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Springer Theses
Recognizing Outstanding Ph.D. Research

Ruijun Hou

Catalytic and Process

Study of the Selective
Hydrogenation
of Acetylene and
1,3-Butadiene
Springer Theses

Recognizing Outstanding Ph.D. Research

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Ruijun Hou

Catalytic and Process Study

of the Selective
Hydrogenation of Acetylene
and 1,3-Butadiene
Doctoral Thesis accepted by
Tsinghua University, Beijing, China

123
Author Supervisor
Dr. Ruijun Hou Prof. Tiefeng Wang
Department of Chemical Engineering Department of Chemical Engineering
Tsinghua University Tsinghua University
Beijing Beijing
China China

ISSN 2190-5053 ISSN 2190-5061 (electronic)

Springer Theses
ISBN 978-981-10-0772-9 ISBN 978-981-10-0773-6 (eBook)
DOI 10.1007/978-981-10-0773-6
Library of Congress Control Number: 2016961697

© Springer Science+Business Media Singapore 2017

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
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Supervisor’s Foreword

This thesis describes the scientific achievements of Dr. Ruijun Hou, which were
made during her doctoral program at the Department of Chemical Engineering,
Tsinghua University. During the five years as a doctoral student, she demonstrated
distinguished ability in scientific research and obtained a number of important
results on the selective hydrogenation reactions of acetylene and 1,3-butadiene in
both catalytic study and process study. As the supervisor of her undergraduate
thesis and doctoral thesis, I can introduce the most important findings of her studies.
Dr. Hou’s work focused on the selective hydrogenation of acetylene and
1,3-butadiene. After an extensive literature survey of several hundred publications,
she chose to study this reaction system by both experiments and DFT calculations.
She combined the experimental catalysis (catalyst synthesis, characterization, and
reaction evaluation), computational catalysis (DFT calculation for metallic sur-
faces), and reaction engineering (process and reactor design).
The catalytic study started from model surfaces by UHV-TPD experiments and
DFT calculations. The unique properties of the Pd-Ni bimetallic model surface
inspired her to further study the supported catalysts. The good correlation between
model surfaces and supported catalysts demonstrated the feasibility of designing
effective bimetallic catalysts for selective hydrogenation reactions. Further,
non-precious metal catalysts were designed by replacing the precious metal with
non-precious metal carbide.
In the chemical process study, Dr. Hou modified the process of selective
hydrogenation of acetylene by coupling the selective absorption with the selective
hydrogenation in a liquid phase. As a result, the ethylene selectivity was greatly
improved, and the heat transfer performance was also greatly enhanced. Lastly, she
proposed a multi-stage slurry bed reactor for potential industrial applications.

v
vi Supervisor’s Foreword

Looking back on Dr. Hou’s scientific achievements, I believe they are of great
importance for both industrial and fundamental catalysis. I hope that the readers
will be inspired by the novel catalysts and the new process in liquid-phase
hydrogenation as a result of the author’s efforts.

Beijing, China Prof. Tiefeng Wang

September 2016
Parts of this thesis have been published in the following journal articles:

1. Hou Ruijun, Lan Xiaocheng, Wang Tiefeng(*), “Selective hydrogenation of

acetylene on Pd/SiO2 in bulk liquid phase: A comparison with solid catalyst
with ionic liquid layer (SCILL)”, Catalysis Today, 2015, 251: 47–52.
2. Hou Ruijun, Chang Kuan, Chen Jingguang G.(*), Wang Tiefeng(*), Replacing
Precious Metals with Carbide Catalysts for Hydrogenation Reactions, Topics in
Catalysis, 2015, 58(4-6): 240–246.
3. Hou Ruijun, Porosoff Marc D., Chen Jingguang G.(*), Wang Tiefeng(*), Effect
of oxide supports on Pd–Ni bimetallic catalysts for 1,3-butadiene hydrogena-
tion, Applied Catalysis A: General, 2015, 490: 17–23.
4. Hou Ruijun, Yu Weiting, Porosoff Marc D., Chen Jingguang G.(*), Wang
Tiefeng(*), Selective hydrogenation of 1,3-butadiene on PdNi bimetallic cata-
lyst: From model surfaces to supported catalysts, Journal of Catalysis, 2014,
316: 1–10.
5. Hou Ruijun, Wang Tiefeng(*), Lan Xiaocheng, Enhanced Selectivity in the
Hydrogenation of Acetylene due to the Addition of a Liquid Phase as a Selective
Solvent, Industrial & Engineering Chemistry Research, 2013, 52(37):
13305–13312.

vii
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Purification of C2–C4 Olefins . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Production of Ethylene from Acetylene. . . . . . . . . . . . . . . 2
1.2 Properties of Selective Hydrogenation Reactions . . . . . . . . . . . . . 3
1.3 Industrial Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Progress in Catalyst Development . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.1 Reaction Mechanism on Pd Catalyst . . . . . . . . . . . . . . . . . 6
1.4.2 Influencing Factors on Pd-Based Catalysts . . . . . . . . . . . . 12
1.4.3 Pd-Based Bimetallic Catalysts . . . . . . . . . . . . . . . . . . . . . . 17
1.4.4 Non-Pd Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5 Thesis Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 Experimental and Theoretical Methods . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1 Chemicals and Instruments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2 Measurements of Model Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2.1 Ultra-High Vacuum (UHV) System . . . . . . . . . . . . . . . . . 31
2.2.2 Preparation of Single-Crystal Surfaces . . . . . . . . . . . . . . . 31
2.2.3 Temperature-Programmed Desorption (TPD) . . . . . . . . . . 33
2.3 Density Functional Theory (DFT) Calculations . . . . . . . . . . . . . . 34
2.4 Catalyst Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.4.1 Supported Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.4.2 Mo2C-Based Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.5 Catalyst Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.5.1 SEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.5.2 TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.5.3 XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

ix
x Contents

2.5.4 TG-DTA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.5.5 Physisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.5.6 CO-Chemisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.5.7 XAFS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.6 Catalyst Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.6.1 Batch Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.6.2 Fixed-Bed Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.6.3 Slurry Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.7 Measurement of Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3 Selective Hydrogenation of 1,3-Butadiene on Pd–Ni Bimetallic
Catalyst: From Model Surfaces to Supported Catalysts . . . . . . . . . . . 45
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.2 DFT Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.1 Adsorption Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.2 Activation Barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.3 UHV Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3.1 Preparation of Single-Crystal Surfaces . . . . . . . . . . . . . . . 49
3.3.2 TPD Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.4 Characterization of Supported Catalysts . . . . . . . . . . . . . . . . . . . . 55
3.4.1 TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.4.2 CO Chemisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.4.3 XAFS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.5 Evaluation of Supported Catalysts . . . . . . . . . . . . . . . . . . . . . . . . 60
3.5.1 Batch Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.5.2 Fixed-Bed Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.6 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4 Effect of Oxide Supports on Pd–Ni Bimetallic Catalysts
for 1,3-Butadiene Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2 Catalyst Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.1 TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.2 CO Chemisorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.2.3 Temperature Programmed Reduction (TPR) . . . . . . . . . . . 76
4.2.4 XAFS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4.3 Catalyst Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.3.1 Bimetallic Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.3.2 Hydrogenation Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.3.3 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Contents xi

4.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.4.1 Bimetallic Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.4.2 Support Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5 Replacing Precious Metals with Carbide Catalysts for
Hydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.2 Catalyst Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.3 Mo2C for the Hydrogenation of Dienes . . . . . . . . . . . . . . . . . . . . 92
5.3.1 1,3-Butadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5.3.2 1,3-Cyclohexadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.3.3 1,4-Cyclohexadiene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.4 Ni/Mo2C for the Hydrogenation of 1,3-Butadiene . . . . . . . . . . . . 97
5.5 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
5.5.1 Hydrogenation Activity and Stability . . . . . . . . . . . . . . . . 98
5.5.2 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.5.3 Potential Advantage in Cost Reduction . . . . . . . . . . . . . . . 103
5.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6 Selective Hydrogenation of Acetylene in Liquid Phase: A Novel
Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
6.2 Catalyst Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.3 Optimization of Operation Parameters . . . . . . . . . . . . . . . . . . . . . 110
6.3.1 Effect of Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6.3.2 Effect of GHSV. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
6.3.3 Effect of H2/C2H2 Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . 114
6.3.4 Comparison with Gas-Phase Reaction . . . . . . . . . . . . . . . . 117
6.4 Solvent Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
6.4.1 Selective Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
6.4.2 Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
6.5 Induction Period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
6.6 Catalyst Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
6.7 A Comparison with Solid Catalyst with Ionic Liquid Layer
(SCILL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6.7.1 A General Comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6.7.2 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6.7.3 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6.7.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
xii Contents

6.8 Process Optimization and Reactor Design . . . . . . . . . . . . . . . . . . 131

6.8.1 Two-Stage Slurry Reactor . . . . . . . . . . . . . . . . . . . . . . . . . 132
6.8.2 Pressure Effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
6.8.3 Design of Multi-Stage Reactor . . . . . . . . . . . . . . . . . . . . . 134
6.9 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Chapter 1
Introduction

1.1 Background

The selective hydrogenation of alkynes and dienes is an important reaction in

chemical industry. They are widely applied in the purification of olefin streams to
remove alkynes/dienes, the gasoline refinery process, and some of the fine chemical
processes. The selective hydrogenation of acetylene also provides a new route for
the production of ethylene from natural gas or coal. The selective hydrogenation is
to hydrogenate the C–C triple bond to double bond or to hydrogenate two C–C
double bonds to one double bond. Thus, the process requires the hydrogenation to
stop at the first hydrogenation step, not to reach complete hydrogenation.

1.1.1 Purification of C2–C4 Olefins

Ethylene is one of the most important products in petrochemical industry. Its

domestic capacity is usually an indicator to measure the development of a country’s
chemical industry. The light olefins from the steam cracker are the monomers or
co-monomers for the production of polyolefin, synthetic materials, organic chem-
icals, and fine chemicals [1]. However, there are about 0.5–5% of alkynes/dienes in
the cracking stream [2–5]. Even the minor amounts of alkynes/dienes will affect the
polymerization process negatively. For example, the alkynes/dienes will poison the
polymerization catalysts [6, 7]; the alkynes/dienes can easily react with the olefins
and will disqualify the products [8]; the C–C triple bond in the alkynes will
complex with the copper in the apparatus and form copper acetylide, which is
explosive and dangerous [9]. As a result, the polymerization-grade olefins require
the concentration of alkynes/dienes in the olefin stream at ppm level. Table 1.1 lists
the requirements for C2–C4 olefin streams.

© Springer Science+Business Media Singapore 2017 1

R. Hou, Catalytic and Process Study of the Selective Hydrogenation of Acetylene
and 1,3-Butadiene, Springer Theses, DOI 10.1007/978-981-10-0773-6_1
2 1 Introduction

Table 1.1 Concentration requirements for alkyne/diene in the polymerization-grade olefin stream
Olefin Alkyne/diene Requirement for Requirement for
initial concentration (%) alkyne (ppm) diene (ppm)
Ethylene [5] 0.5–2.3 5 –
Propene [3, 4] 3–5 5 10
1-Butene [2] *1 10 12

The purification of olefin stream usually uses selective hydrogenation or solvent

extraction processes. Solvent extraction process can recycle the alkynes/dienes as
well as purify the olefin stream, but the process is complicated and the system is
difficult to operate. On the contrary, selective hydrogenation is simple in process
and is more effective in the alkynes/dienes removal. So far, it is the most eco-
nomical and effective method [5, 6] in industry. In the C2–C4 streams, the mole-
cules to be removed are acetylene, propyne, propadiene, and 1,3-butadiene; the
desired products are ethylene, propene, and 1-butene [10]. In the C4 stream,
1-butene is the monomer for the production of polybutene and co-monomer for
polyethylene, so 1-butene is the most desirable among the butene species [6].

1.1.2 Production of Ethylene from Acetylene

The current production of ethylene relies on oil refinery. As an important basic

chemical in industry, the demand of ethylene in China exceeded 16 million tonnes
in 2013 [11]. However, the oil resource in China is not abundant. The external
dependence of oil was 56.4% in 2012 [12], and the number keeps increasing in
recent years. It is important to seek for substitute route to produce ethylene from
non-oil resources, in order to reduce the external dependence of oil.
Shale gas revolution in the USA has made a profound change in the worldwide
energy structure since 2005. China has expanded the production of natural gas in
recent years. The gas proportion of energy consumption is increasing and was about
5% in 2011. Moreover, the West-to-East Natural Gas Transmission Project in China
has increased the utilization of natural gases in the west [13].
On the other hand, as the technology of acetylene production from gas and coal
became mature [14], the supply of the downstream product polyvinyl chloride
(PVC) exceeded the demand. The profit of PVC has become lower, and it is
urgently needed to expand the downstream products of acetylene [15, 16].
Polyethylene (PE) is a possible product because the price of PE fluctuates with the
price of oil, and its downstream products such as ethylene glycol, propylene glycol,
acrylic acid, and polyvinyl alcohol (PVA) have good economic values [11, 17].
Therefore, the selective hydrogenation of acetylene could provide a new route for
ethylene production and will decrease the dependence of ethylene on oil.
1.2 Properties of Selective Hydrogenation Reactions 3

1.2 Properties of Selective Hydrogenation Reactions

Selective hydrogenation of C–C bond is a series reaction. It is desired that the

hydrogenation stops at the first hydrogenation step but not further undergoes the
second step. The selectivity is controlled by the hydrogenation of the C–C bonds.
However, over one certain catalyst, the hydrogenation activities of the first step and
the second step are positively correlated. The selectivity can only be controlled by
controlling the adsorption properties of olefins. If the adsorption energy of olefin is
low, the desired product could desorb quickly from the catalyst and avoid the
complete hydrogenation. Moreover, the control of oligomerization of
alkynes/dienes should not be neglected. To decrease the concentration of
alkynes/dienes on the catalyst is the major way to control the oligomerization
reactions.
Meanwhile, the hydrogenation reactions are exothermic. The reactors used in
industry are fixed-bed reactor. The released heat in the reaction will lead to hot spot
along the reactor and could possibly lead to runaway of temperature. The runaway
of temperature is caused by the low efficiency of heat transfer in the fixed-bed
reactor. It will affect the normal operation and will even destroy the loaded cata-
lysts. The reaction heats of acetylene hydrogenation are listed as an example:
Main reaction:

HC
CH þ H2 ! H2 C¼CH2 þ 174:4 kJ=mol ð1:1Þ

Side reactions:

H2 C¼CH2 þ H2 ! H3 C  CH3 þ 137:0 kJ=mol ð1:2Þ

HC
CH þ 2H2 ! H3 C  CH3 þ 311:4 kJ=mol ð1:3Þ

nHC
CH þ mH2 C¼CH2 ! C4 and green oil ð1:4Þ

As seen from the thermodynamic data, the heat released in the hydrogenation
reactions is enormous. The industrial operation temperature is only slightly higher
than the room temperature, and the temperature control is very difficult. The tem-
perature rise along the reactor could be as high as 20–40 °C [18, 19].

1.3 Industrial Processes

The selective hydrogenation in industry usually utilizes fixed-bed reactor. When the
inlet is gas phase, it is a conventional fixed-bed reactor of gas–solid phase; when the
inlet is liquid phase, it is a trickle-bed reactor with gas, liquid, and solid phases
[20–25].
4 1 Introduction

The fixed-bed process has been improved by several ways to enhance the heat
transfer. One way is to introduce a liquid phase in the fixed-bed process, in which
some of the products are cooled to liquid and are cycled back to the reactor, in order
to dilute the reactants in the inlet and absorb the reaction heat inside the reactor [26,
27]. Another way is to utilize multistage fixed-bed process, in which heat
exchangers are installed between stages in order to control the temperature rise [28].
These methods have enhanced the heat transfer to some extent, but are complicated
in process, with high energy consumption and high investment.
The catalysts in the fixed bed deactivate easily because of the oligomerization
reactions of alkynes/dienes. The catalysts should be regenerated at regular intervals.
A spare reactor is needed for most processes, adding to higher investment in
equipment.
The selective hydrogenation of acetylene is a typical example, and the con-
ventional processes of acetylene hydrogenation are discussed below.
The processes for the selective hydrogenation of acetylene are typically
front-end and tail-end processes. As shown in Fig. 1.1, the hydrogenation reactor
locates before the demethanizer in the front-end process, and locates after the
demethanizer in the tail-end process.
In the front-end process, the gas stream from the cracker goes to the hydro-
genation reactor right after caustic washing and drying. The inlet of the hydro-
genation reactor contains not only C2 species, but also H2, CH4, CO, etc. After the
hydrogenation reaction, the C1 and C3 species are separated from the C2 stream. In
the tail-end process, the C2 species are firstly separated from the other gases; then, a
certain amount of H2 is mixed with the C2 stream, and the mixture is introduced
into the hydrogenation reactor [30].
The gas-phase concentrations in the inlet and the typical operation conditions of
the front-end and tail-end processes are shown in Table 1.2.
The advantages of the front-end process are as follows: (1) No extra H2 is
needed; (2) the separation process is simpler, leading to lower investment and lower
energy consumption; and (3) the high concentration of hydrogen results in lower
green oil formation and higher stability of catalysts. The disadvantages are as
follows: (1) The H2/C2H2 ratio could not be adjusted, so the selectivity to ethylene
is low; (2) the complete hydrogen increases the risk of temperature runaway in the
reactor; (3) the concentration of CO fluctuated in the inlet; because the CO con-
centration deceases the acetylene conversion, the outlet stream might not reach the
requirement for the polymerization-grade ethylene; and (4) there is no spare reactor
and only by stopping the whole process can replace the deactivated catalysts [31].
Compared with the front-end process, the advantages of the front-end process
are as follows: (1) The H2/C2H2 ratio could be adjusted, and the selectivity to
ethylene is higher; (2) the temperature is more easily controlled; and (3) the
operation is steadier. The disadvantages are as follows: (1) The formation of green
oil is higher, and the catalysts are less stable; (2) due to the fast deactivation of
catalyst, a spare reactor is needed for the frequent catalyst regeneration; and (3) the
1.3 Industrial Processes 5

Fig. 1.1 Process chart of front-end (up) and tail-end (down) processes. Reprinted from Ref. [29]
with permission from Taylor & Francis Ltd.

separation process is more complicated, with higher investment and higher energy
consumption [29].
Because of the many differences between the front-end and tail-end processes,
the requirements for catalysts are different. The catalyst for the front-end process
requires the catalyst with high selectivity, while the catalyst for the tail-end process
requires the catalyst with good stability.
6 1 Introduction

Table 1.2 The gas-phase Parameter Front-end Tail-end

concentrations of inlet and
typical operation conditions H2 (molar %) 22 2.4
of front-end and tail-end C2H2 (molar %) 0.2 2
processes C2H4 (molar %) 37 71
CH4 (molar %) 12 –
C2H6 (molar %) 28.4 25
C3H6 (molar %) 0.12 –
CO (ppm) 2800 40
H2/C2H2 110 1.5
Pressure (bar) 35 20
Temperature (K) 343 333
GHSV (h−1) 2000 3000
Reprinted from Ref. [29] with permission of Taylor & Francis
Ltd.

1.4 Progress in Catalyst Development

The catalysts for selective hydrogenation date back to the 1940s. In the selective
hydrogenation of gasoline to remove dienes, nickel sulfide or copper was applied.
However, the catalysts were of low activity and required high operation tempera-
ture, which would lead to more polymerization reactions [1]. In the 1960s, with the
fast development of the ethylene industry, the catalysts for selective hydrogenation
were greatly studied. The active metals were focused on the VIII group metals, such
as Pd [32–36], Pt [36–38], Ni [36], etc. Among them, Pd was widely applied in
industry because of the high hydrogenation activity and the relatively high selec-
tivity to ethylene. However, the selectivity to ethylene on Pd catalyst was far from
satisfaction, and the catalyst stability is relatively low. In the 1970s, the Pd-based
bimetallic catalysts emerged. In the late 1980s, Procatalyse, United Catalysts,
Leunawerke, and AcreonCatalysts developed mature Pd-based bimetallic catalysts
and applied them in production. Since the twenty-first century, the research on
Pd-based bimetallic catalysts has been expanded from experimental to fundamental
by quantum calculation, thus saving considerable amount of manpower, time, and
resources. Other than Pd-based catalysts, the non-Pd catalysts and non-precious
catalysts have also been investigated widely.

1.4.1 Reaction Mechanism on Pd Catalyst

The Pd monometallic catalyst has been extensively studied because of its wide
application in industry. The mechanism, the phase change over the catalyst, and the
deactivation progress in the selective hydrogenation of acetylene are summarized
and discussed below.
1.4 Progress in Catalyst Development 7

1.4.1.1 Reaction Mechanism

The reaction pathways of selective hydrogenation of alkynes/dienes are shown in

Fig. 1.2. It was reported that alkyne/diene firstly adsorbed on the catalyst surface
and then underwent the first step of hydrogenation; the olefin either desorbed from
the catalyst or underwent the second step of hydrogenation. The selectivity was
defined from two sides: (1) kinetic selectivity, if k2 ≫ k4, i.e., the hydrogenation
activity of the first step is much faster than the second step, the catalyst would give
a high selectivity in terms of kinetics; and (2) thermodynamics selectivity: if
k1/k−1 ≫ k3/k−3, i.e., the alkyne/diene adsorbed much faster than olefin, the olefin
could desorb easily from the catalyst, and the catalyst would give a high selectivity
to olefin in terms of thermodynamics. Other than the hydrogenation reactions, there
are oligomerization reactions on the Pd surface. The complete hydrogenation and
the oligomerization reactions are the two main side reactions in the selective
hydrogenation of acetylene [39].
The reaction pathway and the adsorbed intermediates were studied and detected
by FT-IR and EELS under ultra-high vacuum conditions. As shown in Fig. 1.3, the
acetylene firstly adsorbed on the catalyst by π-bond (1); after absorbing one
hydrogen atom, the C2H*3 adsorbed by π–σ-bond; the parallel adsorbed C2H*3 could
be rearranged to vertically adsorbed (4) or (5); (4) and (5) would undergo complete
hydrogenation and form ethane; if the π-bonded C2H*2 rearranged to σ-bonded (2),
or hydrogenated into π-bonded C2H*4, the selective hydrogenation reaction hap-
pened [40].
Borodzinski et al. [41, 42] proposed a reaction mechanism by the analysis of
reaction kinetics on Pd/Al2O3. They believed there were three kinds of active sites
as shown in Fig. 1.4: A1, A2, and E.
A1 site was small Pd assembles separated by the surface hydrocarbon. It could
adsorb acetylene and hydrogen. However, because of the steric hindrance, it hardly
adsorbs ethylene. Hence, only selective hydrogenation and minor oligomerization
reactions happened on A1 site, but little complete hydrogenation reaction.
A2 site was the site covered by hydrocarbon and could only adsorb acetylene.
The adsorbed acetylene reacted with the hydrogen transferred from the hydrocarbon
layer. The ethylene formed on this site could desorb quickly and not undergo
complete hydrogenation.

Fig. 1.2 Reaction pathway of selective hydrogenation of alkynes/dienes. Reprinted from Ref.
[39], Copyright 2001, with permission from Elsevier
8 1 Introduction

Fig. 1.3 Reaction network (up) and the adsorbed intermediates (down) of acetylene hydrogena-
tion. Reprinted from Ref. [39], Copyright 2001, with permission from Elsevier

E site was large area of Pd assembles. It could adsorb all the reactants and
products and could catalyze selective hydrogenation, complete reaction, and
oligomerization reactions.
The ratio of A sites to E sites directly affected the selectivity to ethylene. Under
low partial pressure of acetylene and high partial pressure of ethylene, large amount
of ethylene adsorbed at E sites, and ethane formed at E sites; as a result, acetylene
only adsorbed and was hydrogenated on A1 sites. Under high partial pressure of
acetylene, the hydrogenation of acetylene mainly happed on A2 sites.
Borodzinski’s model has been replenished and revised since 2000. Vincent et al.
[43] proposed two models: One was the competitive adsorption model at low
temperature, in which the hydrogen was provided by adsorbed hydrogen; the other
was the non-competitive adsorption model, and the hydrogen was provided by the
transfer via the surface hydrocarbons. The rate-limiting steps in the two models
were both the hydrogenation of vinyl group. Mei et al. [44] calculated the ele-
mentary reaction kinetics and found that acetylene could easily adsorb on Pd; the
rate-limiting step was the hydrogen adsorption, the hydrogenation of vinyl group,
and the desorption of ethylene; further, they pointed out that the selectivity to
ethylene not only related to the adsorption properties of ethylene and acetylene, but
also related to the interaction between the adsorbed species and the adsorption
kinetics. Hevia et al. [45] investigated the hydrogenation of acetylene under low
pressure in a TAP reactor and found that the adsorption of hydrogen was reversible
and there formed a layer of carbide on the Pd surface at the initial stage of the
reaction.
1.4 Progress in Catalyst Development 9

Fig. 1.4 Reaction mechanism of acetylene hydrogenation [41, 42]. Reprinted from Ref. [41], with
kind permission from Springer Science+Business Media. Reprinted with permission from Ref.
[42]. Copyright 1997 American Chemical Society
10 1 Introduction

With the development of density functional theory (DFT) calculation, the fun-
damental study supported and further explained some of the experimental results.
Sheth et al. [46] and Xie et al. [47] calculated the adsorption energy, the adsorption
geometries, and the activation barriers in acetylene hydrogenation. They found that
the formation of PdHx phase affected the hydrogenation kinetics. Duca et al. [48,
49] studied the effect of carbon deposit and metal dispersion on the surface reaction
kinetics by Monte Carlo method, and they found that the steric hindrance did not
always decrease the surface activity. Li et al. [50, 51] studied the reaction pathway
of acetylene hydrogenation on Pd2–8 clusters.

1.4.1.2 PdHx and PdCx

Pd can absorb a large amount of hydrogen, and the bulk Pd would become bigger in
volume. The Pd metal particles on supported catalysts exist in nanoscale, and their
properties are different from the bulk Pd. Nevertheless, the Pd particles could still
absorb hydrogen. Two phases of Pd hydride have been reported: α-PdHx at low
hydrogen partial pressure and β-PdHx at high hydrogen partial pressure. The phase
diagram is shown in Fig. 1.5.
As shown in Fig. 1.5, the temperature and the partial pressure both affected the
formation of PdHx. In the hydrogenation reactions, the β-PdHx phase showed
higher activity than the α-PdHx phase, but gave lower selectivity to olefins. By
controlling the particle size, little β-PdHx phase formed on small Pd particles less
than 2.6 nm and gave higher selectivity to olefin.

Fig. 1.5 Phase diagram of

α-PdHx and β-PdHx (numbers
on the graph are temperature
in K) [52]. Reprinted from
Ref. [52], Copyright 2001,
with permission from Elsevier
1.4 Progress in Catalyst Development 11

Fig. 1.6 Pd and PdC0.13

phase change during reaction
[29]

Other than the PdHx phase, there was formation of PdCx(0 < x ≤ 0.13) phase
during the hydrogenation reaction. The PdCx phase usually formed in the hydro-
carbon environment under high temperature and decomposed in hydrogen or
oxygen above 403 K. Hydrogen and carbon atoms competed to occupy the
vacancies on the Pd catalyst and formed a Pd–C–H ternary structure. The presence
of carbon atoms decreased the possibility of the β-PdHx phase formation. When the
saturated PdC0.13 formed, the β-PdHx phase did not exist. The carbon atoms in the
PdCx phase could involve in reactions, and the presence of PdCx phase was not in
favor to reduce the carbon deposit or to suppress the oligomerization reactions.
The phase change on Pd and PdC0.13 is depicted in Fig. 1.6 [29]. On Pd, a phase
of PdC0.016 gradually formed as a bulk phase, while on PdC0.13, because the carbon
atoms were already saturated in the bulk phase, only the surface PdCx turned to
PdC0.016. The activities at steady state were the same for the two phases, as verified
by experiment.

1.4.1.3 Deactivation

Larsson et al. [53] proposed that the coke formation was influenced by the coverage
of surface hydrogen. The higher the surface coverage of hydrogen, the more
actively that coke formed. The mechanism of coke formation is shown in Fig. 1.7.
At different coverage of surface hydrogen, two types of green oil formed; at low
hydrogen coverage, the harmful green oil formed and was advantageous for
hydrogen transfer; at high hydrogen coverage, the harmless green oil formed which
covered the active sites. The existence of the two types of green oil was verified by

Fig. 1.7 Deactivation pathway in the hydrogenation of acetylene [53]. Reprinted from Ref. [53],
Copyright 2001, with permission from Elsevier
12 1 Introduction

Ahn et al. [54]. Xu et al. [55] found by TEM that the green oil aggregated around
the Pd particles. The Pd particles were taken away from the support and were
surrounded by green oil. The active sites for the formation of green oil were on the
metal site, and ethylene did not involve in the oligomerization reaction indepen-
dently; as the amount of green oil increased, it migrated onto the support surface
[56]. Moon et al. [54, 57] found that 1,3-butadiene was the precursor for the coke
formation and proposed a three-stage deactivation mechanism: The first step was
the formation of light green oil, during which the deactivation was not significant;
the second step was the formation of heavy green oil, and the green oil covered the
active sites and migrated to the support; and the third step was the formation of
heavy green oil in large amount, and the green oil blocked the support pores and
deactivated the catalyst significantly. Sarkany [58] proposed a mechanism for the
formation of C4 species: During the reaction, the carbon atoms dissolved into the
Pd phase and formed a Pd–H–C ternary phase; the increase of carbon atoms in Pd
decreased the number of available hydrogen atoms, thus decreasing the ethane
formation and increasing the C4 species formation. Esmaeili et al. [59] proposed a
deactivation mechanism based on pore structure. It was found that the branched
green oil easily formed on the supports with small pores. The branched green oil
would block the pores and deactivate the catalyst.
During the regeneration of catalyst, the metal particles aggregated more easily on
used catalyst than on fresh catalyst under low temperatures [56]. The dispersion of
regenerated catalyst decreased by 50%, but the activity was similar as fresh catalyst,
which might be attributed to the fast deactivation of fresh catalyst at the initial stage.
The selectivity of regenerated catalyst was lower than fresh catalyst, because the
harmful coke (Fig. 1.7) formed on the catalyst surface enhanced hydrogen transfer
and decreased the olefin selectivity [60].

1.4.2 Influencing Factors on Pd-Based Catalysts

There are many factors that influence the catalytic properties of Pd, such as metal
dispersion, support, pretreatment, and additives. The detailed effects are discussed
below.

1.4.2.1 Metal Dispersion

Metal dispersion represents the degree of metal utilization on a supported catalyst.

The higher the metal dispersion, the higher degree the metal utilization. The metal
dispersion affects differently the turnover frequency (TOF) and selectivities in
different reaction system.
The low-loading Pd catalyst is usually used in industry in order to control the
complete hydrogenation. The lower metal loading would lead to higher dispersion
and a higher apparent activity, as well as a higher selectivity to olefin [32, 61].
1.4 Progress in Catalyst Development 13

In the selective hydrogenation of alkynes, the high metal dispersion was reported
to result in a higher apparent activity [62–65] but lower TOF [65, 66]. The lower
TOF was attributed to the intrinsic defect of the small metal particles and the
interaction between the defects and the supports. The dispersion effect on selectivity
was reported differently in the literature. In the selective hydrogenation of acet-
ylene, it was commonly agreed that the higher the metal dispersion, the higher the
selectivity to ethylene [62, 67, 68]. However, Duca et al. [32] found that the
selectivity was not affected by metal dispersion by plotting the selectivity against
conversion. Borodzinski [65] also reported that the olefin selectivity was not
affected by the metal particle size when the particles were larger than 4 nm. In the
hydrogenation of phenyl acetylene, TOF was not much affected by metal disper-
sion, while the selectivity to styrene increased with increasing metal dispersion
[69].
Some literature reported that the metal dispersion did not affect the catalytic
properties independently, but showed synergetic effect with other influencing fac-
tors. Feng et al. [70] found that the high surface area, low acidity, and high metal
dispersion together affected the catalyst selectivity, activity, and stability positively.
Komhom et al. [71] also showed that the high surface area and the high metal
dispersion led to high selectivity and activity. Panpranot et al. [64] investigated the
TiO2-supported catalyst and believed that the ethylene selectivity was greatly
affected by the support but not by the metal dispersion; however, McKenna et al.
[72] believed that the TiO2-supported catalytic property was indeed affected by the
metal dispersion: The higher metal dispersion led to higher conversion but lower
selectivity.
Similar to the hydrogenation of alkynes, in the selective hydrogenation of
dienes, the higher metal dispersion usually resulted in higher apparent activity [73,
74] and lower TOF [74, 75]. The metal dispersion affected the catalytic properties
together with other factors [76]. Boitiaux et al. [77] investigated into the catalytic
properties at different metal dispersions for the selective hydrogenation of
1,3-butadiene. When the dispersion was lower than 20%, the TOF was not affected
by the metal dispersion; when the dispersion was higher than 20%, the TOF
decreased with increasing dispersion. The effects of dispersion on selectivity were
reported differently. For example, Pattamakomsan et al. [73] found that the selec-
tivity to olefins increased with increasing dispersion. Gotez et al. [74] reported that
the selectivity to olefin was not affected by dispersion. In the hydrogenation of
1,3-cyclooctadiene, Liotta et al. [75] reported that the selectivity to olefin showed a
volcano relationship with the metal dispersion, i.e., when the dispersion was lower
than 32%, the selectivity increased with increasing dispersion; when the dispersion
was higher than 32%, the selectivity decreased with increasing dispersion.
Borodzinski et al. [29] summarized the dispersion effect in the selective
hydrogenation of acetylene. They believed that on a catalyst with high dispersion,
the metal particles had more defects and would interact with the support more
easily. The defects on the small metal particles contributed more electronic and
geometric effects in the catalytic process. On a small Pd particle, the β-PdHx phase
was less easy to form than the PdCx phase. As a result, the TOF of a small Pd
14 1 Introduction

particle was lower, and the ethylene selectivity was higher for a highly dispersed
catalyst. In the front-end process, the higher partial pressure of hydrogen would
form more β-PdHx phase on the Pd catalyst, and the metal dispersion would affect
more significantly in the front-end process.

1.4.2.2 Support

The active metals are supported on supports in order to increase the metal dis-
persion and the catalytic efficiency [78]. The support surface area, pore structure,
acidity, and the interaction with metal are important factors that affect the catalyst
properties.
The supports with high surface area are commonly chosen for the industrial
catalysts, on which the metal is highly dispersed and is more efficiently used. SiO2
and Al2O3 are two typical industrial supports because they are widely available and
cheap. Primet et al. [79] studied the support effect in the hydrogenation of
1,3-butadiene for the Pt catalyst and found that the support with lower acidity
showed better performance in controlling complete hydrogenation and exhibited
similar hydrogenation activity for the first hydrogenation step. Zhu et al. [80]
investigated into a series of Pd/SiO2 with different SiO2 surface area for the
hydrogenation of acetylene and found that lower surface area was advantageous for
the enhancement of ethylene selectivity. To compare the effect of acidity and the
effect of surface area, Feng et al. [70] synthesized a kind of Mg–Al support with
high surface area. Compared with the conventional Al2O3, the Mg–Al-supported
catalyst had a much higher dispersion and lower acidity. The apparent activity and
selectivity were both enhanced on the Mg–Al-supported catalysts. The acidity on
the catalyst enhanced the oligomerization and the bond transfer reactions and
increased the formation of green oil [81]; the green oil formation on the catalyst on
one side acted as media for hydrogen transfer, which promoted the complete
hydrogenation [82], and on the other side, the green oil aggregated on the catalyst
surface and changed the geometric effect of the active site [83]. Based on the above
reports, the acidity should be lowered in the selective hydrogenation in order to
obtain a high selectivity to olefin.
The metal–support strong interaction (SMSI) is another important factor that
affects the catalytic properties. In 1978, Tauster et al. [84] reported the existence of
SMSI on the TiO2-supported VIII group (Pt, Pd, Ir, Ru, Rh, etc.) metal catalysts. On
a catalyst with SMSI, the support would migrate or even cover on top of the metal
particles. For the selective hydrogenation reactions, the SMSI was found to affect
the catalytic properties. Kang et al. [85] found the SMSI existed on the TiO2-
modified Pd catalyst, and the interaction decreased the hydrogen adsorption on the
catalyst and decreased the activity of acetylene hydrogenation; the modification by
TiO2 changed the Pd exposure rate and the electronic property and decreased the
adsorption energy of ethylene, and the ethylene selectivity was improved. Lee et al.
[86] reported that by the modification of TiO2, the 1,3-butadiene activity was
decreased; the interaction between Pd and TiO2 reduced the isomerization degree of
1.4 Progress in Catalyst Development 15

1-butene. As seen from the above literature, the modification by TiO2 mainly causes
the coverage of Pd active site and the change in electronic properties, thus
decreasing the hydrogenation activity and increasing the selectivity to olefin.
However, not all TiO2 could interact strongly with Pd. Weerachawanasak et al. [87]
reported that on the micron-level TiO2, no SMSI was found on the catalyst.
Besides, the SMSI was also found to be effective on CeO2 [88–90], ZrO2 [91, 92],
La2O3 [93], and Nb2O5 [93].
The crystal phase and size of TiO2 and Al2O3 also affect the catalytic properties.
Komhom et al. [67] found that neither large nor small crystal size of α-Al2O3 was
good for the selective hydrogenation. When supporting Pd on a mixed phase of
Al2O3, the ethylene selectivity was higher than that on a pure phase [71, 94]. On the
TiO2-supported Pd catalyst, different TiO2 phases provided different amount of
Ti3+. Ti3+ changed the electronic properties of the Pd particles and further affected
the selectivity to olefin [64].

1.4.2.3 Promoters/Pretreatment

The addition of promoters or the pretreatment could modify the active sites on the
Pd catalyst and thus modify the catalyst activity and selectivity. The gas-phase
pretreatment and the solid-phase promoters for the Pd catalysts are discussed below.
In the front-end process, CO is co-fed into the reactor. As studied, CO addition
in the C2 stream could enhance the selectivity to ethylene but decrease the
hydrogenation activity [95]. In some cases, CO is also co-fed in the tail-end process
in order to increase ethylene selectivity. It is commonly believed that CO poisons
the Pd surface and adsorbs competitively with C2 species on the active sites. As a
result, the hydrogenation activities of the first step and the second step are both
reduced, and the ethylene selectivity is thus enhanced. The poison of CO on Pd was
reported to be reversible [95]. Perez-Ramirez et al. [96, 97] investigated into the
interaction of CO with Pd by DFT calculation and found that CO not only occupied
some of the active sites, but also changed the electronic properties and decreased
the adsorption energy of ethylene. Zea et al. [98] reported that the addition of CO
increased the activation barrier of ethylene hydrogenation and proposed a model
that in the CO/C2H4 competitive adsorption, only when CO desorbed could the
ethylene hydrogenation proceeded. However, the CO modifications on other metals
are different. On the Au catalyst as reported, CO had little effect on selectivity and
activity. The possible reason might be that the CO did not adsorb on Au, or the CO
adsorption site was different from the active site [99]. On a Cu–Al catalyst, the CO
interaction with the catalyst could improve the selectivity to ethylene at near 100%
conversion. The presence of CO rearranged the atoms on the catalyst and made the
Cu more dispersed [100].
Praserthdam et al. [101–103] investigated into the effect of NOx pretreatment on
the Pd–Ag catalyst. They found that the pretreatment by NO or N2O enhanced the
catalytic performance of the fresh catalyst [101, 102], but played little effect on the
used or regenerated catalysts [103]. The enhancement by N2O for the fresh catalyst
16 1 Introduction

might be attributed to the interaction of N2O with PdAg particles. As shown in

Fig. 1.8, the pretreatment of N2O promoted the oxygenation of Ag on the catalyst
surface and reduced the Ag dilution effect on Pd. Thus, more Pd atoms exposed on
the catalyst surface, and the activity was improved. On the other hand, the rear-
rangement of Pd–Ag modified the electronic effect and improved the ethylene
selectivity. However, over the used or regenerated catalysts, the metal atoms
already rearranged during reaction, and the N2O could not change the structure.
The addition of alkali metals (such as Na, K, and Cs) may modify the acidity of
the catalyst and has been widely investigated in the modification of selective
hydrogenation catalysts [104–106]. Park et al. [107] found that by the modification
of K, the adsorption/desorption properties of acetylene/ethylene were changed, and
the selectivity to ethylene was improved as well as activity; however, the catalyst
stability decreased. Kim et al. [108] reported the K effect on Pd/TiO2 and found that
a titanate salt of K formed during the preparation of catalyst which could promote
the SMSI at a low temperature of 300 °C. Huang et al. [109] analyzed the alkali
metal effect on the zeolite-supported catalyst and compared the modification of Na
and K. The addition of alkali metal decreased the catalyst acidity, and the π-bond of
acetylene with alkali metal ions enhanced the hydrogenation activity; the alkali
metal modified the adsorption energy of ethylene and reduced the hydrogen spil-
lover on the support, thus increasing the ethylene selectivity. Because K was less
acidic than Na, the modification by K was more effective. Moreover, according to
Panpranot et al. [82, 110], the addition of Zn or Ni to Pd/Al2O3 would lead to the
formation of spinels. The spinels decreased the catalyst acidity and suppressed
deactivation.
The modification by reducible oxide support or additives shows similar effect as
the SMSI effect. The Ti-modified Pd/SiO2 exhibited similar properties as Pd/TiO2.
The Ti modification diluted the active sites and changed the electronic and geo-
metric properties of the Pd sites, thus improving the selectivity and stability.
Differently, compared with the TiO2-supported catalyst, the minor addition of Ti
resulted in less decrease of hydrogenation activity [85, 111]. Moon et al. [112, 113]
investigated into the modification by metals with different reducibilities (La, Ti, Nb,
Ce). It was shown that the modification by La and Ti was similar; however, the

Fig. 1.8 Effect of N2O pretreatment on PdAg catalyst. Reprinted from Ref. [101], with kind
permission from Springer Science+Business Media
1.4 Progress in Catalyst Development 17

catalyst modified by La showed higher selectivity and lower activity, indicating a

stronger modification by La. The effect of Nb was similar as Ti and La in selec-
tivity, while showed increased hydrogenation activity due to the enhancement of
hydrogen adsorption and dissociation by Nb. The enhancement of ethylene selec-
tivity followed the order of La > Ti > Nb > Ce. On the La- or Nb-modified
Pd/SiO2, the addition of a third metal (Ti [93], Si [114]) further changed the surface
electronic properties, stabilized the modification by La, and increased the selectivity
to ethylene. Moreover, the deposition of Ag and Cu [115] on Pd changed the
electronic properties and increased the ethylene selectivity to different extents.
Because the Cu atom was small in diameter, it binded more easily with the defect
sites on Pd and showed more significant modification effect than Ag. Other than
that, the addition of La and Ce played a positive effect in the selective hydro-
genation of light hydrocarbons [93, 116], gasoline [117], and benzene [118–120].
The modifications by organic groups have also been investigated. The effects
were classified into four types: (1) to stabilize the metal particles and increase the
dispersion [121, 122], to reduce the metal leaching [123]; (2) to modify electronic
properties or to change metal structure [121, 124–126]; (3) to deactivate the catalyst
and dilute the active sites [122, 123, 127, 128]; and (4) to affect the mass transfer
and to decrease the formation of PdHx phase [72]. The organic species contained N,
P, B, Si, O, S, Cl, etc. Because the organic molecules are different in molecular
sizes, structures, and elements, the modification mechanism was not fully defined.
Boitiaux et al. [129] investigated into the modification of a series organic species
and believed that the modification mainly acted as electronic effect. The effects
were closely related to the chemical groups in the organic species.

1.4.3 Pd-Based Bimetallic Catalysts

By adding a second metal to the Pd catalyst and forming alloy, the selectivity could
be greatly enhanced. Among the many bimetallic systems, Pd–Ag catalyst signif-
icantly improves the selectivity to ethylene and has been widely used in industry.
The addition of Ag effectively increases the dispersion of Pd, decreases the
hydrogenation activity, increases the ethylene selectivity, and increases the catalyst
stability.
The synergetic effect of Pd–Ag could be explained by electronic effect and
geometric effect. The geometric effect was the most important one in the Pd–Ag
system [130–134]. Zhang et al. [130] and Khan et al. [132] investigated structural
change by ambient pressure and ultra-high vacuum TPD experiments, respectively.
After the addition of Ag, the Ag atoms segregated on the surface and diluted the Pd
active sites. When the coverage of hydrogen was high, Pd tended to migrate onto
the surface layer [132, 135]. The segregation of Ag in the sublayer decreased the
amount of adsorbed hydrogen and decreased the formation of β-PdHx phase, thus
increasing the selectivity to ethylene. The adsorption properties of CO could reflect
the catalytic properties. Khan et al. [131, 132], Smith et al. [98, 136], and Ma et al.
Another random document with
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ingredients that the cook must christen it.’[561] The ruling Council of the
State was so organized that the system was an impregnable stronghold
beyond the reach of the people. Nowhere on American soil anything so un-
American or unrepublican. It did its work behind doors closed and barred.
The Congregational clergy were the Cossacks of Connecticut Federalism,
laying the lash of their furious denunciation on the backs of critics. It
required more than a majority to rule under this system, and more than
ordinary courage to challenge its pretensions.[562] The good Doctor Dwight
of Yale was busy damning democrats to perdition. A little later Gideon
Granger and Ephraim Kirby were to take their place beside Bishop, and with
the aid of the ‘American Mercury’ of Hartford and the ‘New London Bee’ to
give blow for blow. But the fighting was against desperate odds, the
Federalists strongly entrenched on a steep hill, the ascent to which could be
raked with canister.
‘The masses are disfranchised,’ cried Bishop. ‘Yes, poor porpoises,’
sneered Noah Webster the Federalist who was soon to become editor of a
New York paper launched by Hamilton.[563] But Bishop and his little coterie
were fighters, and Jefferson took them to his heart.
In New Hampshire, Jefferson had to bide his time. Among the members
of the Senate no one had a better record of unselfish Revolutionary service
than John Langdon. Practical, hard-headed, unimaginative, a lover of money,
he had accumulated some wealth in mercantile pursuits. Fond of company,
pleasing and unaffected in his manner, impressive in appearance, his
senatorial toga became him well.[564] When Hamilton’s financial plans were
pending, he gave them his support, and, alas, profited not a little, but from
the beginning the keen-eyed Jefferson discerned the traits that were
ultimately to separate him from the Hamiltonians. Within two years Langdon
had assumed the leadership of the Jeffersonians in New Hampshire, but as
late as 1798, according to the recollection of a famous Jacksonian, ‘with the
exception of Langdon and a few sterling patriots there could not be said to
be in this State a party favorable to the principles of Thomas Jefferson.’[565]
In Vermont the situation was somewhat similar, albeit the opportunities
there were greater in the absence of a property qualification for the vote.
There, too, was Matthew Lyon, of whom we shall hear much, whose
fanatical devotion to democracy was a heritage from a father who had paid
the penalty of his patriotism on the gallows in Ireland; whose hatred of
aristocracy was but a reaction to the memory of his days of poverty.
Possessing a genius for business, and succeeding, he was irresistibly drawn
to politics, where his Celtic humor, his energy, impetuosity, and sincerity
surrounded him with friends. His radicalism became a flaming torch that
lighted up the granite hills. Not for nothing was he born in the land of the
Donnybrook Fair, for he loved a fight or a frolic, and he was to have much
of both. Enlisting in the Jeffersonian fight in the beginning, he was to fight
unceasingly, take blows, and know the degradation of a cell. There was a
degree of felony in democracy in the New England of the last days of the
eighteenth century.
In Rhode Island, Jefferson sought vainly for an effective leader, though
the field was fertile because of the lingering hostility to centralization and
the poverty and debts of the people.
Leaving New England, the leader found much to interest him in New
York. There was that sturdy, indomitable champion of State rights, and
inveterate enemy of aristocracy, George Clinton, an uncompromising
republican of Cromwellian audacity and decision, with an unequaled hold on
the confidence and affections of the people. There, too, were the
Livingstons, mortally offended by the political stupidity of Hamilton in
defeating the brilliant Chancellor’s aspirations for the Senate. Had this
numerous and powerful family a conference one night to discuss the affront
and to emerge a unit in opposition?[566] Whatever the cause, the effect was
clear—the Livingston clan was only too eager to join the insurgents, and this
was not lost on the astute politician of Monticello. Chancellor Robert R.
Livingston, convincing orator, erudite lawyer, profound statesman,
fascinating personality, possessing the glamour of wealth and tradition so
important to a Jeffersonian leader in New York with its commercial princes
and barons of the soil—here was a man to be cultivated with all the finesse
of which Jefferson was capable. The master of Monticello could speak the
language of the master of the New York manor house.
And Burr? Just what Jefferson expected of Burr is a mystery unsolvable.
He appreciated his brilliancy and professional prestige, but were the
penetrating eyes blind to the weaknesses of character? Just a little while
before Burr had joined with Hamilton against Clinton, and Federalist votes
had sent him to the Senate. There, to be sure, he had arrayed himself on the
popular side, but could he be relied upon? He had played a lone hand,
holding aloof from the Clintonians and the Livingstons, and dining often at
the table of Hamilton; but that he was singled out for assiduous cultivation
we may be sure. No one was closer to Jefferson than Dr. Rush when, in the
early fall of 1792, the latter wrote a wheedling note to Burr. ‘Your friends
everywhere,’ wrote the Doctor, ‘look to you to take an active part in
removing the monarchical rubbish of our government. It is time to speak out
or we are undone.’[567] Previous to this, Jefferson had been most courteous
in permitting the charming Senator from New York to examine papers in the
archives of the State Department until Washington interposed.[568]
Clinton, Livingston, and Burr—a triumvirate that caught Jefferson’s
fancy; but he was interested in opportunities in New York having no direct
connection with any of the three. The less imaginative Maclay had seen in a
parade of the Sons of Tammany only ‘a grotesque scene,’ with the members
‘in Indian dresses,’ and while he had addressed them at a dinner he had
concluded that ‘there is some kind of a scheme’ which was ‘not well
digested as yet.’[569] Jefferson made it his business to learn more. He found
that the strange organization was an answer, in part, to the Cincinnati which
stood, in the popular mind, for aristocracy; that it was rabidly republican and
wholly democratic; that it sympathized with the revolutionists in France, and
resented the property disqualifications of our own Revolutionary soldiers for
the suffrage, while the wealthy, notoriously friendly to England when these
soldiers fought, were being accorded political recognition and place. Here
was a society after his own heart, here a method to make the masses felt—a
combination and coördination of their efforts. All over the land the hundreds
of thousands of inarticulate, unimportant, ineffective, commonplace friends
of democracy, and in one city these had been given a voice, an arm, a
rostrum. It was not ‘grotesque’ to Jefferson. He did not join these imitation
red men in their wigwam, nor drink of their ale, but John Pintard the chief
became his friend and idolater, and with him the great man talked. The non-
partisan society grew more and more democratic, soon intensely partisan,
and at Tammany dinners the welkin rang to the toast to ‘Thomas Jefferson.’
New York became a cock-pit from the start.
But when the Jeffersonian board of strategy turned to New Jersey, the
problem was more difficult. No outstanding leader, strong in the faith, stood
ready to mount and ride. There, true, the Janus-faced Jonathan Dayton was
ready to flirt with any force that might serve his personal ends. He was a
speculator—and worse. Supporting and profiting from the Hamilton policies,
he smiled on the Jeffersonians significantly.
 In Pennsylvania there was the nucleus of a party and virile men to lead it
—men like Mifflin, who, despite his drunkenness, was popular and a power;
like Maclay, who had the force that intense conviction brings in spite of
temperamental handicaps; men like Alexander J. Dallas, aggressive, daring,
able; men utterly unfit for
 ALBERT GALLATIN EDWARD LIVINGSTON
WILLIAM BRANCH GILES JAMES MADISON

the rough-and-tumble combats of practical politics whose characters and

abilities made them potent in the fight—like Rush the physician,
Rittenhouse the scientist, Logan the philosopher, and, looming above the
tops of the Western forests, a young giant and genius, Albert Gallatin.
In Delaware, nothing; in Maryland, John Francis Mercer, fighter and
intriguer, sapper and miner, agitator and organizer, with whom democracy
was a religion, Hamilton a devil, and Jefferson a saint. In Virginia, a
sparkling galaxy, Madison, Monroe, the accomplished Pendleton, the
resourceful Giles, the extraordinary John Taylor of Caroline.
In North Carolina, Jefferson found a leader cut from his own pattern, an
aristocratic democrat, a radical rich man, a consummate politician who
made the history that lesser men wrote without mentioning his name, Willie
Jones of Halifax. His broad acres, his wealth, his high social standing were
the objects of his pride, and he lived in luxury and wore fine linen while the
trusted leader of the masses, mingling familiarly with the most uncouth
back-woodsman, inviting, however, only the select to partake of the
hospitality of his home. There was more than a touch of the Virginia
aristocrat of the time in his habits—he raced, gambled, hunted like a
gentleman. Like Jefferson he was a master of the art of insinuation, a
political and social reformer. He loved liberty, hated intolerance, and
prevented the ratification of the Constitution in the first State Convention
because of the absence of a Bill of Rights. There he exerted a subtle
influence that was not conspicuous on the floor. If he was neither orator nor
debater, he was a strategist, disciplinarian, diplomat, who fought with velvet
gloves—with iron within. A characteristic portrait would show him puffing
at his pipe in the midst of his farmer followers, suggesting, insinuating,
interspersing his political conversation with discussions of the crops,
farming implements, hunting dogs, horses. An Anthony in arousing the
passions by subtle hints, he was an Iago in awakening suspicions.[570] Here
was the man with the stuff that Jefferson required, generous and lovable in
social relations, in politics relentless, hard as iron. He was the Jefferson of
North Carolina—‘a man ... the object of more hatred and more adoration
than has ever since lived’ in that State.[571] Nor did he stand alone without
assistants, for there was Nathaniel Macon, honest, intense, man of the soil
who loved his few acres, his dogs and horses, and his class; and there was
Timothy Bloodworth whose fierce adherence to democracy and fanatical
hatred of privilege may have been a poignant reflection of his poverty.
Jones, the aristocratic lord of many acres; Macon the representative of the
small farmer; Bloodworth the artisan, smithy at the forge, watchmaker,
wheelwright, as well as preacher, doctor, and cultivator of the soil: his
radicalism was born in suffering and in suffering he had grown.[572]
In Georgia, Jefferson had equal cause for satisfaction. There were small
farms, poor industrious men, ardent republicans, with the frontiersmen’s
natural democracy and the debtors’ suspicions of concentrated wealth allied
with governmental power. And there to lead them was James Jackson, idol
of the people, a boisterous, impassioned orator whose eloquence often gave
more heat than light. Historians have been prone to sneer at him, but this
man who came as a child from Devonshire in England to take his place
three years later in the army of Washington, and to receive the keys of
Savannah from the British ten years after his arrival, was something more
than an upstart. He who refused the governorship of his State when twenty-
one, and six years after leaving his English home, to take his chances in the
field, was scarcely an object for jest. He was a power as a leader and was to
strike Titan blows in the cause that Jefferson nationally led.[573]
In South Carolina, dominated by rich commercial Charleston, Jefferson
long looked in vain for a leader for his cause. A friend of the Pinckneys and
the Rutledges, they held aloof or joined their fortunes with Hamilton. Only
toward the close did Charles Pinckney, the most eloquent, resourceful, and
magnetic of his family, part company with his cousins to lunge and lash
with gusty joy for the man of Monticello.
Such were the leaders on whom Jefferson was dependent in welding the
popular parties in the various States into a strong national army marching in
step, with a common policy and purpose.

III

Had Jefferson been even richer than Hamilton in brilliant leaders, he

would not have made the latter’s fatal blunder of assuming them to be
enough. He was too much the practical politician to be impressed with a
brilliant staff of officers—without privates. He set out to arouse the masses,
mobilize, drill, and lead them. Above all, it was his intention to lead. Within
a year, Ames was to observe with desperation and disgust the divisions
among the Federalists and to comment that ‘Virginia moves in a solid
column ... the discipline of the [Jefferson] party is as severe as the Prussian’
and ‘deserters are not spared.’[574]
The first necessity was to get the men to discipline. A vast number of the
masses had no conception of their political power and were indifferent to
the vote. Thousands over the country were disfranchised by property
qualifications, and one of the prime purposes of the new party would be to
break these down. The immediate problem was to awaken the interest of
those who, having the vote, did not appreciate the privilege. With many of
these, this was due to the lack of political consciousness; with others, to the
feeling that it was useless for the unimportant to attempt to influence
governmental action. To the latter it would be necessary to prove the
possibilities of the concerted action of large numbers of uninfluential men
—and there was the Society of Tammany pointing the way. No
squeamishness in the mobilization either—the possession of the vote was
enough. Soon, very soon, strange, disturbing things would be seen even in
New England—cabinetmakers, shoemakers, mechanics perking up on
politics, with evidence of organization here and there. Federalist leaders
would soon be complaining that organization was conspiracy against the
‘government.’ In New Hampshire they would be calling those uniting for
political action ‘insurgents.’ The insolence of the Jeffersonians appealing to
the people for support would be frowned upon as degrading. ‘Of course,’
said a Massachusetts paper, ‘there can be but two parties in a country—the
friends of order and its foes.’[575]
And such people! The very riff-raff that one would never invite into
one’s parlor—‘desperate, embarrassed, unprincipled, disorderly, ambitious,
disaffected, morose men.’[576] Were not these the propertyless who wasted
their earnings in a grogshop?[577] And who were these petty agitators? Who
but ‘Jacobins’ holding forth ‘in the bar-rooms of Rhode Island and Vermont
and trying to stir up opposition.’[578] Wretched offal after all—but what a
pity that Jefferson should countenance, least of all cultivate, such people.
‘Mr. Jefferson appears to have shown rather too much of a disposition to
cultivate vulgar prejudices,’ wrote Wolcott, and ‘accordingly he will
become popular in the ale-houses.’[579]
 Miserable ‘Jacobins!’ Disreputable clowns of the bar-rooms! And such
unthinkable methods! Here—there—everywhere, when a few men could be
gathered together, some one appeared to deliver free lectures on practical
politics. And such subjects! ‘Discipline’; ‘How to Make Men Follow their
File Leaders.’[580]

IV

In arousing and consolidating the widely scattered democrats, Jefferson

instantly appreciated the importance of a national newspaper to the end that
the farmer in Georgia, the planter in Virginia, the frontiersman in western
Pennsylvania, the mechanic in Boston, the shopmen of Rhode Island, and
the reds of Tammany sipping their ale in the New York tavern, might all
talk the same language at the same time. True, the Jeffersonians were not
without able editorial support. There was Thomas Greenleaf pounding away
vigorously in the ‘New York Journal’; Thomas Adams hammering merrily
in the Boston ‘Independent Chronicle’; and in Philadelphia, Benjamin
Franklin Bache was making a mild show of opposition in his ‘Pennsylvania
Daily Advertiser.’ But these were independent supporters, not ‘organs,’ and
it was an ‘organ’ that was needed—something to meet the Hamilton organ
which was becoming increasingly offensive to the democrats.
In estimating the sincerity of the simulated shock of the Federalists when
the Secretary of State encouraged the establishment of a paper to support
his principles, it is well to bear in mind that the Secretary of the Treasury
had done precisely the same thing two years before. Then, as always,
politicians were shocked at the turpitude of their opponents. Just how John
Fenno came to establish the ‘Gazette of the United States’ is an
impenetrable mystery. He was in his thirty-eighth year when he appeared at
the home of Rufus King, perhaps the ablest of Hamilton’s supporters, with a
letter of introduction from Christopher Gore, a member of the inner council
of Boston Federalism who afterward waxed wealthy on speculation in the
funds. The record is meager as to Fenno’s previous career beyond the
revelation that he was born in Boston and taught for several years in the Old
South Writing School. In the letter to King, we have the assurance of Gore
that Fenno’s ‘literary accomplishments are very handsome’; that Gore had
known him long and could testify that ‘his honor and fidelity are
unquestionable’; and, strangely enough, that ‘his talents as the editor of a
public paper are unrivaled in this commonwealth.’ As John Russell was
then editing the ‘Columbian Centinel,’ the tribute would seem strained but
for the intimation that the strength and sparkle of that able journal was due
to Fenno’s contributions; and since the ‘Centinel’ suffered no apparent loss
on his leaving Boston, even this theory seems absurd.
If his origin is a mystery, the purpose of his call on King was made clear
enough in the letter of introduction. The ‘unrivaled’ editor sought
encouragement for the establishment of a newspaper through arrangements
for ‘obtaining the patronage of Congress’ in the printing of its journals and
official papers. If something of the sort could be arranged, Gore was
positive that Fenno would prove ‘capable of performing essential service in
the cause of Federalism and good government.’[581]
The conversation was evidently agreeable, assurances of some sort were
manifestly given, and within a few weeks the ‘Gazette of the United States’
was making its appearance. That Hamilton, who was intimately identified
with King, was consulted, we may he sure; and within four years the
relations between Fenno and Hamilton were so confidential that the former
felt no hesitancy in appealing in a letter to the latter for a loan of two
thousand dollars. Months before, the editor had submitted a schedule of his
debts and credits to the head of the Treasury. The two had talked over the
financial difficulties of the paper. The appeal for the loan was not lightly
brushed aside. Hamilton wrote to King of the troubles of ‘poor Fenno,’ and
proposed that if King would raise a thousand dollars in New York, he would
himself undertake to raise a similar amount in Philadelphia. It is to be
assumed that the money was raised, for the paper continued to appear. It is
significant that in his letter to Hamilton, the editor wrote as one who had
rendered faithful service and was entitled to consideration.[582]
From the beginning Fenno had liked to think of himself as the editor of
‘the court journal.’ Possessing considerable merit, it is impossible to turn its
yellowing pages even now without being oppressed with a sense of
sycophancy and snobbery. There was a fawning on wealth and kow-towing
to power in most of the leading articles. The tone was pronouncedly pro-
English and all Hamiltonian. Democracy was anathema. The critics of the
policies of the leader of the Federalists were inciters to disorder. All the
influence of the Federalist leaders was exerted to throw all possible
governmental patronage into his office.
 Hamilton had his paper before Jefferson got his own.[583] It was to meet
these conditions that James Madison and Governor Henry Lee conceived
the notion of persuading Philip Freneau, ‘the poet of the Revolution,’ to
establish a newspaper in Philadelphia. This fiery petrel of democracy was
eking out a mere existence on a New York newspaper when Madison, who
had been his roommate at Princeton, made the proposal. This was due in
part to personal affection and the feeling that the poet’s sufferings and
losses in the Revolution entitled him to some consideration, but in large
measure to the purity of his republicanism and his zeal for the popular
cause. ‘I entertained hopes,’ wrote Madison later, ‘that a free paper, meant
for general circulation, and edited by a man of genius of republican
principles and a friend of the Constitution, would be some antidote to the
doctrines and discourses circulated in favor of Monarchy and
Aristocracy.’[584] With the view to giving some slight protection to a
precarious enterprise, Madison sought a clerkship for his college friend in
one of the governmental departments. Nor was it to Jefferson that he first
applied.[585] The outcome, however, was the offer of a clerkship of foreign
languages in the State Department at a salary of two hundred and fifty
dollars a year. He accepted, went to Philadelphia, and established the
‘Federal’ or ‘National Gazette.’
The leaders of the new party were plainly pleased with the prospect.
Jefferson himself did not scruple to solicit subscribers among his Virginia
neighbors. Henry Lee, who was to desert to the enemy later, sent in
subscriptions through Madison, in a letter rejoicing because the paper ‘is
rising fast into reputation,’ and lamenting because of the precariousness of
its arrival.[586] ‘His paper in the opinion here,’ wrote Madison
acknowledging Lee’s letter, ‘justifies the expectations of his friends, and
merits the diffusive circulation they have endeavored to procure it.’[587]
The Philadelphians awoke with a start to find that an entirely new note
had been struck in political journalism. Within a few weeks, the ‘Federal
Gazette’ was being extensively copied in the papers over the country. Bache
in his ‘Advertiser’ caught something of Freneau’s fire and audacity, and
began to take a firmer, bolder tone. Fenno found himself forced to defend
himself and his friends in almost every issue. Men and even women
scanned its columns eagerly and with emotions determined by their political
prepossessions. Within a few months the poet-editor was being hotly
debated by the two leading papers of Boston. ‘As all the friends of civil
liberty wish at all times to be acquainted with every question which appears
to regard the public weal,’ said the ‘Independent Chronicle,’ ‘a great
number of gentlemen in this and neighboring towns have subscribed for the
Federal Gazette published by Mr. Philip Freneau at Philadelphia; and it is
hoped that Freneau’s Gazette, which is said to be printed under the eye of
that established patriot, Thomas Jefferson, will be generally taken in the
New England States.’[588] What! wrote a correspondent in the ‘Centinel,’ is
this an avowal that Jefferson is the real editor? A paper hostile to religion
and government! ‘Surely T. Adams ought to be well founded in his
affections before he brings forward Mr. Jefferson as the patron of such a
Gazette.’[589]
Within a short time Freneau had aroused the savage rage of the
Federalist leaders and the zealous loyalty of the democrats everywhere.
Here was a man who was not awed by power, and, brushing aside mild
criticism and vapory innuendoes, struck hard and mentioned names. Soon
the Jeffersonian farmers in Georgia were talking what he was writing, and
Jeffersonian editors generally were following his lead. In the bar-rooms of
Rhode Island men of no consequence were reading the paper aloud over
their mugs, and David Rittenhouse in the library of the Philosophical
Society was chuckling over its vicious thrusts. Just then ‘friends of the
Constitution’ among the Federalists began to regret a certain provision in
the Bill of Rights and to begin the slow incubation of the Sedition Law.
That incomparable political preacher, Timothy Dwight, began to denounce
papers as the ‘vice’ of the people in the new settlements, and another pious
gentleman of the cloth thundered from the pulpit: ‘Many of you in spite of
all the advice and friendly warnings of your religious and political fathers
have taken and continue to take and read Jacobin papers, full of all manner
of mischief and subtlety of the Devil.’[590] The hand-to-hand fighting of
Hamilton and Jefferson was forced by the lusty blows of Freneau, who
deserves to be something more than a name in the Plutarchian struggle.

Philip Freneau had richly earned the right to hold and express opinions
concerning the destiny of his country. Many years before the Revolution,
his Huguenot ancestors had come over from France, and for years his was a
well-known name in the best circles of New York City where he was born.
His childhood had been passed on the thousand-acre estate of his father
near the battle-field of Monmouth, in a fine old mansion fashioned after the
colonial style, with a great hall running through it, and large porticoes
commanding a view of a beautiful country. The house was served by many
domestic slaves. Near by rose Beacon Hill, thickly timbered, and from the
peak could be seen the lower bay and the blue waters of the Atlantic. There
his early childhood was passed under the tender care and training of a
mother of rare intelligence. From her he caught a love of poetry, and of the
things of which poetry is made. The spirit of his liberty-loving ancestors
was strong within him. He had all the impulsiveness, the fighting courage
of the Gael. When not at his studies, he wandered alone into the woods and
upon the hill where he could brood dreamily upon the mystery of the sea.
On the site where the battle of Monmouth was to be fought, he began the
study of Greek and Latin in his tenth year. Even as a child he had a hot
passionate hatred of oppression, an unfathomable contempt for hypocrisy,
and an ardent love of beauty. All this he put into childish verse.
When he entered Princeton (Nassau Hall), great events were beginning
to unfold. The patriots of Massachusetts, protesting against an English law,
had been declared rebels, the leading offenders had been ordered across the
sea for trial, the troops of General Gates had marched into Boston. The
college was a hot-bed of sedition. That superb patriot, John Witherspoon,
was president, and among the students who gathered in the evening in the
room that Freneau shared with Madison, were ‘Light Horse’ Harry Lee,
Aaron Burr, William Bradford, destined to close an exceptionally promising
career as a member of Washington’s Cabinet, and Brockholst Livingston.
Nothing that Freneau ever said or did in after-life that was not
foreshadowed at Princeton can be found. His tongue was sharp, and his pen
dripped the vitriol of satire. He wrote much verse, and long before the
Declaration of Independence, he had a hatred of kings. Even thus early in
his ‘Pyramid of Kings,’ he made profession of his democracy.

‘Millions of slaves beneath their labors fainted,

Who were here doomed to toil incessantly,
And years elapsed while groaning myriads strove
To raise this mighty tomb—and but to hide
The worthless bones of an Egyptian king.’
Under the encouragement of Witherspoon, all the patriotic fire within him
burst into flame.
Long before Washington, Adams, or Franklin were dreaming of a
republic and absolute independence, this was his dream. During the time he
was supposed to be poring over Coke and Blackstone, he was feverishly
plying his pen writing political articles for the press. He was a rebel by
nature. He wrote deliberately to arouse a burning hatred of tyranny and a
militant love of liberty. He sang the songs of hate, and read and studied the
Roman and French satirists to perfect himself in the art he was to use so
effectively later. When the war began he threw himself into the struggle. A
pathetic little figure, this—a mere wisp of a boy charging on ahead to smash
the connection with England, only to find that the other patriots had no such
thought. They were fighting for rights within the empire, not for
independence. Even then he was too radical for his times or the comfort of
his associates. They were thinking of rights, and he of liberty—and in sheer
disgust he sailed away to Jamaica.
There was the illusion of liberty on the sea and there was beauty and
poetry, and there was opportunity, too, to prepare himself for the part he
was to play a little later. It was always his joy to be prepared. On that
voyage he perfected himself in the science of navigation. In the languorous
air of Santa Cruz he luxuriated in the beauties of nature at its richest, and
sought to transcribe to paper all he saw and felt. He had an irresistible
impulse for creation—a poet’s passion for expression.[591] But even here he
was a rebel born to protest. Slavery at its worst was all about him—and he
hit it hard in his descriptions.
It was while a guest of the Governor of Bermuda, writing love sonnets to
the fair daughter of his host, that the news came of the Declaration of
Independence. This was the sort of rebellion Freneau could understand, and
he hurried home to find that a battle had been fought at his very door, and
that the cushions of the Tennant church he had attended had been stained
with blood. Instantly he took out letters of marque and reprisal from the
Continental Congress, and put to sea to battle with the British ships.
Plunging patriotically with all his means he had a ship built for his own use,
named it the Aurora, and sought the enemy. In a battle his ship was struck,
and it was as a prisoner on the deck of an enemy vessel that he saw his ship,
his fortune, sink beneath the waves. The rest was torture and a living death.
The Scorpion on which he was confined was a miserable old hulk converted
into a prison ship, reeking with foul smells and rank disease, and into this
he was packed where the accommodations were not fit for swine. One by
one he saw his fellows perish from disease and neglect, listened in the night
to their shrieks of pain and dying groans. When verging on death, he was
transferred to the Hunter which some sardonic soul had dubbed a ‘Hospital
Prison Ship.’ Its horrors have come down to us in his own poems with its
bitter execration of the Hessian doctor.

‘Here uncontrolled he exercised his trade,

And grew experienced by the deaths he made;
By frequent blows we from his cane endured
He killed at least as many as he cured.’

At length he was exchanged. Leaving the vessel with a raging fever, with
pains in his joints that made walking a torture, he turned toward home,
going through the woods ‘for fear of terrifying the neighbors with [his]
ghastly looks.’[592] This was the background against which he was to view
Washington’s policy of neutrality in the war between France and England.
He hated England from that hour to his death.
Broken in health almost beyond hope of redemption, his ship sunk, his
money gone, the war still on, he turned to his other weapon and took up the
pen. ‘The Prison Ship’ helped to fire the patriots shivering about the cold
camps. The poem of contemptuous imprecation, in imitation of Horace, on
the treason of Arnold, fanned their wrath. That on the victory of Paul Jones
heartened the downcast. Poem followed poem, copied throughout the
country, many published on strips of paper and distributed through the
army. Some were posted in conspicuous places where they could be
committed to memory. Paine wrote ‘The Crisis’ in prose, Freneau wrote of
the crisis in verse; both were a tonic for the wavering. Even Washington did
not then speak of him as ‘that rascal Freneau’ and that characterization even
from Washington cannot rob him of the glory of having been ‘the Poet of
the Revolution’ who gave his health, his entire fortune, almost his life, and
all his heart to the cause of liberty.
The close of the war found him in New York barely existing on crumbs
from the table of an editor. His was a familiar figure in the Merchants’
Coffee-House at Wall and Water Streets where leading men congregated.
The problem then was to get the necessities of life, and literary work was
not then included among the means. This was the condition in which
Madison found him. He knew the story of his poet friend, and thus it came
about that the plan was made for the ‘Federal Gazette.’ He was ideally
fitted for the task. It called for one who could write in the language of the
people, could wield a scorpion lash, whose heart was in the cause—and no
greater master of invective was in view, no keener satirist. He required no
tutoring, and he would accept no orders. He was a rebel still, a radical, a
crusader for democracy, who looked with amusement on ‘aristocracy,’ with
hatred on monarchy. He was an original thinker, a breaker of idols, an
iconoclastic genius. He had the wit, the keenness, the quickness, the felicity
of his French blood, the stern firmness of the Huguenot mind. He was a
gusty warrior with a lusty blade and he kept it shining in the sun.
Soon Philadelphia found him a familiar figure in its streets—a rather
little man with slightly stooped shoulders, thin yet muscular, who walked
briskly like one who knew where he was going. In his office at his work he
was more imposing, for there one could note the high intellectual brow, the
dark gray deep-set eyes that sometimes blazed under the slightly drooping
lids. Usually pensive in repose, his face lighted with animation when he
talked. His manners were courteous and refined and women found him
interesting and gallant. Nor was this democrat a Marat in dress—he wore
the small-clothes, the long hose, the buckled shoes, and cocked hat, long
after others had accepted less picturesque fashions. He had no vanity, no
ambition for place or power, and no fear of either. He wore no man’s collar
and he was no man’s man. He was a law unto himself.
 CHAPTER VIII

THE GAGE OF BATTLE

T HERE was little in the reception of Hamilton’s famous ‘Report on

Manufactures’ during the congressional session of 1791-92 to
foreshadow the part it was to play in American politics. Bristling with
facts and figures laboriously assembled, the plea for protection and bounties
for manufacturers was plausibly presented. Foreseeing the hostility of the
farmers, the most persuasive arguments were reserved for them. The
diversification of industry would increase the demand for the products of
the farm; the elimination of foreign competition would decrease the cost of
manufactured goods; and the certainty of immigration would prevent any
labor shortage with agriculturists. Better still, the factories would afford the
farmers an opportunity to put their wives and children to work in the mills.
[593] Four sevenths of the employees of the cotton mills of England were
women and children, and many of the latter of ‘tender age.’[594] In the
making of nails and spikes young boys were able to do the work.[595] As to
the constitutional objection, that was disposed of by the doctrine of implied
powers.
The newspapers, including Freneau’s, ran the report in full, but nothing
came of it for the moment. No one was shocked at the idea of working
women and children of tender age. After a while a writer in Freneau’s paper
warned that a new field was being opened ‘for favoritism, influence and
monopoly.’[596] Madison wrote to Pendleton that ‘if Congress can do
whatever in their discretion can be done with money ... the Government is
no longer a limited one.’[597] But this ‘Report’ resulted in less controversy
than any that had preceded. There was no storm—just a bare stirring of the
leaves.
But Hamilton was not content to allude to brighter worlds—he led the
way. Long before, he had been impressed with the industrial possibilities of
beautiful Passaic Falls in New Jersey, midway between New York and
Newark at the very door of the market. Just how long he was in interesting
moneyed men in his ambitious plans for a great national manufactory there,
we do not know. But even before the publication of his ‘Report,’ he had
personally appeared with others interested before the New Jersey
Legislature to ‘elucidate anything that may appear obtuse’ in the request for
a charter.[598] It was only a little trip from Philadelphia to Trenton. Then,
one summer day, a group of men appeared at the Falls to purchase land and
select the precise sites for the various mills, and the small but masterful
figure of Hamilton was the center of the group. All sorts of things would be
manufactured, cotton mills predominating, and it would become—this city
of Paterson—the industrial capital of the Republic. Major l’Enfant was
summoned to the task of making this industrial beehive beautiful, and he
responded.[599] Soon there were grumblings among the farmers, outraged
because the charter that Hamilton’s influence had secured gave the
company the right to dig canals on any man’s land. The other manufacturers
were indignant because the new factory was to be free from taxation for ten
years, and its employees were to be excused from military services except
in cases of dire necessity. ‘A Manufacturer’ wrote a vehement protest,
mentioning Hamilton by name, and denouncing the act of the legislature as
vicious beyond comparison.[600] Soon the Philadelphia papers were
advertising that the five letters ‘To the Yeomanry,’ in pamphlet form,
complaining of the privileged nature of the corporation and of the part
played by Hamilton, could be had at the various stores of the city.
But Hamilton was not concerned with the grumblings of the groundlings,
for he was at high tide. In New York men had subscribed for a portrait of
him by Trumbull, and the subscription lists ‘were still open in the coffee-
house.’[601] He had become the idol of the most powerful class. A little
later, Trumbull’s work completed, ‘the best that ever came from his pencil,’
it was placed temporarily in the old city hall in New York.[602] The obscure
boy from the West Indies had become an institution in the city of his
adoption. Even so Hamilton was ever vigilant. He had not liked the Freneau
project from the start, and he was watching it like a hawk.

II

When the poet-journalist took an office on High Street and began the
publication of his paper, there was little to justify grave apprehensions. In
his first issues the editor had pledged himself to the support ‘of the great
principles on which the American Revolution was founded,’ and while this
smacked of the jabberings of Sam Adams, Hancock, and Jefferson, it was
probably only a gesture. The tone of the early editions was temperate,
almost academic. The ordinary reader must have thought it harmless
enough, but Hamilton, who used the press effectively himself, examined the
articles more critically. There were phrases creeping in, innocently, perhaps,
that Fenno would have scorned. The idea that ‘public opinion sets the
bounds to every government, and is the real sovereign of every free
one,’[603] would never have soiled the pages of the ‘Gazette of the United
States.’ The little essays on politics and government were sprinkled all too
freely with these disturbing suggestions. Only an essay on ‘Nobility’—but
why make it the vehicle for the thought that ‘the downfall of nobility in
France has operated like an early frost toward killing the germ of it in
America.’[604] With Fenno chiding the critics of officials, what more
unfortunate than Freneau’s assertion that ‘perpetual jealousy of the
government’ is alone effectual ‘against the machinations of ambition,’ and
his warning that ‘where that jealousy does not exist in a reasonable degree
the saddle is soon prepared for the back of the people.’[605] A defense of
parties coupled with a denunciation of privilege,[606] stiff criticism of
ministerial inefficiency apropos of the St. Clair expedition; forceful protests
against the excise law;[607] and then an article by ‘Brutus’ on the funding
system which could not be ignored—these were bad enough. That system,
said ‘Brutus,’ had given undue weight to the Treasury Department ‘by
throwing the enormous sum of fifty million dollars into the hands of the
wealthy,’ thus attaching them to all the Treasury measures ‘by motives of
private interest.’ Having combined the great moneyed interest, it had been
made formidable by the Bank monopoly. Out of it all had come the
‘unlimited excise laws and imposts’ that ‘anticipated the best resources of
the country and swallowed them all up in future payments.’ Because the
certificates had fallen to the wealthy, ‘the industrious mechanic, the
laborious farmer and poorer classes generally are made tributary to the
latest generation.’[608] Rights of property? Yes—but there is property in
rights.[609] Be loyal to the Union? Yes, but who are the enemies of the
Union? ‘Not those who favoring measures which, pampering the spirit of
speculation, disgust the best friends of the Union.’ ‘Not those who promote
unnecessary accumulations of the debts of the Union.’ Not those ‘who
study by arbitrary interpretations and insidious precedents to pervert the
limited government of the Union into a government of unlimited
discretion.’[610]
With Freneau hitting his stride, the Federalists began to lose their
patience. Soon the ‘United States Chronicle’ of Providence learned that the
‘very extraordinary productions’ were probably ‘the work of some
foreigners who wish to reduce the funds in order to purchase.’[611] The
‘Centinel’ of Boston warned that Freneau’s paper was ‘supported by a junto
for electioneering purposes’ and was filled with ‘the most absurd
misrepresentations of facts, or falsehoods highly injurious to the prevailing
character and principles of our government and people.’[612]
But it took the articles of ‘Sidney’ to force the fighting. These were open
attacks on Hamilton and his principles and were written with a punch. He
assailed the House for abdicating its power to originate money bills to the
Secretary of the Treasury. To delegate that duty was to lie down on a job.
And such ‘reports’! Arguments! Pleas! Sophistries! Thence to the major
attack. ‘If we admit that the Secretary is a fallible mortal, and, however
great his capacity may be, that he is liable to mistakes or to be imposed
upon, or, in range of hypothesis, if we suppose these possible cases, that his
political principles do not correspond with the genius of the government, or
with public opinion; or that he embraces the interests of one class in
preference to the interests of the other classes,—I say admitting any or all
of these circumstances to be possible, then the ministerial mode of
influencing the deliberations of Congress practiced since the change of the
government, is more dangerous than even that which is pursued but loudly
complained of in Britain.’[613] These attacks by Sidney continued with
painful regularity, and Freneau’s paper became a scandal in the best-
regulated families in Philadelphia. Others joined in the fray. ‘A Citizen’
from a remote section, who had visited the capital to ‘know more of men
and measures,’ speedily convinced himself that many members of
government ‘were ... partners with brokers and stock jobbers, and that the
banking schemes have been too powerfully and effectually addressed to
their avarice.’[614] ‘Centinel’ warned that ‘the fate of the excise law will
determine whether the powers of government ... are held by an aristocratic
junto or by the people.’[615] With the pack in hot pursuit of his idol, Fenno
rushed to the defense with a denunciation of the ‘mad dogs’ and ‘enemies