst surface. However, the steps in the mechanism of surface dehydrogenation are presently not clear. Both hydrazine dissociative adsorption (reaction 2) and surface dehydrogenation (reaction 3) occur to some degree in heterogeneous catalyzed decomposi- tions. The nature of the catalyst surface will determine which reaction predominates.

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',1') t-A'uU'iu'i' öl i li.nii'.i". in tin- nuvh.mi sin nl tin' lu-l i-ruj'.t.iii-uus doi'i'inpoH ii ion iM livdraz iiu' wli'u wiv small rhangi's in ratalvst foiupus i I iuii is 1 I'IMKI in tlu1 work ol Voolioi and Kuliu*1**. llii'so wnrkoi >. studifd Liu- JoL'ompos i t. U'n ol ^asoims livdiazlui' on nukol suiiiiorlod by dopi'd MgO, liu- aL'tivaiion oiU'i'^v lot UyUra/.iiU' di'ooiuposil ion was obstTVod in than^.v ! r >;:: 1.' l\i.\i I ino U i or lla+! to Id Koal/molo wlim l.i was usi-d .i.s tin dupuut.

(I) Similarly, iho Soviol scienlisi, V, M. Krovluv, luund ili.it tlio ralo ol doi'oinpos i t ion ol hydraz iuc on (.'.ormani urn di-pondid on lliv i'un- cout rat ton ol antimony dopant in tlio germanium sin^lo crystals (J_U). i'ruvlov atirilmtos ammunia tormation in this study to a reaotion ravolianisin uiialu^ous to (.1) , i .o. ,

i 4 ^4 i (gas) n (ads.)

J.J Heat, Mass Transfer and Catalyst Bed Deai>;n Considerations

(C) A detailed mathematical analysis ot" the steady-state and transient behavior of hydrazine reaetors has been conducted by A. S. besten at L'nited Aircraft Research Laboratories v^JJ . Keston's mathematical model contains a detailed description of the heat and mass transfer processes in the pores of the catalyst pellet. He considers both thermal and catalytic decomposition of reactants, along with simultaneous heat and mass transfer between the free gas phase and the gas within the pores of the catalyst pellets. The results of his steady-state analysis indicate that the steady-state axial temperature in the catalyst bed rises very sharply in the first inch L

C the bed after fuel injection to a

level of about 220Ü°F and then slowly drops off down the length of the bed. The practical implication of this result is the possibility that a very thin active catalyst bed is required to Ignite and sustain hydrazine decomposition. In fact, a long bed appears undesirable because it permits ammonia decomposition which causes the gradual temperature drop in the bulk of the catalyst bed. Experimental data obtained at Rocket Research Corporation agree closely with Keston's theoretical results on axial temperature and gas concentration profiles (1-).

(C) In accordance with these results, J. 0. Drake conducted a study to determine whether a practical catalyst bed consisting of a thin layer of spontaneous catalyst (16.5 volume percent Shell 405) could be used in conjunction with a larger less expensive non-spontaneous catalyst (83.5 percent Harshaw !lA-3) to produce a workable lower cost spontaneous catalytic system(jkiV. Tests were run with a fuel containing 63 percent hydrazine, 27 percent water, and 10 percent hydrazine nitrate. The results of Drake's experiments wore promising but inconclusive. Spon- taneous ignition took place over a wide range of temperatures but not at the very cold -^"F level. Ignition delay times wore high; approximately 0.1 sec. Vpparently, a higher spontaneous catalyst loading is required for very low (-()'j0i) ignition. Further work in this area is required to develop the concept. The idea seems oven mure practical for a pure hydrazine propellant which operates above }0(:.

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■4. [.Xl'KRlMKNTAI. IXH! 1 l'Mi:M' l-'OK (.ATAl.YST l-VAl.l'A'r I (>N

^U) The basic iulorinaLlon rotiuirud lu ;..a i si.n t nr 11 v diiim the per tormaut't' ol a liyJia/. ino dt't'ompüsiLiun caLalybl iucliidcs ilu iho- Uieniul low-teinperaturt' activity and l\\v aiiparent activation IMILI , v I ur the decomposition process. Tlie Latter is obtained by ineasuretnentb ol the catalytic activity at several temperature levels and the coiistrucl iun ot an Arrheulus plot with this data. The slope ot a plot ol the lo,^ ul the rate ot decomposition vs. the reciprocal absolute temperature is taKen as the apparent activation energy tor a given catalyst-reactanl system.

4.1 Isothermal Rate Measurement Apparatus and Method

(U) The method used to evaluate the isothermal rate ol hydra- ülne decomposition consists of measuring the change In pressure ol a calibrated constant volume container over a period ol time during the decomposition reaction. Tills technique was previously used by Lhe Shell Development Company and was shown to produce reliable results^*. The apparatus used to make the measurements Is a replica of the one used by Shell scientists and Is depicted in Figure I. In a typical run, powdered catalyst material Is placed In the 5 cm-' glass reactor which contains a Teflon coated magnetic stirrer. The entire apparatus is evacuated, ^as collector vessel isolated, and the glass reactor filled several times with helium. A hypodermic needle Is used to inject hydrazine into the glass reactor which has been previously chilled with dry ice. The reactor is deliberately kept very cold when the hydrazine is injected to guard against a sudden gas surge with an active catalyst. A temperature for study is chosen, the dry Ice bath removed and replaced with a constant temperature bath mounted on a magnetic stirrer. A small charge of catalyst is used in the reactor so that isothermal conditions are approached by active stirring of the catalyst-hydrazlne reaction slurry. As gas is formed in the reactor, it passes into the gas riser leg shown in Figure 1 and is discharged into the gas collection chamber. The decomposition is followed by observing the change in gas pressure in the collector vs. time. This technique has been found to yield substantially linear plots of gas formation vs. time for almost all runs. The rate of decomposition of hydrazine at a specific reactor temperature is taken as the slope of this line.

4.2 Five Pound Hydrazine Monopropellant

Thruster ___________________

(U) Evaluation of a hydrazine decomposition catalyst in an actual monopropellant catalyst engine is required to completely characterize its start-up performance and life. Thus, a 5 lb. thruster was designed

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and construe tod lor our catalyst evaluation. The basic unit consists oj a l"D x 3"L Typo 304 S.S. catalyst chamber inslrumonttd witli 1/10" intunel sheathed cliromo 1-a lumol thormocouplob and Tolodyno prossun- t ransduct-rs. Ignition delay and fuel pulse duration is measured by a direct writing oclllograph with a Iroquency response ol 5000 cps. Fuel is stored under nitrogen gas pressure and injected through a HO0 cone fuel injector. Nitrogen gas automatically covers the catalyst bed when no fuel (hydrazine) is llowing. The test thruster is not designed for flight operation. Its purpose was to provide a system to measure the comparative performance of several catalysts in adiabatic engine operation.

4.3 Laboratory Adiabatic Spontaneous Decomposition Test

(U) A simple test aimed at simulating raonopropellant engine Ignition and thereby repeatedly subjecting catalyst pills to high temperatures was constructed and used In our laboratories. This test consisted of partially filling a glass tube with catalyst and charging the tube with cold hydrazine. Observations made during the test Included the time required to start the reaction, the duration of the reaction, the physical condition of the catalyst pills after firing and the number of times the high temperature reaction could be sustained. The unit, de- pleted In Figure 2 , provided a convenient and rapid means of determining catalyst relative activity and strength.

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• ')

I untv 1

ISOTHLRMAL RATE STUDY APPARATUS

Hi-VAC PUMP

o

Hi-VAC STOPCOCKS

VENT -•

ROTAMETER

H2 He

5 cm REACTOR

TEMP. CONTROL

BATH

MAGNETIC STIRRER

GAS RISER II LEG

ca. 1 cm ID FILLED WITH

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10 -

Figure i-

Laboratory Adiabatic Spontaneous IK1 L ompos i t ion Test

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k

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b. UJBALT hAShl) CATALYSUS - l-.übi) lull M.Kll.S

i. I CaljLyst l'f opat Ml ion

(C) TliL' tsso IUI catalyst cousisls ul OU wL. I cubull uictul .iiid

40 wt. X AljOj, both cu-preclpitated from aqueous solution. The co- precipitation technique offers a unique way of dispt-rsln^ active metal cobalt crystallites In a matrix of alumina, thereby providing a means of preventing cobalt sintering and concomitant loss of active catalyst area. Details of the Ksso 101 preparation process are given in Appendix li.

(U) Binary metal compositions used in this study were obtained by introducing the required stoichiometric amount of iron and nickelous nitrate salts, respectively, before precipitation.

(U) The hybrid catalyst metal variations discussed in the next section of this report are fabricated by means of impregnating the Essu 101 catalyst in the "as calcined" stage with noble metals, drying the impregnated catalyst and reducing the mixture as above.

5.2 Isothermal Rate Studies of Esso 101

(U) Isothermal decomposition rate measurements of hydrazine on the basic Esso 101 catalyst powder were made in our glass reactor. As can be seen in Table 2, these measurements indicated that Esso 101 had a much lower room temperature activity than Shell 405.

Table 2

Low-Temperature Activity of Esso 101 Powder \

Catalyst

Hydrazine Decom- position Rate at 230C

cm3 (STP)/min-gir

Apparent* Activation Energy

Kcals/Mole

Esso 101

Shell 405

75

2,200

i ii i ill

23-28 |

17-22 |

*The term "apparent activation enersr" refers to the activation energy displayed by catalyst particles. It includes any effects due to mass transfer through the catalyst pores. The apparent activation energy is obtained by measuring the slope of a plot of hydrazine decomposition activity vs. the reciprocal ofvrhe absolute temperature.

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(Li) rin' activation energy, »MI liw itluT hand, appeart-d tu 1J. somewhat higluT than that reported by Shell scientlHts for Shell *!).. Shell's «dentists found in the rum se ol their work, that a i-atalvst must liave a minimum aftlvltv of 7') em'/min-gm to be spontaneous. I'lius, at liiw temperatures, Ksso 101 would have too ton^; an ij»nitlop deiav time. ignition delay measurements on Kssu 101 in our ') lb. thruster confirmed tiiis prediction. Work was thus conducted to improve clu- low temperature activity of Ksso 11)1. One approach tried at improving low-temperature activity v^^s to increase the cobalt loading ot the catalvst.

'). 1. Kttect of Cobalt Concentration

(C) The basic composition ol Lssu 1UI is bU wL. / Co -4b wt. Al20j. To determine whether a change in cobalt concentration would affect the catalytic activity, we prepared catalyst powders with 5Ü and 7U wt. I cobalt, respectively. These formulations were tested in the isothermal reactor at three different temperatures. The results, depicted in Figures 3 and 4, showed a definite effect of cobalt, concentration. The 7Ü wt. 7o cobalt formulation was more active than the 60 wt. formulation; the 5Ü wt. A formulation had significantly lower activity. Increasing the concentration to 8Ü and 907» gave further improvement in activity though the relative increase appears to level off at very high cobalt concentrations. Higher cobalt concentrations gave higher catalyst activity, dispite the fact that the total BET surface area was lower.

(U) The apparent activation energy for catalyst hydrazine decomposition, on the other hand, was not altered. It, thus, appears that increasing the cobalt concentration in the catalyst formulation could result in some reduction in the low-temperature ignition delay but that this reduction would not be sufficient to yield a catalyst that affected spontaneous hydrazine decomposition at 0oC. Thus, other approaches were tried.

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1000 900 800 700 600

500

400

300

200

i- to < >

I- O CO O

s O Ü LÜ O

i

äs a > E X u

100 - 90 - 80 " 70 60

50

40

30

20 h

10 9 8 7 6

51-

3h

n - Finnrc )

KTLCT OF COBALT CÜNCLNTKATION ON ACTIVITY

OF Cü-AI?03 CATALYSTS

T 1 T T'

70% Co

J I

3.10 3.20 3.30 3.40 3.50 3.60 3.70

1/T X 103 "K"1

UNCLASSIFIED

UNCLASSIFIED

- 14

FIGURE 4

EFFECT OF COBALT CONCENTRATION ON ISOTHERMAL ACTIVITY

o o in

< >

u <

o

en o a. o o LU a

x CM

LÜ >

UJ

50 60 70 80

WEIGHT % COBALT

100

UNCLASSIFIED

UNCLASSIFIED

• laiRi: ■)

EFFECT OF COBALT CONCENTRATION ON SURFACE AREA OF CATALYST

<NJ

180

160

E

J

140

E 120 < Ul a: < 100 UJ o < u. cr

CO

80

60

401-

201-

70 80

WEIGHT % COBALT

100

UNCLASSIFIED

-»v.

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K)

5.4 Ettcct ot Othtir Transitioti Metals

(U) Altering the "d band" vacancy ol a transit ion metal tutalysl Is anuther means of changing its catalytic activity. In another approach at improving the low-temperature activity ot the basic ESBO 101 1 (jrmula- tlon, we attempted to study the effect ot introducing the metals, nickel and Iron, into the Ksso 101 formulation. Modifications containing cu- precipitated nickel and iron, respectively, were screened In the laboratory Isothermal reactor. The resulting activity ot these catalysts are presented In Table 3.

Table 3

(C) Effect of Co-Precipitating Nickel and Iron witti Cobalt

! Catalyst Composition

Hydrazine | Decomposition Rate at 230C

cm3 (STP)/min-Eir !

60 wt. % Co-40 wt. % Al 0 | (Esso 101) l J

80 |

40 wt. % Co-20 wt. % Ni

40 wt. % A1203

18

40 wt. % Co-20 wt. 1 Fe

40 wt. % A1203

1 j

(U) Both the nickel-cobalt and iron-cobalt formulations showed much lower isothermal low-temperature activity than the basic Esso 101 formulation. It is difficult to explain this severe loss in activity resulting from binary transition metal formulations. However, the negative results of the preliminary binary transition metal formulation studies did not justify any further effort on this approach with nickel and iron.

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i.b hltect ot Calalvst Ptc-paratiuLi Tcchnimic-

(U) The basii- I'.ssu hydrazine decomposition catalyst consists of cobalt and alumina co-precipltatcd from aqueous solution. The catalyst was originally prepared by dissolution of the nitrate salts of cobalt and alumina followed by the co-precipitation of the oxides of these metals and subsequent reduction of the cobalt oxide to the metal. In the original preparation procedure, precipitation was affected by means of the slow addition of ammonium bicarbonate to a well stirred solution of the nitrate salts at 150oF. The von Weimarn theory of precipitation predicts that IIIKI"

surface area precipitates result from precipitation under conditions that yield a high degree of local supersaturatlon--rapid addition of precipitating agent, no stirring of solution, low temperature of solution. We attempted to utilize this theory to Increase the surface area of the resulting pre- cipitate and hopetully also Improve the low temperature activity of the resulting catalyst.

(C) Two variations in the precipitation procedure were tried: (a) the low temperature (0oC) addition of amnonium bicarbonate to a solution which was not stirred and (b) the addition of the cobalt and aluminum nitrate salts to a cold solution of ammonium bicarbonate, i.e., using a mixture of the nitrate salts as the precipiting agent. The results of this experiment are given in Table 4.

Table 4

(C) The Effect of Precipitation Procedure on the Surface Area of Co-Precipitated Cobalt-Alumina Catalysts (D

Procedure Surface Area

nr/am

Convent ional

Low Temperature

Low Temperature-Salt Precipitation

61

100

129

(1) All preparation procedures resulted in a catalyst composition of 83% Co-17% Al 0

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(C) Bolli mud i 1 ILUL iuns in Uu1 [irec ipi lut iun iJiocvdurt' rubul leu in uu iv a.sod catalyst aiirtact' area. Low icmjiL'raturt.- proi i pi t .ii i un in- creasoJ tlu1 surlawe area hU'L .md tlie li>w uiiii>i'i,iiiii i-, nitrate :..il i piit i- pitation mort' than doubled thv smt.Ki' area wluu compart-d with t IK-

conventionally prepared catalyst. Untort unalely, the low tetuperatiirt- activity per J.IMIH ol catalyst was not improved Uy these modi 1 icat i ons in catalyst preparation procedure. ihis implies that the increase in surtace area was mainly due to an increase in the alumina surtace are.i, and not the cobalt. Substantial improvements in the heat ul wetlin,, largely a tnnction ol the support surtace area, would be expected 1ur the bisher surtace area catalysts. However, it seemed unlikely that these improvements would substantially improve the low temperature icti- vity ol the tinisbed catalysts. Thus, further pursuit ol this approach was abandoned.

3.b Screening ot Non-Noble Metal Catalyst Materials

(C) Several non-noble metal and metal oxide catalysts were screened for low temperature hydrazine activity using our laboratory adiabatic screening test, i.e., by observing the presence of any gas evolution when cold hydrazine (20C) was added to catalyst samples in a test tube reactor. We took advantage of the availability of a wide range of complex inorganic materials which were synthesized in the Esso laboratories for electronic and electrocatalytic applications. These materials included transition-metal phosphides, non-stoichiometric oxides and non-stoichiometric tungstates. The materials tested are presented in Table 5. None showed any sufficient level of activity to warrant further evaluation.

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Table' 5

(C) Screening of 1'otential Nun-Nohlf Metal (analyst Materia 1 s

Material Hydrazine Decumuoaltion Activity 2°C (^»C2)

Nickel Phosphide NIP No Activity

Cobalt Phosphide C02P No Activity

Titanium Phosphide T1XP No Activity

Chromium Phosphide Cr2P No Activity

Manganese Phosphide Mn3P2 No Activity

Niobium Phosphide Nb? No Activity

Rhenium Metal Slight Activity

CrW03 Slight Activity

Cr + 1.45 W03 No Activity

Cr203'W02 No Activity

CR2W4O4 No Activity

Cr203.W02 No Activity

Co.263W03 No Activity

Cr.145W03 No Activity

Cr203W03 No Activity

Cr02 Slight Activity

W + W03 + Cr203 No Activity

Cr203 + W02 Slight Activity

(1) Test consists of the addition of anhydrous hydrazine at 2SC to powdered catalyst samples and observing the gas evolution.

(2) No Activity - defined as no noticeable effervescence of hydrazine after 5 minutes.

Slight Activity - defined as some effervescence but less than what would be observed with a similar charge of Esso 101 powder.

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6. HYBRID CATALYST STUDIES

(C) Another approach to reducing the low-temperature ignition delay of Esso 101 was to incorporate small quantities of readily reduced transition metals into the catalyst formulation. Small additions of these metals could provide appreciable surface area which would not have any oxide layer resulting from desensitization procedures. Furthermore, low concentrations of readily reduced metals (less than I wt. 7.) such as platinum and palladium have been observed to enhance the activation of nickel catalysts by hydrogenUfO. Similar enhancement was expected for cobalt. The cost of Incorporating small quantities of these readily reduced transition metals would not be great; e.g., 1 wt. 7. of a metal costing $100/troy ounce would add only $15/lb to the cost of the catalyst. This approach appeared promising and was, thus, studied in the laboratory.

6.1 The Effect of Low Concentrations of Noble Metals

(C) Readily reduced transition metals were added to the basic Esso 101 preparation after the calcining step. Salts of palladium, platinum silver and gold were dissolved and impregnated into different batches of calcined Esso 101, dried, and reduced as described in the standard procedure for fabricating Esso 101 catalyst powder. The various preparations were then individually tested in the isothermal laboratory reactor. The results of these isothermal rate measurements are given in Table 6.

Table 6

(C) Isothermal Rate Measurements of Esso 101 Catalyst Powders Containing Small Quantities of Readily Reduced

Transition Metals

i Catalyst Hydrazlne Decomposition Rate j

at 23°C cm3 (STP)/mln-Rra

101 80

101 + 1% Pd 100

101 + 1% Pt 55 i

101 + 1% Ag 42

101 + 1% Au 65 |

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(C) Only Llio i>.i 1 1 ail luiiL turmulatiun sliuwi1».! any activity nuprovt- ment over the basit.' tssi.) 101 catalyst at 2J0(.:. On the- otlu-r lianii, lormu- lations Lacurporatin^ plat iiiiun, ^old, and silver appuared tu IJC- somcwlial loss active. In terms ol llicsc results ahme, one would not expect a s L^nil icant miproveiiieiit in low-temperature ignition delay (leilormance ul the modilied catalysts. However, we lelt tlial tlie advanLagt ot having some metal surtace which is unal teeted by tlie passivation step, present in the cobalt catalyst lonmilation, may not have been clearly seen in the isothermal laboratory reactor tests. We thus evaluated the ignition delay of these preparations in our rj lb thruster. We also continued screening other readily reduced transition metals.

b.l Ettect of Hiuher Cuucentrations ol Noble Metals

(C) Initial studies indicated that the incorporation of palladium metal into the cobalt-alumina catalyst formulations, at the 1 wt. % level caused an improvement in low temperature activity. Thus, higher palladium metal loadings were studied. In addition, higher loadings of platinum on the cobalt-alumina catalyst were evaluated. The results of the isothermal low temperature decomposition tests using these and other hybrid formulations are presented in Table 7.

Table 7

(C) Effect of Readily Reduced Transition Metals on the | Low Temperature Hydrazine Decomposition Activity j

' of Cobalt-Alumina Catalysts 1

1 „ , Hydrazine Decomposition lute f 1 Catalyst ar 9i

0n ^^TPS/m<„_om 1

s Esso 101 i 80 (base)

101 + 1% Pd 105 ! 101 + 10% Pd 128 1

101 + 1% Pt 56 1

1 101 + 10% Pt 160 j

1 101 + 1% Rb 80 j

| Raney Co»Pt alloy 64 | 10% Pt

| Shell ^ 270 (10*0 |

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ilU.-d (C) Iticrous iiij.; thf palladium cunct" ntrat ion lu 10 wi . '/. rebuJ m a b0% Lucrt'ast' in iäütheriuul activity; incrtasin, tin.- plaLiimm LumtMi- iration to 10 wl . "L yieidt'd .i cal-alysl with twiit the activity ol hsbu 101 at J.b0C. Tlii'.si' improvcmcuts wcrc very im DUI a^i ii,> However, tlit> still were »üt nearly large enougti t > aller» spoutaneuuH catalyst i^nitiin J'C. Some iiuprovenient would he expected in the ignition delay ol catalysts tired at room temperature. Such was actually observed when a cobalt-alumina catalyst, containing 10 wt. I I'd was tired in a b lb thruster. Table b sununari^es the results ol this test.

Table h

(C) Ignition Delay of Palladium | Cobalt Hybrid Cataljüt

(n IgnltionVfc'j;

Catalyst Delay at 230C msecs |

| Coba It-Alumina Catalyst 1,200 j

j Coba It-Alumina + 10 wt% Pd 400 j

(1) Catalyst consisted of 83% cobalt - 17% Al 0 packed in 1/2" x ! 1/2" S.S. wire baskets. l i

1 C2) Runs compared on the 3ri! firing in 3 in tnruster.

(3) Ignition oeiay time does not include valve response and fuel j flow dead time which is apnrnximatplv fiO mR*»cs in our test

j svs.tem. !

(C) The incorporation of 10 wt. % Pd into the cobalt-alumina catalyst improved the ignition delay of the catalyst after the bed ..as activated by two initial firings.+ However, this improvement was insuf- ficient to affect spontaneous ignition of the catalysts in the 5 lb thruster.

6.3 Isothermal Evaluation of Cobalt- Ruthenium Hybrid Catalysts

(C) The Incorporation of readily reduced transition metals into our cobalt catalyst formulation have improved the low temperature activity and iynition delay of the cobalt catalyst system. The experimental data indicated that the incorporation o platinum and palladium into alumina supported cobalt preparations improved the isothermal

*The Ksso 5 lb. thruster does not represent a flight typo design. Ignition delay data are thus useful only on a comparative basis.

♦-Catalyst performance was evaluated on the third firing to avoid any confounding effects of residual oxide.

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activity and ignition delay ot iLaao 1U1 type cutalystü. This wurk was ex- tended to ru tlieiuum-cobal t hybrid catalysts. Kut heniani was a particularly attractive transition metal to work with because ol its wide availability and reasonable cost. Inl ornuil ion made available to l.ssu Research and Engineering Co., indicated that there is about 1!JU,ÜUU troy ounces of ruthenium/year available, primarily Irum two sources: the Johnson Matthey and Co. (as a by-product ol gold and platinum refining) and the International Nickel Co. (as a by-product of copper and nickel refining). There is also believed to be a substantial backlog ol this metal presently available.

(C) Several ruthenium-cobalt-aluniina catalysts were prepared by different fabrication techniques. These included 107, ruthenium on oxide sintered cobalt-alumina (prepared by co-precipitation), Esso 201; a structure consisting of 12"/, ruthenium prepared by co-impregnation of alumina with cobalt ruthenium solution, Esso 2Ü2; and a structure consisting of 22% ruthenium prepared by co-impregnating a ruthenium on alumina support with cobalt ruthenium solution, Esso 204. The results of the isothermal hydrazine decomposition tests, using these structures, are presented in Table 9 and Figure 6.

Table 9

(C) ISOTHERMAL DECOMPOSITION RATE OF COBALT-RUTHENIUM HYBRID CATALYSTS

1 1 Catalyst Description

Hydrazine Decomposition Rate at 230C

cm3 (STP)/min-Rm

i Apparent Activation Energy

Kcals/gm-mole 1

1 Esso 201 10% Ru, 75% Co on oxide sintered cobalt-alumina

10 19

Esso 202 12% Ru, 33% Co co-impregnated alumina

25 24

Esso 204 22% Ru, 33% Co co- impregnated Ru-alumina

50 24 |

Esso 203 12% Ru, 33% Co, 55% Alumina co-precipitated

15 24

j

Esso 101 70% Co, 30% Alumina co-precipitated

75 26 |

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1000

Figure fa

(C!) ISOTHERMAL HYDRAZINE DECOMPOSITION RATE ON HYBKID COBALT-RUTHENIUM CATALYSTS

1 1 1 1 1

" 100 — t-

E u UJ

2

CO O Q.

O U

UJ

N

2 5

10

Esso 204 22% Ru, Co-Ru-Co-iinpreqnation of Ru-Al203

Esso 202 12% Ru, Co-Ru-Co- / Impregnation of Al_0,

Esso 201 10% Ru on Oxide Sintered Co-ALO-

3.0 3.1 3.2 3.3 3.4 3 .„-1 1/T X 10^ 0K

3.5 3.6 3.7

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(C) Several interesting observations way be made about the data in Table 8 and Figure 7. First, the isothermal hydrazine decomposition rate oi the cobalt-ruthenium hybrid catalysts was less than that of the basic Esso 101 catalyst which contained no ruthenium. Surface area differences were believed to be partly responsible for this difference in activity. Surface area data indicated that the impregnated hybrid catalysts had considerably>less surface area than the co-precipitated Esso 101 preparation. However, the magnitude uf this surface area difference could not possibly account for the entire activity difference observed. For instance, Esso 201 had about one half the surface area of Esso 101 with comparable cobalt loadings. Yet, the isothermal activity of the Esso 101 catalyst was about seven times greater. This implied Chat a negative synergistic effect exists for the cobalt-ruthenium catalyst system. Further evidence of this is seen in a subsequent section on the evaluation of ruthenium-alumina catalysts. Despite the poor isothermal decomposition rate exhibited by the ruthenium-cobalt hybrid catalyst preparations. It was important to pursue evaluation of these catalysts in motor firing studies. Significant improvements in ignition delay might still be seen with hybrid catalysts having appreciable noble metal area, not affected by desensitization procedures. This hypothesis was confirmed in subsequent motor firing studies.

(C) The performance of cobalt ruthenium hybrid catalysts appeared to be dependent on the fabrication procedure. Esso 202 and 203 had the same component formulation but different isothermal activity. Surface area differences resulting from different fabrication techniques were held to be a contributing factor. The lower apparent activation energy of Esso 201 compared with other hybrid catalyst preparations was probably also a result of fabrication differences. One possible explanation for this lower activation energy is the increased pore diffusional contribution resulting from the presintering of the substrate used on Esso 201.

6.4 Five Pound Thruster Evaluation of Cobalt-Ruthenium Hybrid Catalysts

(C) The ignition delay of cobalt-ruthenium hybrid catalysts in our 5 lb thruster using hydrazine fuel was measured at several catalyst bed temperature levels. Catalyst pellets 1/8"D x 1/8"L were used in all cases. The results of these studies are presented in Table 10 and Figure 7.

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.■I)

TAbLK 1U

((') U;SmON DKIAY HI COIiAl.T-KllTHKNIUM UYHKID IA1A1.YSIS

Igniiion Del IV t'.lt.l Ivst DcscriptIon .it 2)"(J msec .cur

j Ks«o 101 70',': Co, U)": Aluiniii.i co- piiH' i pit ;it t'd

>f),ÜÜU

llssii 202 12% Ku, iiX Co CD-Impreg- nated alumina

1 , r)()0

| Ks s o 201 10% Ru, 75% Co on oxidt sintered cobalt alumina

2,000

| F.sso 10} 12% Ru on cobalt Impreg- nated alumina

750

(C) Tlie Incorporation of ruthenium into cobalt-alumina catalyst formulations is seen to dramatically reduce the ignition delay. Further- more, the degree to which the ignition delay is reduced depends on the mode of preparation of the catalyst. Catalysts 202, 201 and 200 all had approximately the same ruthenium content, but differed in fabrication technique. Esso 200 was prepared by first depositing the cobalt on an alumina support and then depositing the ruthenium on top of the cobalt. In this case, maximum availability of the ruthenium surface was probably achieved. Esso 202 utilized a co-impregnation of cobalt and ruthenium salts. This technique probably resulted in less available ruthenium surface. Esso 201 utilized a ruthenium impregnation of a cobalt alumina support and, thus, should also have readily available ruthenium metal surface. However, the cobalt alumina support was presintered yielding a support with about one half the surface area of Esso 200. This support surface area difference Is a possible explanation of the longer Ignition delay exhibited by Esso 201 In comparison to Esso 200. Despite the significant Improvement In Ignition delay resulting from the use of ruthenium In cobalt-ruthenium hybrids, performance had not approached that of Shell 405. Emphasis was thus shifted to the more promising ruthenium on alumina catalysts.

(1) The Ksso 5 lb. thruster does not represent a flight type design. Ignition delay data are thus useful only on a comparative basis.

(2) Ignition delay time does not Include valve response and fuel flow dead time which Is approximately 60 msecs in our test system.

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10,000

Fijgure 7

(C) PERFORMANCE OF COBALT-RUTHENIUM-HYBRID CATALYSTS IN 5 LB. THRUST ENGINE

1 —i 1- i- -7- r

Hyl)rld-201 10% Ru on Oxidt- Sintered Al-Q.

1000

> 5

z o

z

100

Hybrid-202 Co- > impregnation of

Ru-Co on AlpOo

Shell-405 Price Evans Data^

10 J L

(1) NASA Technical Report 32-1227

1.6 2.0 2.4 2.8 3.2 3.6 4.0 4.4

1/T X 103 "K-1

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' • (O Kin'HKMUM liASKD HATAl.VST S'lUDll-S

'•1 I .soiln'i ni.i 1 Rdtt' StuiHt'S ol AlumiiKi Su|i|H'rl fi.1 Kut lull i inn (iit.ilvsts

(C) A siTU'-s ol rut lien i urn mi alumiiui catalysis were jirtparfd lo (.letot'inino whether perl'ormam-'e could he imjjruved hy reinuvin^ tin- cobalt troiu the system. The ctlccL ul rulhcui urn concent r.i t i on, catalytil support typt", as well as the addition ol platimui), on catalyst isotiiermal hydra/, ine decompositiuu activity were .studied. The results are presented in Table 11 and Figure b and discussed in the following paragraphs.

TABLE 11

(C) ISUTHKRMAL HYDRAZINK DECOMl'USITIüN RATK ON RUTHENIUM CATALYSTS

llydrazine Decomposit ion Apparent Rate at 230C Activation Energy

Catalyst Description cm'3 CSm/irin-gm Kcals/gm-mo1e |

Es so 206 12% Ru on Alumina 170 19

Esso 207 23% Ru on Alumina 210 19 j

Esso 208 36% Ru on Alumina 360 19 j

Esso 209 33% Ru on Silica- Alumina (6% SiO )

280 19 |

Esso 210 5% Pt, 33% Ru on Alumina

359 Not Measured |

1

(C) Catalyst isothermal activity increased with ruthenium metal concentration and was more than 5 times as active as Esso 101 at the 36% ruthenium level. The cobalt free, 12% ruthenium on alumina, catalyst was far more active than any of the cobalt-ruthenium hybrids having the same ruthenium content. This data further supported the fact that there was a negative synergistic effect exhibited by cobalt-ruthenium hybrid catalysts toward hydrazine decomposition and that the performance of a ruthenium

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.">

(.C) ISOTHLRMAl HYDRA/INt Dl COMPOSITION KATf ON RUTHCNIUM CATALYSTS

1000 r

100 a. i—

E u UJ l-

2

O Q. 5 o o

< 10 o >

-Al203

_J I 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.0

1/T X 103 "K-1

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id

catalyst depeiuit-'d on I hi' iiaturi1 nl tlu- biniport uaed in llic- 1 .iln u at i mi. I'ho relative pcilomiaucv ol rutlietiiiim*aliunitia .ind uobal t-ruthfriium-uluiiijiia iratalyöts in llie motor t i i i ny, siudies, iliaciissed in the lollouinj.' paragraphs, i'avo tlu' s.imi' conclusion. The isothermal data su^ested that higher ruthenium levels would yield more active catalysis. However, measurements made in the > 1!'. thrust engine indicated that tiiere was a leveling oil in the ignition delay as the J'J/ ruthenium content was approached. The activation energy ol ruthenium alumina catalysts was lower than 111,it ol the cohal t-rut hcnium-alumi na hybrids. The hybrids would thus be expected to be more active above 2UU0C. However, at the adtabalic tiring temperature, the reactivity ol the catalyst is undoubtedly diffusion limiled. The apparent activation energy ol the catalysis would then be primarily controlled by pore diffusion effects. The use ol a silica-alumina support (llarshaw 1602) did not appear to oiler any great advantage over alumina in terms ot Isothermal activity. The incorporation of YL platinum into the formulation by co-impregnation appeared to improve the isothermal activity. This improvement was reflected in a very short ignition delay during the first firing ol this catalyst in the b ib thruster. However, this activity was lost in subsequent 5 lb thrust motor firings.

(C) The addition of 5 wt. % platinum to a ruthenium-alumina catalyst, by means of the co-impregnation of platinum and ruthenium salts, produced a catalyst that gave a very short hydrazine ignition delay for the first firing. This concept was thus explored further. Ruthenium- plat inum-alumina supported catalysts were prepared by co-impregnation of the halide salts and subsequent reduction with hydrogen. Catalysts were prepared with ruthenium/platinum weight ratios of 3.0 and 4.5, at a total metals content of 17 and 30 wt. %. Isothermal rate measurements were made using these catalysts. The results are presented in Figure 9 and Table 11. The data show that the incorporation of platinum into the alumina supported ruthenium catalyst reduces the apparent activation energy for hydrazine decomposition. Both 17 and 30 wt. % binary ruthenium- platinum metals catalysts gave activation energies of 14 kcal/g-mole as opposed to 19 kcals/g-mole for the pure ruthenium catalyst. This lowering of the activation energy also meant that the activity of the 30 wt. 7» binary catalyst was higher at 50C than that of the 33% alumina supported ruthenium catalyst; the ruthenium-alumina catalyst was, however, still slightly more active at 250C.

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10ÜÜ

» 100 a.

S u

en

2 s o o a

IN

a >

10

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(C) ISOTHLRMAL PERFORMANCE ÜF ALUMINA SUI'I'URTLD RUTHENIUM-PLATINUM CATALYSTS

30WT%METAL- Ru/Pt = 3-4.5

ON Al203

7WT%METAL Ru/Pt = 3-4.5-1

0NAI203

33% Ru 0NAI203 -

3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9

1/T "K X 103 "K"1

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lalilv I

(C) ISOIUKKMM. I'l.KIOKMANt.l, n| Al.lM 1 NA SlI'l'OKl l.D KrillKNU'M-l'l.ATlM'M LA1A1.YS1S

IVrnporaturo llyJraziiu' Detniuposi t ion K.n V

AppariMit Ai-11 vat iun 1

K. al/j--muU- t'.it alvs t Coui^us i i ton oin1 (Sl'lO/miii-jn mi' (OTyrn -III i 11*

| Rut lion i uiii-l' Lit i num-A 1 urn I tia ') R) 7H 14 | 1 ,' wt Metals Ku,i't - i.O Jr) 170 440

"* • 1 23 170 440 I

Ruthonium-riat iiuun-Al umina r) 50 130 14 )0 wt '. Mot a Is Ru/l't = J.O 23 2 70 700 I

"* • ^ 25 270 700

j J 3'. Rutluniam-Alumina

i

5 25

30 350

78 910

19 i

l*Volurae of product gas STP per volume of catalyst per minute.

(C) The isothermal data imply that the binary ruthenium- platinum alumina supported catalysts would provide a shorter hydrazine ignition delay at temperatures in the vicinity of 50C. This is not countinp the instantaneous possible hypergolic effect resulting from the presence of platinum oxide. This effect cannot be defined in the isothermal reactor. it can only be detected in catalyst bed ignition studies. We have not tested the start-up characteristics of these new ruthenium platinum-alunina catalysts at 50C. Our present test facility would have to be modified to do so in a reliable manner. However, preliminary motor firing tests with the 30 wt % ruthenium-platinum catalysts at 250C did not show any advantage over pure ruthenium-alumina catalysts. In addition, the first start platinum oxide hypergolic effect was much less pronounced than that observed with the 5 wt % platinum, 33 wt % ruthenium on alumina catalyst (Esso 210). Thus, though this area offered further potential to reduce the low temperature hydrazine ignition delay, we felt that we could best utilize our effort by devoting full time to the study of other thermally stable substrates for ruthenium.

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i >

j.l I'lvt- I'IHUHI Ihiustii Kva lu.il i nn ul Aluiiiin.i S>n'iH'it itl Kut luii i urn r.it .i 1 ys t ;.

(C) Tin.' lilnl> low lomptTuttirt' Lsulhermal aclivity ul cobalt trt'o inihi'iiimil mi alumina i.ii.ilvsis w.is irauulalud iniu a si^nilicaiit reduttimi In iguitiun delay. Testa on I/ö"U x 1/H"L pulli-L.s labricated by ru t lieu iuin salt imprev.nat ion ot pre-formed Harsliaw 14U4 alumina vave engine start-up performance which approached that ol Shell 4U!). Tlie results ol these tests are presented in Table 1 * and Figure 10 and dis- enssed in the following paragraphs.

Table IJ

(C) IGNITION ÜELAV OF ALUMINA SUPPORTED RUTHENIUM CATALYSTS IN 5 LB. THRUST ENGINE

| Catalyst Description Ignition Delay at 2 30C msec. (1.2)|

Esso 205 33% Ru on Alumina 120



Esso 209 33% Ru on Silica-Alumina 6% Silica

100

Esso 210 5% Pt, 33% Ru on Alumina 5 (first firing) 100

(C) The ignition delay was seen to depend on the ruthenium concentration, decreasing as the catalyst ruthenium content increased. The incremental reduction in ignition delay in going from 23 to 33% ruthenium was much less than that in going from 12 to 237=. Data on a higher ruthenium concentration catalyst further indicated a leveling off of the Ignition delay. Thus, very high ruthenium loadings (>50%) are not expected to result in any further significant reduction in ignition delay.

(1) The Esso 5 lb. thruster does not represent a flight type design. Ignition delay data are thus useful only on a comparative basis.

(2) Ignition delay time does not include valve response and fuel flov dead time which Is approximately 60 msecs in our test system.

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FiRure lü

(C) PERFORMANCE OF RUTHENIUM CATALYSTS IN r) LB. THRUST ENGINE 10.000 f- -i- -r " 1 1 I 1

1000 —

u Si E

>

LÜ o

100 —

2.0

Esso 205 33% Ru

Shell-405 Price Evans Data (1)

NASA Technical Report 32-1227

4.4 4.8 3 „.-I 1/T X 10^ 0K

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[{') I'lii' i lu'orpoi .it Ion ol i |> 1 .it i iiuiü , liv I'uMii-. .-I tin ru-impriy nation ot |i Kit iuutn .nui i in lu'ii i uri salts, |)i inliui'il .i i.tliilvst th.ii showi-il ,i vi'iv short U'.uition Jt'lav i or l\\v lirsl I i r i ii>'. HoWfViT, subsociut'tit tiiin,1

JU not show ,uiv .iilv.uit.iy.o ovi-r tho pl.iliimiM I I ci- oalillvsl havinj' .i icilnpar.ih It lutlii'iiiuin konti'iit. Owe possiljU1 oxp 1 an.it i on lot tlio via v sliort ignition di'lav obsi'ivod (.luring the tirst t iiiu>', ol tlu' platinum rutiu'iiiuiti oalalvst was tht? celativo ease in whicli plaiinum uxiile was reduced. All catalysts, prepared bv hvdrogen rediiftiun, are subsequent lv exposed to air and, lieiut.-, have a thin oxide layer on the surface. This oxide, which is easily reduced, reacts with hvdrazlne In a bipropellaut mode for a trait ion u! a seiend .^ivi'i); the system an extra "kick". Platinum oxide is easier to reduce than ruthenium oxide and hence may have accounted for the rapid start. The ignition delay during the first tiring ol platinum free ruthnnium catalysts was usually lower than the next lew subsequent firings. The difference.', however, was not nearly as great as that observed with the ruthenlum-p latir.ui:. catalvst. Kurther evidence of surface oxide effects was obtained by re- admitting air into a catalyst bed at room temperature alter it had been fired a number of times. A significant reduction in ignition delay, (usually about 50%)and ignition spike pressure was observed in each case in whicn air was admitted to the reactor bed. However, the shortened ignitlun delay effect is, again, only present for the Initial firing after exposure to ir

7.3 Isothermal Performance of Tungsten Carbide Supported Ruthenium Catalysts

(C) Tungsten carbide possesses several properties which make it an excellent candidate for a high temperature thermally stable catalyst s'ipport. It has a much higher melting point than alumina (2780CC as opposed to 2000oC) and thus should be more resistant to sintering than alumina. It has a much higher density than alumina (15.7 gms/cnH as opposed to 2.6) and thus has the potential to store more active catalyst in a fixed volume. 1' should be stable in a reducing atmosphere at high temperature. Most synthetic procedures utilize the reaction of tungsten with a hydro- carbon in a mixture of H2 and N2 at temperatures ranging from 1,000 to 2,200^. However, the high temperatures required for the synthesis of WC limit the surface areas that can be obtained with this material. This appeared to be its chief disadvantage. Though the maximum surface area of WC available today is about 10 mVgm, it was felt that the material possessed enough encouraging properties to warrant Investigation. Tt ws«? felt that Company potential unique technology could be used to increase the WC surface area if ruthenium was shown to be active toward hydrazine decomposition when used in conjunction with a WC support.

(C) Thus, WC supported ruthenium catalysts were prepared at the 10, 23 and 30 wt. 7» ruthenium level using ruthenium halide impregnation and hydrogen reduction. Samples of catalyst powder were evaluated in the isothermal reactor at several temperature levels. The results are presented in Figure 11 and Table 14.

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(c;) ISOTHLRMAl PERFORMANC RUTHI NIUM CATAl VS1S

".I 01 TUNGSTEN CARBIDI bUPPORTl I)

1000

30% Ru ON WC

23% Ru ON WC

10% Ru ON WC

3.5 3.6 3.7

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T;il)li' 14

(C) ISiMHKKMAl. ACTIVITY Dl Kl TIII.M I M -1 TNLS'I l..\ CAKIHDK CAIAI.VSTS

Apparent HvUraziiu.' Ueconmosition RaU.' .i\.2'j'Jc.

Ait I vat ion laiergy ■* ------ ---_

rm^ßTl')/r,„J-n,inA Uatalvst Compos i t ion Kcals/g mole mi3 (STl')/mln^n

WC substrate .ilonc U (J

10Z Ru on WC ^r) 1 IG

JJ;; Ru on WC U 22 345

iOZ Ru on WC 13 38 5%

4Ü"„ Ru on WC Not Measured 13 204

J3% Ku on Alumina 19 330 910 I

* volume of product gas STP per volume of catalyst per minute

(C) The data indicated that tungsten carbide supported ruthenium catalysts had considerable activity toward hydrazine decomposition and the decomposition rate appeared to be very dependent on the ruthenium concentration, increasing markedly between 10 and 307. ruthenium and then apparently decreasing at the 407. ruthenium level« The absolute activity of these catalysts, on a mass basis, is not great--only 38 cm^/gm-min as compared with 350 cm-Vgm-min for alumina supported ruthenium at about the same 307= metal loading. However, the much higher density of the tungsten carbide support makes this catalyst look much more attractive on a volume basis. Since most potential applications for the hydrazine monopropellanl system are volume limited (their design and size are fixed by other factors) a more meaningful comparison of catalysts can be made on a volume basis. High support density cannot fully be translated into catalyst storage savings because of catalyst pill porosity and the bulk density factor. However, the activity per cm3 does appear to be a more practical figure of merit for hydrazine decomposition catalysts. When compared on a volume basis, the activity of the 307. ruthenium on tungsten carbide catalyst at 250C is less than one half that of the 337. ruthenium on alu-nina. This is very encouraging in view of the fact that the tungsten carbide support had only 10 m^/gm of surface area. If tungsten carbide supports can be prepared with surface areas of 20-30 m^/gm, the activity of the 307. ruthenium loaded catalyst should be equivalent to that of 337. ruthenium on alumina on a volume basis. It is recommended that further work be conducted on the WC substrate.

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JH

'•^ Performance of I'l'N Supported Ruthenium Cutalysts

(U) Esso Research developed a unique relractory tatalybt support material which lias both high surface area and resistance to sintering at high temperatures in a humid environment. The stability of this support to sintering in a 807„ H2-20I H^O at 11ÜU,>C environment is shown in Table 13.

Table 15

THERMAL STABILITY OF KSSO PTN SUPPORT

Samples Steamed for 1/2 Hour in 80% Hj-IOZ W.O at 110üoC

BET Surface Area

| Support m^ / Km % Decrease

in Surface Area Before After

j Esso PTN* 159 121 24 |

1 AI2O3 { (H-1404)

152 7Ü 59 j

AI2O3-SIO2 | (H-1602)

211 92 56 |

*Esso PTN Is a specially prepared form of Boron Nitride which was developed under Company-sponsored research.

(U) The very encouraging results achieved in this sintering test for the PTN material clearly made it a potential candidate support for the non-strategically limited ruthenium metal. However, it remained to be seen whether ruthenium would be active on the PIN support and whether catalyst pellets of sufficient strength could be fabricated. Thus, ruthenium was deposited on the surface of the PTN support by halide salt impregnation and hydrogen reduction. Catalysts were prepared at the 23 and 45/!. ruthenium metal loading. The results of isothermal rate measurements using these catalysts are presented in Table 16 and Figure 12.

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(C) ISOTUKRMAL ACTIVITY UK I'TN SDl'l'DKTKU RUTHKNIUM CATALYSTS

Apparent Activat ion Kn^rgy

llydraziin.' Üt'compi s i i iun Kate at 2J'J(.

Sur1 ace Area Catalyst Compüsltion Reals/K-raule cm3 (STl'Wmin-jMn cm-' S'll'/^m -miitfr m2/üm i

\li ut Z Ku on PTN 18 2 70 but) 77

|4b WL o Ru on PTN 18 2 7U 6U0 4 A

JJ wt % Ru on 19 350 91U 7-i 1 Alumina

* volume of product gas STP per volume of catalyst per minute

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(C) IS01III Iv'MAl l'tRIÜKMANCI ül I'IN AM) f.1.,() MIIM'OIM I I) K'UIHl NIUM CATAI VMS

,000 -T" ~T'_

100 a

(•■\

<

o a. o u

N < K Q > x

ioh

ON MgO

■ 45% Rn ON PTN

A 23% Ru ON PTN

3.2 3.3 3.4 i.

3.5 3.6

1/T X 103 "K*1

3.7 ' 3.8 3.9

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A« can hv sii'ii truiu i\w data, tla- I'l'N supporlt'd rutht-niuiu tutalyst \ni-.- sossi's appiof iabli- aclivity. Tliou^.h liuLh tin- Z[i wt . I and '♦'J wi . / Ku tatalysis wort' less aclLvc i li.m tin.' aluuiiua suppurted ii wi. /, ruLlienimi] catalyst, the luj'h level ol activity was still uxtremuly CUCDUI a^ i u^. Since tlic surlacf area ol tlic base 1'TN suppDii used was low (80 v.i^/yui), we loll that the activity could be improved. The- tact that no noticeable increase in catalyst activity was observed in increasiiiK the rut heni urn concentration Irom l.i to 45 wt . , is partly explained by an apparent loss in suriace area. The 4J wt. I ruthenium catalyst had a total BET surlace area ot -+4 iii«-/^m as opposed to // m^/ym lor the 2i wt. l ruthenium catalyst. A change in fabrication conditons such as rutlieniniii halide solution concentration and temperature may oiler alternate ways ol achieving higher activity at a high metal loading.

(C) The refractory support, PTN, was prepared in a large quantity (1ÜÜ gms) and was used to fabricate a scaled-up batch of ruthenium-PTN catalyst. As with the earlier small batches, ruthenium metal was deposited on the refractory PTN support by a series of ruthenium chloride impregnations and calcinations followed by reduction with hydrazine. A large batch of PTN supported ruthenium catalyst was prepared at the 4U wt. % metal level and tested in the isothermal decomposition rig. The results are compared with those obtained using catalysts prepared in small quantities in Figure 13.

(C) The scaled-up catalyst preparation showed somewhat higher hydrazine decomposition activity than that of the material processed in small batches. Since very little difference in catalyst activity was observed among small batches containing 23 to 45% ruthenium, the apparent improvement in catalyst activity, observed for the scaled-up batch, was not believed to be due to differences in ruthenium average bulk concentration. Neither was it believed to be a result of differences in catalyst surface area which were substantially the same for large and small batch preparations. A more likely explanation was in the improved dispersion of the metal on the surface of the large batch of PTN material. Much higher solution concentration gradients and high localized deposits of ruthenium can be expected when small batches of catalyst material are processed by a multiple impregnation technique.

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FiKurt' 1J

(C) ISOTHERMAL PERFORMANCE OF SCALEO-UP RUTHEMUM-PTN CATALYST

1000 , , , , , ,

E I

I; 100 a

c^

$

O a S o U4 a

< on o > X

10

T

40% Ru ON PTN LARGE BATCH

PREPARATION drCgms)

23-45% Ru ON PTN SMALL BATCH

PREPARATIONS (10 gms)

3.2 3.3 3.4 3.5 3.6 3.7

1/T X 103 "K"1

3.8 1.9

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(U) l'TN suppurtud i utheiii um tjlulybl pclltits (1/\u "L x \/ti"U) wert; prupaitd by means ol j SLokcb IVlUt I'rcsb. Pcllttti as lormed irun Uie press had iow crusli strength. Thus, the- .sinter strtagthfuini-: tedi- aique, successtully employed with the Loh.ilt-alunmia catalysts, wab applied to the Ru-PTN system. Fellets were subjected to binUi ircui- monts at ditterent temperatures lor a specilled lime in a Cube turnave. Argon gas was used to protect the pellets against oxidation. The effect ol sintering treatment on catalyst pellet crush strength is shown in Table 17.

Table 17

EFFECT UF SINTER STRENGTHENING ON CRUSH STRENGTH OF Ru-PTN CATALYST PELLETS

-T

Sinter I'emperature "C Sinter Time Mlns. Average Teilet Crush _ Strength Lbs.*

No Sinter T 7.0

1200 10 8.0

1 300 }0 12(1 3f)0

1A.0 11.(1

r).()

«Average of (10) 1/8" D Pellets

(U) The data in Table 17 indicate that considerable improvement in Ru-PTN pellet crush strength can be achieved through the sinter strengthening technique. Pellets sintered at IJOU'F fur M minutes have almost twice the crusli strength as pellets receiving no sinter treatment. Increasing the sinter times, however, produced increasingly weaker pellets. This was contrary to what was expected and observed with cobalt-alumina catalysts.

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r

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/. s Pt'rlormanct? oi Relractory Oxitlt' Supported Kutlu-ui um (aUilysls

(C) Several refractory oxides liavc properties Llui make them potential candidate tliennally stable supports lor rutlienium. lliese include tungsten oxide, magnesium oxide, and /.irconiinn oxide. i'liese materials liave very liikJ,l> meLting points, are chemically stable at high temperatures and tan be prepared in high surtace area* Thus, several ui these materials were impregnated with ruthenium halide solution to the JU wt. X metals level, reduced with hydrogen and tested In the isothermal rig. The results are depicted in Table 18 and Figure IA.

Table lb

(C) PKRFORMANCE OF RKFRACTOKY 0X11)K SUPPORTED RUTHKNIÜM CATALYSTS

Catalyst

Cata Area

yst Surface

m /«m

Isothermal NoH, Decomposition Rate cm3 (STP)/min-gm at 250d

3ü7o Ru on Zr02 37 250

307. Ru on WO 2 3 163 •

307. Ru on MgO 21 ■300 |

307, Ru on M0O3 14 Negligible Activity j

3 37, Ru on AUO 70 _ .. .. 1

350 |

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Figure LA

(C) ISOTHERMAL PERFORMANCl OF REFRACfORY OXIDE SUPPORTED RUTHENIUM CATALYSTS

1000

100 -

CA

S

O Q. 5 o o

rsi < a >

10

T T T

30% Ru ON MgO PRODUCED EY CALCINATION

OF MgCO,

30% Ru ON ZrO.,

30% Ru ON W0-

3.2 3.3 3.4 3.5 3.6 3.7 3.8

1/T X 103 "K'1

3.9

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■ ii

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(C) UilliTt.Mi<.fs in calalvsl surtace area i annul txpluin this witif lauî- ol iihulis in Uydraziiu.' decuiuposjitijj n activity, in I at i , tlu- most active hydra/me dec jmpoaitioii catalyst, jUX Ku uu Myü, liaü a burlace area ol only 21 m'^/m- Ûv results are more likely i'ut- to the strung chemical Luturactioii ot catalyst and substrate which strongly determine« the resulting supported catalyst liydiaz me- decomposition activity. The Lsothermal hydraziue decomposition activity ol the magnesia supported lutheiuum catalyst was high enough to aliect spontaneous hydra/ine ignition at temperat nies as low as 50C. Tims, it was considered a very promising system Lor tilts project and was subjected to further evaluation.

/.o Preparation and Perfurmance ol High Surface Areî M.ignesia

(,U) lliyh surface area magnesium oxide was prepared by calcining MgCOj and Mg(0H)2 under specified conditions. IVo temperature levels and two calcination duration periods were evaluated. The BET surface areas resulting from specific process treatments are presented in Table 1^.

Table 19

EFFECT OF PROCESS CONDITIONS ON THE SURFACE AREA OF RESULTING MgO SUBSTRATES

Source of Magnesia

Run Identification

Calcining Temperature, "F

Calcining Time, hrs.

Magnesia BET Sur. Area nWgmi

114 216 ;

62 90 I

! MgC03 B

A

D C

1000 1000

615 615

2 15

2 15

Mg(OH)2 F E

1000 1000

Vitro Magnesia

2 135 | 15 85

60

(U) The MgO substrates resulting from MgCOß decomposition showed surface areas ranging from 62 to 216 m2/gm, surface areas increasing with the severity of treatment. Substrates resulting from Mg(0H)2 decomposition at 1000oF showed a decrease in surface area with an increase in calcining time. Preliminary tests at 6150F indicated this temperature level was too low to affect significant Mg(0H)2 decomposition. The lower surface area resulting from the longer calcination period, using Mg(0H)2 as the source, implies that the H2O formed during decomposition may have catalyzed sintering. The results of our steam sintering tests discussed later in this section support this theory.

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(.t;) Tin' process cunditiuns yU'lditi^ th».- Iii^licst suriate art-a MgO (Rim A) was used to tabricale an Rti-MgU catalyst at the ,10 wt . /„ metal level. This catalyst was prepared in a similar manner tu the Vitro MyO supported catalyst using multiple ruthenium lial ide sulutiüii impregnation, calcination and hydrogen reduction. isotlieimal catalyst activity tests were run on tlie hi^h surlace area M«ü-Ru catalyst. The results are compared with the pertormance ol the Vitro MgO supported Ru catalyst in Table 20.

Table 20

(C) PKRFORMANCi; OF MAGNKSIA SUPPORTED RUTHKNIUM CATALYSTS

1

Catalyst

f Substrate Surface Area m /KI«

Temperature 0C

Isothermal N2H/, Decomposi- tion Rate cm"3 (STPWmin-om

307, Ru on Vitro Magnesia

60 1 15 25

25 ! 125 ; 500 !

307o Ru on MgO (MgO from Prep. A above)

216 1 15 25

1

50 163 i 500

The high surface area MgO supported Ru catalyst showed considerably higher activity than the Vitro MgO supported Ru catalyst at low temperatures; no difference in activity was noted at 250C. The high surface area MgO supported Ru catalyst should be active enough to affect spontaneous hydrazine ignition at 50C. A large batch of high surface area MgO was prepared and was used in pilling studies. The results of sinter strengthening experiments on 1/8"D x 1/8"L Ru-Mg0 catalyst pellets were discouraging. Cracks were formed in the catalyst pellets during the sinter strengthening process. One possible explanation for the crack formation was a further decomposition of some remaining MgCOß during the sinter strengthening operation. It was felt that an acid treatment might help remove MgC03 that has not been completely removed during the calcination step. Acid treatment of the MgO formed from calcination of MgC03 or Mg(0H)2 might also provide additional substrate surface area. The results of an acid leaching treatment are discussed in the following paragraphs.

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(C) MgÜ substrate samples produced troni buth My (OH) 2 Ji'd M^CÜj sources were treated with 0.Ü3 M phosphoric acid. Phosphoric acid ib a jood halide tree leachant a»d this treatment ol refractory oxides ius also been shown to inhibit sintering in a H2Ü environment (2). Treatment consisted ot equilibrating calcined substrate materials with Ü.ü'j M phosphoric acid, drying at 250oF, and calcining at 730°*' lor unly I hour. This procedure was conducted twice witli each suhstrflte sample. The resulting change in substrate surface area is given in Table 21.

Table 21

timer OF Püospuüiuc ACU LüACLING ON

MAGNESIA SUBSTRATh: SURFACE AiU.A

Substrate Identification

2 ' BET Surface Area 111 /gm

Before Leaching 1 Alter Leaching 1

MgO (From Mg(X) )

A 216 ; 232 1 1

MgO (From Mg(0H)2)

E 85 252

i

1

(C) The data presented in Table 21 show that the leaching treatment produced a significant increase in substrate surface area for both samples. The increase is much greater for the substrate initially produced from Mg(0H)2 decomposition indicating that this substrate had a greater fraction of the source which was not decomposed by calcination. As in our calcination studies, we wanted to see if the higher surface area produced by the acid treatment could be translated into higher supported ruthenium hydrazine decomposition activity. Thus, a portion of a phosphoric acid treated substrate was used to fabricate a Ru loaded catalyst. A catalyst containing about 30.0 wt 7o Ru on phosphoric acid treated, MgC03 calcined substrate (Run A) was fabricated by the standard multiple ruthenium chloride solution impregnation technique followed by calcination and reduction. The hydrazine decomposition activity of this catalyst was measured in the Isothermal test rig. The results are compared with the activity of a catalyst prepared from calcined MgC03 which had not been acid treated in Table 22. The acid treated catalysts were found to be less active than catalysts prepared from the calcined substrate.

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T;il.If 21

(C) PERFORMANCE OF ACID LEACHED MAGNESIA SUPPORTED CATALYSTS

Catalyst

Substrate BET Surface Area

iWum Temperature 0C

Isothermal N^H/, 1 Decomposition Kate

cm' (STP)/min-»n |

307, Ru on Acid Treated MgO

252 t

1 1 25 | 15 125

30% Ru on as Calcined MgO

21b 1 50 15 163

(C) Magnesium oxide appears to show considerable promise as a support for ruthenium. The activity of the MgO-supported ruthenium toward hydrazine decomposition is quite high and the substrate can be prepared in high surface area. However, several questions exist pertinent to the physical strength of MgO granules and pellets. Further work in this area is required to define the magndtinle of this problem.

7.7 High Temperature Stability of Various Hydrazine Decomposition Catalysts and Substrates

(C) Several catalysts and substrates were subjected to high temperature sintering tests in N2-H2-NH3 and H2-H2O atmospheres respectively- The results of these tests are presented in Tables 23 and 24. Of the bstrates tested, the tungsten carbide appeared to show the highesL csistance to sintering in both the water free and water containing environment, decreasing less than 107. in surface area during both teat periods. The PTN material was the second most stable support tested, though a considerably greater loss in surface area was observed in comparison to our first sinter stability test run on PTN reported earlier in this program. This difference in stability is most likely a result of slight variations in PIN composition from batch to batch and not a result of the difference in the gaseous ambient used in the tests. This is borne out by the fact that the PTN desurfaced about the same amount in both current stability tests in a H2-N2- NH3 environment and in the H2-H2O environment. The fact that the PTN and WC support were as stable in a gaseous environment containing 20 vol. 7. H2O as they were in a H2O free ambient implies that these substrates may be used with fuels containing hydrazine nitrate.

(C) The PTN supported ruthenium catalyst at the 23 wt. 7. metal loading was almost as stable as the metal free substrate itself and also showed little difference in surface area loss in both a water free and water rich gaseous environment. The tungsten carbide supported ruthenium catalyst, on the other hand, decreased in surface area consid» rably in

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both tests with a more drastic loss takiny place in the Ho-l^O gas test. This loss is believed to be a result oi the tact that the high loading of ruthenium deposited on the low surface area WC substrate was probably not well dispersed, allowing ruthenium crystallites to sinter together easily. This is further supported by the fact that the 30 wt. % ruthenium on tungsten carbide catalyst showed much higher initial total BET surface area than the substrate itself, indicating that a good portion of the ruthenium produced was "unsupported" and actually physi- cally mixed with the tungsten carbide.

(C) The refractory oxide substrates and supported ruthenium catalysts showed very poor stability characteristics with the exception of the Harshaw 1602 alumina-silica substrate which was reasonably stable. The very active magnesia supported ruthenium catalysts and the magnesia substrates themselves were notably unstable, desurfacing sharply in both tests, though to a greater extent in the H2-H2O atmosphere. The standard Harshaw 1404 alumina substrate desurfaced considerably in the water free NH3-N2-H.2 environment and almost completely in the H2-H2O ambient. Catalysts fabricated with Harshaw 1404 alumina will have an extremely short life when hydrazine nitrate is used in the fuel blend. Zirconium oxide and tungsten oxide substrates were also unstable in the H2O containing environment though considerably more stable than the Harshaw 1404 alumina.

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MM Mfl

wmm

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Tabh; 2 3

(C) HIGH TKMl'KKATURK STABILITY OV IIYDKAZINK DKCOMl'OSl TION CATALYSTS

Tt-at Tt'tnperature - 1 l()()0(;

Timt' - 1/2 hour

(las Environment - 2r) vol t N , 25 vo] % II 50 vol 7 NH

Total BET

I Catalyst or Substrate Surface y> rea m^/&m Before [ After

WC 2.3

t

2.1 30% Ru on WC 11.2 1.5 i PTN 73.4 38.4 237o Ru on PTN 77.0 24.7 : MgO from Calcined MgC03 216 9.3 1 MgO from Calcined Mg(0H)2 85.1 0.1 1 30% Ru on MgO from MgCOß 21.0 1.2 i Vitro MgO 60.0 3.2 { 40% Ru on MgO 11.8 2.6 j Vitro Zr02 25 6.2 30% Ru on Vitro Zr02 12 2.0 Vitro WO3 38 5,4

30% Ru on WO3 12.0 <1.0 1 Harshav Sintered AI2O3 (1404) 95 12.6 Harshaw Sintered Al 0 -Si0_

(1602) 145 46

Table 24

(C) HIGH TEMPERATURE STABILITY OF HYDRAZINE DECOMPOSITION CATALYSTS

Test Temperature - 1100oC

Time - 1/2 hour

Gas Environment - 80 vol % H2, 20 vol % H20

Total BET Area m /gm 1

| Catalyst or Substrate Surface Before After j

j WC 3.0 2.7 ] 30% Ru on WC 11.2 .3 23% Ru on PTN 77.0 21.8 Vitro MgO 60.0 7.5

! 30% Ru on Vitro MgO 18.7 6.0 j Vitro W03 30% Ru on WO3

38.0 1.6 | i2 1.9

1 Harshaw Sintered Al?03 (1404) 95 1 .6 Harshaw Sintered Al203-Si02 145 | 45

(1602) 1 1 t

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52 -

PROMOTED RUTHENIUM CATALYSTS ESSÜ 5ÜG SERIES

THE

(C) Considerable evidence is present in the literature to indicate that the incorporation of foreign ions into Y-alumina can substantially improve the thermal stability of this refractory oxide. For example, Krischner, et a1. have found that the Incorporation of alkaline earth ions into Y-alumina markedly enhanced its thermal stability (15). Similar observations have been made in our Company high temperature petroleum processing catalyst studies. On the basis of this information, and the fact that hydrazine decomposition appears to increase with increased substrate basicity, we prepared a number of "doped" substrate catalysts which we called the Esso 500 series. These catalysts have been extensively tested in our 5 lb. thruster and isothermal reactor and characterized in our laboratories. One of them was evaluated by Air Force personnel in 25 lb. and 5 lb. thrust engines. The results of these tests are discussed in the following paragraphs.

8.1. Characterization of the Esso 500 Series Catalysts

(C) The Esso 500 series catalysts have been characterized in our laboratories. Their approximate compositions are as follows*:

Esso 500 - 5% SrO, 5% Si02, 60% AI2O3, 30% Ru 501 - 5% CaO, 5% 8102, 60% AI2O3, 30% Ru 502 - 5% La203, 5% Si02, 60% AI2O3, 30% Ru 503 - 5% BaO, 5% 8102, 60% AI2O3, 30% Ru 504 - 10% BaO, 5% Si02, 55% AI2O3, 30% Ru 505 - 10% CaO, 5% Si02, 55% AI2O3, 30% Ru 506 - 10% La203, 5% 8102, 55% AI2O3, 30% Ru 507 - 10% SrO, 5% 8102, 55% AI2O3, 30% Ru

Data have been obtained on catalyst surface area, substrate surface area, ruthenium crystallite size and catalyst isothermal activity. These data are presented in Table 25.

I

*See Appendix for detailed procedure for preparing the Esso 500 series catalysts.

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UM.

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lüotheriuai cated Crush tallite Size BET Surface Area m^/gtit Activity em* Strength A

1 Catalvst Substrate 1 Clalaivst (STT)/min-cm at 250C Ih«.

bis so 500 ISJ.4 128.0 49'J 40 13 5 tlsso 501 178.0 1U.5 420 41 124 Esso 502 185.Ö 128.5 455 41 124 fclsso 50 J 184. 7 12 3.1 385 36 HI Esso 504 175.8 lib.8 630 41 126 Esso 505 181.8 118.0 420 41 165 iisso 50 o lbb.2 117.0 530 46 145 Esso 50 7 173.4 117.5 420 43 140

Conventional i

Supported Ruthenium

144.6 91.4 350

Catalyst

*Based on 1/8" x 1/8"D Pellets

(U) The properties of the Esso 500 series catalysts, given in Table 25, are seen to be superior to those of the conventional alumina supported ruthenium catalysts. Both substrate and final catalyst surface area are considerably higher than those of the conventional supported ruthenium catalyst. Isothermal hydrazine decomposition activity of the Esso 500 series catalysts is seen to range from 10 to 80% higher than the conventional alumina supported ruthenium catalyst. Additional data on metal crystallite size and on surface areas and activity after motor firing are presented in the following paragraphs.

8.2. Performance of Esso 500 Series Catalysts In Esso's 5 lb. Thruster

(U) Eight different Esso 500 Series catalysts were fabricated in 1/8" x 1/8" pellets and tested in our instrumented static 5 lb. thrust engine. Propellant grade hydrazine was supplied to the engine at 250C using pulse mode propellant injection cycles of 1 second on 5 seconds off. Reactor chamber pressure and degree of catalyst attrition during engine firing were recorded. The results are presented in Table 26.

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Table 26

(C) PERFORMANCE OF ESSO 500 SERIES CATALYSTS IN A 5 LB. THRUST ENGINE^1)

% Change in Catalyst Loss | Catalyst Bed Pressure Drop Wt %/Sec. !

Esso 500 None 0.15 1 Esso 501 None 0.17 1 Esso 502 None 0.13 |

Esso 503 None 0.12 Esso 504 None 0.052 |

| Esso 505 None 0.078 1 Esso 506 None 0.038 \

Esso 507 None 0.083

(1) Ignition program - 1 sec. on-5 sees, off - 40 total pulses.

(C) As can be seen from the data in Table 26, the Esso 500 series catalysts all performed very well in the pulse mode operation of our 5 lb. thruster. All catalysts showed excellent mechanical strength and resistance to attrition during engine firing as indicated by the low level of catalyst lost and bed pressure drop stability. These very encouraging results using the Esso 500 series catalysts prompted us to request that the Air Force evaluate one of them in actual flight type hardware. We believed that such a test was essential before studies in this area were pursued further.

8.3. Air Force Engine Firing Evaluation of Esso 500

(C) About 50 gms of Esso 500 1/8" x 1/8" pellets and 25 gms of Esso 500 20-40 mesh granules were sent to Edwards Air Force Base for motor firing evaluation in a 25 lb. thrust flight type monopropellant engine. The Air Force test results using a bed composed of about 10 vol. % granules, the remainder pills, were extremely encouraging. Esso 500 was found to give ignition delays comparable to Shell 405 with propellant grade hydrazine at 30oF and 100oF. Furthermore, no steady-state performance degradation in engine chamber pressure was observed during 350 sees, of hydrazine fuel burn using 2000 pulses of fuel injection. Low catalyst attrition was observed during this firing program and the catalyst was observed to have very good strength properties.

8.4. High Stability of the Esso 500 Series Catalysts

(C) The promoted substrate and final catalysts for the Esso 500 series have extremely high stability. Catalyst surface area, isothermal activity and pellet crush strength all showed little or no change after four

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mm* - ■KMUBa.

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minutes of firing; the catalyst evaluated by the Air Force, and which received 24 minutes of total tiring, also showec! nu loss in surface area. This data is presented in Table 27 and in Figure 16 which depicts the remarkable surface stability of Ksso 5Ü0 in contrast to Shell Wj. Esso 5ÜÜ is seen to maintain its original "as fabricated" surface area during 24 minutes of total firing time. Shell 4üc>, on the other hand, drastically desurfaces during the first 5 minutes of firing. This unique surface area stability of Esso 500 is a property associated with its unusually stable promoted substrate. It is suggested that surface area stabilization may be affected by the alkaline earth ion retardation of the transformation of yalumina to u-alumina.

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SHELL 405 AFTER FIRING (JPL REPORT 32-1227)

10 15 20

TOTAL RUN TIME - MINUTES

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UNCLASSIFIED 58

BIBLlOtlRAPHV

1. Armstrong, W. L. , Morgan, C. '/.. , and Rylaud, 1.. li., "Ut;Velupm«nt ui Catalyst« lor Munopropellent üecumpuslliun ot Hydrazine" (U), Shell Development Company Report S-li'M/ (Confidential), 19f)4.

2. Marx, P. C, Aerospace Corporatier. Report No. TÜR62162, AL)-28rjÜ8J (Unclassified report), August, 1962.

J. Hang, P. A. and Ward, S. R., Army Ballistic Missile Agency, Test Laboratory Report No. ABMA 8 (Unclassified), August, 1957.

4. Liengme, Ü. V. and I'ompkins, F. C, Bull. Acad. Polon. Sei., Ser. Chim. 14(2) 111-18 (1966) Eng.

5. Grant, A. F., Jr., "Catalysts for the Thermal Decomposition of Hydrazine When Used as a Monopropellent", Publication 15, (February, 1953) and Report 20-27 (December, 1954), Jet Propulsion Laboratory Pasadena, California.

6. Eberstein, I. J. and Classman, I., Air Force Office of Scientific Research, Contract No. AF 18(600)-1527 (Unclassified Report) Report No. TW60-352, AD-235951.

7. Eberstein, I. J. and Classman, I., "Considerations of Hydrazine Decomposition", ARS Preprint 1247-60 (1960).

8. Leiber and Monrite, "The Use of Raney Nickel", Vol. J, Advances in Catalysis, 1953.

9. Voelter, J. and Kuhn, W., Z. Anorg. Allgem. Chem. 340(3-4), 216-24 (1965) (Ger.).

10. Frovlov, V. M., Kinitika i Kataliz 6(1) 149-54 (1965) (Russ.).

11. Keston, A. S., "Analyticcl Study of Catalytic Reactors for Hydrazine Decomposition", Part I: Steady-State Behavior of Hydrazine Reactors. Part II: Transient Behavior of Hydrazine Reactors. Chapters on "Hydrazine Monopropellent Technology Symposium" (U), (Confidential), CPIA Publication No. 160, December, 1967.

12. Rocket Research Corporation Report RRC-66-R-76, January, 1967, "Development of Design and Scaling Criteria for Monopropellent Hydrazine Reactors Employing Shell 405 Spontaneous Catalyst.

13. Drake, J. 0., Jr., "Minimization of Spontaneous Catalyst in a Catalyst Reactor", Chapter in "Hydrazine Monopropellent Technology Symposium" (U), (Confidential), CPIA Publication No. 160, December, 1967.

14. Koros, R. M. and Nowak, E. J., Journal of Catalysis 7, 50-56 (1967).

15. Krischner, H., Torkar, K., and Hornisch, P., Monatschefte für Chemie 99, 220-229 (1968).

UNCLASSIFIED

mm ■BM

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- 59 -

APPENDIX A

(C) CATALYST FIRING DATA - 5 LB. Tl 1RUST ENGINE

Catalyst No. 428-73 (Esso 200)

Description:

Fuel Temp., 0C

Bed Start-up Temp. 0C

Bed Inlet Steady Temp. 0C

Bed Center Steady Temp. 0C

Bed Inlet Steady Pressure, psig

Bed Outlet Steady Pressure, psig

Bed Pressure Drop, psi

Ignition Spike Pressure, psi

Ignition Delay msec*

Wt. % Catalyst Loss and Fines/Cold Start

Pulse Duration, sec.

Remarks

12% Ruthenium on 33% Cobalt Impregnated Preformed 1A04 1/8" Alumina

Run No.

24 24

24

60 70 60 60

158 310 240 235 245 230

158 300 760 915 915 915

0 spike 180 162 150 145

0 spike 115 115 115 122

-- — 65

not recorded

1,000

47 35 23

4,000 7,800 500 400 700

T 2 15 15 15 15

*Ignition Delay time does not include valve response and fuel flow "dead" time which is approximately 60 msecs

in our test system.

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■ A

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60

(C) APPENDIX A

Catalyst No. 428-74 (Ksso 201)

DescrljJtion: 10% Ruthenium un CÜ- Preclpltated Oxide Sintered Cobalt Alumina (75% Cobalt)

Fuel Temp. , "C

Bed Start-up Temp. "C

Bed Inlet Steady Temp. 'C

Bed Center Steady Temp. "C





Ignition Delay msec.



Remarks

Run No. 1 2 3 4

._ 0 c,

5 6 7 8

25 60 65 65 65 116 240 25

375 510 220 850 900 235 240 205

385 635 845 850 860 830 830 830

25 27 120 105 105 95 110 105

20 25 80 100 100 90 95 90

5 2 40 5 5 5 15 15

4,500 1,100 900 1,000

n s

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(C) Al'l'KNDlX A

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Fuel Temp., "C

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Remarks

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- 72 -

(C) APPENDIX A

PERFORMANCE OF ESSO 500 SERIES CATALYSTS IN THE 5 LB. THRUSTEÄ

Data Code

P = Hydrazine Tank Pressure, psig

P., = Upstream Reactor Chamber Pressure, psig

P„ = Downstream Reactor Chamber Pressure, psig

AP = Bed Steady State pressure drop, psi

TCB A) ~ Bed ^-Saition temperature, 0C

T, = Upstream Reactor Chamber Temperature, 0C

T. ■ Downstream Reactor Chamber Temperature, 0C

Spike - Ignition spike pressure - Reactor Chamber pressure, psi

DUR = Hydrazine pulse duration, E, :s.

DT - Ignition Delayt msecs.

^Ignition Delay time does not include valve response and fuel flow dead time which is approximately 60 msecs in our test system.

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- 81 -

(C) APPENDIX B

CATALYST PREPARATION PROCESSES

Plocess for Preparing Esso 101 Hydrazlne Decomposition Catalysts

Basis 100 gms of Einal Catalyst

• Add 443 gms of Co(N03)2-6 H2O and 229 gms of M(N03)-9 1120 to 1000 cm3 of distilled H2O.

a To this solution add 120 gms of. NH^HCO^.

• Allow to stand overnight.

• Heat solution to 150oF.

• Add an additional 175 gms of NH4HCO3.

• Filter solution in a Büchner Funnel.

• Dry filtrate for 18 hours at 120oC.

• Calcine for 4 hours at 750oC in air.

• Press into 1/8" D cylindrical pills.

• Reduce at 950oF for 6 hours in hydrogen.

« Passivate by slow, careful drying in methyl alcohol.

CONFIDENTIAL

■ ■■ ■ 11—1 *—mam^~~ J

CONFIDENTIAL

B2

{O Al'PENÜlX Ü (Cunt 'd)

Process ior Preparing I'.sso ')()() Spontaneous Hydraztne DecomposLtlun Catalysts

Hlgli purity slilca-alumlna is heated to 18()Ü0I'' tor r) hours in air to stabilize the substrate lattice.

A solution of "dopant" salt Is prepared by dissolving 50 gms of an alkaline eartli nitrate salt In 1 liter of delonlzed HO.

The stabilized slilca-alumlna Is saturated with the dopant solution, dried in air at 25Ü0F for 2 hours and calcined at 75Ü0F In air for 5 hours. This procedure Is repeated until the desired dopant level is reached.

A ruthenium trichloride solution is prepared by dissolving 25 gms of RuClß in an isopropyl alcohol-l^O mixture (90 vol. % isopropyl alcohol).

The doped substrate is saturated with the ruthenium trichloride solution, dried at 250oF for 2 hours and calcined at 750oF in air for an hour. This procedure is repeated several times until the desired metal level is reached. 30 wt % Ru in the Esso 500 series.

The calcined catalyst is reduced in flowing hydrogen for 5 hours at 1000oF.

CONFIDENTIAL

r

UNCLASSIFIED

- 83 -

CPIA DISTRIBUTION LIST

SEPTEMBER 1969

Major Recipients

NOTE: This is a general distribution list primarily tor use in whole or in part for In-House Laboratory Technical Documentary Reports. For contractor reports, it is necessary to consult the latest CPIA distribution list (the individual report producer) in order to determine the quantity of reports. The CPIA list will run about 20 copies more for a popular producer. This list can also be used for contractor reports, in cases where the contractor is not listed as a producer on the CPIA distribution list.

NUMBER OF REPORTS - (MAJOR RECIPIENTS) -

All Categories (Basic) - 124

SPECIAL CATEGORIES (Note special categories are not Included in basic list)

1. Propellant Ingredient Synthesis Programs - 11 Total •

2. Solid Propellant and Rocket Motor Programs - 17 Total ■

3. Liquid Propellant and Rocket Engine Programs - 10 Total •

4. Structural Materials for Rocket Motors and Engines 8 Total ■

Changes through NO 84, SEP 1969 Incorporated

135

141

134

132

NOTICE

THIS DISTRIBUTION LIST HAS BEEN VERIFIED FOR SECURITY CLEARANCE UP TO AND INCLUDING CONFIDENTIAL LEVEL ONLY. REFERENCE CPIA MAILING LIST DATED MAY 1967, CPIA PUBLICATION NO. 147.

UNCLASSIFIED

■ ■■- MM

ALL CATEGÜRIES:

UNCLASSIFIED

- 84 -

UlSTKllumON

Bureau of Mines Atta: ERC Library 4800 Forbes Avenue Pittsburgh, Pa 15213

Central Intelligence Agency Attn: CRS/ADD-Standard Dist. Washington. D.C. 20505

Chemical Propulsion infor Agency Applied Phyiscs Lab-JHU 8621 Georgia Avenue Silver Spring, Md. 20910

Defense Documentation Center Attn: TSR Cameron Station, Bldg 5 Alexandria, Virginia 22314

Defense Rsch. & Engr. Pentagon, 3D1065 Attn: Propulsion Technology Washington, D.C. 20301

Institute for Defense Analyses Attn: Classified Library 400 Army-Navy Drive Arlington, Virginia 22202

NASA Lewis Research Center Attn: Librarian 21000 Brookpark Road Cleveland, Ohio 44135

NASA Scientific & Tech Infor Facility

Attn: SAF/DL, ACQ Div P. 0. Box 33 College Park, Md. 20740

NASA Goddard Space Flight Center Attn: Library, Code 252 Greenbelt, Maryland 20771

1 NASA J l.angley Research Center Attn: Librarian Langley Station Hampton, VA 2 3565

1 NASA 1 Manned Spacecraft Center Attn: Library/Code hM6

2 Houston, Texas 77058

NASA 1 Kennedy Space Center Attn: Library-ATS-132C

20 Kennedy Space Center, Fla 32899

NASA 1 Attn: Code RPS, R. W. Ziem Washington, DC 20546

1

Air Force Systems Command 1 Director of Laboratories Attn: SCTSP Andrews AFB, Wash DC 02331

1 AF Office of Scientific Res. 1 Attn: SREP 1400 Wilson Blvd Arlington, VA 22209

1 Air Force Rocket Propulsion Lab Attn: RPC Edwards, Calif 93523

Air Force Rocket Propulsion Lab 2 Attn: RPR

Edwards, Calif 93523

Air Force Rocket Propulsion Lab Attn: RPM Edwards, Calif 93523

UNCLASSIFIED

IMHI

UNCLASSIFIED

ALL CATtXIuRIES: (Continued)

H'>

AFRPL Attn: Technical Library Edwards, California 9 352}

Foreign Technology Dlv Attn: TDBTL Wright-Patterson AFB, Ohio 45433

Army Ballistic Res. Labs Attn: AMXBR-1 Aberdeen Proving Ground, Md. 21ÜÜ5

Army Missile Conunand Redstone Scientific Info Center Attn: Chief, Document Section Redstone Arsenal, Alabama 35809

Army Research Office Attn: CRD-AA-IP Box CM, Duke Station Durham, North Carolina 27706

Frankford Arsenal Attn: (C2300-Library-B51-2 (for Propellant & Expl. Section)

Philadelphia, Pa. 19137

Picatinny Arsenal Scientific & Tech Info. Br. Attn: SMUPA-VA6, Librarian Dover, New Jersey 07801

White Sands Missile Range Attn: Technical Library White Sands MR, New Mexico 88002

Naval Air Systems Cmd. Attn: AIR-6042, Tech Library Washington, DC 20360

Naval Air Systems Cmd AIR-53671 Washington, D.C. 20360

Naval Air Systems Cmd. Attn: AIR-5366 Washington, DC 20360

Naval Air Systems Cmd At til: AIK-33U Washington, DC 20360

Naval Ordnance Sys Cmd Attn: ÜKÜ-Ü331 Washington, DC 20360

Naval Missile Center Attn: Code 56 32.2, Tech

Library Point Mugu, Calif 93041

Naval Ordnance Laboratory Attn: Library White Oak Silver Spring, Maryland 20910

Naval Weapons Center Attn: Code 753-Tech Library China Lake, Calif 93555

Naval Postgraduate School Attn: Library, Tech Rpts

Section-2124 Monerey, California 93940

Naval Ordnance Station Attn: Technical Library Indian Head, Maryland 20640

Naval Research Branch Office Attn: Librarian 1030 East Green Street Pasadena, Calif 91101

Naval Research Attn: Code 429, Power Branch Washington, DC 20360

Naval Ordnance Sys Cmd Attn: ORD-9132

Tech Library Washington, DC 20360

Naval Special Projects Attn: Technical Library Washington, DC 20360

UNCLASSIFIED

«■H A_

UNCLASSIFIED 8b

AU. CATKCÜRIES: (t.'oiil iiuani)

Naval Underwater Woapons Res Eng Sta

Attn: Tech Library (CS12) Newport. R.l. 02840

Aerojet-General Corp Attn: Tech Library P. Ü. Box J9b Azusa, Calif 91702

Aerojet-General Corp. Attn: Librarv 11711 South Woodruff Ave Downey, Calif 90241

Aerojet-General Corp Attn: Tech Library-2432-2015A P.O. Box 15847 Sacramento, Calif 95813

Aerospace Corp Attn: Tech Info Ctr. Doc. Group P.O. Box 95085 Los Angeles, Calif 90045

Aerotherm Corp. Attn: Library 485 Clyde Ave. Mountain View, CA 94040

Allied Chemical Corp Attn: Security Officer P. 0. Box 70 Morristown, New Jersey 07960

ARO, Inc. Attn: Technical Documents Library Arnold AF Station, Tenn 37389

Bell Aerosystems Co. Attn: Technical Library P. 0. Box 1 Buffalo, New York 14240

Boeing Co. Attn: Aerospace Library-8K-38 P.O. Box 3999 Seattle, Washington 9S124

California Inst of Technology Jet Propulsion Laboratory Attn: Library, TDS 4800 Oak Grove Drive Pasadena, California 91103

Dow Chemical Co. j Scientific Projects Lab. Attn: K.S. Karpiuk, Bldg 1710 Midland, Michigan 48641

Dul'ont Co. j Kastern Division Attn: Report Clerk,

A. R. Steward Gibbstown, N.J. 08027

Garrett Corp. j Alresearch Mfg. Div. Attn: Tech Library 2525 W. 190th St. Torrance, CA 90509

Esso Research & Eng. Co. ] Govt. Rsch. Lab. Attn: Defense Security Officer P.O. Box 8 Linden, N.J. 07036

General Dynamics Corp. ] Pomona Division Attn: Div. Library,

Mail Zone 6-20 P.O. Box 2507 Pomona, CA 91766

General Dynamics/Convair 1 Library & Info Services P.O. Box 12009 San Diego, Calif 92112

General Electric Co. 1 Attn: Acquisitions Bldg 4, Room 109 Daytona Beach, Florida 32015

Hercules, Inc. 1 Allegany Ballistics Lab Attn: Tech Library P.O. Box 210 Cumberland, Md 21502

Hercules, Inc. 1 Research Center Attn: Tech Info Center Wilmington, Delaware 19899

UNCLASSIFIED

UNCLASSIFIED

ALL CATEGORIES: (Continued)

8/

III Kesearcli lust itutt- Atta; Document Library 10 West J5th Street Chicago, Illinois bOblb

Lockheed Missiles & Space Co. Attn: Tech Info Ctr. 50-14 3231 Hanover St. I'alto Alto, Calif 94304

Lockheed Propulsion Co. Attn: Library P.O. Box 111 Redlands, Calif 92373

Marquardt Corp Attn: Library P. 0. Box :>013, So. Annex Van Nuys, Calif 91409

Martin Marietta Corp. Attn: Library - Mail No. 6366 Denver Division P. 0. Box 179 Denver, Colorado 80201

McDonnell Douglas Corp. Douglas Missile & Space Sys Div. Attn: Library A2-260 3000 Ocean Park Blvd Santa Monica, Calif 90406

North American Rockwell Rocketdyne Division Attn: Library Dept 086-306 6633 Canoga Avenue Canoga Park, Calif 91304

North American Rockwell Spate it Info Sys Div Attn: Tech Info Ctr -096-722 12214 Lakewoud lUvd Downey, Calif 90241

I'lii Ico-Ford Corp Aeronutronic Ulv Attn: Tech info Svcs-

Acquisitions Ford Road , Newport Beach, Calif 92663

Princeton University Forrestal Campus Library Attn: Librarian P. 0. Box 710 Princeton, N.J. 08540

Rocket Research Corp Attn: Technical Library York Center Willow Road at NE 116th St. Redmond, Washington 98052

Rohm & Haas Co. Redstone Research Labs Attn: Tech Library Huntsville, Alabama 35807

Stanford Research Inst Document Center For Propulsion Sciences 333 Ravenswood Avenue Menlo Park, California 94025

Susquehanna Corp. Atlantic Research Group Attn: Library Shirley Highway at Edsall Rd. Alexandria, VA 22314

Texaco Experiment, Inc. Attn: Librarian P. 0. Box 2407 Richmond, VA 23202

UNCLASSIFIED

■

_—„ ■MMI

r UNCLASSIFIED

ALL CATEGORIES: (Continued)

- 88

Thiokoi Chemical Corp Wasatch Division Attn: Technical Library Brlgham City, Utah 84302

Thiokoi Chemical Corp Elkton Division Attn: Tech Info Center Elkton, Md. 21921

Thiokoi Chemical Corp Huntsville Division Attn: Technical Library Huntsville, Alabama 35807

TRW Systems, Inc. Attn: Technical Info Center One Space Park Redondo Beach, Calif 90278

United Aircraft Corp Attn: Acquisitions Librarian 400 Main Street East Hartford, Conn 06108

United Aircraft Corp Pratt & Whitney Aircraft Uiv Attn: Head Librarian P. O. Box 2691 West Palm Beach, Florida 33402

United Technology Center Attn: Technical Library F. 0. Box 358 Sunnyvale, Calif 94088

University of Denver Denver Research Institute Attn: Security Officer P. 0. Box 10127 Denver, Colorado 80210

SAMSO (SMMAP) Attn: Mercury AF Unit Post Office Los Angeles, CA 90045

UNCLASSIFIED

MMM^MM^M —"i^BM

UNCLASSIFIED - 89 -

PmV VI.LANT 1 Nt; RK1) mrr SYNT 1 IKS IS m)CRAMS (Category 1J

Los Alamos Scientific Laboratory Attn: Report Library P. 0, Box 168J Los Alamos, New Mexico 87544

Hq USAF Attn: AFRDDG, A. Eaffy Wasliington, D.C. 20330

AF Rocket Propulsion Lab Attn: RPCE Edwards California 93523

Ethyl Corporation Attn: Program Mgr P. 0. Box 53091 Baton Rouge, Louisiana 70805

Hercules, Inc. Bacchus Works Attn: Library 100-H-2 P. 0. Box 98 Magna, Utah 84044

Martin-Marietta Corp 1 Res Insl for Adv Studies Attn: Security Officer 14 50 Soutli Rolling Road Baltimore Md. 21227

Midwest Research Institute 1 Attn: Library-Documents 425 Volker Blvd Kansas City, Missouri 64110

Northrop Carolina, Inc. 1 Attn: Library P. 0. Box 3049 Asheville, N.C. 28802

Olin Mathieson Chemical Corp. 1 Main Control Room, Attn: Asst

Librarian 275 Winchester Avenue New Haven, Connecticut 06504

Shell Oil Co. 1 Shell Development Co. Div Attn: Technical Files 1400 53rd Street Emeryville, Calif 94608

SOLID PR0PELLANT AND ROCKET MOTOR PROGRAMS (Category 2)

Foreign Technology Div Attn: TDPMP Wright-Patterson AFB, Ohio 45433

Army Anuno. Procurement & Supply Agency

Attn: RDL, Quality Assurance Tech Library

Joliet, Illinois 60431

Naval Air Systems Command Attn: AIR-53672 Washington, D.C. 20360

Aerospace Corp Attn: Library P. 0. Box 1308 San Bernardino, Calif 92402

McDonnell Douglas Corp 1 Attn: Library P. 0. Box 516 St. Louis, Missouri 63166

North American Rockwell 1 Rocketdyne Division Attn: Library McGregor, Texas 76657

Olin Mathieson Chemical Corp 1 Attn: Research Library P. 0. Drawer G Marion, Illinois 62959

Purdue University 1 School of Mechanical Engineering Attn: B. A. Reese Lafayette, Indiana 47907

I

LIQUID IROPELLANT AND ROCKET ENGINE PROGRAMS (Category 3)

FMC Corporation Chemical R&D Center Attn: Library P.O. Box 8 Princeton, New Jersey 08540

Northrop Corp Norair Division Attn: Technical Information 3901 West Broadway Hawthorne, Calif. 90250

UNCLASSIFIED

CONFIDENTIAL Confidential 9U -

S«curitY CU»«ific«t»on

DOCUMENT CONTROL DATA -R&D (Security clmiMttlcmlton ol Ijll*. body ot mbitrmct and tndtKlng mnnolmlton a'U»l h§ 9nt9nä whmn thm ovmtmtl rmpntl I» clm*»tll*d)

I omaiNATiNS ACTIVITY (Cotporml* »tilhot)

Esso Researcli & Engineering Company Linden, New Jersey

la. nEPonT KcuniTT CLARIFICATION

Confidential ab. GNOUP

I mtfonr TITLI

Development of a Low Cost Catalyst for Hydrazim' (U)

I f TVp« ol tepott and Incluaiv« d«f*«>

Final Report, January 15, 1968 I AuTHOnil) (WraliiMM, mIMtm Initial, f»tnmm»)

Martin Lieberman William F. Taylor

November 15, 1969

«- RC»0*T OATI

January, 1970 M. CONTRACT OR ORANT NO.

Contract No. FO4611-68-C-004A ». PROJECT NO.

Ta. TOTAL NO. OF PASIt 91

76. NO. OP RIPt

15 •a. ORISINATOR'* REPORT NUkfVERI*!

GR-7-DCH-70

M. OTHER REPORT NOII) (Any eAar niaikan Aal mmy b* aatlanad Ml« nporl)

AFRPL-TR-70-7 10. OKTRIBUTION STATEMENT

In addition to security requirements which must be met, this document is subject to special export controls and each transmittal to foreign governments or foreign nationals may be made only with prior approval of AFRPL (RPPR/STINFO) , Edwards, Cal.

II. tUPPLEMENTARV NOTES

I*. AXTRACT

12. SPONtORIN« MILITARY ACTIVITY

Air Force Rocket Propulsion Laboratory Edwards Air Force Base, California

(C) A low cost, active, highly stable hydrazine monopropellant decomposition catalyst has been developed. This catalyst labeled Esso 500, utilizes ruthenium for its active component and thus does not contain any costly and strategically limited iridium metal. Laboratory and 5 pound thruster studies conducted at Esso Research and Engineering Company and 5 and 25 pound thruster studies conducted at the Air Force Rocket Propulsion Laboratory Indicate that Esso 500 is highly active at low ignition temperatures and shows unusually high resistance to loss of surface area during motor firing. Data obtained at both laboratories actually indicated that Esso 500 showed no loss of surface area after up to 24 minutes of pulse mode firing with hydrazine.

(U) A cobalt containing catalyst called Esso 101 was also developed. This catalyst has much lower activity than Esso 500 for hydrazine decomposition at 50C. Esso 101, however, is active at higher temperatures and can be employed where short ignition delays at low temperature is not required and where extremely low cost is a desired property.

(U) Results of studies with various cobalt containing catalysts, cobalt-noble metal hybrid catalysts and ruthenium containing catalysts using several different substrate materials are also reported.

DD f «•« •• 14 7a oMOL«Tt po« PONM UTI, I JAM «4, «miCM I*

ARMY uta. Confidential

CONFIDENTIAL Security Ciaaalllcation

Mta ■ MHMMMB.

I'nc lass i 1 li'd "—~ Sacurily Claidrtcsllon

UNCLASSIFIED 91

HIT mono» not. ■ | ■ '

I. Hydrazltw

1. Mouoproiu'llanl

i. Catalyst

.',. AnuiK'iiia Deoompusit ion

5, Hydrazine Decumpositlon

b. Refractory Oxides

7. riiermally Stable Supports

8. Doped substrate

■A

ivr m UNCLASSIFIED

Unclassified Security OiMtflcaUoa