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 Ethanol
Science and Engineering

Edited by
Angelo Basile

Adolfo Iulianelli

Francesco Dalena

T. Nejat Veziroglu
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

Copyright © 2019 Elsevier Inc. All rights reserved.

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the Publisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional
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List of Contributors

Hussein T. Abdulrazzaq
University of Maine, Orono, ME, United States
Elham Aryafard
Department of Chemical Engineering, Shiraz University, Shiraz, Iran
Angelo Basile
Institute on Membrane Technology of the Italian National Research Council
(CNR-ITM), Rende, Italy
Marco Basile
University of Calabria, Rende, Italy
Abhijeet P. Borole
Oak Ridge National Laboratory, Oak Ridge, TN, United States; The University of
Tennessee, Knoxville, Knoxville, TN, United States
Bernd Cermenek
Graz University of Technology, Institute of Chemical Engineering and
Environmental Technology, Graz, Austria
Marcello Contestabile
Imperial College London, London, United Kingdom
Francesco Dalena
University of Calabria, Rende, Italy
Monica Dan
National Institute for Research and Development of Isotopic and Molecular
Technologies, Cluj-Napoca, Romania
Luisa Di Paola
University Campus Bio-Medico of Rome, Rome, Italy
Fausto Gallucci
Inorganic Membranes and Membrane Reactors, Eindhoven University of
Technology, Eindhoven, Netherlands
Kamran Ghasemzadeh
Urmia University of Technology, Urmia, Iran
Viktor Hacker
Graz University of Technology, Institute of Chemical Engineering and
Environmental Technology, Graz, Austria

xv
xvi List of Contributors

Risto Ilves
Estonian University of Life Sciences, Tartu, Estonia
Cristina Italiano
Institute for Advanced Energy Technologies (ITAE) “Nicola Giordano”, National
Research Council (CNR), Messina, Italy
Adolfo Iulianelli
Institute on Membrane Technology of the Italian National Research Council
(CNR-ITM), Rende, Italy
Elham Jalilnejad
Urmia University of Technology, Urmia, Iran
Simin Keshtkari
Department of Chemical Engineering, Shiraz University, Shiraz, Iran
Marcel Kohler
University of KwaZulu-Natal, Durban, South Africa
Arne Küüt
Estonian University of Life Sciences, Tartu, Estonia
Keio Küüt
Estonian University of Life Sciences, Tartu, Estonia
Mihaela D. Lazar
National Institute for Research and Development of Isotopic and Molecular
Technologies, Cluj-Napoca, Romania
Zongyuan Liu
Brookhaven National Laboratory, Upton, NY, United States
Lie Meng
Arizona State University, Tempe, AZ, United States
Maria Mihet
National Institute for Research and Development of Isotopic and Molecular
Technologies, Cluj-Napoca, Romania
Jüri Olt
Estonian University of Life Sciences, Tartu, Estonia
Alfredo Pacheco Tanaka
Inorganic Membranes and Membrane Reactors, Eindhoven University of
Technology, Eindhoven, Netherlands
 List of Contributors xvii

Alessandra Palella
Institute for Advanced Energy Technologies (ITAE) “Nicola Giordano”, National
Research Council (CNR), Messina, Italy
Lidia Pino
Institute for Advanced Energy Technologies (ITAE) “Nicola Giordano”, National
Research Council (CNR), Messina, Italy
Mohammad Reza Rahimpour
Department of Chemical Engineering, Shiraz University, Shiraz, Iran
Johanna Ranninger
Graz University of Technology, Institute of Chemical Engineering and
Environmental Technology, Graz, Austria
Kaie Ritslaid
Estonian University of Life Sciences, Tartu, Estonia
Alirio E. Rodrigues
University of Porto, Porto, Portugal
José A. Rodriguez
Brookhaven National Laboratory, Upton, NY, United States
Seyyed Mohamad Sadati Tilebon
Iran University of Science & Technology, Tehran, Iran
Thomas J. Schwartz
University of Maine, Orono, ME, United States
Sanjaya D. Senanayake
Brookhaven National Laboratory, Upton, NY, United States
Alessandro Senatore
University of Calabria, Rende, Italy
Lacrimioara Senila
INCDO-INOE 2000, Research Institute for Analytical Instrumentation,
Cluj-Napoca, Romania
Ramona O. Stef
anescu-Mih ail
a
Spiru Haret University, Bucharest, Romania
Prakash D. Vaidya
Institute of Chemical Technology, Mumbai, India
Martin van Sint Annaland
Inorganic Membranes and Membrane Reactors, Eindhoven University of
Technology, Eindhoven, Netherlands
xviii List of Contributors

Antonio Vita
Institute for Advanced Energy Technologies (ITAE) “Nicola Giordano”, National
Research Council (CNR), Messina, Italy
Yi-Jiang Wu
East China University of Science and Technology (ECUST), Shanghai, China
Taher Yousefi Amiri
University of Zanjan, Zanjan, Iran
Preface

The rapid growth in global energy demand, greenhouse gas emissions, and global
warming, associated with the use of fossil fuels, is stimulating a continuous research
for alternative and renewable fuels showing a very low environmental impact.
In addition, nowadays, the energy dependence on fossil fuels creates a strong
instability in the global market because the world reserves of fossil fuels are running
out with a relative instability of fuel prices.
At present, ethanol is considered a viable competitor over those derived from
fossil fuels, representing one of the best biofuels for transportation. Indeed, it can
be burned directly or blended with petrol to improve fuel combustion in vehicles,
resulting in lower CO2 emission to reduce greenhouse gases in the atmosphere.
Furthermore, ethanol is not only considered an excellent fuel but also it represents
an extreme versatile chemical product. It is an important raw material for both
food processing and the production of chemical products, and it is also particularly
used in the pharmaceutical industry. Its applications increase day by day and turn out
to be of crucial importance from a world research point of view. The aim of this book
is to provide, with contributions coming from some of the most representative
scientists in the field, an overview on the state of the art about the most recent
researches on ethanol production, application, and its economical role in the global
market as deeply discussed in the dedicated four sections of this book.
In the first section (Science and Production), Chapter 1 (Abdulrazzaq and
Schwartz) describes the catalytic conversion of ethanol to commodity and specialty
chemicals of industrial and commercial interest. Chapter 2 (Dalena, Senatore, Iulia-
nelli, Di Paola, M. Basile, and A. Basile) gives an overview on the ethanol produc-
tion processes and their future perspectives related to the biomass exploitation.
Chapter 3 (A. Küüt, Ritslaid, K. Küüt, Ilves, and Olt) deals with an overview about
the state of the art on the conventional processes for ethanol production. Chapter 4
(Jalilnejad and Ghasemzadeh) concludes the first section of the book with bioethanol
production process and the criticisms related to the food versus fuel utilization.
In the second section (Application and Innovation), Chapter 5 (Liu, Senanayake,
and Rodriguez) involves a review on the most common catalysts used in the ethanol
reforming processes. Steam reforming, partial oxidation, and autothermal reforming
of ethanol for hydrogen production in conventional reactors are the topics dealt with
in Chapter 6 (Vita, Pino, Italiano, and Palella), in which the most important ethanol
reforming processes in the field of hydrogen production are reviewed. The same
topic was discussed using membrane reactors technology in Chapter 7 (Iulianelli,
Dalena, and Basile), giving details about the benefits of this technology over the con-
ventional systems. In Chapter 8 (Ilves, Küüt, and Lot), ethanol utilization as an
internal combustion engine fuel is extensively discussed, while Chapter 9 (Borole)
deals with the opportunities given by the ethanol exploitation for electricity and
hydrogen production via bioelectrochemical systems. Chapter 10 (Lazar, Senila,
Dana, and Mihet) describes the challenges of using crude bioethanol for hydrogen
xix
xx Preface

production by ethanol steam reforming reaction, pointing out the benefits and draw-
backs of this approach. Section two concludes with Chapter 11 (Meng), which is
dedicated to ethanol utilization in automotive applications, including the environ-
mental impacts of ethanol exploitation in terms of air pollution and greenhouse
gas emissions as well.
Section three of the book (Modelling and Technology) starts with Chapter 12
(Ghasemzadeh, Jalilnejad, and Tilebon), in which the opportunities given by ethanol
exploitation in the field of hydrogen production technologies are reviewed. Chapter
13 (Vaidya, Wu, and Rodrigues) analyzes from a kinetic point of view ethanol pro-
duction processes for hydrogen production. Chapter 14 (Gallucci, Pacheco Tanaka,
and van Sint Annaland) illustrates ethanol reforming in thermally coupled, fluidized
bed, bubble column, and membrane reactors, reviewing the advantages and disad-
vantages of each kind of reactor to produce high-grade hydrogen.
The topic of Chapter 15 (Cermenek, Ranninger, and Hacker) is represented by
the alkaline direct ethanol fuel cell, which represents a promising environment-
friendly energy converter for the production of clean and efficient power. Chapter
16 (Contestabile) contributes to this book pointing out the role of bioethanol utiliza-
tion in batteries, hydrogen fuel cells, and passenger cars, whereas Chapter 17
(Rahimpour, Keshtkari, and Aryafard) points out the benefits and unsolved issues
regarding ethanol as a potential substitute to current aviation fuel.
The last section of this book (Environment and Economy) starts with Chapter 18
(Amiri and Ghasemzadeh), in which the authors describe the impact of an ethanol
economy on the environment as well as on demand and marketing. Chapter 19
(Kohler) undertakes an economic assessment of ethanol production based on
the volatile nature of international crude oil prices, growing global concerns over
energy security, and GHG emissions. Last but not less important, Chapter 20
(Mihaila-Sxtefanescu) ends this book presenting a technical and economic compari-
son of bioethanol exploitation within agriculture and industry.
In conclusion, the editors appreciate the hard work done by the authors and wish
to thank them all for the fruitful cooperation in the preparation of this book. The au-
thors also thank all the staff of Elsevier for their precious and irreplaceable help in
preparing, step by step, this volume.

Angelo Basile
Adolfo Iulianelli
Francesco Dalena
T. Nejat Veziroglu
 CHAPTER

Catalytic Conversion of
Ethanol to Commodity and
Specialty Chemicals 1
Hussein T. Abdulrazzaq, Thomas J. Schwartz
University of Maine, Orono, ME, United States

CHAPTER OUTLINE
1. Introduction ........................................................................................................... 3
2. Products From Direct Ethanol Conversion: Commodity Chemicals .............................. 5
2.1 Ethylene................................................................................................. 5
2.2 Propylene ............................................................................................... 6
2.3 Acetaldehyde .......................................................................................... 7
2.4 Acetic Acid and Ethyl Acetate .................................................................. 8
3. Products From Ethanol Dimerization and Oligomerization: High-Value Commodities
and Specialty Chemicals ...................................................................................... 10
3.1 Butadiene............................................................................................. 10
3.2 Butanol, Higher Alcohols, and Aromatics................................................. 13
3.3 Lubricants ............................................................................................ 17
4. Conclusion and Future Trends ............................................................................... 18
List of Abbreviation ................................................................................................... 19
References ............................................................................................................... 19

1. INTRODUCTION
Using renewable resources for producing fuels and high-value chemicals is an
important next step for the chemical industry because of the finite nature of global
natural gas and petroleum resources. In addition, the use of fossil resources as the
primary source for fuels and chemicals has led to long-term environmental con-
cerns. In particular, the use of petroleum-derived fuels is widely recognized as
the main driver for increased levels of carbon dioxide in the atmosphere. Several
alternatives to fossil-based resources have been proposed for the production of
fuels and chemicals, among which biomass is the most prominent (Chheda
et al., 2007; Huber et al., 2006; Alonso et al., 2010; Luterbacher et al., 2014).
However, recent developments in enhanced oil and gas recovery have mitigated
concerns about the availability of carbon for fuel production (Gerard, 2016;
Wood et al., 2012), although the impact on the chemical industry has been

Ethanol. https://doi.org/10.1016/B978-0-12-811458-2.00001-8 3
Copyright © 2019 Elsevier Inc. All rights reserved.
4 CHAPTER 1 Catalytic Conversion of Ethanol

somewhat more complex. Although the availability of cheap natural gas liquids has
led to interest in building new ethane crackers in the United States (Greenwood,
2016), there has been a concomitant shift in the availability of industrial chemicals
with four or more carbons (Siirola, 2014). Thus, there remains a desire to use
biomass as a feedstock for chemical production. In particular, strategies that
combine both chemical and biological catalysis offer significant flexibility to
selectively retain the functionality native in biomass and efficiently produce
high-value chemicals from biomass (Schwartz et al., 2014, 2016; Shanks and
Keeling, 2017). A general feature of such strategies is the use of biologically
derived platform molecules that can be upgraded to several different end products.
The choice of the target product is a nontrivial consideration when converting
biomass to chemicals. There have been many reports of the conversion of biomass
into industrial commodity chemicals such as olefins, hydrogen, methane, etc.
(Rass-Hansen et al., 2007; Christensen et al., 2008). However, it would be difficult
to completely meet the demand for ethylene, for example, if biomass is used as the
sole feedstock. As a conveniently available reference metric, one can compare the
350 million metric tons corn grown in the United States in 2013 (Capehart, 2017)
with the 143 million metric tons ethylene produced worldwide that same year
(True, 2013). Recognizing that the mass yield of ethanol from glucose is approxi-
mately 50 wt%, replacing fossil-based ethylene with biobased ethylene would
require redirecting nearly all of the corn produced in the United States (as a
representative biomass feedstock and assuming it is 100% starch). Consequently,
it is more appropriate to choose lower volume, higher value chemical products to
target for research.
Ethanol is suitable for use as a platform chemical because it can be converted to
many different end products. Bioethanol can be obtained from biomass resources
by fermentation of raw materials such as corn, sugarcane, and lignocellulose. The
push to produce fuel ethanol from biomass has led to the development of microor-
ganisms that can convert diverse biomass feedstocks to ethanol (Geddes et al.,
2011). In this chapter, we will highlight important catalytic processes for the
conversion of this bioethanol to both commodity and specialty chemicals. The
aim is not to provide an exhaustive review but, rather, to focus on processes that
are historically significant and emerging technologies that have the potential to
fill the gaps left by changes in petroleum feedstocks that have occurred in the first
two decades of the 21st century. Historically, ethanol has been upgraded directly to
C2eC4 species using relatively simple reactions (i.e., via dehydration, dehydroge-
nation, etc.). Recent trends have expanded on this chemistry to obtain highecarbon
number species. Our discussion will begin with the direct conversion pathways that
generally produce commodity chemicals and conclude by highlighting recent
advances in oligomerization chemistry that lead to higher value specialty
chemicals and lubricants.
 2. Products From Direct Ethanol Conversion: Commodity Chemicals 5

2. PRODUCTS FROM DIRECT ETHANOL CONVERSION:

COMMODITY CHEMICALS
2.1 ETHYLENE
Ethylene is one of the most significant commodity chemical in production today. It
is the platform molecule of choice for the synthesis of polyethylene, polyvinyl
chloride, polyethylene terephthalate, polystyrene, ethylene glycol, ethylbenzene,
and many other chemical products. Ordinarily, ethylene is produced industrially by
cracking naphtha and gas oils, with approximately 98%e99% of world production
based on this method. Currently, the shale gas revolution has shifted attention to
the use of ethane as a feedstock, which is abundant in many shale wells. The impor-
tance of steam cracking of ethane has increased dramatically in recent years, and it is
considered to be a productive alternative route for ethylene production. Leading up to
this shift, many technologies and methods were developed to use alternative resources
for ethylene production instead of using conventional cracking processes (Drumm,
2006; Sanders et al., 2007), and some technology development in this area continues
to this day.
In the years following the Second World War, the practice of ethylene production
via ethanol dehydration was not uncommon, and in the intervening years the dehy-
dration reaction has been evaluated using many different types of catalysts such as
metal oxides, alumina, clays, silica, H-ZSM-5 and other zeolites, amorphous silica
alumina, and phosphates, among others (Rass-Hansen et al., 2007; Zhang and Yu,
2013; Angelici et al., 2013; Morschbacker, 2009).
Ethanol dehydration is an endothermic reaction requiring high temperatures,
generally reported in the range of 473e723 K (Angelici et al., 2013). The most chal-
lenging factor in ethanol dehydration is the tendency to produce side products such
as diethyl ether. In particular, high-temperature reactions lead to ethylene whereas
low-temperature reactions tend to increase the possibility of forming diethyl ether
and other products.
A variety of catalysts have been tested for this process. Early reports focused on
phosphoric acid (Morschbacker, 2009), whereas more recent studies have shown
that alumina-containing catalysts are the most promising. In particular, H-ZSM-5
afforded a high yield of about 95% (Bi et al., 2010; Zhang et al., 2008) compared
with g-Al2O3, which gave a yield of approximately 80% at low temperatures
(Angelici et al., 2013). Other catalytic systems have also been examined
for low-temperature dehydration. Silicoaluminophosphate (SAPO) catalysts doped
with Mn2þ and Zn2þ showed 97.8% yield of ethylene at 613 K (Chen et al.,
2010). Zhang et al. (2008) probed four different catalysts, Al2O3, H-ZSM-5,
Silicoaluminophosphate-34 (SAPO-34), and Ni-doped SAPO-34 (NiSAPO-34), and
tested them under different conditions. The most active catalysts were H-ZSM-5
6 CHAPTER 1 Catalytic Conversion of Ethanol

and NiSAPO-34. Both showed high selectivity and greater than 90% yield toward
ethylene, whereas the others showed low selectivity. The authors attributed the low
selectivity over the other catalysts to an abundance of strong acid sites in their struc-
tures. Alumina is one of the most active catalysts for this reaction, with ethylene pro-
duction occurring in a temperature range of 300e500 C, obtaining high ethylene
yields between 94% and 99% (Zhang and Yu, 2013).

2.2 PROPYLENE
In addition to ethylene, it is also possible to also produce higher olefins from ethanol.
The success of the ExxonMobil (formerly Mobil) Methanol-to-Olefins process has
driven the use of H-ZSM-5 as a catalyst for the conversion of ethanol to propylene.
In particular, the group of Tadahiro Fujitani has been quite prolific in this area. As
early as 2009, their group showed that H-ZSM-5 is active for the production of pro-
pylene from ethanol using commercial zeolites purchased from Zeolyst (Song et al.,
2009). The highest selectivities observed in that work were w30% and obtained using
a Zr-impregnated H-ZSM-5, which the authors attribute to the presence of moderately
acidic active sites that promote the formation of C3þ hydrocarbons from ethanol. In a
follow-up study, this group synthesized a series of zeolites with Mordenite Framework
Inverted (MFI) topology, and they concluded that the reactivity is independent of
the acid site density (i.e., all acid sites in these catalysts are equally active for this re-
action) (Xia et al., 2010). The use of metal-containing H-ZSM-5 zeolites also leads to
w30% selectivity in the reaction. For example, the propylene yield using SreHZSM-
5 was 32% at complete ethanol conversion. This material showed similar stability to
the Zr-impregnated zeolite (Goto et al., 2010).
Similar results were obtained by Inoue et al. (2010) using loweAl content
H-ZSM-5 catalysts. Impregnation of these catalysts with La led to similar selectiv-
ities of w30%. Importantly, deactivation was observed for all the catalysts described
thus far, although the La-promoted catalyst of Inoue’s group is qualitatively more
stable than the Zr-promoted material from Fujitani et al.
Motivated by the previous success of phosphorous impregnation of ZSM-5 to
improve stability in other reactions, Fujitani et al. evaluated this same catalyst
for propylene formation (Song et al., 2010). Similar propylene selectivities were
obtained (w30% maximum), although catalyst deactivation was eliminated during
short (w8 h) reactions. In a follow-up study (Takahashi et al., 2012), this same
group showed that the P-containing H-ZSM-5 catalyst deactivates only slightly
over the course of 100 h of time-on-stream, whereas an unpromoted H-ZSM-5
catalyst loses all of its activity within 20 h at the same conditions. They note
that the improved stability is dependent on the presence of water vapor in the
reactor.
Direct conversion of ethanol to propylene is not the only process available.
Before the development of the ZSM-5ebased catalysts described earlier, Braskem
undertook development of a biomass-derived ethanol-to-propylene process. In their
route, ethanol is first dehydrated to ethylene, which is oligomerized to butene.
 2. Products From Direct Ethanol Conversion: Commodity Chemicals 7

Using the Lummus process, the butene is subsequently converted to propylene and
ethylene via olefin metathesis (Bruijnincx and Weckhuysen, 2013). It is worth
noting, though, that the prevalence of cheap shale gas in the United States in the
early part of the 21st century has made both bioethanol-to-ethylene and
bioethanol-to-propylene processes economically unattractive. Notably, a significant
amount of propane is recovered with methane and ethane in shale gas, and there is
well-established technology (i.e., Houdry dehydrogenation for converting propane
to propylene and steam cracking for converting ethane to ethylene) that may be
more economically attractive as long as shale gas liquids are inexpensive relative
to lignocellulose.

2.3 ACETALDEHYDE
Acetaldehyde is another significant chemical that can be produced catalytically from
ethanol. It is a commodity chemical which is commonly used as an intermediate
in the synthesis of important industrial chemicals, such as acetic acid, ethyl acetate,
crotonaldehyde, butadiene, pentaerythritol, butylene glycol, and many others
(Sun and Wang, 2014). Importantly, because ethanol is natively oxygenated, produc-
tion of acetaldehyde from ethanol avoids the hazards associated with hydrocarbon
oxidation.
Historically, acetaldehyde has been produced commercially by hydrating acety-
lene to vinyl alcohol, which then tautomerizes to acetaldehyde (Wittcoff, 1983).
This process was often performed in the presence of sulfuric acid as a catalyst.
As the price of ethylene dropped in the 1960s, ethylene saw use as a raw material
in the process of acetaldehyde production. In this case, acetaldehyde is produced
either by hydration of ethylene to ethanol followed by dehydrogenation or by partial
oxidation of ethanol with air over a silver gauze catalyst to give acetaldehyde.
Currently, the most common process for acetaldehyde synthesis is the Wacker
process, which directly oxidizes ethylene to acetaldehyde over palladium or copper
chlorides.
Acetaldehyde can be produced biorenewably by the dehydrogenation of ethanol.
This process has been performed over many different types of catalysts and has been
tested at a wide range of temperatures, from 150 to 350 C. Generally, the process is
highly selective using noble metals such as silver or gold. Copper has also been
observed to be effective for the dehydrogenation reaction.
Guan and Hensen (2009) investigated the use of a range of silica-supported gold
nanoparticle catalysts for the catalytic oxidation of ethanol. They studied the influ-
ence of both the support structure and the gold nanoparticle size in both the presence
and absence of oxygen. Acetaldehyde selectivity in the absence of oxygen at
temperatures below 350 C was between 60% and 80%, depending on Au particle
size, at complete conversion. At 400 C the selectivity to acetaldehyde was above
90% at complete ethanol conversion regardless of the Au particle size. The best
results were obtained using catalysts with midsized particles, suggesting
there is an optimum in Au nanoparticle size for acetaldehyde production.
8 CHAPTER 1 Catalytic Conversion of Ethanol

Additionally, co-feeding oxygen with ethanol led to increased activity and selec-
tivity toward acetaldehyde relative to reactions carried out under anaerobic
reactions. The highest conversion was obtained in the presence of oxygen using
an MCM-41esupported Au catalyst at 250 C, which resulted in 90% selectivity
toward acetaldehyde at 20% ethanol conversion. In contrast, Wittcoff previously
reported the oxidation of ethanol over silver oxide or silver gauze at much higher
temperatures (e.g., 480 C), with conversions ranging between 74% and 82% and
selectivities to acetaldehyde of around 80% (Wittcoff, 1983).
Using Au/TiO2 as catalyst leads to about 65% acetaldehyde selectivity at 35%
ethanol conversion at 90 C and 42% selectivity at 95% ethanol conversion at
280 C in the presence of oxygen (Simakova et al., 2010). However, at elevated tem-
peratures the catalyst deactivated and the selectivity to acetaldehyde was only
approximately 40%. Liu and Hensen (2013) have reported that a ternary spinel
MgCuCr2O4-supported gold nanoparticle catalyst is highly active and able to
achieve 90% stable conversion with 85% selectivity toward acetaldehyde at 200 C.
Chang et al. (2006) have tested various loadings of copper supported on Rice
Husk Ash (RHA), which has a high content of amorphous silica. At 275 C using
a 5.75 wt% Cu/RHA catalyst, this group obtained over 80% ethanol conversion
and nearly quantitative selectivity to acetaldehyde. The Cu/RHA was also more
active than copper supported on silica gel prepared by the same procedure (Angelici
et al., 2013). The improvement using RHA as a support was ascribed to changes in
the particle size and surface area of the copper particles in the catalyst. Also using
noneprecious metal catalysts, Kim et al. (2008) studied the conversion of ethanol to
acetaldehyde using vanadiumetungsten mixed oxide catalysts with various ratios of
vanadium-to-tungsten. A catalyst containing 95% vanadium showed the best perfor-
mance over a different range of temperatures, with the highest yield of acetaldehyde
of about 90% at 300 C.

2.4 ACETIC ACID AND ETHYL ACETATE

Related to acetaldehyde production, ethanol can be further oxidized to acetic
acid and ethyl acetate. Industrially, acetic acid is produced by either the oxida-
tion of acetaldehyde with dioxygen or by carbonylation of methanol or methyl
acetate and some is also produced by direct oxidation of butane (Wagner,
2014). Renewable acetic acid can be obtained by oxidation of ethanol-derived
acetaldehyde.
Aerobic conversion of ethanol leads to mixtures of acetaldehyde, acetic acid, and
ethyl acetate. Pd-based catalysts are particularly useful in this regard. For example,
Gaspar et al. (2010) showed that palladium oxide supported on monoclinic zirconia
(PdO/m-ZrO2) can be used to produce acetic acid, ethyl acetate, and acetaldehyde
(32%, 35%, and 25% selectivities, respectively, at 32% ethanol conversion) from
ethanol at 175 C in the presence of dioxygen. Notably, the phase of the ZrO2 support
is significant for achieving high selectivity. Physical mixtures of the Pd-containing
catalyst with other zirconias lead to a near-complete deactivation of the acetic acid
Discovering Diverse Content Through
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care of. The passengers were pretty restive at first, but the coming of
light seemed to work wonders. This first glimmer of power is another.
About nine or ten who were able to do so were having severe cases
of skysickness." He smiled ruefully. "I'm not too sure that I like no-
weight myself."
"Have you been in the observation dome?" asked Don.
"Yes. It's pierced, you know."
"Did the meteor hit the telescope?"
"No, why?"
"Because I'm going to have to get a sight on Venus Equilateral
before we can do anything. We'll have to beam them something, but
I don't know what right now."
"Can we discuss that over a dinner?" asked the captain. "I'm starved,
and I think that the rest of this gang is also."
"You're a man after my own heart," laughed Channing. "The bunch
out at the Station wouldn't believe me if I claimed to have done
anything without drawing it up on a tablecloth."

"Now," said Channing over his coffee. "What have we in the way of
electronic equipment?"
"One X-ray machine, a standard set of communicating equipment,
one beam receiver with 'type machine for collecting stuff from your
Station, and so on."
"You wouldn't have a betatron in the place somewhere?" asked Don
hopefully.
"Nope. Could we make one?"
"Sure. Have you got about ten pounds of No. 18 wire?"
"No."
"Then we can't."
"Couldn't you use a driver? Isn't that some kind of beam?"
"Some kind," admitted Channing. "But it emits something that we've
never been able to detect except in an atmosphere where it ionizes
the air into a dull red glow."
"You should have been wrecked on the Sorcerer's Apprentice,"
laughed Hadley. "They're the guys who have all that kind of stuff."
"Have they?" asked Johannson.
"The last time I heard, they were using a large hunk of their upper
hull for a VanDerGraf generator."
"That would do it," said Channing thoughtfully. "But I don't think I'd
know how to modulate a VanDerGraf. A betatron would be the thing.
You can modulate that, sort of, by keying the input. She'd give out
with hundred-and-fifty-cycle stuff, but so what? We made the
Empress of Kolain sit up and say uncle on hundred-cycle stuff. How
much of a trick is it to clear the observation dome from the top?"
"What do you intend to do?"
"Well, we've got a long, hollow tube in this ship. Knock out the
faceted dome above, and we can rig us up a huge electron gun.
We'll turn the ship to point at the Station and beam 'em a bouquet of
electrons."
"How're you going to do that?"
"Not too tough, I don't think. Down here," and Channing began to
trace on the tablecloth, "we'll put us a hot cathode. About this level
we'll hang the first anode, and at this level we'll put the second
anode. Here'll be an acceleration electrode, and up near the top we'll
put a series of focusing anodes. We'll tap in to the driver-tube supply
and take off voltages to suit us. Might use a tube at that, but the
conversion to make an honest electron gun out of it would disrupt
our power, and then it would be impossible to make a driver out of it
again without recourse to a machine shop."
"How are you going to make electrodes?"
"We'll use the annular gratings that run around the central well at
each level," said Channing. "We'll have a crew of men cut 'em free
and insulate the resulting rings with something. Got anything?"
"There is a shipment of methyl-methacrylate rods for the Venus
Power Co. in Hold 17," said the cargo master.
"Fine," said Channing. "What size?"
"Three inches by six feet."
"It'll be tricky work, and you'll have to wait until your cut edge has
cooled before you hook on the rods," mused Don. "But that's the
ticket."
"Which floors do you want?"
"Have you got a scale drawing of the Solar Queen?"
"Sure."
"Then this is where my tablecloth artistry falls flat. The focusing of an
electron beam depends upon the electrode spacing and the voltage.
Since our voltage is fixed if we take it from the driver electrodes, we'll
have to do some mighty fine figuring. I'll need that scale drawing."

Channing's tablecloth engineering was not completely wasted. By

the time the scale drawing was placed before him, Channing had
half of the table filled with equations. He studied the drawing, and
selected the levels which were to serve as electrodes. He handed
the drawing to Hadley, and the power engineer began to issue
instructions to his gang.
Then the central well began to swarm with spacesuited men who
bore cutting torches. Hot sparks danced from the cut girders that
held the floorings, and at the same time, a crew of men were running
cables from the various levels to the instrument room. More hours
passed while the circular sections were insulated with the plastic
rods.
The big dome above was cut in sections and removed, and then the
sky could be seen all the way from the bottom of the ship where the
pilot's greenhouse should have been.
Channing looked it over and then remarked: "All we need now is an
electron collector."
"I thought you wanted to shoot 'em off," objected Hadley.
"I do. But we've got to have a source of supply. You can't toss
baseballs off of the Transplanet Building in Northern Landing all
afternoon, you know, without having a few brought to you now and
then. Where do you think they come from?"
"Hadn't thought of it in that way. What'd happen?"
"We'd get along for the first umpty-gillion electrons, and then all the
soup we could pack on would be equalized by the positive charge on
the ship and we couldn't shoot out any more until we got bombarded
by the sun—and that bombardment is nothing to write home about
as goes quantity. What we need is a selective solar intake plate of
goodly proportions."
"We could use a mental telepathy expert, too. Or one of those new
beams that Baler and Carroll dug up out of the Martian desert. I've
heard that those things will actually suck power out of any source,
and bend beams so as to enter the intake vent, or end."
"We haven't one of those, either. Fact of the matter is," grinned
Channing ruefully, "we haven't much of anything but our wits."
"Unarmed, practically," laughed Hadley.
"Half armed, at least. Ah, for something to soak up electrons. I'm
now wondering if this electron gun is such a good idea."
"Might squirt some protons out the other direction," offered Hadley.
"That would leave us without either," said Don. "We'd be like the man
who tossed baseballs off of one side and himself off the other—Hey!
Of course we have some to spare. We can cram electrons out of the
business end, thus stripping the planetary rings from the atoms in
our cathode. From the far side we'll shoot the canal rays, which in
effect will be squirting protons, or the nuclei. Since the planetaries
have left for the front, it shouldn't be hard to take the protons away,
leaving nothing. At our present voltages, we might be able to do it."
Channing began to figure again, and he came up with another set of
anodes to be placed beyond the cathode. "We'll ventilate the
cathode and hang these negative electrodes on the far side. They
will attract the protons, impelled also by the positive charge on the
front end. We'll maintain a balance that way, effectively throwing
away the whole atomic structure of the cathode. The latter will fade,
just as the cathodes do in the driving tubes, only we'll be using
electronic power instead of sub-electronic. Y'know, Hadley, some
day someone is going to find a way to detect the—we'll call it
radiation for want of anything better—of the driver. And then there
will open an entirely new field of energy. I don't think that anybody
has done more about the so-called sub-electronic field than to make
a nice, efficient driving device out of it.
"Well, let's get our canal-ray electrodes in place. We've got about
two hours before they realize that we aren't going to come in at
Mojave. Then another two hours worth of wild messages between
the Relay Station and Mojave. Then we can expect someone to be
on the lookout. I hope to be there when they begin to look for us. At
our present velocity, we'll be flirting with the Asteroid Belt in less than
nothing flat. That isn't too bad—normally—but we're running without
any meteor detector and autopilot coupler. We couldn't duck
anything from a robin's egg on up."
"We'll get your anodes set," said Hadley.

Walt Franks grinned at Arden Channing. "That'll burn him," he

assured her.
"It's been on the way for about twenty minutes," laughed Arden. "I
timed it to arrive at Terra at the same time the Solar Queen does.
They'll send out a special messenger with it, just as Don is getting
aboard his little scooter. It'll be the last word, for we're not following
him from Terra to here."
"You know what you've started?" asked Franks.
"Nothing more than a little feud between husband and self."
"That's just the start. Before he gets done, Don will have every ship
capable of answering back. I've found that you can catch him off
base just once. He's a genius—one of those men who never make
the same mistake twice. He'll never again be in a position to be on
the listening end only."
"Don's answer should be on the way back by now," said Arden.
"Could be you're right. Something should be done."
"Sure I'm right. Look at all the time that's wasted in waiting for a
landing to answer 'grams. In this day and age, time is money,
squared. The latter is to differentiate between this time and the first
glimmering of speedy living."
"Was there a first glimmering?" asked Arden sagely. "I've often
thought that the speed-up was a stable acceleration from the dawn
of time to the present."
"All right, go technical on me," laughed Walt. "Things do move. That
is, all except that message from your loving husband."
"You don't suppose he's squelched?"
"I doubt it. Squelching Donald Channing is a job for a superbeing.
And I'm not too sure that a superbeing could squelch Don and make
him stay squelched. Better check on Mojave."
"Gosh, if Don missed the Solar Queen and I've been shooting him all
kinds of screwy 'types every hour on the hour; Walt, that'll keep him
quiet for a long, long time."
"He'd have let you know."
"That wouldn't have been so bad. But if the big bum missed and was
ashamed of it—that'll be the pay-off. Whoa, there goes the 'type!"
Arden drew the tape from the machine:
MESSAGE BEING HELD FOR ARRIVAL OF SOLAR
QUEEN.
Walt looked at his watch and checked the course constants of the
Solar Queen. He called the beam-control dome and asked for the
man on the Solar Queen beam.
"Benny," he said, "has the Solar Queen arrived yet?"
"Sure," answered Benny. "According to the mechanical mind here,
they've been on Mojave for twenty minutes."
"Thanks." To Arden he said: "Something's strictly fishy."
Arden sat at the machine and pounded the keys:
SOLAR QUEEN DUE TO ARRIVE AT 19:06:41. IT IS
NOW 19:27:00. BEAM CONTROL SAYS
TRANSMISSIONS ENDED BECAUSE OF
COINCIDENCE BETWEEN TERRA BEAM AND
STATION-TO-SHIP BEAM. PLEASE CHECK.
Arden fretted and Walt stamped up and down the room during the
long minutes necessary for the message to reach Terra and the
answer to return. It came right on the tick of the clock:
HAVE CHECKED COURSE CONSTANTS. SOLAR
QUEEN OVER-DUE NOW FIFTY MINUTES. OBVIOUSLY
SOMETHING WRONG. CAN YOU HELP?
Walt smiled in a grim fashion. "Help!" he said. "We go on and on for
years and years with no trouble—and now we've lost the third ship in
a row."
"They claim that those things always run in threes," said Arden.
"What are we going to do?"
"I don't know. We'll have to do something. Funny, but the one reason
we must do something is the same reason why something can be
done."
"I don't get that."
"With Channing on the Solar Queen, something can be done. I don't
know what, but I'll bet you a new hat that Don will make it possible
for us to detect the ship. There is not a doubt in my mind that if the
ship is still spaceworthy, we can narrow the possibilities down to a
thin cone of space."
"How?"
"Well," said Franks, taking the fountain pen out of the holder on the
desk and beginning to sketch on the blotter, "the course of the Solar
Queen is not a very crooked one, as courses go. It's a very shallow
skew curve. Admitting the worst, collision, we can assume only one
thing. If the meteor were small enough to leave the ship in a floating
but undirigible condition, it would also be small enough to do nothing
to the general direction of the ship. Anything else would make it
useless to hunt, follow?"
"Yes, go on."
"Therefore we may assume that the present position of the Solar
Queen is within the volume of a cone made by the tangents of the
outermost elements of the space curve that is the Solar Queen's
course. We can take an eight-thousand-mile cylinder out of one
place—for the origin of their trouble is between Mars and Terra and
the 'shadow' of Terra in the cone will not contain the Solar Queen."
"Might have passed close enough to Terra to throw her right into the
'shadow' of Terra by attraction," objected Arden.
"Yeah, you're right. O.K., so we can't take out that cylinder of space.
And we add a sort of side-wise cone on to our original cone, a
volume through which the Queen might have flown after passing
close enough to Terra to be deflected. I'll have the slipstick experts
give a guess as to the probability of the Queen's course, and at the
same time we'll suspend all incoming operations. I'm going to set up
every kind of detector I can think of, and I don't want anything
upsetting them."
"What kind of stuff do you expect?" asked Arden.
"I dunno. They might have a betatron aboard. In that case we'll
eventually get a blast of electrons that'll knock our front teeth out.
Don may succeed in tinkering up some sort of electrostatic field. We
can check the solar electrostatic field to about seven decimal places
right here, and any deviation in the field to the tune of a couple of
million electron volts at a distance of a hundred million miles will
cause a distortion in the field that we can measure. We'll ply
oscillating beams through the area of expectation and hope for an
answering reflection, though I do not hope for that. We'll have men
on the lookout for everything from smoke signals to helio. Don't
worry too much, Arden, your husband is capable of doing something
big enough to be heard. He's just the guy to do it."
"I know," said Arden soberly. "But I can't help worrying."
"Me, too. Well, I'm off to set up detectors. We'll collect something."

"Have we got anything like a piece of gold leaf?" asked Channing.

"I think so, why?"
"I want to make an electroscope. That's about the only way I'll know
whether we are getting out with this cockeyed electron gun."
"How so?" asked Hadley.
"We can tell from the meter that reads the beam current whether
anything is going up the pipe," explained Channing. "But if we just
build us up a nice heavy duty charge—as shown by the electroscope
—we'll be sure that the electrons are not going far. This is one case
where no sign is good news."
"I'll have one of the boys set up an electroscope in the instrument
room."
"Good. And now have the bird on the telescope forget trying to find
Venus Equilateral by dead reckoning and sight. Have him set the
scope angles to the figures here, and then have him contact
Darlange and have the ship slued around so that Venus is on the
cross hairs. That'll put us on a line for the Station by a few thousand
miles. We can afford to miss. A bundle of electrons of our magnitude
zipping past the detectors that Walt can set up will make a reading."
Hadley called the observation dome. "Tim," he said, giving a string of
figures, "set your 'scope for these and then get Darlange to slue the
crate around so that your cross hairs are on Venus."
"O.K.," answered Tim. "That's going to be a job. This business of
looking through a 'scope while dressed in a spacesuit is no fun. Here
goes."
He called Darlange, and the communicator system permitted the
men in the instrument room to hear his voice. "Dar," he said, "loop us
around about forty-one degrees from Driver 3."
Darlange said: "Right!" and busied himself at his buttons.
"Three degrees on Driver 4."
"Right."
"Too far, back her up a degree on 4."
Darlange laughed. "What do you think these things are, blocks and
tackles? You mean: 'Compensate a degree on 2.'"
"You're the pilot. That's the ticket—and I don't care if you lift it on one
hand. Can you nudge her just a red hair on 3?"
"Best I can do is a hair and a half," said Darlange. He gave Driver 3
just a tiny, instantaneous surge.
"Then take it up two and back one and a half," laughed Tim. "Whoa,
Nellie, you're on the beam."
"Fine."
"O.K., Dar, but you'll have to play monkey on a stick. I'll prime you for
any moving so that you can correct immediately."
"Right. Don, we're on the constants you gave us. What now?"
"At this point I think a short prayer would be of assistance," said
Channing soberly. "We're shooting our whole wad right now."
"I hope we make our point."
"Well, it's all or nothing," agreed Don as he grasped the switch.
He closed the switch, and the power demand meters jumped up
across their scales. The gold-leaf electroscope jumped once; the
ultra-thin leaves jerked apart by an inch, and then oscillated stiffly
until they came to a balance. Channing, who had been looking at
them, breathed deeply and smiled.
"We're getting out," he said.
"Can you key this?" asked Hadley.
"No need," said Channing. "They know we're in the grease. We know
that if they can collect us, they'll be on their way. I'm going to send
out for a half-hour, and then resort to a five-minute transmission
every fifteen minutes. They'll get a ship after us with just about
everything we're likely to need, and they can use the five-minute
transmissions for direction finding. The initial shot will serve to give
them an idea as to our direction. All we can do now is to wait."
"And hope," added Captain Johannson.

Electrically, Venus Equilateral was more silent than it had ever been.
Not an electrical appliance was running on the whole station. People
were cautioned about walking on deep-pile rugs, or combing their
hair with plastic combs, or doing anything that would set up any kind
of electronic charge. Only the highly filtered generators in the power
rooms were running and these had been shielded and filtered long
years ago; nothing would emerge from them to interrupt the ether. All
incoming signals were stopped.
And the men who listened with straining ears claimed that the sky
was absolutely clear save for a faint crackle of cosmic static which
they knew came from the corona of the sun.
One group of men sat about a static-field indicator and cursed the
minute wiggling of the meter, caused by the ever-moving celestial
bodies and their electronic charges. A sunspot emission passed
through the Station once, and though it was but a brief passage, it
sent the electrostatic field crazy and made the men jump.
The men who were straining their ears to hear became nervous, and
were jumping at every loud crackle.
And though the man at the telescope knew that his probability of
picking up a sight of the Solar Queen was as slender as a spider's
web, he continued to search the starry heavens. He swept the
narrow cone of the heavens wherein the Solar Queen was lost
according to the mathematical experts, and he looked at every bit of
brightness in the field of his telescope as though it might be the
missing ship.
The beam-scanners watched their return-plates closely. It was
difficult because the receiver gains were set to maximum, and every
tick of static caused brief flashes of light upon their plates. They
would jump at such a flash and watch for it to reappear on the next
wipe, for a continuous spot of light indicated the ship they sought.
Then, as the spot did not reappear, they would go on with their
beams to cover another infinitesimal portion of the sky. Moving
forward across the cone of expectancy bit by bit, they crossed and
recrossed until they were growing restive.
Surely the ship must be there!
At the South End landing stage, a group of men were busy stocking
a ship. Supplies and necessities were carried aboard, while another
group of men tinkered with the electrical equipment. They cleared a
big space in the observation dome, and began to install a replica of
the equipment used on the Station for detection. No matter what kind
of output Channing sent back, they would be able to follow it to the
bitter end.
They made their installations in duplicate, with one piece of each
equipment on opposite sides of the blunt dome. Balancing the inputs
of each kind by turning the entire ship would give them a good
indication of direction.
Franks did not hope that the entire installation could be completed
before the signal came, but he was trying to outguess himself by
putting some of everything aboard. When and if it came, he would be
either completely ready with everything or he at least would have a
good start on any one of the number of detectors. If need be, the
equipment from the Station itself could be removed and used to
complete the mobile installation.
Everything was in a complete state of nervous expectancy. Watchers
watched, meter readers squinted for the barest wiggle, audio
observers listened, trying to filter any kind of man-made note out of
the irregular crackle that came in.
And the Station announcing equipment was dead quiet, to be used
only in case of emergency or to announce the first glimmer of
radiation, whether it be material, electrical, kinetic, potential, or wave
front.
Long they listened—and then it came.

The Station announcing equipment broke forth in a multitude of

voices.
"Sound input on radio."
"Visual indication on scanner plates!"
"Distortion on electrostatic field indicator."
"Super-electroscopes indicate negative charge!"
"Nothing on the telescope!"
There were mingled cheers and laughter as the speaker system
broke away from its babel, and each group spoke its piece with no
interference. Walt Franks left the ship at the South End and raced to
the Beam Control dome, just as fast as the runway car would take
him. He ran into the dome in spacesuit and flipped the helmet back
over his shoulders. "What kind of indication?" he yelled.
Men crowded around him, offering him papers and shouting figures.
"Gosh," he said, "Don can't have everything going up there."
"He's hit just about everything but the guy squinting through the
'scope."
"What's he doing?" asked Franks of no one in particular.
One of the radiation engineers who had been busy with the
electrostatic field indicator said: "I think maybe he's using some sort
of electron gun—like the one you tried first off on the meteor-
destroyer-job, remember?"
"Yeah, but that one wouldn't work—unless Don has succeeded in
doing something that we couldn't do. Look, Charley, we haven't had
time to set up a complete field indicator on the ship. Grab yours and
give the boys a lift installing it, hey?"
"Sure thing."
"And look, fellows, any indication of direction, velocity, or distance?"
"Look for yourself," said the man on the beam scanner. "The whole
plate is shining. We can't get a fix on them this way—they're
radiating themselves and that means that our scanner-system finder
is worthless."
"We can, but it's rough," offered one of the radio men. "It came from
an area out beyond Terra—and as for our readings it might have
covered a quarter of the sky."
"The field indicator is a short-base finder," explained Charley. "And
no less rough than the radio boys. I'd say it was out beyond Terra by
fifty million miles at least."
"Close enough. We'll have to track 'em down like a radio-equipped
bloodhound. Charley, come along and run that mechanico-electro-
monstrosity of yours. Gene, you can come along and run the radio
finder. Oh yes, you, Jimmy, may continue to squint through that
eyepiece of yours—but on the Relay Girl. We need a good, first-
class squinter, and you should have an opportunity to help."
Jimmy laughed shortly. "The only guy on the Station that didn't get
an indication was me. Not even a glimmer."
"Channing didn't know we'd be looking for him, or he'd probably light
a flare, too. Cheer up, Jimmy, after all this crude, electrical
rigamarole is finished, and we gotta get right down to the last
millimeter, it's the guy with the eye that polishes up the job. You'll
have your turn."
Twenty minutes after the first glimmer of intelligent signal, the Relay
Girl lifted from the South End and darted off at an angle, setting her
nose roughly in the direction of the signal.
Her holds were filled with spare batteries and a whole dozen
replacement cathodes as well as her own replacements. Her crew
was filled to the eyebrows with gravanol, and there must have been
a mile of adhesive tape and cotton on their abdomens. At 6-G she
left, and at 6-G she ran, her crew immobilized but awake because of
the gravanol. And though the acceleration was terrific, the tape kept
the body from folding of its own weight. When they returned, they
would all be in the hospital for a week, but their friends would be with
them.
Ten minutes after take-off, the signals ceased.
Walt said: "Keep her running. Don's saving electricity. Tell me when
we pick him up again."
Franklen, the pilot, nodded. "We haven't got a good start yet. It'll be
touch and go. According to the slipstick boys, they must be clapping
it up at between twenty-five hundred and five thousand miles per
second to get that far—and coasting free or nearly so. Otherwise
they'd have come in. Any suggestions as to course?"
"Sure. Whoop it up at six until we hit about six thousand. Then
decelerate to four thousand by using 1-G. We'll vacillate in velocity
between four and five until we get close."
Forty-one hours later, the Relay Queen made turnover and began to
decelerate.

Channing said to Captain Johannson: "Better cut the decel to about

a quarter-G. That'll be enough to keep us from bumping our heads
on the ceiling and it will last longer. This is going to be a long chase,
and cutting down a few MPS at a half-G isn't going to make much
never-mind. I'll hazard a guess that the boys are on their way right
now."
"If you say so," said Johannson. "You're the boss from now on. You
know that wild bunch on the Station better than I do. For myself, I've
always felt that an answer was desirable before we do anything."
"I know Franks and my wife pretty well—about as well as they know
me. I've put myself in Walt's place—and I know that Walt would do.
So—if Walt didn't think of it, Arden would—I can assume that they
are aware of us, have received our signals, and are, therefore,
coming along as fast as they can. They'll come zipping out here at
from five- to seven-G to what they think is halfway and then
decelerate again to a sane velocity. We won't catch sight of them for
sixty or seventy hours, and when we do, they'll be going so fast that
it will take another twenty hours worth of manipulation to match their
speed with ours. Meanwhile, I've got the gun timed to shoot our
signal. When the going gets critical, I'll cut the power and make it
continuous."
"You're pretty sure of your timing?"
"Well, the best they can do as for direction and velocity and distance
is a crude guess. They'll place us out here beyond Terra somewhere.
They'll calculate the course requirements to get us this far in the time
allotted, and come to a crude figure. I'd like to try keying this thing,
but I know that keying it won't work worth a hoot at this distance.
Each bundle of keyed electrons would act as a separate negative
charge that would spread out and close up at this distance. It's tough
enough to hope that the electron beam will hold together that far, let
alone trying to key intelligence with it. We'll leave well enough alone
—and especially if they're trying to get a fix on us; there's nothing
worse than trying to fix an intermittent station. Where are we now?"
"We're on the inner fringe of the Asteroid Belt, about thirty million
miles North, and heading on a secant course at thirty-four hundred
MPS."
"Too bad Jupiter isn't in the neighborhood," said Channing. "We'll be
flirting with his orbit by the time they catch us."
"Easily," said Johannson. "In sixty hours, we'll have covered about
six hundred and fifty million miles. We'll be nearer the orbit of Saturn,
in spite of the secant course."
"Your secant approaches a radius as you get farther out," said Don,
absently. "As far as distances go. Ah, well, Titan, here we come!"
Johannson spoke to the doctor. "How're we doing?"
"Pretty well," said Doc. "There's as pretty an assortment of fractured
ribs, broken limbs, cracked clavicles, and scars, mars, and abrasions
as you ever saw. There are a number dead, worse luck, but we can't
do a thing about them. We can hold on for a week as far as food and
water goes. Everyone is now interested in the manner of our rescue
rather than worrying about it." He turned to Channing. "The words
Channing and Venus Equilateral have wonderful healing powers," he
said. "They all think your gang are part magician and part sorcerer."
"Why, for goodness' sake?"
"I didn't ask. Once I told 'em you had a scheme to contact the Relay
Station, they were all satisfied that things would happen for the
better."
"Anything we can do to help you out?"
"I think not," answered Doc. "What I said before still goes. Your job is
to bring aid—and that's the sum total of your job. Every effort must
be expended on that and that alone. You've got too many whole
people depending on you to spend one second on the hurt. That's
my job."
"O.K.," said Channing, "But it's going to be a long wait."
"We can afford it."
"I hope we're not complicating the job of finding us by this quartering
deceleration," said Johannson.
"We're not. We're making a sort of vector from our course, but the
deviation is very small. As long as the fellows follow our radiation,
we'll be found," Channing said with a smile. "The thing that is tough
is the fact that all the floors seem to lean over."
"Not much, though."
"They wouldn't lean at all if we were running with the whole set of
equipment," said Darlange. "We run a complete turnover without
spilling a drop from the swimming pool."
"Or even making the passengers aware of it unless they're looking at
the sky."
"Stop worrying about it," said Doc. "I'm the only guy who has to
worry about it and as long as the floor is still a floor, I can stand
sliding into the corner once in a while."
"We might tinker with the turnover drivers," offered Don. "We can
bring 'em down to a place where the velocity-deceleration vectors
are perpendicular to the floor upon which we stand while our ship is
sluing. We've got a lot of time on our hands, and I, for one, feel a lot
happier when I'm doing something."
"It's a thought," said Hadley. "Wanna try it?"
"Let's go."

Thirty hours after the Relay Girl left the Station, Walt and Franklen
held a council of war, in which Charley Bren was the prime factor.
"We've come about two hundred million miles, and our present
velocity is something like four thousand miles per second," said Walt.
"We're going out towards Mars on a slightly-off radial course, to the
North of the ecliptic. That means we're a little over a quarter of a
billion miles from Sol, or about to hit the Asteroid Belt. Thinking it
over a little, I think we should continue our acceleration for another
thirty hours. What say?"
"The field has shown no change in intensity that I can detect," said
Bren. "If they haven't dropped their radiated intensity, that means
that we are no closer to them than we were before. Of course, we'd
probably have to cut the distance by at least a half before any
measurable decrement made itself evident."
"They must be on the upper limit of that four thousand MPS,"
observed Walt. "There's one thing certain, we'll never catch them by
matching their speed."
"Where will another thirty hours at 6-G put us and how fast?" asked
Franklen.
Silence ensued while they scribbled long figures on scratch paper.
"About eight hundred million miles from Sol," announced Walt.
"And about eight thousand MPS," added Charley.
"That's a little extreme, don't you think?" asked Franklen.
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