Jennifer Lindsey Suder Klettlinger

Glenn Research Center, Cleveland, Ohio

Fischer-Tropsch Cobalt Catalyst Improvements

With the Presence of TiO2, La2O3, and ZrO2 on

an Alumina Support

NASA/TM—2012-216020

October 2012
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Jennifer Lindsey Suder Klettlinger

Glenn Research Center, Cleveland, Ohio

Fischer-Tropsch Cobalt Catalyst Improvements

With the Presence of TiO2, La2O3, and ZrO2 on

an Alumina Support

NASA/TM—2012-216020

October 2012

National Aeronautics and

Space Administration

Glenn Research Center

Cleveland, Ohio 44135
Acknowledgments

I would like to express my gratitude to my advisor Dr. Steven S. C. Chuang for his guidance and support during my thesis research.

I would also like to thank Dr. Bi-min Zhang Newby and Dr. George Chase who were my committee members. I appreciate the

Center for Applied Energy Research at The University of Kentucky, namely Dr. Burt Davis and Dr. Gary Jacobs for their guidance

and continued support in catalyst characterization. I would also like to express my appreciation to my colleagues at NASA Glenn

Research Center: Chia (Judy) Yen, Angela Surgenor, Leah Nakley, Rachel Rich, Ana De La Ree, Lauren Best, and Al Hepp for

their understanding and patience during my completion of this work. I am appreciative of the support from my supervisor, Dr. ChiMing Lee and the funding received from NASA Glenn Research Center for completion of my thesis and graduate coursework. I am

deeply grateful to my husband for his ongoing love and encouragement, as well as my parents for their dedication, encouragement,

and many years of support throughout my life. The work in this thesis would not have been possible without those mentioned in

the above acknowledgment.

Available from

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7115 Standard Drive

Hanover, MD 21076–1320

National Technical Information Service

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Available electronically at http://www.sti.nasa.gov

Trade names and trademarks are used in this report for identi¿ cation

only. Their usage does not constitute an of¿ cial endorsement,

either expressed or implied, by the National Aeronautics and

Space Administration.

This work was sponsored by the Fundamental Aeronautics Program

at the NASA Glenn Research Center.

Level of Review: This material has been technically reviewed by technical management.

Supplementary Notes

This report was submitted as a thesis in partial ful¿ llment of the requirements for the degree of Master of Science to the

graduate faculty of the University of Akron, Akron, Ohio, May 2012.
ABSTRACT

The objective of this study was to evaluate the effect of titanium oxide,

lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The

hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium

oxide would reduce the interaction between cobalt and the alumina support. This

was of interest because an optimized weakened interaction could lead to the most

advantageous cobalt dispersion, particle size, and reducibility. The presence of

these oxides on the support were investigated using a wide range of

characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction

(XRD), temperature programmed reduction (TPR), temperature programmed

reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse

reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated

the reduction of cobalt oxide species in reference to pure alumina supported cobalt

catalysts, however further investigation is needed to determine the effect of ZrO2 on

the reduction profile. Results showed an increased corrected cluster size for all

three doped supported catalysts in comparison to their reference catalysts. The

increase in reduction and an increase in the cluster size led to the conclusion that

the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also

likely that the interaction decreased upon presence of ZrO2 on the alumina, but

Fischer-Tropsch Cobalt Catalyst Improvements With the Presence

of TiO2, La2O3, and ZrO2 on an Alumina Support

Jennifer Lindsey Suder Klettlinger

National Aeronautics and Space Administration

Glenn Research Center

Cleveland, Ohio 44135

NASA/TM—2012-216020 iii
further research is necessary. Preliminary results have indicated that the aluminasupported catalysts with titanium oxide and lanthanum oxide present are of interest

because of the weakened cobalt support interaction. These catalysts showed an

increased extent of reduction, therefore more metallic cobalt is present on the

support. However, whether or not there is more cobalt available to participate in

the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the

cluster size. On one hand, increasing cluster size alone tends to decrease the active

site density; on the other hand, by increasing the size of the cobalt clusters, there is

less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during

Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the

extent of reduction while increasing the particle size slightly may be beneficial for

maintaining the sites, even if there is a slight decrease in overall initial active site

density.

NASA/TM—2012-216020 iv
TABLE OF CONTENTS

LIST OF TABLES .....................................................................................................................................

LIST OF FIGURES ....................................................................................................................................

CHAPTER

I. INTRODUCTION .................................................................................................................................. 1

1.1 Fischer Tropsch Synthesis................................................................................. 1

1.2 Fischer-Tropsch Cobalt Catalysts ................................................................... 1

1.3 Objectives and Hypothesis ................................................................................ 2

1.4 Outline ....................................................................................................................... 3

II. BACKGROUND OF THE STUDY .................................................................................................... 4

2.1 Principles of Cobalt Fischer-Tropsch Catalysis ......................................... 4

2.2 Fischer-Tropsch Cobalt Catalyst Oxide Support Interaction Effect .. 5

2.3 Cobalt Metal Loading and Size ......................................................................... 6

2.4 Promoter Metals .................................................................................................... 7

2.5 Preparation Method.............................................................................................8

2.6 Pore Size...................................................................................................................9

2.7 Mixed Oxide Supports ......................................................................................... 9

2.7.1 Titanium oxide (TiO2) ............................................................................. 9

2.7.2 Lanthanum Oxide (La2O3) .................................................................. 11

2.7.3 Zirconium Oxide (ZrO2) ....................................................................... 13

NASA/TM—2012-216020 v

viii

ix
2.8 Brunauer Emmet Teller (BET) Surface Area Measurements ........... 14

2.9 Temperature Programmed Reduction and Temperature

Programmed Reduction After Reduction ................................................. 17

2.10 Hydrogen Chemisorption and Pulse Reoxidation ................................. 18

2.11 X-ray Diffraction ................................................................................................. 23

III. EXPERIMENTAL PROCEDURES .............................................................................................. 24

3.1 Catalyst Preparation ......................................................................................... 24

3.2 Catalyst Characterization................................................................................ 29

3.2.1 Scanning Electron Microscopy and Electron Dispersed

Spectroscopy ....................................................................................................... 29

3.2.2 Brunauer Emmet Teller (BET) Surface Area Measurements and

Barrett Joyner Halenda (BJH) Pore Size Distributions ........................ 30

3.2.3 Temperature Programmed Reduction (TPR) ......................................... 30

3.2.4 Temperature Programmed Reduction After Reduction ..................... 31

3.2.5 Hydrogen Chemisorption with Pulse Reoxidation ............................... 31

3.2.6 X-ray Diffraction ................................................................................................. 32

IV. CATALYST CHARACTERIZATION RESULTS ...................................................................... 34

4.1 Scanning Electron Microscopy and Electron Dispersed

Spectroscopy ....................................................................................................... 34

4.2 Brunauer Emmet Teller (BET)4 and Barrett Joyner Halenda (BJH)33

Measurements..................................................................................................... 45

4.3 Temperature Programmed Reduction ...................................................... 50

NASA/TM—2012-216020 vi
4.4 Temperature Programmed Reduction After Reduction (TPR-AR) 55

4.5 Hydrogen Chemisorption ............................................................................... 57

4.6 X-Ray Diffraction (XRD) .................................................................................. 65

4.7 Discussion ............................................................................................................. 70

4.8 Conclusions .......................................................................................................... 74

BIBLIOGRAPHY ..................................................................................................................................... 77

APPENDIX A. Pore Size Distribution Profiles ............................................................................ 80

NASA/TM—2012-216020 vii
LIST OF TABLES

Table Page

2.1 BET Data from Literature ........................................................................................................ 16

2.2 Hydrogen Chemisorption Data from Literature ............................................................. 20

2.3 XRD Data from Literature ........................................................................................................ 23

3.1 Catalyst support composition................................................................................................ 25

4.1 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

quantitative results for 9.7%TiO2-Al2O3 ............................................................................ 38

4.2 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

quantitative results for 3.0%La2O3-Al2O3.......................................................................... 41

4.3 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

quantitative results for 3.1%ZrO2-Al2O3. ........................................................................... 44

4.4 BET surface area measurements and BJH pore volume and pore radius

measurements.............................................................................................................................. 49

4.5 Hydrogen chemisorption / pulse reoxidation results following 10 hour

hydrogen reduction at 350oC. ................................................................................................ 64

4.6 X-ray Diffraction results from XRD plots and Scherrer Equation ............................ 70

NASA/TM—2012-216020 viii
LIST OF FIGURES

Figure Page

3.1 Calcination reactor drawing .............................................................................................. 27

4.1 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 9.7%TiO2-Al2O3 where Al2O3 is pink (left) and TiO2 is

green (right). ........................................................................................................................... 35

4.2 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results overlayed on scanning electron microscopy image for

9.7%TiO2-Al2O3where Al2O3 is pink (left) and TiO2 is green (right). ............... 36

4.3 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 9.7%TiO2-Al2O3 overlaid on scanning electron

microscopy image. Alumina is highlighted in pink and titania is highlighted

in green. ..................................................................................................................................... 37

4.4 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

quantitative results for 9.7%TiO2-Al2O3 support. .................................................... 38

4.5 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 3.0%La2O3-Al2O3where Al2O3 is pink (left) and La2O3 is

green (right).. .......................................................................................................................... 39

4.6 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results overlaid on scanning electron microscopy image for

3.0%La2O3-Al2O3 where Al2O3 is pink (left) and La2O3 is green (right). .......... 40

4.7 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 3.0%La2O3-Al2O3 overlaid on scanning electron

microscopy image (Al203 in pink and La2O3 in green). ........................................... 40

4.8 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

Quantitative Results for 3.0%La2O3-Al2O3. .................................................................. 41

4.9 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 3.1%ZrO2-Al2O3where Al2O3 is pink (left) and ZrO2 is

green (right). ........................................................................................................................... 42

NASA/TM—2012-216020 ix
4.10 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results overlaid on scanning electron microscopy image for

3.1%ZrO2-Al2O3where Al2O3 is pink (left) and ZrO2 is green (right). ............... 42

4.11 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

mapping results for 3.1%ZrO2-Al2O3 overlaid on scanning electron

microscopy image where Al2O3 is pink (left) and ZrO2 is green (right)........... 43

4.12 Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

Quantitative Results for 3.1%ZrO2-Al2O3 ..................................................................... 44

4.13 Expected BET surface areas of (a) 15%Co/9.7%TiO2-Al2O3, (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3 ......................................... 46

4.14 BET surface area comparison of (a) 15%Co/9.7%TiO2-Al2O3 , (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3

HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3 SBA200. ............ 47

4.15 Barrett Joyner Halenda (BJH) average pore radius adsorption data for (a)

15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c)

15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3

SBA150, and (f) 15%Co/Al2O3 SBA200. ....................................................................... 48

4.16 Barrett Joyner Halenda (BJH) average pore volume desorption data for (a)

15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c)

15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3

SBA150, and (f) 15%Co/Al2O3 SBA200. ....................................................................... 48

4.17 H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3; (b)

15%Co/3.0%La2O3-Al2O3; and (c) 15%Co/3.1%ZrO2-Al2O3. ............................... 51

4.18 H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3, (b)

15%Co/Al2O3 SBA 150, and (c) 15%Co/Al2O3 HF14/150 .................................... 52

4.19 H-TPR profiles of, moving upward, (a) 15%Co/Al2O3 SBA 150, (b)

15%Co/3.0%La2O3-Al2O3, and (c) 15%Co/Al2O3 SBA 200.................................... 53

4.20 H-TPR profiles of, moving upward, (a) 15%Co/Al2O3 SBA 150; (b)

15%Co/3.1%ZrO2-Al2O3 and (c) 15%Co/Al2O3 SBA 200. ..................................... 54

4.21 H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3 , (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3

HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3 SBA200. ............ 54

NASA/TM—2012-216020 x
4.22 H-TPR (solid) and (dashed) H-TPR-AR profiles of, moving upward, (a)

15%Co/9.7%TiO2-Al2O3; (b) 15%Co/3.0%La2O3-Al2O3; and (c)

15%Co/3.1%ZrO2-Al2O3. Reduction was carried out in hydrogen for 10

hours at 350oC. ....................................................................................................................... 55

4.23 H-TPR (solid) and (dashed) H-TPR-AR profiles of, moving upward, (a)

15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c)

15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3

SBA150, and (f) 15%Co/Al2O3 SBA200. ....................................................................... 56

4.24 Temperature programmed desorption data for comparison of all catalysts

with their corresponding reference catalysts. ........................................................... 59

4.25 Extent of reduction results from pulse reoxidation testing for each catalyst in

comparison to its corresponding reference catalyst. .............................................. 60

4.26 Pulse reoxidation cluster size data, which is corrected for extent of reduction

for each catalyst in comparison to it’s reference catalysts. ................................... 61

4.27 Corrected dispersion data for each catalyst in comparison to its reference

catalysts ..................................................................................................................................... 62

4.28 X-ray diffraction profile of 15%Co/9.7%TiO2-Al2O3 (a) and 9.7%TiO2-Al2O3

(b). ............................................................................................................................................... 65

4.29 X-ray diffraction profiles of 15%Co/3.0%La2O3-Al2O3 (a) and 3.0%La2O3-Al2O3

(b). ............................................................................................................................................... 66

4.30 X-ray diffraction patterns of calcined samples 15%Co/3.1%ZrO2-Al2O3 (a)

and 3.1%ZrO2-Al2O3 (b). ..................................................................................................... 67

4.31 X-ray diffraction patterns of calcined samples 15%Co/Al2O3 HP14/150 (a)

and Al2O3 HP14/150 (b). .................................................................................................... 68

4.32 X-ray diffraction patterns of calcined samples 15%Co/Al2O3 SBA150 (a) and

Al2O3 SBA150 (b). .................................................................................................................. 68

4.33 X-ray diffraction patterns of calcined samples 15%Co/Al2O3 SBA200(a) and

Al2O3 SBA200(b). .................................................................................................................. 69

4.34 Adsorption pore size distribution of (left) 9.7%TiO2-Al2O3 and (right)

15%Co/9.7%TiO2-Al2O3. .................................................................................................... 80

4.35 Desorption pore size distributions of 9.7%TiO2-Al2O3(left) and

15%Co/9.7%TiO2-Al2O3(right) ........................................................................................ 80

NASA/TM—2012-216020 xi
4.36 Adsorption pore size distribution of 3.0%La2O3-Al2O3 (left) and

15%Co/3.0%La2O3-Al2O3 (right) .................................................................................... 80

4.37 Desorption pore size distribution of 3.0%La2O3-Al2O3 (left) and

15%Co/3.0%La2O3-Al2O3 (right) ..................................................................................... 81

4.38 Adsorption pore size distribution of 3.1%ZrO2-Al2O3 (left) and

15%Co/3.1%ZrO2-Al2O3 (right) ...................................................................................... 81

4.39 Desorption pore size distributions of 3.1%ZrO2-Al2O3(left) and

15%Co/3.1%ZrO2-Al2O3 (right). ..................................................................................... 81

4.40 Adsorption pore size distribution of Al2O3 HP14/150 (a)& (b) and

15%Co/Al2O3 HP14/150 (c) & (d). ................................................................................ 82

4.41 Desorption pore size distribution of Al2O3 HP14/150 (a)& (b) and

15%Co/Al2O3 HP14/150 (c) & (d). ................................................................................ 83

4.42 Adsorption pore size distributions of (a) & (b): SBA 150 Al2O3 and (c) & (d):

15%Co/SBA 150 Al2O3. ....................................................................................................... 84

4.43 Desorption pore size distributions of (a) & (b): SBA 150 Al2O3 and (c) & (d):

15%Co/SBA 150 Al2O3. ....................................................................................................... 85

4.44 Adsorption pore size distributions of (a) & (b): Al2O3.SBA 200 and (c) & (d):

15%Co/Al2O3.SBA 200 ........................................................................................................ 86

4.45 Desorption pore size distributions of (a) & (b): Al2O3.SBA 200 and (c) & (d):

15%Co/Al2O3.SBA 200 ........................................................................................................ 87

NASA/TM—2012-216020 xii
CHAPTER I

INTRODUCTION

CHAPTER 1

1.1 Fischer Tropsch Synthesis

The Fischer-Tropsch process has three distinct steps: gasification, synthesis,

and product upgrade. The gasification step produces syngas (hydrogen and carbon

monoxide) from many carbon resources. The synthesis involves the conversion of

syngas to syn-crude. Product upgrade processes the syn-crude and separates it into

useable liquid fuels. The synthesis step can be optimized to increase yields and

reduce energy inputs into the overall process.

1.2 Fischer-Tropsch Cobalt Catalysts

Cobalt-based Fischer-Tropsch catalysts are typically cobalt oxides on various

ceramic supports (e.g., alumina, silica, titanium oxide, etc). The support adds

mechanical stability, as well as an increased surface area for dispersion of the active

metal, cobalt. Support modification can change the interaction of the cobalt with the

support in order to increase activity and selectivity to the desired product. The

supported cobalt catalyst requires a reduction treatment to convert cobalt oxides to

metallic cobalt which catalyzes F-T synthesis reactions. This reduction step

NASA/TM—2012-216020 1
becomes a very important step in the process and the development of the cobalt

based catalysts and potentially their modified supports.

1.3 Objectives and Hypothesis

The objective of the presented work is to evaluate the effect of a few

structural promoters in the form of oxides on alumina supported cobalt catalysts.

Of these structural promoters, the modification of alumina with titanium,

lanthanum, and zirconium were the focus. The presence of these oxides on the

support was investigated using a wide range of characterization techniques such as

SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed

reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and

hydrogen chemisorptions/pulse reoxidation. These characterization techniques

were used as a screening mechanism for the variety of cobalt/mixed oxide catalysts.

Since the physical properties of these mixed oxide supports were inherently

different, three different baseline alumina supported catalysts were used as

reference catalysts. The presence of these structural promoters in the form of

oxides could modify the alumina support properties and weaken the interaction of

cobalt with alumina. An optimized weakened interaction could lead to the most

advantageous cobalt dispersion, particle size, and reducibility. This optimization

could maintain the high number of active sites, while minimizing cobalt aluminate

formation. The hypothesis is that the presence of titanium oxide, lanthanum oxide,

NASA/TM—2012-216020 2
and zirconium oxide will reduce the interaction between cobalt and the alumina

support.

1.4 Outline

Chapter II will provide an extensive literature survey and provide

background information on the topic of interest. Previous research is presented in

the area of titanium, lanthanum, and zirconium as both a structural and reduction

promoter on alumina and similar ceramic supports. Chapter III provides the

experimental procedures used in making the catalysts and the characterization of

the catalysts in this research. Chapter IV provides all characterization results on the

three improved catalysts, as well as the three reference catalysts, as well as

discussion and conclusions.

NASA/TM—2012-216020 3
CHAPTER II

BACKGROUND OF THE STUDY

CHAPTER 2

2.1 Principles of Cobalt Fischer-Tropsch Catalysis

Fischer-Tropsch (F-T) synthesis takes gaseous hydrogen and carbon

monoxide and converts it into various hydrocarbon chain length product

distributions. It is considered a network of parallel and consecutive reactions which

take place on the surface and in the pores of catalysts5. Cobalt based catalysts have

good activity and selectivity6 and are known to produce high molecular weight

paraffinic waxes that can be hydrocracked to produce lubricants and diesel fuels,

which make them of high interest in F-T synthesis. The use of supported cobalt

catalysts in F-T synthesis has led to complex development of catalyst design.

Changes in support, support modifications/promotion, cobalt loading and additional

promoter metals have been shown to change the performance of these catalysts

drastically.

NASA/TM—2012-216020 4
2.2 Fischer-Tropsch Cobalt Catalyst Oxide Support Interaction Effect

In order to increase the cobalt active sites, the cobalt metal is dispersed as

clusters on high surface area supports, typically oxides or mixed oxides. The oxides

are of particular interest because they are a highly porous structure, which is

theoretically inert in the F-T reaction. The physical properties of the supports help

increase surface area and distribute the cobalt metal clusters over the surface of the

support. The dispersion of active metal on the catalyst support is dependent on the

interaction of the support with the active metal, in this case cobalt. If the support

has a strong interaction with cobalt, it is likely that the cobalt will be highly

dispersed in small clusters on the surface of the oxide support. The support type

and physical properties determine the number of active sites after reduction, and

also influence the percentage of cobalt oxide species that can be reduced7.

Many different oxides can be used as the support for cobalt catalysts in

Fischer-Tropsch synthesis. A few of the most common supports are SiO2, TiO2, and

Al2O3; each of which has its own advantages and disadvantages. Al2O3 has a strong

interaction with cobalt, TiO2 has a moderate interaction with cobalt, and SiO2 has a

weak interaction with cobalt8. Khodakov et al. show that the second reduction step

(CoO to Coo) is strongly influenced by the cobalt particle size, such that smaller and

more interacting particles (6nm) are more difficult to reduce than larger cluster

sizes (20-70nm) in studying SiO2 as the support9. These interactions play an

important role in the activity of the catalysts because of the tendency to form cobaltoxide complexes such as cobalt aluminate, cobalt silicate, or cobalt titanate. For

example, TiO2 has a strong metal-support interaction with cobalt, which makes TiO2

NASA/TM—2012-216020 5
catalysts difficult to reduce3. This has been attributed to the strong cobalt-oxide

interaction with the support and shifts the reduction temperature to much higher

than preferred3. The properties of the support have been shown to play a role in the

F-T kinetics8 and have been linked to the catalytic performance. It is in the best

interest of researchers to determine a means to reduce the use of promoters and

expensive metals, while at the same time increasing the performance of these cobalt

catalysts3.

Alumina tends to be favorable due to the mechanical properties10,

particularly in applications such as continuously stirred tank reactors11 where

agitation is present. Previous research has shown that alumina supported cobalt

does not completely reduce from cobalt oxide to cobalt metal because of the high

cobalt metal-support interactions7. This high interaction of alumina with cobalt11

results in the tendency to form cobalt aluminate species, which is likely inactive

cobalt. With cobalt aluminate formation, usually cobalt loadings need to be higher

than 20% in order to achieve desired activity.

2.3 Cobalt Metal Loading and Size

Increasing the cobalt loading on alumina has been shown to decrease the

reduction temperature in both unpromoted and promoted catalysts. The cobalt

cluster size has been linked to the interaction of cobalt with the support8, where

having a very strong interaction of cobalt with the support results in small cluster

sizes and a very dispersed active metal on the surface of the catalyst.

NASA/TM—2012-216020 6
Wang and Chen 12 showed that when low loadings of cobalt are used, cobalt

aluminate is favored. Cobalt aluminate can only be reduced at high reduction

temperatures, which aren’t feasible because of cobalt agglomeration. Their research

also indicated that higher loadings of cobalt resulted with Co3O4 crystallites that

were easier to reduce, showing a single broadened TPR peak12. It has also been

shown that the cluster size and the support effect play a role in the F-T kinetics8 and

that the kinetic reaction orders vary based on the size of the metal crystallites13.

2.4 Promoter Metals

One key concern with handling cobalt based catalysts is that the active form

of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air.

Therefore, cobalt catalysts require a reduction step before F-T synthesis can occur.

Since some cobalt-support interactions are high, it becomes difficult to fully reduce

the available cobalt metal on the surface of the support. Noble metals, such as Ru,

Pt, and Re are commonly added as reduction promoters in order to produce more

cobalt metal surface sites by facilitating reduction of cobalt species that interact

with the support14. In most cases, the application of a promoter is used in order to

enhance the reduction of cobalt oxide (CoO) to cobalt metal (Coo). The addition of

the platinum to the surface of a Co/Al2O3 catalyst has been proven to decrease the

reduction temperature of the catalysts, most likely due to hydrogen spillover from

the metallic promoter7. It has been found that the addition of Pt promoter to the

NASA/TM—2012-216020 7
cobalt catalyst not only enhances the reducibility of the clusters, it also causes a

small decrease in cobalt cluster size7.

2.5 Preparation Method

In cobalt catalyst synthesis, there are many different ways to load the cobalt

onto the ceramic support. Some of the common methods are: impregnation, coprecipitation, sol-gel, chemical vapor deposition, and plasma15. Of these ways,

impregnation is one of the most popular, having two common impregnation

methods: incipient wetness impregnation (IWI) and slurry phase impregnation.

Previous research has shown that incipient wetness impregnation procedures have

been found to produce a wider range of cluster sizes than the slurry phase

impregnation procedure7. It is widely accepted that TiO2 as a support leads to a

stronger cobalt- support interaction than SiO2

16, but it was found that the addition of

TiO2 to SiO2 only improved catalyst performance when applying 3 out of 4

preparation techniques16. Improvements were found in precipitation,

impregnation, and hydrolysis-reflux, although not in sol-gel methods16. It has been

shown in other instances that preparation procedure can change the outcome of the

results, which should be considered in the evaluation of the structural promoter

discussion in this work.

NASA/TM—2012-216020 8
2.6 Pore Size

The pore size of the ceramic support is important because it allows for the

diffusion of reagents and products inside the catalyst channels and pores. This

means that the pore size could limit the reaction, or possibly favor one reaction over

another in F-T synthesis. Khodakov et. al 15 express that support pore size could

affect the diffusion and capillary condensation of products in these pores and that

narrow pores are more likely to be filled with liquid products than the wider pores

in the catalyst. Liu et all found that the pore size of SiO2 supports greatly influence

the activity of the catalyst in a 0.5L CSTR17. Their research showed an optimum

average pore size of 10nm in order to increase the activity17.

2.7 Mixed Oxide Supports

Much research has been done in the area of mixed oxide supports. The focus

has been on SiO2 and TiO2 supports, however some research has been done on

Al2O3.

2.7.1 Titanium oxide (TiO2)

Titanium oxide has been used as a ceramic support alone in F-T catalysis. It

has a high interaction with cobalt, although not as high as alumina. In one study, the

addition of TiO2 to SiO2 catalyst supports had drastically affected the structure and

catalytic performance of the cobalt F-T catalysts16, likely by modification of the

interaction between cobalt and silica. Preliminary results indicate that

NASA/TM—2012-216020 9
impregnation method resulted in the highest activity and selectivity for C5+16. The

preparation procedures had drastic affected the reduction profiles of these catalyst,

through addition of a third (small) peak, which the authors attributed to an

interaction compound16. This indicates that TiO2 promoted catalysts were more

difficult to reduce16, which is expected since TiO2 has a stronger interaction with

cobalt. The cobalt particle size decreased upon addition of TiO2

16, which was

expected since smaller particles are also considered to interact more strongly with

the support and be more difficult to reduce. The XRD profile showed slightly

broader peaks for Co3O4 crystallites on the TiO2 promoted catalysts16 and using the

Scherrer equation, the silica only supported catalyst was found to have the largest

Co3O4 crystallite sizes16. These results confirm that the stronger interaction

between titania and cobalt produce higher dispersed catalysts with smaller cobalt

particles and that the addition of TiO2 to silica support can provide an added benefit

to the catalyst surface composition.

Wan et al. found a clear change in morphology from pure Al2O3 by the

addition of TiO2 to the surface by the sol-gel method, where with increasing TiO2

weight percent, XRD profiles indicate an increase in peak intensity in anatase18,

which signifies an increase in TiO2 cluster size. It is important that the oxide dopant

is well dispersed for a uniform structure and more predictable catalytic activity.

NASA/TM—2012-216020 10
2.7.2 Lanthanum Oxide (La2O3)

Lanthanum has also been known to increase activity in Fischer-Tropsch

synthesis. A study by Vada et al. concludes that La3+ increased the overall activity

and chain-growth probability when a low loading of La3+ (La/Co=0.05) was present

on a Co/Al2O3 catalyst, however methane production increased as well19. The

authors of this study also found that the catalyst activity decreased with higher

loadings of La (La/Co )

19. Since methane is not a desirable product in F-T

synthesis, these results indicate that there is likely a positive and negative effect of

lanthanum as a structural promoter on F-T cobalt alumina supports, which may be

dependent on the amount of cobalt loaded on the support. There is significant need

to determine the optimal loading of lanthanum on alumina, as well as the

preparation procedure. Further investigation is necessary in order to determine the

physical and kinetic influence of lanthanum as an oxide support modification.

The preparation procedure for loading lanthanum on alumina was studied by

Ledford et al. and found that there was only a significant change in reducibility and

cobalt metal dispersion when La3+ was impregnated before cobalt loading20. The

authors also determined that higher La3+ loadings (La/Al>0.026) resulted in

formation of a La-Co mixed oxide and enhanced the dispersion of cobalt on the LaAl2O3

20. The increase in dispersion showed little correlation to the reducibility in

this study and the effect of increased dispersion on reducibility should be further

explored.

NASA/TM—2012-216020 11
Cai et al. also compared preparation procedures by preparing La2O3-doped

alumina catalysts through impregnation and co-precipitation and found that the coprecipitation method reduced more readily and resulted in higher F-T synthesis

activity and lower methane selectivity21. DRIFTS studies indicated that CO adsorbed

most easily on the co-precipitated support catalyst than on the SASOL commercial

support21.

Zhang et al. promoted titania with lanthanum nitrate at varying atomic ratios

of La/Ti, calcined the support to drive off the nitrate and proceeded to load 12%

cobalt to the La promoted Ti22. They found that as the La content increased, the

cluster size of Co3O4 decreased, while the percent reduction increased22. This was

not to be expected because typically, larger clusters reduce easier. It appears that as

the La loading increases, the reduction peak narrows and shifts to a lower

temperature. It is also interesting to note that the nitrate peak shifted to a higher

temperature and the area increased as the La loading increased, which was

explained as a possible stabilization of nitrate during the calcination process22. The

authors found that La inhibits nitrate degradation during calcination and may

require higher temperature calcination if used as a structural promoter. The study

completed x-ray diffraction spectroscopy and found little indication of change in

crystal size in varying La promotion levels22. In comparison of non-promoted

catalysts to La promoted catalysts, there is no indication of lanthanum crystallites in

the XRD profile22. This suggests that the lanthanum is in highly dispersed form22

and that it had little effect on the cobalt crystallite size. Using the Sherrer’s

equation, the crystalline size of Co3O4 was calculated and it indicated that the

NASA/TM—2012-216020 12
average particle size decreased with increasing lanthanum content, which results in

a much higher dispersion22. The introduction of lanthanum on a titania supported

cobalt catalyst could have a positive effect on the dispersion, which has been linked

to the activity of the catalyst.

2.7.3 Zirconium Oxide (ZrO2)

A significant amount of research has been done in the addition of ZrO2 to SiO2

and TiO2, with little on the modification of Al2O3. The effect of zirconium

modification to all supports seems to be controversial; however there is also

differences in the preparation of these catalysts among authors. As previously

discussed, it is difficult to separate the effect of preparation procedures, cobalt metal

loading, and calcination temperatures to the zirconium loading effect.

Some research has shown higher activity and C5+ selectivity23 in FischerTropsch synthesis. Ali et al. 24suggested that the promotion of zirconium on silica

created an active interface with Co, which facilitates CO dissociation and thus

increasing the activity. Rohr et al. 25 concluded that the modification of ZrO2 on

Co/Al2O3 increased the activity and selectivity to heavier hydrocarbons, which was

attributed to changes in surface coverage of reactive intermediates.

Some research has shown a weaker cobalt-zirconium interaction on Co/SiO2

catalysts, which led to an increase in reducibility26. Other research indicates that

there is no decrease in reduction for the addition of zirconia to Co/SiO2 catalysts27.

Moradi et al. 23 also found that the addition of zirconia to silica favors reduction at a

NASA/TM—2012-216020 13
lower temperature concluding that the cobalt-silica interaction is replaced by the

cobalt-zirconia interaction. The deposition of zirconia on silica support was proven

to prevent the formation of cobalt silicate,27 which also may mean that the cobaltsilica interaction is affected by the zirconia being present. Michalak et al, found that

the addition of ZrO2 had no impact on the surface area of the catalyst, but it

decreased the extent of reduction for Co/Al2O3 catalysts27. This may suggest that

ZrO2 inhibits the reduction of cobalt catalysts, supported on alumina.

XRD signals of both amorphous alumina and the addition of ZrO2 to the

alumina did not indicate any changes in signal, which leads us to believe that there

was a strong interaction between ZrO2 and the oxide composite.28 This strong

interaction likely resulted in highly dispersed ZiO2 on alumina.

Xiong et al. synthesized ZrO2-Al2O3 through impregnation of zirconium to a

Al2O3 and found that the cobalt oxide crystallite size increased with

increasing zirconium, while the zirconia inhibited formation of cobalt aluminate in

those catalysts29. Xiong also found that an increase in zirconia decreased the

methane selectivity, increased CO hydrogen activity, and C5+ selectivity in FischerTropsch synthesis.

2.8 Brunauer Emmet Teller (BET) Surface Area Measurements

Brunauer, Emmet, Teller (BET)4 surface area measurements are important

for Fischer-Tropsch catalysts because the results provide surface area data, which

are necessary to determine the available surface area for the reaction to take place.

NASA/TM—2012-216020 14
The surface area of granulated powders is measured by determining the quantity of

gas that adsorbs as a single layer of molecules, which is completed near the boiling

point of the adsorbate gas. At the boiling point, the area covered by each gas

molecule is known within minimal error and the sample surface area is calculated

directly from the number of absorbed molecules, the conditions, and the area

occupied by each molecule. In most instances, 30% nitrogen in helium mixture is

used at atmospheric pressure and at liquid nitrogen temperature. The adsorption of

gas on a solid surface is described by the following equation4 :

1

1 =

1

+

1

=

=

= ( )

=

The surface area (S) of the sample is determined by the monolayer of

absorbed gas volume (Vm) at standard temperature and pressure, given in the

following equation:

=

=

=

=

Applicable BET surface area data and BJH adsorption data of Fischer-Tropsch

cobalt catalysts available in literature is presented in Table 2.1. This data provides a

NASA/TM—2012-216020 15
means for comparison of data collected in the work presented in this thesis to other

literature available.

Table 2.1: BET Data from Literature

BET

Surface

Area

(m2/g)

Single Point

adsorption

average pore

volume (cm3/g)

Single point

adsorption average

pore radius (nm)

Ref.

15%Co/Al2O3 144 0.38 5.25 29

15%Co/1%Zr/Al2O3 159 0.4 5.0 29

15%Co/5%Zr/Al2O3 133 0.35 5.2 29

15%Co/9%Zr/Al2O3 123 0.31 5.1 29

Al2O3 136 27

8.5%ZrO2/Al2O3 120 27

10%Co/Al2O3 103 27

10%Co/ZrO2/Al2O3 75 27

TiO2 49.5 27

8.5%ZrO2/TiO2 47.6 27

10%Co/TiO2 38.3 27

10%Co/ZrO2/TiO2 38.0 27

**Blank spaces were left when data was unavailable

NASA/TM—2012-216020 16
2.9 Temperature Programmed Reduction and Temperature Programmed

Reduction After Reduction

Since Fischer-Tropsch cobalt catalysts oxidize readily in air, it is critical that

the catalysts are reduced before introducing them to the reaction. If reduction is not

completed at the optimum conditions, the catalyst may sinter and/or agglomerate

during the process. Thermodynamics determine the best conditions at which a

catalyst can be reduced, but are only useful if the catalyst particles are equivalent30 ,

meaning that the cobalt particle sizes are uniform and is typically not the case with

Fischer-Tropsch catalysts.

TPR provides useful information on the temperature that is needed for the

complete reduction of the catalyst 30. However, this temperature is often not the

optimum condition for reduction, many other factors are considered for this

determination. The area under the TPR curve represents the total hydrogen

consumption and is commonly expressed in moles of H2 consumer per mole of metal

atoms (H2/M)30. Most frequently, TPR profiles are interpreted on a qualitative basis

and not a quantitative.

During TPR, the metal oxide (cobalt oxide) reacts with hydrogen to form

pure metal (cobalt metal). This reaction is also known as reduction. During the

TPR, argon is used as the carrier gas because it has a very low relative thermal

conductivity. The argon is blended in a fixed proportion with hydrogen, the

reduction gas, which has a much higher thermal conductivity. The gas mixture flows

through the analyzer, the sample, and then the detector. A baseline reading is

established by the detector when the initial H2/Ar gas flows over the sample. This

NASA/TM—2012-216020 17
occurs at a low enough temperature that no reduction has begun. As the

temperature is increased at a fixed ramp rate, the hydrogen atoms begin to react

with the sample. This reaction produces H2O molecules, which are removed from

the gas stream using a cold trap. The production of H2O results in a decrease in the

amount of hydrogen, thus shifting the total gas thermal conductivity towards the

argon’s thermal conductivity. As previously mentioned, argon has a lower thermal

conductivity than hydrogen, so the total gas thermal conductivity decreases. The

signal the instrument records is the electrical demand, also known as the detector

signal. This demand is described as the amount of electricity it takes to keep the

TCD at a constant filament temperature. So, as the total gas thermal conductivity

decreases, the flowing gas removes heat from the filament more slowly, therefore it

requires less electricity to maintain the filament temperature.

2.10 Hydrogen Chemisorption and Pulse Reoxidation

Hydrogen chemisorption and pulse reoxidation provide useful information

about the catalyst’s active site density, dispersion, cluster size, and reducibility. The

hydrogen temperature programmed desorption (TPD) provides data on the active

site density and is also used to calculated uncorrected dispersion. These

calculations are done under the assumption that all of the cobalt was reduced and

that one hydrogen atom attaches to one surface cobalt metal atom. Since it was not

completely reduced, the use of pulse reoxidation becomes important. The pulse

reoxidation date is used to calculate the extent of reduction, which is then used to

determine the corrected dispersion and cluster size. The assumption in this

NASA/TM—2012-216020 18
calculation is that for every two oxygen molecules consumed, there are three moles

of bulk cobalt metal atoms previously reduced.

NASA/TM—2012-216020 19
Table 2.2: Hydrogen Chemisorption Data from Literature

Catalyst Description

H2

desorbed

per gcat

Uncorrected

Dispersion

(%)

Uncorrected

Diameter (nm)

moles O2

consumed

per gcat

%

Reduction

Corrected

Dispersion

(%)

Corrected

Diameter

(nm)

Ref

.

10%Co-0%Mn-TiO2 7.16 11.8 31

10%Co-0.03%MnTiO2 6.03 9.7 3110%Co-0.32%Mn- TiO2 7.16 10.4 3110%Co-0.96%Mn- TiO2 2.50 9.2 3110%Co-3.43%Mn- TiO2 1.77 9.6 31

15%Co-SiO2

CS

7.4

91.1 17.2 16

15%Co-TiO2/SiO2

CTSP

8.8

64.6 14.6 16

NASA/TM—2012-216020 20
Catalyst Description

H2

desorbed

per gcat

Uncorrected

Dispersion

(%)

Uncorrected

Diameter (nm)

moles O2

consumed

per gcat

%

Reduction

Corrected

Dispersion

(%)

Corrected

Diameter

(nm)

Ref

.

15%Co- TiO2/SiO2

CTSI

8.7

69.9 14.7 16

15%Co- TiO2/SiO2

CTSHR

8.6

61.2 14.8 16

15%Co- TiO2/SiO2

CTSSG

10.2

35.4 12.6 16

12%Co-Ti-0La 81.66 15.7 22

12%Co-Ti-1/2000La 82.90 15.8 22

12%Co-Ti-1/200La 84.12 13.9 2212%Co-Ti-1/120La 87.25 12.1 22

12%Co-Ti-1/20La 88.76 12.8 22

15%Co/Al2O3 88.4 6.94 14.9 898.4 52.68 13.2 7.9 29

15%Co/0.5%Zr/Al2O

3

74.0 5.82 17.7 959.1 53.24 10.4 10.0 29

15%Co/1%Zr/Al2O3 74.2 5.83 17.5 910.2 53.37 10.9 9.3 29

NASA/TM—2012-216020 21
Catalyst Description

H2

desorbed

per gcat

Uncorrected

Dispersion

(%)

Uncorrected

Diameter (nm)

moles O2

consumed

per gcat

%

Reduction

Corrected

Dispersion

(%)

Corrected

Diameter

(nm)

Ref

.

15%Co/5%Zr/Al2O3 102.5 8.05 12.8 855.8 50.18 16.0 6.4 2915%Co/9%Zr/Al2O3 99.2 7.01 14.7 1005.8 58.95 11.9 8.7 29

15%Co/15%Zr/Al2O

3

100.0 7.73 13.4 1020.4 59.91 15.1 8.0 29

10%Co/Al2O3 0.4 67 270 27

10%Co/8.5%ZrO2/Al

2O3

1.1 61 101 27

**Blank spaces were left when data was unavailable

NASA/TM—2012-216020 22
2.11 X-ray Diffraction

X-ray diffraction provides a way to estimate the cobalt oxide crystallite size.

29. and spinel cobalt oxide is found at 31.3,

36.9, 45.1, 59.4, and 65.432. Table 2.3 provides XRD data from literature for a

baseline comparison to the data presented in this study.

Table 2.3: XRD Data from Literature

Catalyst Average diameter of

Co3O4 domains (nm)

Ref.

15%Co/Al2O3 18.3 29

15%Co/0.5%Zr/Al2O3 18.2 29

15%Co/1%Zr/Al2O3 19.1 29

15%Co/5%Zr/Al2O3 19.3 29

15%Co/9%Zr/Al2O3 18.4 29

15%Co/15%Zr/Al2O3 20.8 29

NASA/TM—2012-216020 23
CHAPTER III

EXPERIMENTAL PROCEDURES

CHAPTER 3

3.1 Catalyst Preparation

In this study, Puralox SCFa-140/L3 (Sasol), Puralox SCFa-200Zr3 (Sasol), and

Puralox TH 100/150 Ti10 (Sasol) were used as the explored catalyst supports.

Puralox HP14/150 Al, Catalox Al2O3 SBA200, and Catalox Al2O3 SBA150 were used

as the reference catalyst supports. These reference pairs were chosen because of

their surface area and pore size data collected: 9.7%TiO2-Al2O3 compared to both

Al2O3 SBA 150 and Al2O3 HF14/150, 3.1%ZrO2-Al2O3 compared to both Al2O3 SBA

150 and Al2O3 SBA 200, and 3.0%La2O3-Al2O3 compared to both Al2O3 SBA 150 and

Al2O3 SBA 200. All six supports are readily available for purchase from Sasol North

America. Table 3.1 shows the composition, surface area, loose bulk density, and

particle size distribution data provided by Sasol North America upon delivery of

these supports.

NASA/TM—2012-216020 24
Table 3.1: Catalyst support composition

Support Name Composition Surface

Area

(m2/g)

Loose Bulk

Density

(g/l)

Particle Size

Distribution

%

Puralox TH 100/150 Ti10 90.3%Al2O3

9.7%TiO2

135 0.33 <25 μm 50.6

<45 μm 82.5

<90 μm 100

Puralox SCFa-140/L3

Lot No: BD2186

97% Al2O3

3%La2O3

143 0.61 <25 μm 33

<45 μm 60

<90 μm 94.7

>150

μm

0.1

Puralox SCFa-200 Zr3

Lot No: BD2801

96.9%Al2O3

3.1%ZrO2

196 0.67 <25 μm 49.2

<45 μm 82.1

<90 μm 100

>150

μm

0

Puralox HP14/150 Al 100%Al2O3 150

Catalox Al2O3 SBA200 100%Al2O3 200

Catalox Al2O3 SBA150 100%Al2O3 150

Support calcination is necessary to drive off any water that may be absorbed

on the support from the atmosphere. The support calicnations were carried out

using a tubular reactor and a clamshell furnace. A Lindberg/Blue M control console

was used to set the parameters of the experiment and control the internal

temperature of the support throughout the calcination procedure.

NASA/TM—2012-216020 25
For all three catalyst supports, approximately 30 grams were loaded into the

reactor. The reactor was then loaded into the furnace, and the air supply turned on

at a flow rate of approximately 2.0 L/min set on a rotameter. The source of the air

used in the experiment was a gas cylinder of zero air. The controller was set to

ramp at 2°C/min from room temperature to 400°C and then it was held at 400oC for

four hours. The sample was then kept under air flow until reaching room

temperature and then removed from the tubular reactor and stored in an oven at

100oC until the first cobalt loading began. Figure 3.1 shows the diagram of the

calcination reactor, a plug flow reactor (PFR). The air flows from the top of the

reactor over the catalyst bed and out the bottom of the reactor, with a thermocouple

located in the middle of the catalyst bed.

NASA/TM—2012-216020 26
Figure 3.1: Calcination reactor drawing

Impregnation is one of the many different methods for synthesizing FischerTropsch (F-T) catalysts, which can be done through incipient wetness impregnation

(IWI) or slurry impregnation. Incipient wetness impregnation uses a loading

solution that is equal to the exact volume of pores in the support, while slurry

impregnation requires the final loading solution to be equal to 2.5 times the total

pore volume of the support. Previous research has shown that incipient wetness

impregnation procedures have been found to produce a wider range of cluster sizes

than the slurry phase impregnation procedure7. Because of the wide range of

NASA/TM—2012-216020 27
cluster sizes in IWI procedures, slurry phase impregnation was chosen for this

study.

The catalyst was prepared using slurry impregnation and two separate

loadings of cobalt were made using cobalt nitrate and water. The first loading

required half of the cobalt nitrate needed for 15% by weight loading. This cobalt

nitrate was dissolved in de-ionized water so that the total volume was equivalent to

2.5 times the total pore volume for the specified support. The solution was then

added (drop wise via a burette and a rotating round bottom flask) to the catalyst

support until approximately 1⁄4 of the solution was dispensed. At this time, the

round bottom flask was removed from the rotating mechanism and thoroughly

mixed by shaking and scraping the walls of the round bottom flask. This process

was continued until the entire solution was added to the support. The round

bottom flask was then transferred to the rotary evaporator where the vacuum was

controlled to ensure very slow drying of the catalyst. The second loading of cobalt

was completed using the same methods.

After completion of both cobalt nitrate loadings, the nitrate must be driven

off through catalyst calcination. This calcination was completed using the same

furnace and control system previously mentioned in the support calcination

description; however a separate tubular reactor was used to avoid contamination.

Zero air flow was set to approximately 2L/min and the temperature controller was

set to ramp up at a rate of 2oC/min from room temperature to 350oC and hold at

350oC for 4 hours. After completion of calcination, the air flow was maintained until

proper cool down of the catalyst.

NASA/TM—2012-216020 28
3.2 Catalyst Characterization

A number of catalyst characterization techniques were used including:

Scanning electron microscopy (SEM) and electron dispersed spectroscopy(EDS),

Brunauer Emmet Teller (BET), Barrett Joyner Halenda (BJH), temperature

programmed reduction (TPR), temperature programmed reduction after reduction

(TPR-AR), hydrogen chemisorption with pulse reoxidation, and x-ray diffraction

(XRD).

3.2.1 Scanning Electron Microscopy and Electron Dispersed Spectroscopy

Scanning electron microscopy (SEM) images were gathered on only doped

alumina supports using a Hitachi S-3000N equipped with an EDAX detector for

electron dispersed spectroscopy (EDS) measurements. The SEM was set to 25kV for

imaging and the EDAX working distance was set to 15mm before measurements

were taken. SEM-EDS measurements were gathered on each of the doped alumina

supports in order to better understand the surface morphology of the dopants. The

samples were prepared and mounted on copper tape before measurements were

taken.

NASA/TM—2012-216020 29
3.2.2 Brunauer Emmet Teller (BET) Surface Area Measurements and Barrett

Joyner Halenda (BJH) Pore Size Distributions

BET (Brunauer, Emmet, and Teller4) and BJH (Barrett Joyner Halenda 33)

measurements were conducted on all of the supports, as well as the catalysts to

determine the loss of surface area after loading cobalt metal. These measurements

were conducted using a Micromeritics Tri-Star system. Approximately 0.5 grams of

sample was prepared by slowly ramping to 160oC and evacuating to 50mTorr. This

preparation step was completed in order to remove any water or other

contaminants on the surface of the catalyst or support. The BET surface area

measurements were completed with nitrogen and argon as the adsorption gases.

3.2.3 Temperature Programmed Reduction (TPR)

Temperature programmed reduction (TPR) profiles were obtained for each

of the calcined catalysts using a Zeton Altamira AMI-200 unit. Each sample was

loaded into a Zeton Altamira sample tube with a target mass of 0.1 grams. The

sample tubes were installed on the instrument and then set to undergo argon

pretreatment. The samples were heated to 350oC at a rate of 10oC/min under argon

flow of 30cm3/min in order to remove any residual water or nitrate. After argon

pretreatment, the sample was cooled to 50oC and held under continuous flow of

argon for 15 minutes. The flow was then switched from pure argon to 10%

hydrogen in argon (remaining at a constant 30 cm3/min). At this point the TCD

NASA/TM—2012-216020 30
signal started recording and the ramp rate was set to 10oC/min from 50oC to 1100oC

and the sample was held at 1100oC for a minimum of 30 minutes.

3.2.4 Temperature Programmed Reduction After Reduction

Temperature programmed reduction after reduction (TPR-AR) profiles were

obtained for all of the calcined catalysts using a Zeton-Altamira AMI-200 unit. The

first step was argon pretreatment step, which was mentioned previously in the TPR

section. After argon pretreatment, the sample was reduced under 30cm3/min flow

of 33% hydrogen in argon at a ramp rate of 1oC/min from room temperature up to

350oC and held for 10 hours. The flow was then switched to 10% hydrogen in argon

and the TCD began recording. The sample was then heated to 1100oC at a ramp rate

of 10oC/min.

3.2.5 Hydrogen Chemisorption with Pulse Reoxidation

Hydrogen chemisorption with pulse reoxidation measurements were

performed on the calcined catalysts using a Zeton Altamira AMI-200 unit, which

incorporates a thermal conductivity detector. Each sample weight was

approximately 0.22 grams. The catalyst was loaded via a sample tube and activated

at 350oC for 10 hours using a flow of 33% hydrogen in argon and then cooled under

hydrogen flow to 100oC. The sample was held at 100oC, while switching the flow to

pure argon in order to prevent physisorption of weakly bound species. The sample

was then slowly increased to activation temperature and held under flowing argon

NASA/TM—2012-216020 31
to desorb the remaining chemisorbed hydrogen and the TCD signal returned to

baseline. This TPD spectrum was integrated in order to find the number of

hydrogen moles desorbed in comparison to the area of the calibrated hydrogen

pulse’s peaks. The hydrogen TPD results are then used for calculating uncorrected

dispersion.

The same sample was reoxidized by injecting pulses of pure oxygen in helium

in reference to pure helium gas at the activation temperature. The number of moles

of oxygen consumed by the sample was determined by integration of the peaks and

using the same calibration method for hydrogen chemisorption. Assuming that all

of the Coo reoxidized to Co3O4, the percentage reduction was calculated. The

uncorrected dispersions are based on the assumption of complete reduction, where

the corrected dispersions include the percentage of reduced cobalt. The number of

Coo moles on the surface is determined by the number of hydrogen desorbed during

TPD and the total number of moles of Coo in the sample is the preparation target

weight percent of cobalt.

3.2.6 X-ray Diffraction

X-ray diffraction profiles were obtained for each of the calcined catalyst using

a Philips X’Pert unit. A long range scan was ran from 15 to 80o with 0.02o steps at 5

seconds/step. In order to quantify the average Co3O4 cluster sizes using the

o, which represents (3 1 1), a shorter range scan was

NASA/TM—2012-216020 32
also made. The shorter scan range was from 30 to 45o with 0.01o steps at 15

seconds/step.

NASA/TM—2012-216020 33
CHAPTER IV

CATALYST CHARACTERIZATION RESULTS

CHAPTER 4

4.1 Scanning Electron Microscopy and Electron Dispersed Spectroscopy

Figure 4.1 shows the scanning electron microscopy-energy dispersive

spectroscopy (SEM-EDS) mapping results for both alumina and titanium for the

9.7%TiO2-Al2O3 support. The left image highlights the alumina in pink and the right

image highlights the titanium in green. The alumina appears to be the stronger

presence and highlights the particles shapes because of the concentration of

alumina being detected by SEM-EDS. The titanium appears to be highly dispersed

and have less concentration on the sample. This relationship was expected as the

9.7%TiO2-Al2O3 support contains less than 10% titanium. Since SEM-EDS has a

penetration of approximately 2μm, it is likely that most of the titanium is on or near

the surface of the support, which make it available to contribute to the F-T reaction.

NASA/TM—2012-216020 34
Figure 4.1: Scanning Electron Microscopy-Energy Dispersive Spectroscopy

(SEM-EDS) mapping results for 9.7%TiO2-Al2O3 where Al2O3 is pink (left) and TiO2 is

green (right).

Figure 4.2 shows the overlay of the SEM-EDS mapping results for both

alumina and titanium separately on the actual SEM image of the 9.7%TiO2-Al2O3

support. The left image highlights the alumina only (in pink) and the right image

highlights the titanium only (in green). As previously discussed, the alumina shows

a higher concentration and highlights the support particles structure because of this

higher concentration. The titanium appears to be uniformly dispersed over all

support particles in this image.

NASA/TM—2012-216020 35
Figure 4.2: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results overlayed on scanning electron microscopy image for

9.7%TiO2-Al2O3where Al2O3 is pink (left) and TiO2 is green (right).

Figure 4.3 shows the overlay of both alumina and titanium SEM-EDS

mapping results on top of the actual SEM image of the 9.7%TiO2-Al2O3 support.

shows the SEM-EDS mapping overlay. This image puts previous conclusions into

perspective. It difficult it is to see the titanium among the alumina mapping results,

likely because of the highly dispersed titanium on the surface.

NASA/TM—2012-216020 36
Figure 4.3: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results for 9.7%TiO2-Al2O3 overlaid on scanning electron microscopy

image. Alumina is highlighted in pink and titania is highlighted in green.

Figure 4.4 and Table 4.1 show the SEM-EDS quantitative results for

9.7%TiO2-Al2O3. Figure 4.4 shows three distinct peaks: alumina, titanium, and the

copper tape used to mount the sample. Results indicate an atomic % of titanium as

8.17%, which is in order with the expected 9.7% of titanium.

NASA/TM—2012-216020 37
Figure 4.4: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) quantitative results for 9.7%TiO2-Al2O3 support.

Table 4.1: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) quantitative results for 9.7%TiO2-Al2O3

Element Wt% At% K-Ratio Z A F

AlK 86.35 91.83 0.7122 1.01 0.8162 1.0006

TiK 13.65 8.17 0.1128 0.9282 0.8904 1.0000

Figure 4.5 shows the scanning electron microscopy-energy dispersive

spectroscopy (SEM-EDS) mapping results for both alumina and lanthanum for the

3.0%La2O3-Al2O3 support. The left image highlights the alumina in pink and the

right image highlights the lanthanum in green. Again, alumina appears to be the

stronger presence and highlights the particles shapes because of the concentration

of alumina being detected by SEM-EDS. The lanthanum appears to be highly

dispersed and have less concentration on the sample, even less than the previously

discussed titanium. This relationship was expected as the 3.0%La2O3-Al2O3 support

NASA/TM—2012-216020 38
contains only 3% lanthanum. Since SEM-EDS has a penetration of approximately

2μm, it is likely that most of the lanthanum is on or near the surface of the support.

Figure 4.5: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results for 3.0%La2O3-Al2O3 where Al2O3 is pink (left) and La2O3 is

green (right)..

Figure 4.6 shows the SEM-EDS mapping results overlaid on the SEM image

for the 3.0%La2O3-Al2O3 support. The alumina is highlighted in pink on the left

image and shows the formation of the support particles. The lanthanum is shown

highlighted in green on the right and appears to have a high dispersion.

NASA/TM—2012-216020 39
Figure 4.6: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results overlaid on scanning electron microscopy image for

3.0%La2O3-Al2O3 where Al2O3 is pink (left) and La2O3 is green (right).

Figure 4.8 shows the SEM-EDS mapping of both alumina and lanthanum

overlaid on the SEM image. Similar to the titanium doped catalyst, the lanthanum is

difficult to see and is likely well dispersed throughout the alumina. It is highly likely

that the lanthanum is on or near the surface of the support and will play a role in the

catalytic reaction.

Figure 4.7: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results for 3.0%La2O3-Al2O3 overlaid on scanning electron

microscopy image (Al203 in pink and La2O3 in green).

NASA/TM—2012-216020 40
Figure 4.8: and Table 4.2 show the SEM-EDS quantitative results for the

3.0%La2O3-Al2O3 support. The figure displays peaks relating to alumina, lanthanum

and the copper tape used in mounting the sample. The quantitative results indicate

1.59% lanthanum, which is well within experimental error for the expected value of

3% lanthanum.

Figure 4.8: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) quantitative results for 3.0%La2O3-Al2O3.

Table 4.2Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)

quantitative results for 3.0%La2O3-Al2O3.

Element Wt% At% K-Ratio Z A F

AlK 92.33 98.41 0.7041 1.0116 0.7537 1.0002

LaL 7.67 1.59 0.0636 0.8007 1.0346 1.0000

NASA/TM—2012-216020 41
Figure 4.9: Scanning Electron Microscopy-Energy Dispersive Spectroscopy

(SEM-EDS) mapping results for alumina highlighted in pink (left) and zirconium

highlighted in green (right) on the 3.1%ZrO2-Al2O3 support.Figure 4.9

Figure 4.9: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results for 3.1%ZrO2-Al2O3where Al2O3 is pink (left) and ZrO2 is

green (right).

Figure 4.10: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results overlaid on scanning electron microscopy image for

3.1%ZrO2-Al2O3where Al2O3 is pink (left) and ZrO2 is green (right).

NASA/TM—2012-216020 42
Figure 4.11: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) mapping results for 3.1%ZrO2-Al2O3 overlaid on scanning electron microscopy

image where Al2O3 is pink (left) and ZrO2 is green (right).

NASA/TM—2012-216020 43
Figure 4.12: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) quantitative results for 3.1%ZrO2-Al2O3

Table 4.3: Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEMEDS) quantitative results for 3.1%ZrO2-Al2O3.

Element Wt% At% K-Ratio Z A F

AlK 91.23 97.23 0.8451 1.0104 0.9157 1.0013

ZrL 8.77 2.77 0.0336 0.8724 0.4387 1.0000

NASA/TM—2012-216020 44
4.2 Brunauer Emmet Teller (BET)4 and Barrett Joyner Halenda (BJH)33

Measurements

Surface area measurement by nitrogen adsorption and desorption results are

shown in Table 4.4. The surface areas and average adsorption pore radii of Puralox

TH 100/150 Ti10, Puralox SCFa-200 Zr3, and Puralox SCFa-140/L3 supports were

measured to be 137.94 m2/g and 13.327 nm, 152.63 m2/g and 3.74 nm, and 142.26

m2/g and 6.27 nm respectively. The baseline support surface areas can be used to

calculated the expected surface area of each support after the cobalt was loaded.

Since BET was completed on the catalysts before reduction, the surface areas take

into account cobalt oxide not cobalt metal. In order to determine potential pore

blockage on the surface, the catalyst cobalt weight percents must be corrected to

cobalt oxide weight percents. A weight percent of 15% cobalt metal is equivalent to

20% cobalt oxide (Co3O4). If we assume that the support is the only contributor to

area, then the area of 15%Co/9.7%TiO2-Al2O3 would be expected to be 0.80 x

137.94m2/g (the area of 9.7%TiO2-Al2O3)= 110.35 m2/g, which is within

experimental error of the measured surface area of 113.26 m2/g. Similarly, the area

of 15%Co/3.0%La2O3-Al2O3 should be 0.8 x 142.26 m2/g (the surface area of

3.0%La2O3-Al2O3) = 113.81 m2/g, which also corresponds to the measured surface

area of 124.41 m2/g quite well. Likewise, the area of 15%Co/3.1%ZrO2-Al2O3

should be 0.8 x 183.5 m2/g (the area of 3.1%ZrO2-Al2O3)=146.8 m2/g, which

matches the measured surface area of 152.63 m2/g reasonably well. These results

can be compared more clearly in Figure 4.13.

NASA/TM—2012-216020 45
Figure 4.13: Expected BET surface areas of (a) 15%Co/9.7%TiO2-Al2O3, (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3

The BET surface area results of the supports and their corresponding

catalysts are shown in Figure 4.14. The surface area of the catalyst in relation to it’s

bare support was expected to be lower, which was shown to be true for all supports

upon addition of cobalt.

0

20

40

60

80

100

120

140

160

180

a b c

Surface Area (mm2/g)

expected actual

NASA/TM—2012-216020 46
Figure 4.14: BET surface area comparison of (a) 15%Co/9.7%TiO2-Al2O3 , (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3

HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3 SBA200.

Along with surface area measurements, Table 4.4 also displays the BJH

adsorption average pore radius. The BJH adsorption average pore radius data is

also displayed in Figure 4.15 and the BJH desorption average pore volume is shown

in Figure 4.16. In comparing each adsorption average pore radius, the cobalt

loading decreased the pore radius on all three supports. The most significant

reduction in pore radius was seen in the loading of 15% cobalt on the 9.7%TiO2-

Al2O3 support, where the support and catalyst pore radii were measured to be 13.37

nm and 10.92 nm respectively, which also had the largest pore radius. Since the

pore radius decreased upon addition of cobalt to all of the supports, the data

suggests that the pores were filled uniformly. The pore volume decreased slightly

upon addition of cobalt to the support, as expected.

0

50

100

150

200

250

a b c d e f

Surface Area (mm2/g)

support catalyst

NASA/TM—2012-216020 47
Figure 4.15: Barrett Joyner Halenda (BJH) average pore radius adsorption data for

(a) 15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-

Al2O3, (d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3

SBA200.

Figure 4.16: Barrett Joyner Halenda (BJH) average pore volume desorption data for

(a) 15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-

Al2O3, (d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3

SBA200.

0

2

4

6

8

10

12

14

16

a b c d e f

Average Pore Radius (nm)

support catalyst

0

0.2

0.4

0.6

0.8

1

1.2

a b c d e f

Desorption Average Pore

Volume (cm3/g)

support catalyst

NASA/TM—2012-216020 48
Table 4.4: BET surface area measurements and BJH pore volume and pore radius

measurements

BET

Surface

Area

(m2/g)

Single

Point

adsorption

average

pore

volume

(cm3/g)

BJH

adsorption/

desorption

average pore

volume

(cm3/g)

Single

point

adsorption

average

pore

radius

(nm)

BJH

adsorption/

desorption

average pore

radius (nm)

9.7%TiO2-Al2O3 137.9 1.012 1.01/1.01 --- 13.37/11.10

15%Co/9.7%TiO2-

Al2O3

113.3 0.6634 0.67/0.67 12.18 10.92/9.99

3.0%La2O3-Al2O3 142.26 0.5310 0.54/0.54 7.47 6.27/5.43

15%Co/3.0%La2O3-

Al2O3

124.41 0.3681 0.37/0.37 6.14 5.49/5.05

3.1%ZrO2-Al2O3 183.5 0.4291 0.44/0.43 4.68 3.74/3.29

15%Co/3.1%ZrO2-

Al2O3

152.63 0.3180 0.32/0.32 4.17 3.64/3.31

HP14/150 Al 152.6

149.8

0.9185

0.9003

0.92/0.92

0.91/0.91

12.55

12.53

10.33/9.02

10.31/9.03

15%Co/Al2O3

HP14/150

112.5

113.4

0.5320

0.5728

0.57/0.57

0.60/0.61

9.46

10.09

8.90/8.12

9.34/8.38

Al2O3 SBA150 140.2

135.1

0.4357

0.4190

0.44/0.44

0.42/0.42

6.47

6.46

5.14/4.50

5.08/4.45

15%Co/Al2O3

SBA150

109.8

110.2

0.3103

0.3051

0.32/0.32

0.31/0.31

5.65

5.54

4.80/4.31

4.76/4.30

Al2O3 SBA200 197.0

202.2

0.4730

0.4847

0.48/0.48

0.49/0.49

5.00

5.00

3.79/3.37

3.80/3.36

15%Co/Al2O3

SBA200

165.0

165.4

0.3351

0.3375

0.34/0.34

0.34/0.34

4.06

4.08

3.41/3.09

3.42/3.10

NASA/TM—2012-216020 49
Pore size distribution figures are attached in Appendix A of this document.

Figure 4.34-Figure 4.45 show the adsorption and desorption pore size distributions

of all supports and their corresponding catalysts. Upon addition of cobalt, all pore

size distributions show a decrease in pore volume, while most of the overall pore

size distribution trends remain the same. This is to be expected because cobalt is

filling some of the volume, which used to be available for nitrogen adsorption.

These results are in line with the data provided in Table 4.4. Figure 4.36

(3.0%La2O3-Al2O3) and Figure 4.37 (15%Co/3.0%La2O3-Al2O3) pore size

distribution trend shifts slightly to the left upon addition of the cobalt, resulting in a

smaller pore radius as well. This is also consistent with the data presented inTable

4.4.

Figure 4.40 through Figure 4.45 all provide pore size distributions on the

reference catalysts and their corresponding supports. These pore size distributions

include duplicate trends, which show that the pore size distributions are relatively

repeatable, with minimal error.

4.3 Temperature Programmed Reduction

Figure 4.17 shows the TPR profiles of all three catalysts, which have a similar

profile of two distinct reduction peaks. The first peak is attributed to the reduction

of Co3O4 to CoO oxide. The second broad peak represents the reduction from CoO to

Co metal. The reductions step are Co3O4 + H2 3CoO + H2O and 3CoO + 3H2 3Co

NASA/TM—2012-216020 50
+3H2O. The second peak is typically about three times that of the first peak is in line

with this viewpoint. Jacobs et al.34 demonstrated this with the use of TPR-EXAFS

and TPR-XANES.

The Zr doped alumina shows a significant widening of the second peak, while

the La doped alumina shows only a slight widening of the second peak in

comparison to the titanium-doped supported catalyst. This widening is attributed

to the interaction of cobalt oxide (CoO) surface species with the support. The Ti

doped alumina appears to have both peaks shifted furthest to the left, which is due

to the Ti weakening the interaction between cobalt and the alumina and thereby

facilitating the reduction.

Figure 4.17: H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3; (b)

15%Co/3.0%La2O3-Al2O3; and (c) 15%Co/3.1%ZrO2-Al2O3.

NASA/TM—2012-216020 51
Figure 4.18 shows the TPR profile 15%Co/9.7%TiO2-Al2O3 in comparison to

two reference catalysts, 15%Co/Al2O3 SBA 150 and 15%Co/Al2O3 HF14/150. These

references were chosen because the physisorption data suggests that they have

comparable surface areas and pore sizes. As previously discussed, support surface

area, pore volume, and pore radius can affect the performance of the catalysts, so

Al2O3 SBA 150 was chosen because it has a surface area lower (approximately

109m2/g), 9.7%TiO2-Al2O3 has a surface area of approximately 137m2/g, and Al2O3

HF14/150 has a surface area of approximately 152m2/g. This provides a high and a

low point. In comparison to both reference catalysts, the catalyst with TiO2 present

has a distinct shift of the second reduction peak to lower temperatures.

Figure 4.18: H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3, (b)

15%Co/Al2O3 SBA 150, and (c) 15%Co/Al2O3 HF14/150

T(oC)

0 200 400 600 800 1000

(a)

(b)

(c)

NASA/TM—2012-216020 52
Figure 4.20 shows the TPR profile of 15%Co/3.1%ZrO2-Al2O3 in comparison

to two reference catalysts, 15%Co/Al2O3 SBA 150 15%Co/Al2O3 SBA 200. These

reference catalysts were chosen for 15%Co/3.1%ZrO2-Al2O3 because of the support

surface area. According to this TPR profile, the presence of ZrO2 in the support

appears to cause a slight shift of the second reduction peak to lower temperatures.

Figure 4.19: H-TPR profiles of, moving upward, (a) 15%Co/Al2O3 SBA 150, (b)

15%Co/3.0%La2O3-Al2O3, and (c) 15%Co/Al2O3 SBA 200

T(oC)

0 200 400 600 800 1000

(a)

(b)

(c)

NASA/TM—2012-216020 53
Figure 4.20: H-TPR profiles of, moving upward, (a) 15%Co/Al2O3 SBA 150; (b)

15%Co/3.1%ZrO2-Al2O3 and (c) 15%Co/Al2O3 SBA 200.

Figure 4.21: H-TPR profiles of, moving upward, (a) 15%Co/9.7%TiO2-Al2O3 , (b)

15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3, (d) 15%Co/Al2O3

HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3 SBA200.

T(oC)

0 200 400 600 800 1000

(a)

(b)

(c)

T (oC)

0 200 400 600 800 1000

(a)

(b)

(c)

(d)

(e)

(f)

NASA/TM—2012-216020 54
4.4 Temperature Programmed Reduction After Reduction (TPR-AR)

The temperature programmed reduction after reduction profiles are shown

as dashed lines along with the original TPR profiles in Figure 4.22. These profiles

provide information on the amount of unreduced cobalt present on the surface, after

the reduction step occurs. The titania promoted supported catalyst (a) profile

corresponds to minimal unreduced cobalt, where lanthanum promoted (b) shows a

small peak indicating a small fraction of cobalt remained unreduced. On the

contrary, (c), zirconium promoted support, shows a significant amount of cobalt

being reduced after reduction occurs.

Figure 4.22: H-TPR (solid) and (dashed) H-TPR-AR profiles of, moving upward, (a)

15%Co/9.7%TiO2-Al2O3; (b) 15%Co/3.0%La2O3-Al2O3; and (c) 15%Co/3.1%ZrO2-

Al2O3. Reduction was carried out in hydrogen for 10 hours at 350oC.

NASA/TM—2012-216020 55
Figure 4.23: H-TPR (solid) and (dashed) H-TPR-AR profiles of, moving upward, (a)

15%Co/9.7%TiO2-Al2O3 , (b) 15%Co/3.0%La2O3-Al2O3, (c) 15%Co/3.1%ZrO2-Al2O3,

(d) 15%Co/Al2O3 HP14/150, (e) 15%Co/Al2O3 SBA150, and (f) 15%Co/Al2O3

SBA200.

T (oC)

0 200 400 600 800 1000

(a)

(b)

(c)

(d)

(e)

(f)

NASA/TM—2012-216020 56
4.5 Hydrogen Chemisorption

The hydrogen TPD results were used to calculate uncorrected dispersion.

Uncorrected dispersion calculations are made under the assumption that all of the

cobalt was reduced. In this calculation, it is assumed that one hydrogen atom

attaches to one surface cobalt metal atom. The Altamira instrument provides

hydrogen TPD results of desorbed. In order to determine the uncorrected

dispersion the calculations are as follows.

# =2× ×

1

1 6

% . =

#

 # : . . ,

=

#

( )( % )

TPD results provided data on the active site density of each catalyst. In

assumption that we have one cobalt surface atom for every one hydrogen atom, we

can use the amount of hydrogen desorbed to determine the active site density. The

active site density is clearly presented in Figure 4.24, where the compared catalyst

is in red and displayed on the x-axis and the reference catalysts are labeled in the

graph legend. 15%Co/9.7%TiO2-Al2O3 2/gcat, which also

cat. In reference to this catalyst’s reference

catalysts (15%Co/Al2O3 HP14/150 and 15%Co/Al2O3 SBA150), which resulted in

NASA/TM—2012-216020 57
145.4 and 149.4 balt/gcat. 15%Co/3.0%La2O3-Al2O3resulted in 142

cat, in reference to this catalyst’s reference catalysts

(15%Co/Al2O3 SBA150 and 15%Co/Al2O3 SBA200), which resulted in 149.4 and

105.8 cat. 15%Co/3.1%ZrO2-Al2O3

surface cobalt/gcat in reference to this catalyst’s reference catalysts (15%Co/Al2O3

SBA150 and 15%Co/Al2O3 SBA200), which resulted in 149.4 and 105.8

surface cobalt/gcat. (15%Co/Al2O3 SBA150 and 15%Co/Al2O3 SBA200), which

resulted in 149.4 and 105.8 cat. At a first look, this appears

to be a decrease in active site density as a result of increased cluster size on all three

catalysts in question.

NASA/TM—2012-216020 58
Figure 4.24: Temperature programmed desorption data for comparison of all

catalysts with their corresponding reference catalysts.

The pulse reoxidation data is used to calculate the extent of reduction, which

is then used to calculate the corrected dispersion, as follows. In this calculation, we

assume that for every two oxygen molecules consumed, there are three moles of

cobalt metal atom that were reduced.

3 + 2

%

=

#

 #

3

2

% . =

#

( )( % )(% )

0

10

20

30

40

50

60

70

80

15%Co/9.7%TiO2-Al2O3 15%Co/3.0%La2O3-Al2O3 15%Co/3.1%ZrO2-Al2O3

Hydrogen Desorbed ( mol/gcat)

15%Co/Al2O3 HP14/150 Catalyst 15%Co/Al2O3 SBA150 15%Co/Al2O3 SBA200

NASA/TM—2012-216020 59
Chemisorption results indicate that there was a wide range of reduction

degree of the three doped alumina supported catalysts. Chemisorption, extent of

reduction, dispersion and cluster size are shown in Table 4.5. Figure 4.25 through

Figure 4.27 show some of the baseline data comparisons. Figure 4.25 shows the

extent of reduction of each catalyst (red) in comparison to the relevant reference

catalysts. Figure 4.26 shows the corrected cluster size of each doped support in

comparison to each of the catalyst’s reference catalyst cluster sizes. Similarly,

Figure 4.27 shows the corrected dispersion for each of the catalysts in comparison

to each reference catalyst.

Figure 4.25: Extent of reduction results from pulse reoxidation testing for

each catalyst in comparison to its corresponding reference catalyst.

0

10

20

30

40

50

60

70

80

15%Co/9.7%TiO2-Al2O3 15%Co/3.0%La2O3-Al2O3 15%Co/3.1%ZrO2-Al2O3

Reduction (%)

15%Co/Al2O3 HP14/150 Catalyst 15%Co/Al2O3 SBA150 15%Co/Al2O3 SBA200

NASA/TM—2012-216020 60
Figure 4.26: Pulse reoxidation cluster size data, which is corrected for extent of

reduction for each catalyst in comparison to it’s reference catalysts.

0

2

4

6

8

10

12

14

16

15%Co/9.7%TiO2-Al2O3 15%Co/3.0%La2O3-Al2O3 15%Co/3.1%ZrO2-Al2O3

Cluster Size (nm)

15%Co/Al2O3 HP14/150 Catalyst 15%Co/Al2O3 SBA150 15%Co/Al2O3 SBA200

NASA/TM—2012-216020 61
Figure 4.27: Corrected dispersion data for each catalyst in comparison to its

reference catalysts

The TiO2 doped alumina supported catalyst (15%Co/9.7%TiO2-Al2O3) had

the largest cluster size (14 nm vs. 10.5/10.4nm) and the highest extent of reduction

(71%). Since TiO2 is known to have a weaker interaction with cobalt than pure

alumina, this is consistent with what was expected. The larger average cluster size

and increased extent of reduction on TiO2 doped alumina are indicative of a weaker

interaction with the support.

The cobalt cluster size and extent of reduction of 15%Co/3.0%La2O3-Al2O3

and 15%Co/3.1%ZrO2-Al2O3 were 10.5nm and 57% and 10.4nm and 45%

respectively. Both the 15%Co/9.7%TiO2-Al2O3 and 15%Co/3.0%La2O3-Al2O3

0

2

4

6

8

10

12

14

15%Co/9.7%TiO2-Al2O3 15%Co/3.0%La2O3-Al2O3 15%Co/3.1%ZrO2-Al2O3

Dispersion (%)

15%Co/Al2O3 HP14/150 Catalyst 15%Co/Al2O3 SBA150 15%Co/Al2O3 SBA200

NASA/TM—2012-216020 62
catalyst have a significantly higher extent of reduction than any of the reference

catalysts and an increased cluster size. This which indicates that the cobalt-alumina

interaction has been weakened.

Although 15%Co/3.1%ZrO2-Al2O3 has a slightly lower extent of reduction

(45%) than that of the two of the reference catalysts (15%Co/Al2O3 SBA150, and

15%Co/Al2O3 HP14/150)closely related to its properties (45% and 50%), it isn’t

clear if the zirconium has inhibited the reduction or not. These extent of reduction

results are in line with the TPR-AR profiles.

NASA/TM—2012-216020 63
Table 4.5: Hydrogen chemisorption / pulse reoxidation results following 10 hour

hydrogen reduction at 350oC.

Catalyst

Description

H2 desorbed

cat)

Duncor

(%)

duncor

(nm)

O2 consumed

cat)

Red

(% )

Dcor (%) dcor

(nm)

15%Co/9.7%

TiO2-Al2O3

66.3 5.2 19.8 1198 71 7.4 14.0

15%Co/3.0%

La2O3-Al2O3

71.0 5.6 18.5 968 57 9.8 10.5

15%Co/3.1%

ZrO2-Al2O3

56.3 4.4 23.3 757 45 9.9 10.4

15%Co/Al2O3

HP14/150

72.7 18.1 5.71 816 48 11.9 8.7

15%Co/Al2O3

SBA150

74.7 5.87 17.6 855 50 11.6 8.9

15%Co/Al2O3

SBA200

52.9 4.15 24.8 558.5 33 12.6 8.2

NASA/TM—2012-216020 64
4.6 X-Ray Diffraction (XRD)

X-ray diffraction profiles are shown in Figure 4.28 through Figure 4.33. Each

profile has labeled peaks for known components at the indicated angles. Simionato

et al. have shown that is corresponding to Al2O3

35.

o was used to determine the crystallite size.

Figure 4.28: X-ray diffraction profile of 15%Co/9.7%TiO2-Al2O3 (a) and 9.7%TiO2-

Al2O3 (b).

10 20 30 40 50 60 70 80 90

2

2 Al2O3

(a):15%Co/9.7% TiO -

*

*

*

*

3 4

* 2 3

:

:

Co O

Al O

R rutile

A anatase

A A

2 Al2O3

(b) :9.7%TiO -

A

A

AA

A

A

A

A

R

*

NASA/TM—2012-216020 65
Figure 4.29: X-ray diffraction profiles of 15%Co/3.0%La2O3-Al2O3 (a) and

3.0%La2O3-Al2O3 (b).

10 20 30 40 50 60 70 80 90

2

2 3 Al2O3

(a) :15%Co/3.0%La O -

*

*

*

*

2 3

2 3

3 4

#:

*:

:

La O

Al O

Co O

#

#

#

#

#

#

2 3 Al2O3

(b):3.0%La O -

*

*

NASA/TM—2012-216020 66
Figure 4.30: X-ray diffraction patterns of calcined samples 15%Co/3.1%ZrO2-Al2O3

(a) and 3.1%ZrO2-Al2O3 (b).

10 20 30 40 50 60 70 80 90

2

*

Z cubic zirconia

Al O

Co O

:

*:

:

2 3

3 4

*

*

*

Z

Z

Z

2 Al2O3

(b): 3.1%ZrO -

2 Al2O3

(a):15%Co/3.1%ZrO -

*

*

NASA/TM—2012-216020 67
Figure 4.31: X-ray diffraction patterns of calcined samples 15%Co/Al2O3 HP14/150

(a) and Al2O3 HP14/150 (b).

Figure 4.32: X-ray diffraction patterns of calcined samples 15%Co/Al2O3 SBA150

(a) and Al2O3 SBA150 (b).

10 20 30 40 50 60 70 80 90

2

( ) :15%Co/Al O 14 /150 a 2 3 HP

*

*

*

*

3 4

*

2 3

Co O

Al O

( ) :Al O 14 /150 b 2 3HP

*

*

10 20 30 40 50 60 70 80 90

2

(a):15%Co/Al2O3 SBA150

*

*

*

*

3 4

2 3

*

Co O

Al O

(b):Al2O3 SBA150

*

*

NASA/TM—2012-216020 68
Figure 4.33: X-ray diffraction patterns of calcined samples 15%Co/Al2O3 SBA200

(a) and Al2O3 SBA200(b).

Table 4.6 below shows the particle size estimate from XRD line broadening

analysis o and using the Scherrer equation, as follows.

=

0.89

:

: (1.54 Å)

: ( )

After reduction, it is expected that the cobalt cluster size should be around

75% of the original cobalt oxide cluster size, so a contraction factor of 0.75 was used

10 20 30 40 50 60 70 80 90

2

(a) :15%Co/Al2O3 SBA200

*

*

*

*

3 4

2 3

*

Co O

Al O

( ): Al O 200 2 3b SBA

*

*

NASA/TM—2012-216020 69
for converting Co3O4 to Coo. The results give expected cobalt metal cluster sizes for

15%Co/9.7%TiO2-Al2O3, 15%Co/3.1%ZrO2-Al2O3 , and 15%Co/3.0%La2O3-Al2O3 as

12.1 nm, 7.8 nm, and 8.5 nm, respectively. These results are in line with the

chemisorption results previously discussed.

Table 4.6: X-ray Diffraction results from XRD plots and Scherrer Equation

Catalyst Average diameter of Co3O4

domains nm)

Expected average Co0

domain diameter (nm) by

applying 0.75 contraction

factor

15%Co/9.7%TiO2-Al2O3 15.3 11.5

15%Co/3.0%La2O3-Al2O3 11.7 8.8

15%Co/3.1%ZrO2-Al2O3 11.3 8.5

15%Co/Al2O3 HP14/150 10.4 7.8

15%Co/Al2O3 SBA150 9.9 7.4

15%Co/Al2O3 SBA200 9.6 7.2

4.7 Discussion

TPR profiles have indicated narrowing and a significant shift in the second

reduction peaks to lower temperatures of both the La2O3 and TiO2 doped supported

catalysts. The TPR-AR profiles show that after reduction has occurred, these doped

supports have significantly increased the active cobalt present on the surface of the

support, in comparison to all three reference supported catalysts. Along with both

TPR and TPR-AR results, the pulse reoxidation measurements of the hydrogen

chemisorptions have confirmed these findings. The extent of reduction of the La2O3

doped supported catalyst was 57% in comparison to referenced alumina supported

NASA/TM—2012-216020 70
catalysts (48%, 50%, and 33%). The extent of reduction of the TiO2 doped

supported catalyst was 71%. In comparison to the referenced pure alumina

supported catalysts, this is a significant increase in reducibility. All of these results

indicate that both La2O3 and TiO2 doped supports have facilitated the reduction of

cobalt oxide species in reference to pure alumina supported cobalt catalysts.

There was a slight shift in the second reduction peak of the ZrO2 doped

supported catalyst to a lower temperature, however TPR-AR results are not clear as

to whether or not the reduction of ZrO2 doped supported catalyst facilitated the

reduction or not. In further investigation, the hydrogen chemisorption data resulted

in an extent of reduction of 45% in comparison to pure alumina SBA150 and

SBA200 (48% and 33% respectively). While it is not apparent that the doped ZrO2

supported catalyst facilitated the reduction, it is also unclear whether or not it

inhibited the reduction. Further investigation of the effect of ZrO2 doping is

necessary. A suggestion is that a better reference support is used in further

research and that various doping levels of ZrO2 on alumina are explored.

The hydrogen chemisorption and pulse reoxidation results have shown an

increased corrected cluster size for all three doped supported catalysts. The pure

alumina supported reference catalysts had corrected cluster size diameters of 8.2,

8.9, and 8.7 nanometers. The three doped supported catalysts: TiO2, La2O3, and ZrO2

had corrected cluster size diameters of 14.0, 10.5, and 10.4 nanometers

respectively. Although this may not be a significant increase in cluster size for all

three doped supports, it has been shown that increasing the particle size to 10nm

NASA/TM—2012-216020 71
may be beneficial from a stability standpoint 36. It has also been shown that

catalysts with smaller cluster size were found to have a permanent and more

sensitive deactivation in the presence of water37. Never the less, the cluster size has

been affected by the dopant being present on the support. Cobalt cluster size was

also measured using XRD, which provided a cross reference for the pulse

reoxidation data. The XRD data required the use of a contraction factor in order to

compare the data, since XRD is completed on cobalt oxide and reduced cobalt metal.

The results of XRD were in line with pulse reoxidation data.

Since the TiO2 and La2O3 doped supported catalysts have displayed an

increase in reduction and an increase in the cluster size, it is likely that the supportmetal interaction was weakened by the addition of TiO2 and La2O3. ZrO2 results in

both reduction and cluster size data lead to the conclusion that the interaction was

likely decreased upon presence of ZrO2 on the alumina, but further investigation is

recommended. Pore size distributions showed only a slight decrease in pore

volume upon addition of cobalt to the supports in question. This likely means that

the cobalt cluster size was dependent upon the surface interaction of cobalt oxide

with the support, rather than the pore radius. On all three catalysts, TPD results

provided a baseline for active site density. In comparison to their reference

catalysts, all three catalyst showed a decrease in active site density, which was likely

caused by the increased cobalt cluster size previously discussed.

The quality of data in this report appears to be high, multiple

characterization techniques were compared and various techniques resulted in the

NASA/TM—2012-216020 72
same conclusions. TPR results were in line with oxygen titration extent of reduction

results, as well as XRD cluster size results agreeing with hydrogen chemisorptions

and pulse reoxidation data. It is suggested that this research be continued in order

to fully understand the impact these catalysts will have on Fischer-Tropsch

synthesis. The catalyst characterization results indicate that the titanium oxide and

lanthanum oxide doped alumina supported catalysts are of interest because of the

weakened cobalt support interaction and potential decrease in catalyst cost. By

increasing the extent of reduction, there is more metallic cobalt present on the

support. However, whether or not there is more cobalt available to participate in

the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the

cluster size in addition to the extent of reduction. On the one hand, while increasing

cluster size alone tends to decrease the active site density, on the other hand, by

increasing the size of the cobalt clusters, there is less likelihood of forming oxidized

cobalt complexes, such as cobalt aluminate, during Fischer-Tropsch synthesis. Thus,

from the standpoint of stability, improving the extent of reduction while increasing

the particle size slightly may be beneficial for maintaining the sites, even if there is a

slight decrease in overall initial site density. For catalysts with significant metalsupport interactions, there is often a reduction promoter present in the form of a

precious metal, like platinum. It is in the best interest of researchers to find ways to

minimize the dependency on reduction promoters that are expensive metals, while

at the same time increasing the performance of these cobalt catalysts3. These

catalyst should be studied in a continuously stirred tank reactor to study their long

term stability. The reaction kinetics will also provide data on activity and

NASA/TM—2012-216020 73
selectivity, which will be useful in determining the overall catalytic improvements

upon titanium and lanthanum oxide doping of alumina. As for zirconium oxide

doped alumina supports, it is suggested that an in depth study be conducted, which

has already begun. The goal of this study is to have a more representative reference

support and that various amounts of zirconium oxide modifications be made to the

alumina support. This study will provide information on the affect zirconium oxide

has on the final cobalt catalyst and whether or not zirconium oxide inhibits

reduction.

4.8 Conclusions

TPR results indicated that both La2O3 and TiO2 doped supports facilitated the

reduction of cobalt oxide species in reference to pure alumina supported cobalt

catalysts, however further investigation is needed to determine the effect of ZrO2

doping on the reduction profile. The hydrogen chemisorption/pulse reoxidation

and XRD results have show an increased corrected cluster size for all three doped

supported catalysts in comparison to their reference catalysts. Since the TiO2 and

La2O3doped supported catalysts displayed an increase in reduction and an increase

in the cluster size, it is likely that the support-metal interaction was weakened by

the addition of TiO2 and La2O3. Results for ZrO2 were unclear whether zirconium

oxide facilitated the reduction or inhibited it, but cluster size was slightly increased

when zirconium oxide was present on the support. This leads to the conclusion that

the interaction was likely decreased with the presence of ZrO2 on the alumina, but

further investigation is recommended on a better representative support to

determine how zirconium oxide affects the reduction of the cobalt catalysts.

NASA/TM—2012-216020 74
Furthermore, pore size distributions showed only a slight decrease in pore volume

upon addition of cobalt to the supports in question. This likely means that the

cobalt cluster size was dependent upon the surface interaction of cobalt oxide with

the support, rather than the pore radius, thus leading to a conclusion of weakened

interaction between the doped supports and cobalt.

By increasing the extent of reduction, there is more metallic cobalt present

on the support. However, whether or not there is more cobalt available to

participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms)

depends also on the cluster size in addition to the extent of reduction. On the one

hand, while increasing cluster size alone tends to decrease the active site density, on

the other hand, by increasing the size of the cobalt clusters, there is less likelihood of

forming oxidized cobalt complexes, such as cobalt aluminate, during FischerTropsch synthesis. Thus, from the standpoint of stability, improving the extent of

reduction while increasing the particle size slightly may be beneficial for

maintaining the sites, even if there is a slight decrease in overall initial site density.

For catalysts with significant metal-support interactions, there is often a reduction

promoter present in the form of a precious metal, like platinum. It is in the best

interest of researchers to find ways to minimize the dependency on reduction

promoters that are expensive metals, while at the same time increasing the

performance of these cobalt catalysts3. The hypothesis was that the presence of

lanthanum oxide, titanium oxide, and zirconium oxide on alumina oxide would

reduce the interaction between cobalt and the alumina oxide support in FischerTropsch catalysis. This hypothesis has been verified for both lanthanum oxide and

NASA/TM—2012-216020 75
titanium oxide, but further studies are needed to verify the interaction affect of

zirconium oxide. A follow-up study should be conducted using a reference alumina

support and doping various amounts of zirconium oxide on the support and the

reduction should be examined to see if there is variation in the reduction profile in

correlation to the amount of zirconium oxide present.

NASA/TM—2012-216020 76
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NASA/TM—2012-216020 79
APPENDIX A. Pore Size Distribution Profiles

Figure 4.34: Adsorption pore size distribution of (left) 9.7%TiO2-Al2O3 and (right)

15%Co/9.7%TiO2-Al2O3.

Figure 4.35: Desorption pore size distributions of 9.7%TiO2-Al2O3(left) and

15%Co/9.7%TiO2-Al2O3(right)

Figure 4.36: Adsorption pore size distribution of 3.0%La2O3-Al2O3 (left) and

15%Co/3.0%La2O3-Al2O3 (right)

NASA/TM—2012-216020 80
Figure 4.37: Desorption pore size distribution of 3.0%La2O3-Al2O3 (left) and

15%Co/3.0%La2O3-Al2O3 (right)

Figure 4.38: Adsorption pore size distribution of 3.1%ZrO2-Al2O3 (left) and

15%Co/3.1%ZrO2-Al2O3 (right)

Figure 4.39: Desorption pore size distributions of 3.1%ZrO2-Al2O3(left) and

15%Co/3.1%ZrO2-Al2O3 (right).

NASA/TM—2012-216020 81
(a) (b)

(c) (d)

Figure 4.40: Adsorption pore size distribution of Al2O3 HP14/150 (a)& (b) and

15%Co/Al2O3 HP14/150 (c) & (d).

NASA/TM—2012-216020 82
(a) (b)

(c) (d)

Figure 4.41: Desorption pore size distribution of Al2O3 HP14/150 (a)& (b) and

15%Co/Al2O3 HP14/150 (c) & (d).

NASA/TM—2012-216020 83
(a) (b)

(c) (d)

Figure 4.42: Adsorption pore size distributions of (a) & (b): SBA 150 Al2O3 and (c) &

(d): 15%Co/SBA 150 Al2O3.

NASA/TM—2012-216020 84
(a) (b)

(c) (d)

Figure 4.43: Desorption pore size distributions of (a) & (b): SBA 150 Al2O3 and (c) &

(d): 15%Co/SBA 150 Al2O3.

NASA/TM—2012-216020 85
(a) (b)

(c) (d)

Figure 4.44: Adsorption pore size distributions of (a) & (b): Al2O3.SBA 200 and (c) &

(d): 15%Co/Al2O3.SBA 200

NASA/TM—2012-216020 86
(a) (b)

(c) (d)

Figure 4.45:Desorption pore size distributions of (a) & (b): Al2O3.SBA 200 and (c) &

(d): 15%Co/Al2O3.SBA 200

NASA/TM—2012-216020 87