Catalytic Methanol Synthesis

Catalytic conversion of
syngas to ethanol and higher

alcohols over Rh and Cu
based catalysts
Luis Gagarin Lopez Nina
Doctoral Thesis in Chemical Engineering

KTH Royal Institute of Technology
School of Chemical Science and Engineering
Department of Chemical Engineering and Technology
Stockholm, Sweden 2017
Catalytic conversion of syngas to ethanol and higher alcohols over Rh
and Cu based catalysts
LUIS GAGARIN LOPEZ NINA
TRITA-CHE Report 2017:2

ISSN 1654-1081
ISBN 978-91-7729-206-7
Akademisk avhandling som med tillstånd av Kungliga Tekniska

Högskolan i Stockholm framlägges till offentlig granskning för avläggande
av teknologie doktorsexamen fredagen den 27 januari 2017 kl. 10:00 i sal
Q2, KTH, Osquldas väg 10, Våning 2, Stockholm.
Fakultetsopponent: Prof. Mario Montes Ramírez, Department of Applied
Chemistry, University of the Basque Country, San Sebastián, Spain.
© Luis Gagarin Lopez Nina 2017
Tryck: Universitetsservice US-AB

“To Mom, Hemilse, Mati and Family”
Abstract
The thermochemical process converts almost any kind of biomass
to a desired final product, i.e. gaseous or liquid transportation fuels
and chemicals. The transportation fuels obtained in this way are
renewable biofuels, which are alternatives to fossil fuels. During
the last few years, thermochemical plants for the production of
bioethanol have been launched and another is under construction.
A total of about 290 million liters of ethanol are expected to be
processed per year, mostly using municipal solid waste.
Considerable efforts have been made in order to find a more
selective catalyst for the conversion of biomass-derived syngas to
ethanol.
The thesis is the summary of five publications. The first two

publications (Papers I and II) review the state of the art of ethanol
and higher alcohols production from biomass, as well as the
current status of synthetic fuels production by other processes
such as the Fischer-Tropsch synthesis. Paper III analyses the
catalytic performance of a mesoporous Rh/MCM-41 (MCM-41 is a
hexagonal mesoporous silica) in the synthesis of ethanol which is
compared to a typical Rh/SiO2 catalyst. Exhaustive catalytic testing
including the addition of water vapor and modifying the hydrogen
partial pressure in the syngas feed-stream which, in addition to the
catalyst characterization (XRD, BET, XPS, chemisorption, TEM
and TPR) before and after the catalytic testing, have allowed
concluding that some water vapor can be concentrated in the pores
of the Rh/MCM-41 catalyst. The concentration of water-vapor
promotes the occurrence of the water gas shift reaction, which in
turn induces some secondary reactions that change the product
distribution, as compared to results obtained from the typical
Rh/SiO2 catalyst. These results have been verified in a wide range
of syngas conversion levels (1-68 %) and for different catalyst
activation procedures (catalyst reduction at 200 °C, 500 °C and no-
reduction) as shown in Paper IV. Finally, similar insights about the
i
use of mesoporous catalyst have been found over a Cu/MCM-41
catalyst, shown in Paper V. Also in Paper V, the effect of metal
promoters (Fe and K) has been studied; a noticeable increase of
ethanol reaction rate was found over Cu-Fe-K/MCM-41 catalyst as
compared to Cu/MCM-41.
Keywords: thermochemical process, ethanol, higher alcohols,

mesoporous catalysts, rhodium, copper, metal promoters.
ii
Sammanfattning
Den termokemiska förgasningsprocessen konverterar nästan alla
typer av biomassa till en önskad slutprodukt, det vill säga
gasformiga eller flytande drivmedel och kemikalier. De drivmedel
som erhållits på detta sätt är förnyelsebara biobränslen, som är
alternativ till fossila bränslen. Under de senaste åren har
termokemiska anläggningar för produktion av bioetanol lanserats
och andra är under uppbyggnad. Totalt kan cirka 290 miljoner
liter etanol per år förväntas bli producerade via den termokemiska
processen, mestadels från fast kommunalt avfall. Stora
ansträngningar har gjorts för att hitta en selektiv katalysator för
den önskade produkten, d.v.s. etanol.
Avhandlingen är en sammanfattning av fem publikationer. De två

första publikationerna (I och II) sammanfattar aktuella
forskningsläget kring etanol och högre alkoholer producerade från
biomassa, liksom nuvarande status för syntetiska bränslen
producerade via andra processer såsom Fischer-Tropsch-syntes.
Publikation III analyserar den katalytiska prestandan hos en
mesoporös Rh/MCM-41-katalysator (MCM-41: hexagonal
mesoporös kiseldioxid) vid syntes av etanol och jämfört den med
konventionell Rh/SiO2-katalysator. Från omfattande katalytiska
tester inklusive effekten av vattenångtillsats och vätepartialtrycket
i syntesgasen samt katalysatorkarakterisering (XRD, BET, XPS,
kemisorption, TEM och TPR) före och efter den katalytiska
reaktionen, kan slutsatsen dras att en del vattenånga kan
koncentreras i porerna hos en Rh/MCM-41-katalysator.
Koncentrationen av vattenånga främjar förekomsten av vatten-gas
skiftreaktionen, som i sin tur framkallar sekundära reaktioner som
ändrar produktfördelningen jämfört med resultaten från den
konventionella Rh/SiO2-katalysatorn. Dessa resultat har bekräftats
för ett brett spektrum av syntesgasomsättningar (1-68 %) och vid
olika förfaranden för katalysatoraktivering (reduktion vid 200 °C,
500 °C eller ingen aktivering), som visas i Publikation IV. Slutligen
iii
har liknande slutsatser om användningen av mesoporösa
katalysatorer erhållits över en Cu/MCM-41-katalysator, vilket visas
i publikation V. I Publikationen V, har effekten av
metallpromotorerna (K och Fe) studerats, där de mest intressanta
resultaten från Cu-Fe-K/MCM-41-katalysator var den märkbara
ökningen av reaktionshastigheten till etanol i jämförelse med
Cu/MCM-41-katalysator.
Nyckelord: termokemisk process, etanol, högre alkoholer,

mesoporösa katalysatorer, rodium, koppar, metalliska promotorer.
iv
List of appended papers
The work presented in this doctoral thesis is based on the following
publications. The papers are appended at the end of the thesis and
referred to in the text using Roman numerals (I – V).
I. R. Suárez, L. Lopez, J. Barrientos, F. Pardo, M. Boutonnet,

S. Järås
Catalytic conversion of biomass-derived synthesis gas to
fuels
Catalysis Book Series, Royal Society of Chemistry, 27 (2015)
62-143.
II. J.A. Velasco, L. Lopez, M. Velasquez, M. Boutonnet, S.

Cabrera, S. Järås
Gas to liquids: A technology for natural gas
industrialization in Bolivia
Journal of Natural Gas Science and Engineering, 2 (2010)
222-228.
III. L. Lopez, J. Velasco, V. Montes, A. Marinas, S. Cabrera, M.

Boutonnet, S. Järås
Synthesis of ethanol from syngas over mesoporous
Rh/MCM-41 catalyst; effect of water on the product
selectivity
Catalysts, 5 (2015) 1737-1755.
IV. L. Lopez, Jorge Velasco, Saul Cabrera, Magali Boutonnet,

Sven Järås
Effect of syngas conversion and catalyst reduction
temperature in the synthesis of ethanol: concentration of
water vapor in mesoporous Rh/MCM-41 catalyst
Catalysis Communications, 69 (2015) 183-187.
v
V. L. Lopez, V. Montes, H. Kušar, S. Cabrera, M. Boutonnet,
S. Järås
Syngas conversion to ethanol over a mesoporous
Cu/MCM-41 catalyst: effect of K and Fe promoters
Applied Catalysis A: General, 526 (2016) 77-83.
Contribution to appended papers
I. I have contributed to all sections by discussion with the all

the authors. The following sections were written in
cooperation with R. Suárez: Abstract, Introduction and
Conclusions. I wrote the section Ethanol and mixed alcohols.
II. J. Velasco is the main author of this paper and I had

contributed to the discussion and conclusion sections,
especially the situation in Bolivia.
III. I am the main author of this paper. J. Velasco helped in TPR

experiments and V. Montes performed the TEM and helped
with interpretation of data.
IV. I am the main author of this paper. J. Velasco helped with

the analysis of data.
V. I am the main author of this paper. V. Montes performed the

TEM and helped with interpretation of data.
vi
Other publications and conference presentations
Peer-reviewed publications
J.A. Velasco, L. Lopez, S. Cabrera, M. Boutonnet, S. Järås

Synthesis gas production for GTL applications:
thermodynamic equilibrium approach and potential for
carbon formation in a catalytic partial oxidation pre-reformer
Journal of Natural Gas Science and Engineering, 20 (2014) 175-
183.
J.A. Velasco, C. Fernandez, L. Lopez, S. Cabrera, M.

Boutonnet, S. Järås
Catalytic partial oxidation of methane over nickel and
ruthenium based catalysts under low O2/CH4 ratios and with
addition of steam
Fuel, 153 (2015) 192-201.
L. Lopez, L. Quispe, P. Crespo, M. Litter, S. Cabrera.

Structural and morphological comparison of TiO2 obtained
from novel “atrane route” and conventional route using the
sol-gel processes
(Comparación estructural y morfológica de TiO2 sintetizados
por la Ruta de los Atranos y la ruta convencional en el método
sol-gel)
Bolivian Journal of Chemistry, Vol. 28 no. 2 (2011) 106-112.
L. Quispe, L. Lopez, V. Teixeira, S. Cabrera

Novel titanium oxides doped (Yb, Nd, La and Li) for the
photocatalytic reduction of hexavalent chrome
(Nuevos Óxidos de Titanio Dopados (Yb, Nd, La y Li) para la
Reducción Fotocatalítica de Cromo Hexavalente)
vii
L. Quispe, M.C. Arteaga, E. Cárdenas, L. Lopez, C. Santelices,
E. Palenque, S. Cabrera.
Elimination of Cyanide by means of combined UV/ H2O2/TiO2
system
(Eliminación de Cianuro mediante sistema combinado
UV/H2O2/TiO2)
M. Alacama, L. Lopez, J. Velasco, F. Gracia, W. Yapu, S.

Cabrera
Ni-Cu/MCM-41 catalyst synthetized by the atrane route for the
etanol reforming
(Catalizadores Ni-Cu/MCM-41 sintetizados por la ruta de los
atranos para el reformado de etanol)
Book chapters
S. Cabrera, L. Lopez (editors)

Science and Technology in Bolivia: state of the art of industrial
processes for Hydrocarbons and Petrochemistry
(Ciencia y Tecnología en Bolivia: estado del arte de procesos
industriales para el sector de hidrocarburos y petroquímico)
Book, Natural Gas Institute, Higher University of San Andres,
La Paz-Bolivia, (2016) 300.
L. Lopez (author)
Ethanol and Higher Alcohols: state of the art
(Evaluación de la tecnología disponible para la producción de
etanol y alcoholes superiores)
Book chapter, Natural Gas Institute, Higher University of San
Andres, La Paz-Bolivia, (2016) 237-289.
viii
Conference contributions
L. Lopez, M. Boutonnet, S. Cabrera, S. Järås
Production of ethanol from synthesis gas
Oral presentation, Swedish Catalysis Society, Perstorp, Sweden,
2009.
L. Lopez, L. Quispe, P. Crespo, M. Boutonnet, S. Järås, M. Litter, S.

Cabrera
Effect of precursor in structural-morphological properties of TiO2
obtained by sol gel method; new titanatrane precursor
Poster presentation, European Catalysis Congress IX, Salamanca,
Spain, 2009.
L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

Rhodium catalysts promoted by Lithium on Si/Zr mesoporous
support for the conversion of syngas to oxygenates
Poster presentation, 16th International Zeolite Conference and 7th
International Mesoporous Materials Symposium, Maiori, Italy,
2010.

Syngas conversion into C1-C2 hydrocarbons and oxygenates over
a novel Rh-Li/Zr-MCM-41
Poster presentation, 14th Nordic Symposium on Catalysis,
Helsingør, Denmark, 2010.

Syngas conversion into ethanol and short hydrocarbons on
Rh/MCM-41: Catalyst Characterization After Reaction
Poster Presentation, 22nd North American Catalysis Meeting,
Detroit-USA, 2011.

Support stabilization for Rhodium catalyst in synthesis gas
conversion: Rh/Zr-MCM-41
ix
Poster Presentation, European Catalysis Congress IX, Glasgow,
Scotland, 2011.
L. Lopez, S. Cabrera
Conversion of Bolivian natural gas to national interest products
(Conversión de gas natural boliviano a productos de interés
Nacional)
Oral presentation, VII Bolivian Congress on Chemistry, La Paz,
Bolivia, 2012.

Syngas to ethanol over Rh/MCM-41 catalyst
Poster presentation, 2nd Summer School on Catalysis for
Sustainability, Rolduc Abbey, The Netherlands, 2013.
x
Table of Contents
CHAPTER 1: Introduction…………………………………………………………………………. 1
1.1 Setting the scene……………………………………………………………………………………………. 1
1.2 Scope of the work.…………………………………………………………………………………………. 2
CHAPTER 2: Thermochemical processing of biomass: fuels for the
transportation sector………………………………………………………………………………. 3
2.1 Biomass pre-treatment and gasification…………………………………………………………. 5
2.2 Syngas cleaning and conditioning…………………………………………………………………… 8
2.3 Catalytic synthesis of fuels……………………………………………………………………………… 9
2.3.1 Synthetic Natural Gas……………………………………………………………………………….. 11
2.3.2 Gasoline and Diesel…………………………………………………………………………………… 11
2.3.3 Di-Methyl Ether………………………………………………………………………………………… 12
2.3.4 Ethanol and Higher Alcohols…………………………………………………………………….. 13
CHAPTER 3: Ethanol and Higher Alcohols Synthesis…………………………………. 15
3.1 Alcohols as motor fuels………………………………………………………………………………….. 15
3.2 Industrial process development……………………………………………………………………… 16
3.2.1 Process configurations for direct synthesis of alcohols……………………………… 16
3.2.2 Process configurations for multi-step synthesis of ethanol……………………….. 18
3.2.3 Current projects for the thermochemical production of ethanol………………. 19
3.2.4 Preliminary considerations for ethanol production from biomass: the case
of Bolivia……………………………………………………………………………………………………………. 21
CHAPTER 4: Catalytic conversion of synthesis gas to ethanol and higher
alcohols…………………………………………………………………………………………………… 23
4.1 Thermodynamic considerations……………………………………………………………………… 23
4.2 Types of catalysts…………………………………………………………………………………………… 24
4.2.1 Rh-based catalysts……………………………………………………………………………………. 25
4.2.2 Cu-based catalysts……………………………………………………………………………………. 25
4.2.3 Role of the catalyst’s support……………………………………………………………………. 25
4.2.3.1 Ordered Mesoporous Silica (MCM-41): the “atrane route”………………….. 26
4.3 Reaction mechanisms…………………………………………………………………………………….. 30
CHAPTER 5: Experimental methods…………………………………………………………. 33
5.1 Catalyst preparation………………………………………………………………………………………. 33
5.1.1 Mesoporous Silica MCM-41……………………………………………………………………... 33
5.1.2 Metal impregnation…………………………………………………………………………………. 34
5.2 Catalyst characterization……………………………………………………………………………….. 34
5.2.1 N2-Physisorption………………………………………………………………………………………. 34
5.2.2 X-Ray Diffraction (XRD)…………………………………………………………………………….. 35
5.2.3 H2-Chemisorption…………………………………………………………………………………….. 35
5.2.4 Transmission Electron Microscopy (TEM)…………………………………………………. 35
xi
5.2.5 Temperature Programmed Reduction (TPR)……………………………………………… 35
5.2.6 X-Ray Photoelectron Spectroscopy (XPS)………………………………………………….. 35
5.2.7 Thermogravimetric analysis (TGA)……………………………………………………………. 36
5.3 Catalytic testing……………………………………………………………………………………………… 36
5.3.1 Reactor set-up and procedures………………………………………………………………… 36
5.3.2 Product analysis and data treatment………………………………………………………… 38
CHAPTER 6: Catalytic performance of a typical Rh/SiO2 catalyst and a
mesoporous Rh/MCM-41 catalyst…………………………………………………………… 41
6.1 Product distribution and selectivity to C2-oxygenated compounds..………………. 41
6.1.1 Effect of syngas conversion………………………………………………………………………. 43
6.1.2 Effect of the catalyst reduction temperature……………………………………………. 44
6.1.3 Effect of hydrogen partial pressure………………………………………………………….. 44
6.1.4 Effect of water addition……………………………………………………………………………. 45
6.2 Catalyst characterization before and after catalytic testing……………………………. 47
6.2.1 Specific surface area and pore size distribution………………………………………… 47
0 3+
6.2.2 Surface composition: Rh and Rh ……………………………………………………………. 49
6.2.3 Porous ordering by XRD and TEM……………………………………………………………… 49
6.2.4 Metal support interactions……………………………………………………………………….. 51
6.3 Interpretation of the catalytic performance of Rh/MCM-41 compared to
Rh/SiO2…………………………………………………………………………………………………………………. 52
6.3.1 Water vapor concentration in mesoporous Rh/MCM-41 catalyst……………… 52
6.3.2 Higher ethanol selectivity as consequence of the water vapor
concentration in mesoporous Rh/MCM-41 catalyst…………………………………………… 54
CHAPTER 7: Effect of Fe and K promoters on Cu/MCM-41 catalyst..………… 57
7.1 Catalysts characterization: XRD,TGA, N2 physisorption, TEM, XPS and TPR..…… 57
7.2 Catalytic testing: product selectivity trends……………………………………………………. 60
7.2.1 Effect of K as promoter…………………………………………………………………………….. 62
7.2.2 Effect of Fe as promoter…………………………………………………………………………… 62
7.2.3 Effect of K and Fe addition……………………………………………………………………….. 62
7.3 Selectivities to alcohols and other oxygenated compounds……………………………. 63
7.4 Anderson–Schulz–Flory (ASF) distribution……………………………………………………… 64
CHAPTER 8: Conclusions………………………………………………………………………….. 67
8.1 Main results of this work………………………………………………………………………………… 67
8.2 Final remarks and future work……………………………………………………………………….. 69
Nomenclature…………………………………………………………………………………………. 71
Acknowledgements…………………………………………………………………………………. 73
References……………………………………………………………………………………………… 76
Appendices: Papers I-V
xii
CHAPTER 1
Introduction
1.1 Setting the scene

Concerns about climate change, energy resources and energy
efficiency are discussed both locally and internationally context.
Although attempts to reduce the use of highly polluting energy
resources such as fossil oil and coal have been made during the last
decades, they still are represent the major contributors to the
world energy supply: 70.7 % in 1973 and 59.9 % in 2014 [1]. Less
contaminating resources such as natural gas and renewable energy
like biofuels and wastes, are the other major contributors to the
energy world supply: 26.5 % in 1973 and 31.5 % in 2014. Increase
in the use of renewable biofuels and waste from 10.3 % in 2014 to
about 15 % by 2040 is estimated [1]. On the other hand, the world
population is estimated to growth from 7.34 billion in 2015 to 9.15
billion by 2040 [2], which means an increase in the energy
demand. Moreover, by 2040 CO2 emissions are forecast to increase
by 13 %, in comparison with year 2014 [1].
Biofuels are produced from renewable organic material (obtained

directly from plants, or indirectly from agricultural, commercial,
domestic, and/or industrial wastes). An interesting route for
biofuel production is thermochemical processing in which almost
any kind of organic material or biomass is converted to a desired
fuel. In this process, biomass is converted to an intermediary
mixture of gases known as “synthesis gas” or “syngas”, consisting
mainly of CO, CO2 and H2. The syngas is then catalytically
converted to produce i) conventional fuels such as diesel and
gasoline via the Fischer-Tropsch Synthesis, but also ii) alternative
fuels such as di-methyl-ether (DME), ethanol and higher alcohols
using similar catalytic processes.
1
1.2 Scope of the work
The objective of the thesis was to study the influence of operating
conditions as well as catalyst properties and composition on the
catalytic performance during the catalytic conversion of syngas to
ethanol and higher alcohols. The latter, within the context of
generation of renewable fuels for the transportation sector,
especially the thermochemical process using biomass-derived
syngas. In particular the work was focused on; (I) The effect of
reaction conditions (temperature, pressure, space velocity and
syngas H2/CO ratio) and the catalyst activation procedure
(different reduction temperatures) on the conversion of syngas to
ethanol; (II) The catalytic performance and characterization of
novel mesoporous catalysts using a hexagonal mesoporous silica
(i.e. MCM-41) as catalyst support and Rh as the active metal for the
synthesis of ethanol; (III) The effect of Fe and K promoters on the
catalytic behavior of mesoporous Cu/MCM-41 catalyst for the
synthesis of ethanol and higher alcohols.
The work included in this thesis was mostly conducted at the

Department of Chemical Engineering and Technology at KTH
Royal Institute of Technology, Stockholm, Sweden. Experimental
work was also performed at the Natural Gas Institute at the Higher
University of San Andres, La Paz, Bolivia.
2
CHAPTER 2
Thermochemical processing of biomass: fuels for

the transportation sector
Biomass is biological material derived from living, or recently
living organisms. This material is used to produce energy; in fact,
this represents around 10 % of the world‟s primary energy supply
[3]. The four main types of biomass for energy purposes are: i)
forest products (e.g. fuelwood, residues and processing, and
municipal solid waste), ii) energy crops, iii) agricultural residues
(harvesting residue and processing residue) and iv) animal manure
[4]. It is estimated that world energy supply from biomass could
increase from 56 EJ in 2010 to 97-147 EJ by 2030 [4]. From this,
about 38-45 % would originate from agricultural residues and
waste. The remaining supply is shared between energy crops (26-
34 %) and forest products (28-30 %).
The composition of biomass depends on its origin. Proximate

analysis of various sources of biomass, Table 2.1. [5], indicates that
biomass is mostly composed of volatile matter (material that is
released from biomass when it is heated up to approx. 400-500
°C), followed by moisture and fixed carbon. Ash content varies
considerably, being low in woody biomass (mean of 2.7 wt.%) and
high in animal manure (mean of 28.8 wt.%). On a dry and ash-free
basis, biomass is composed by >40 wt.% carbon, 20 wt.% oxygen,
4 wt.% hydrogen and minor amounts of other elements. For
manufacturing purposes, the major elements of biomass (carbon,
oxygen and hydrogen) are chemically converted into a desired fuel,
such as ethanol. However, some minor elements, such as sulfur
and chlorine, should be eliminated since they represent potential
sources of poisoning during chemical conversion.
3
4
Table 2.1. Chemical composition of various types of biomass and some solid fossil fuels. Adapted from Vassilev et al. [5],
Copyright (2010), with permission from Elsevier.
Ultimate analysis (wt.%)
Proximate analysis (wt.%)
(dry and ash-free basis)
SOURCE Range
Volatile Fixed
Moisture Ash C O H N S Cl
matter carbon
Minimum 30.4 6.5 4.7 0.1 48.7 32.0 5.4 0.1 0.01 0.01
WOOD AND WOODY
Mean 62.9 15.1 19.3 2.7 52.1 41.2 6.2 0.4 0.08 0.02
BIOMASS
Maximum 79.7 24.1 62.9 8.4 57.0 45.3 10.2 0.7 0.42 0.05
HERBACEOUS AND Minimum 41.5 9.1 4.4 0.8 42.2 34.2 3.2 0.1 0.01 0.01
AGRICULTURAL Mean 66.0 16.9 12.0 5.1 49.9 42.6 6.2 1.2 0.15 0.20
BIOMASS Maximum 76.6 35.3 47.9 18.6 58.4 58.4 9.2 3.4 0.6 0.83
Minimum 43.3 12.4 2.5 23.4 57.3 20.8 6.8 6.2 1.20 0.50
ANIMAL BIOMASS* Mean 52.5 12.8 5.9 28.8 58.9 23.1 7.4 9.2 1.45 0.69
Maximum 61.7 13.1 9.3 34.3 60.5 25.3 8.0 12.2 1.69 0.87
Minimum 40.9 0.5 2.5 3.2 45.4 16.4 6.0 0.2 0.01 0.04
CONTAMINATED
Mean 63.7 8.0 11.6 16.7 53.6 37.0 7.3 1.7 0.46 0.31
BIOMASS**
Maximum 79.0 14.5 38.1 43.3 70.9 46.1 11.2 6.1 2.33 0.83
OTHER TYPES OF BIOMASS
Wheat straw 67.2 16.3 10.1 6.4 49.4 43.6 6.1 0.7 0.17 0.61
Straw 64.3 13.8 12.4 9.5 48.8 44.5 5.6 1.0 0.13 0.54
Rice husks 56.1 17.2 10.6 16.1 49.3 43.7 6.1 0.8 0.08 0.12
Soya husks 69.6 19.0 6.3 5.1 45.4 46.9 6.7 0.9 0.10 -
Sugar cane bagasse 76.6 11.1 10.4 1.9 49.8 43.9 6.0 0.2 0.06 0.03
Marine macroalgae 45.1 23.1 10.7 21.1 43.2 45.8 6.2 2.2 2.60 3.34
SOLID FOSSIL FUELS
Peat 57.8 24.3 14.6 3.3 56.3 36.2 5.8 1.5 0.2 0.04
Lignite 32.8 25.7 10.5 31.0 64.0 23.7 5.5 1.0 5.8 0.01
Coal 30.8 43.9 5.5 19.8 78.2 13.6 5.2 1.3 1.7 0.03
* Based on chicken litter and meat-bone meal. ** Furniture waste, waste paper, sewage sludge and others.
One route for biomass manufacturing is the thermochemical
process [6]. This process can be divided in three sections; i)
pretreatment and gasification, ii) cleaning and conditioning and,
iii) catalytic synthesis and purification, as schematically shown in
Figure 2.1. Thus, a variety of synthetic fuels can be obtained from
biomass, either traditional fuels such as Gasoline, Diesel and
Natural Gas or alternative fuels such as Di-Methyl Ether (DME),
Ethanol and Higher Alcohols.
Renewable Feedstock
(Municipal solid wastes, forest and agricultural biomass, other).
i) Pretreatment and ii) Cleaning and

Gasification Conditioning
iii) Catalytic Synthesis and

Purification
- Synthetic Natural Gas

- Gasoline and Diesel (via Fischer-Tropsch
Technology or Methanol to Hydrocarbons)
- Di-Methyl Ether
- Ethanol and Higher Alcohols
Figure 2.1: Fuels obtained from the thermochemical processing of biomass.

Author’s own elaboration.
2.1 Biomass pre-treatment and gasification
Raw biomass must be pretreated and converted into a suitable

form for subsequent gasification. This includes:
− Size reduction, smaller particles have larger surface area

per unit of mass which facilitates higher rates of heat
5
transfer and gasification. This could be further enhanced
with porous particles. The smaller particles also favor the
yield to CO and H2, while the yield to CO2 is diminished.
− Drying, biomass with low moisture (<10 %) is desired for
the gasification process. Drying is an energy-consuming
process and for that reason several dryer configurations
have been used to dry biomass (e.g. bin dryer, band
conveyor dryer, rotary cascade dryer) [7].
After the pretreatment step, the biomass is thermally processed via

gasification. The gasification takes place at high temperature (600-
1 000 °C) in the presence of an oxidizing agent (air, steam, oxygen
or a combination of them). During this process, the large
polymeric molecules are decomposed into lighter ones (e.g. CO,
H2, CH4 and short hydrocarbons); ash, char, tar and minor
contaminants are also obtained. Char and tar are the result of
incomplete conversion of biomass. The overall reaction involved in
the biomass gasification can be represented by the following
equation (2.1)
( ) (2.1.)
The product composition, obtained from the gasification, depends

on various parameters, such as:
- Type of gasifier. Various kinds of gasifiers have been

developed. The most used are fixed-bed and fluidized bed
[8]. Fixed-bed gasifiers can be either updraft
(countercurrent) or downdraft (cocurrent). In the updraft
gasifier, the biomass is introduced from the top and moves
downwards while the gasifying agent is introduced at the
bottom. The product gas moves upwards and the
temperature decreases to 500 °C in the gasifier exit and, as
a consequence, the resulting products contain large
amounts of tar. In the downdraft gasifier, biomass and
6
product gas move downdraft and thus the exit temperature
is high (800 °C), so most of the tar is consumed. On the
other hand, fluidized gasifiers have better heat and mass
transfer which increases the reaction rates and conversion
efficiencies. Typically, silica or alumina is used as fluidizing
medium. Solid catalysts can also be used to increase
conversion efficiency and reduce tar formation. For that,
the catalyst must be stable at high temperatures and
resistant to poisoning.
- Biomass flow rate, type and properties. Overfeeding of
biomass can lead to plugging and reduce conversion
efficiency, while starve-feeding results in lower yield.
Moreover, the biomass type (Table 2.1) affects the product
composition.
- Air and steam flow rate. Air flow rate directly affects the
degree of combustion and the gasification temperature,
which in turn affect the biomass conversion and the
product composition. Supplying steam increases the partial
pressure of H2O and, thus water gas shift (WGS) and
methane steam reforming (MSR) reactions are favored. As
a consequence, the resulting syngas contains more
hydrogen.
- Gasification temperature profile. The gasification
temperature is one of the most important factors for
controlling the product composition and properties. At
temperatures of 750-800 °C, the WGS and MSR reactions
dominate favoring the H2 production. At 850-900 °C, the
MSR and Boudouard reactions dominate, resulting in
higher CO content and, as consequence, a decrease in tar
formation and an increase of gas yield are observed [5].
7
2.2 Syngas cleaning and conditioning
The gasification product needs further processing in order to

achieve an adequate synthesis gas composition. Thus,
contaminants such as particulates, tars, alkalis, nitrogen and,
sulfur should to be eliminated. The type of contaminant and the
degree of purification depend on the subsequent application; for
the production of fuels a low level of contaminants is typically
needed while for power generation relatively high amounts of
contaminants can be tolerated.
- Particulate removal. Particulates consist of unconverted
biomass products such as ash and char. Depending on their
particle sizes, they can be removed by using i) cyclones in
the case of large particles (i.e. >5 m), ii) porous solid
filters for a wide range of particle sizes (0.5-100 m) or iii)
electrostatic separation.
- Alkali removal. Alkali compounds (CaO, K2O, P2O5, MgO,
N2O) are vaporized at high temperatures during
gasification, but they condense and form particles in the
posterior equipment. Specific alkali removal devices are
under research and development; for example, a bauxite
filter which can remove most of the Na and K compounds,
at temperatures of around 650-725 °C [9].
- Nitrogen compounds. Most of the nitrogen content of the
biomass is converted to ammonia during gasification,
which can be further removed by wet scrubbing (at low
temperatures) or destroyed at higher temperatures using
either dolomites, or Ni-based or Fe-based catalysts.
- Sulfur compounds. Most of the sulfur content of the
biomass is converted to H2S and SO2 during gasification,
which can be then removed by adsorption on limestone,
dolomite or CaO (at low temperatures) or calcined at high
temperatures.
8
- Tar removal. Tar consists of compounds that are not
decomposed and remain in the product gas. They are mixed
oxygenates, phenolic ethers, alkyl phenolics, heterocyclic
ethers, short and large poly-aromatic hydrocarbons. Two
approaches are applied for tar removing [10]; i) optimizing
the gasification operation conditions together the use of
catalysts (so called in-bed catalysts) and ii) a secondary
reactor for tar destruction and achievement an acceptable
level in the product gas.
2.3 Catalytic synthesis of fuels
Traditional fuels such as gasoline and diesel as well as alternative

fuels such as ethanol, higher alcohols and DME, are produced from
the catalytic conversion of syngas. Syngas can be obtained from
renewable sources like biomass or from non-renewable sources
like natural gas or coal. Various projects have been identified for
biomass conversion to final fuels, as is summarized in Table 2.2.
The preferred route to produce diesel is the Fisher-Tropsch (FT)
Synthesis. An important aspect is the syngas composition obtained
from biomass gasification and from natural gas processing,
respectively. The syngas composition derived from biomass or
natural gas yields a H2/CO equal to 0.5-1.0 [11] and 1.6-4.0 [12],
respectively. Thus, additional treatment of the biomass-derived
syngas is required for a process that needs higher H2/CO1, e.g.
Fischer-Tropsch Synthesis, Synthetic Natural Gas and ethanol and
higher alcohols (as will be shown in the following sections).
9
10
Table 2.2. Status on facilities for the conversion of biomass (via gasification) to transportation fuels [13].
Company/ Technology
Location Startup Status Raw material Fuel
Institution level
Alexandria LA Demonstration Under Gasoline-type products
Cool Planet 2016 Forest residues
(USA) - Commercial construction (30 000 t/y)
Swindom Demonstration Under Organic residues and Synthetic Natural gas
Go Green Fuels Ltd. 2018
(UK) - Commercial construction waste streams (1 500 t/y)
Gothenborg Demonstration Synthetic Natural gas
Goteborg Energi AB 2014 Operational Lignocellulosic crops
(Sweden) plant (11 200 t/y)
- DME (608 t/y)
Karlsruhe Institute of Karlsruhe Demonstration
2014 Operational Lignocellulosic crops - Gasoline-type fuels
Technology (Germany) plant
(360 t/y)
Consortium Groen Alkmaar, Demonstration Synthetic Natural gas
2018 Planned Lignocellulosic crops
Gas 2.0 (Netherlands) plant (6 500 t/y)
Gebze Fischer-Tropsch liquids
TUBITAK Pilot plant 2013 Operational Forest residues
(Turkey) (250 t/y)
GTI Gas Technology Des Plaines IL - Fischer-Tropsch liquids
Pilot plant 2012 Operational Lignocellulosic crops
Institute (USA) - Gasoline-type fuels
- Fischer-Tropsch liquids
Dunkirk
BioTfuel-consortium Pilot Plant 2012 Operational Lignocellulosic crops (60 t/y)
(France)
- Jet fuel
Oberhausen Diesel-type hydrocarbons
Greasoline GmbH Pilot plant 2011 Operational Oil crops, oils and fats
(Germany) (2 t/y)
2.3.1 Synthetic Natural Gas
The simplest reaction that converts syngas into a fuel is the

methanation reaction, equation (2.2.), which uses a Ni-based
catalyst. This reaction is carried out at high temperatures of 200-
700 °C, resulting in high reaction rates. Also, the heat of reaction
can be used to produce high quality steam and thus a quite energy
efficient process can be achieved.
(2.2.)
The effects on the methanation reaction of the low H2/C ratio and
the inherent impurities of the biomass-derived syngas are
currently under investigation. Especially, novel configurations for
biomass gasifiers such as i) absorption-enhanced gasification/
reforming, ii) internally circulating fluidized beds and others types
of reactors are being investigated, in order to generate a hydrogen-
rich syngas [11]. A commercial project (the GoBiGas project) in
Göteborg (Sweden) is being developed which aims at the
production of both methane equivalent to 20 MW and gas
equivalent to 80-100 MW. Also, it is expected that the gas
production will reach 1 TWh by 2020, which represents about 30
% of the gas consumption in Gothenburg city or the fuel needed for
100 000 cars [14].
2.3.2 Gasoline and Diesel
The Fischer-Tropsch Synthesis (FTS) refers to the conversion of

syngas to a wide range of liquid and gaseous products following a
polymerization reaction, equation 2.3. Gasoline and diesel can be
obtained after upgrading and purification steps. If gasoline is the
desired product, the FTS synthesis is conducted using Fe-based
catalysts at high temperature (HTFT), i.e. 300-350 °C. If diesel (or
middle-distillate products) is desired, the FTS synthesis is
11
performed using Co-based catalysts at low temperature (LTFT), i.e.
200-240 °C.
(2.3.)
Considerable efforts have been made by several institutions in

order to scale-up the processes for gasoline and diesel generation,
as can be noted from Table 2.2, and a commercial plant is expected
to be launched soon. On the other hand, FT Synthesis is already
commercialized using natural gas (so-called Gas to Liquids, GTL)
and coal (Coal to Liquids, CTL), as raw materials [12]. The
production volume of these commercial plants, both situated in
South Africa, varies between 2 500 bpd (e.g. Sasolburg plant) to
165 000 bpd (e.g. Secunda plant). This technology becomes
important for diesel production, especially in regions where no
heavy oil is available.
2.3.3 Di-Methyl Ether
DME is an alternative fuel for compression-ignition engines

because of its high cetane number (55-60), low emissions
(particulates, SOx and NOx) and low engine noise. DME can also be
blended with diesel thus increasing the viscosity, density and
heating value. The synthesis involves three reactions; i) methanol
synthesis, ii) methanol dehydration and iii) water gas shift
reaction, which can be summarized by equation (2.4.). DME can be
obtained by direct conversion of syngas using a bifunctional
catalyst (methanol synthesis and methanol dehydration). It can
also be in two consecutive steps; methanol synthesis using
traditional Cu-Zn/Al3O2 catalyst and methanol dehydration using
an acid catalyst (-alumina or HZSM-5).
(2.4.)
12
In 2014, a demonstration plant was installed in Germany by
academia and industry jointly. The plant uses lignocellulosic crops
as main raw material, which is processed via fast pyrolysis and
gasification to produce syngas. The final products are DME (608
tons/year) and gasoline-type fuels (360 tons/year). With the
results from the demonstration plant, the next step for
commercializing can be planned. However, so far no news has
been release about the DME production at commercial scale.
2.3.4 Ethanol and Higher Alcohols
Currently, ethanol grade fuel is being obtained from biochemical

processes (so-called first-generation bioethanol) using sugar,
starch and oil seed-based feedstocks, which are also food
resources. However, this bioethanol involves some controversial
issues: global food supply; limited GHG (greenhouse gases)
emissions reduction; and environmental impacts, such as
competition for water supplies or impact of land use change [15].
Thus, the sustainability of first-generation bioethanol is being
questioned, second-generation bioethanol is emerging, since it is
based on non-food resources (e.g. energy crops, forest and
agricultural residues, municipal waste, etc.) [16, 17]. Second-
generation biofuels can be produced by means of either a
biochemical or a thermochemical route. The main drawback of the
biochemical alternative is the low conversion achieved, since lignin
contained in the biomass cannot be processed and it represents 25-
30 wt.% of the biomass. Hydrolysis of cellulose and hemicellulose
is also difficult and there are some recalcitrant materials that must
necessarily be thermochemically handled [18].
The production of ethanol, and also higher alcohols, via the

thermochemical route will be covered in the following chapters,
since it is the main concern of this thesis.
13
CHAPTER 3
Ethanol and Higher Alcohols Synthesis
3.1 Alcohols as motor fuels
Table 3.1 summarizes the basic properties of alcohols as compared

to other types of fuels. Alcohols make excellent motor fuels with
high octane values and allow high compression ratios and thus
increase efficiency with improved power output per cylinder.
Alcohols can run at lean air-fuel ratios with better energy efficiency
than gasoline. However, alcohols have very low cetane numbers
and cannot be used in compression-ignition diesel-type engines,
unless gas temperatures are high at the time of injection. Some
companies of heavy-duty engines have developed several types of
systems to assist autoignition of directly injected alcohols [19]. The
blending of additives to the alcohol fuels has turned out to be
effective in improving the cetane number. Another way is to add
small amount of diesel in order to improve the ignition of the
alcohols.
Table 3.1. Basic properties of fuels (From Paper I). Adapted from [11] with
permission from The Royal Society of Chemistry.
Mixed
FT FT
SNG Methanol Ethanol alcohols DME
Gasoline Diesel
(Octamix)
Formula CH4 CH3OH C2H5OH C1-8OH CH3OCH3 C6-C12 C12-C20
MW (g/mol) 16.80 32.04 46.07 41.68 46.07 100-105 200

b
Density (kg/L) 0.41- 0.792 0.789 0.807 0.661 0.745 0.77-
0.5a 0.78
b
Energy content 24.9a 15.4-15-6 21.3 18 18.2-19.3 32.4 33.1-
(MJ/L) 34.3
Blending RON >127 133 130 118-123 n/a 95 n/a
Cetane number n/a 5 5 n/a 55-60 n/a 70-80
a
Values corresponding to liquefied natural gas (LNG).
b
Values corresponding to conventional gasoline.
15
The most commercialized alcohol used as fuel is ethanol. Vehicles
known as flexible fuel vehicles (FFV) can run either with pure
ethanol, pure gasoline or a mixture of both. For example, pure
ethanol vehicles are largely commercialized in Brazil. A mixture of
gasoline and ethanol (abbreviated as EX, where X indicate the
percentage of ethanol e.g. E85 has 85 % of ethanol) is
commercialized in the USA and Europe. Today, most vehicles are
able to run with at least 10 % ethanol (E10) blended into the
gasoline.
3.2 Industrial process development

3.2.1 Process configurations for direct synthesis of
alcohols
Various process configurations have been patented for the direct

synthesis of alcohols [11]. These processes involve a single or a few
main reactor units in series for the conversion of syngas to
alcohols. The produced alcohols are, mostly, in the range of C2-
4OH. It should be mentioned that a mixture of alcohols is allowed
to be blended with gasoline in many regions around the world. For
example, in Europe the limit of alcohol content varies between 3 %
and 15 % (volume), and the range of alcohols from methanol to
octanol (alcohols with boiling point lower than 210°C). Due to the
toxicity of methanol, it should preferably be the lowest amount in
the alcohol mixture ( 3 %).
16
Admixing H2 rich gas
Alcohol-synthesis gas
Alcohol
Synthesis Reactor Stripper syngas SYNGAS
Crude
alcohol
SNG
Hydrogenation
Reactor
Methanator
Gas-Liquid
Separator
Hydrogenated
crude alcohol
Lower Alcohols
Destillation
Section
Higher Alcohols
Figure 3.1. Basic flow diagram for the synthesis of alcohols (C2–4OH) [20].
The flow diagram of a process from Haldor Topsøe for alcohol

synthesis is shown in Figure 3.1 [20]. This process uses a main
reactor unit to convert syngas to alcohols and a secondary
hydrogenation unit to convert other types of oxygenated by-
products (e.g. ketones, esters, and/or aldehydes) to the
corresponding alcohol. The resulting products are sent to a gas–
liquid separator, from which the gas fraction (composed mostly of
methane and unreacted syngas) is sent to a methanation reactor
unit to produce synthetic natural gas and the liquid fraction is sent
to a stripper unit. In the latter unit, short alcohols (mostly
methanol) are stripped from the liquid fraction using a stream of
17
fresh syngas and recycled to the main reactor unit. The latter is
done in order to promote the carbon chain growth to higher
alcohols, via alcohol homologation or alcohols coupling. The main
reactor unit operates at 20 bar and 270-400 °C and uses a Cu-
ZnO/Al2O3 based catalyst. The hydrogenation reactor unit operates
at similar pressure but in a temperature range of 100-220 °C using
a typical noble metal-based catalyst (e.g. Pt and/or Pd) or a Cu–
ZnO/Al2O3-based catalyst.
3.2.2 Process configurations for multi-step synthesis of

ethanol
The latest patented process configurations for the synthesis of

ethanol use various reactor units, this in order to maximize the
overall ethanol yield [11]. Various projects regarding multi-step
ethanol synthesis have been developed around the world by private
and state institutions. One of the companies that has patented
various process configurations is Enerkem, which in 2014
launched the first commercial plant for ethanol production from
municipal solid waste (MSW). Although the actual process
configuration for this plant is not known, it is possibly based on a
multistep configuration like that shown in Figure 3.2. In a
gasification island the MSW is converted to syngas, which after
conditioning and cleaning enters to the methanol island. Methanol
synthesis is a mature technology in the petrochemical sector, and
pure methanol can be obtained. The produced methanol is mixed
with carbon monoxide in a carbonylation and esterification reactor
unit, where methyl acetate is produced. Then, methyl acetate is
hydrogenated to methanol and ethanol, from which ethanol is
purified.
18
Figure 3.2. Block diagram for the multistep synthesis of ethanol by Enerkem [21].
3.2.3 Current projects for the thermochemical production

of ethanol
The thermochemical route for ethanol production is under

development at several companies. The current status of some of
these projects is shown in Table 3.2. With the operation of the
Edmonton plant in 2014 and the other projects to be in operation
soon, a relatively mature technology for the thermochemical
production of ethanol has been developed.
19
20
Table 3.2. Current projects for thermochemical production of ethanol.

COMPANY LABORATORY PILOT PLANT DEMOSTRATION PLANT COMMERCIAL PLANT
2002 – 2008 2009 – 2013 2014 –

Enerkem Alberta Sherbrooke University Sherbrooke plant Westbury facilities (Canada). Biorefinería de Edmonton (Canada),
Biofuels LP [22] (Canada). (Canada). 2014.
Evaluation of:
Evaluation of: Evaluation of: - Verify the results from the pilot Evaluation of:
- Pure compound feeding. - Simulation of processes. plant. - Final equipment design and operation
- Selectivity/ conversion. - PFD diagram. - Process integration and recycling. conditions.
- Recycling. - PID diagram. - Preliminary cost estimation. - Cost estimation.
- Process integration and - Catalyst stability. - Production of 151 million liters of
recycling. - Continuos operation 24h/day. ethanol / year.
Vanerco( Enerkem - Gasification and synthesis of fuels. Varennes (Canada), 2016.
& Greenfield
Ethanol) [13] - Under construction.
- Ethanol production (30 000 tons
/year).
Tembec Chemical - Demonstration plant: Gasification and synthesis of fuels - Ethanol (13 000 tons/ year)
Group [13]
Coskata [23] - Hybrid process: - Pilot plant in Demonstration plant in Madison,
gasification and Warrenville, Illinois (USA). Pennsylvania (USA).
biochemical.
- Ethanol production (120 tons/
year)
- Under operation for 21 months.
Ineos [24] * Hybrid process: * Pilot plant in operation
gasification and for 9 years.
biochemical.
3.2.4 Preliminary considerations for ethanol production
from biomass: the case of Bolivia
In this section Bolivia is presented as a particular example of

ethanol production from biomass. Bolivia has large forest
resources, which constitute an important source of biomass. A
preliminary estimation of biomass in the form of woody material,
animal manure and bagasse has been reported to be about 408
million tons [25]. On the other hand, about 1.9 million of tons of
waste are generated every year in all Bolivia‟s municipalities [26].
In spite of this, few projects have been implemented in order to
process the biomass. One of the few projects, was located in the
city of Montero which produced 600 000 liters/year of ethanol and
was commercialized in the European market (Germany, Spain and
Italy) [27]. Presumably, the production is based on first-generation
technology using residues of sugar cane as raw material.
A preliminary economic evaluation of the thermochemical

production of ethanol from biomass in Bolivia, has been made
[28]. A relevant variable in the production economy is the cost of
biomass, which in Bolivia is lower than for other regions; about 40
$US/ton in Bolivia compared to 60 $US/ton in Europe [18]. This
constitutes an attractive aspect of ethanol production in Bolivia. A
sensitivity analysis was also made, one of the most important
production variables was found to be the plant capacity; a
production greater than 200x103 ton of ethanol/year is desired to
reach a favorable economy of scale. A lower effect is estimated
from changes in the capital investment. The latter results are in
agreement with other studies made in other locations [18, 29, 30].
In Bolivia there is no specific regulation regarding the use of

alcohols as motor fuel, but a regulation for oxygenates compounds
indicates a maximum of 2.7 wt.% in a mixture with gasoline [31].
Also, the local market for transportation fuel is reduced; for
21
example, assuming 10 vt.% of ethanol blended with gasoline to be
sold in Bolivia this would require a production of about 102x10 3
ton/ year which does not take advantage of the economy of scale
[28]. Then, a larger percentage (>10 vt.%) of ethanol blended with
gasoline may be appropriate to justify ethanol production. On the
other hand, ethanol could be produced for the external market. In
the Latin American region most countries have a neutral balance
between production and consumption, with the exception of
Mexico which imports around 100 ktons/year of ethanol. Larger
markets such as the USA, Canada and Europe could be
investigated as potential markets.
22
CHAPTER 4
Catalytic conversion of synthesis gas to ethanol and

higher alcohols
4.1. Thermodynamic considerations
A thermodynamic evaluation of the basic reactions involved in the

synthesis of ethanol and higher alcohols from syngas is important
in order to know the limits of the reactions. If only alcohols, in the
range of C1OH to C8OH, are considered to be formed from syngas
(Figure 4.1. a) two comments arise: high syngas conversion is
expected at low temperature (<350 °C) and C5-8OH are the most
stable alcohols. When CO2 is allowed to be formed, via the water
gas shift reaction [32], together with the alcohols: a similar
composition profile is expected as shown in Figure 4.1. b, where
CO2 is an important product at intermediate temperatures (250-
550 °C). When CH4 is expected to be formed, via the methanation
reaction [32], the product profile change drastically (Figure 4.1. c);
almost no alcohols are formed and CH4 is favored up to around
520 °C. Finally, when both CO2 and CH4 are allowed to be formed,
shown in Figure 4.1. d; in this case, almost no alcohols are
expected to be formed in the whole range of temperatures.
Regarding the catalyst design for the synthesis of ethanol, some

ideas can be extracted from the analyzed profiles (Figure 4.1.): i)
the catalyst should have low reactivity to both methanation and
WGS reactions and ii) the catalyst should not promote the
formation of larger compounds (i.e. low activity for
polymerization).
23
24
28
20 a) b)
24 CO
C5-8OH
Mass rate (g/h)

Mass rate (g/h)
16 CO 20
H2O 16 C5-8OH
12 CO2
12
8 H2O
8
H2 H2
4 4
C1-4OH C1-4OH
0 0
200 250 300 350 400 450 500 200 300 400 500 600 700
T ( C) T ( C)
18 c) 18 d)
15 15
CO
Mass rate (g/h)
Mass rate (g/h)

H2O CH4 CO2 CO
12 12
9 9
CH4 H2O
6 6
3 H2 3 H2
C1-8OH C1-8OH
0 0
200 300 400 500 600 700 800 200 300 400 500 600 700 800
T ( C) T ( C)
Figure 4.1. Chemical equilibrium composition in syngas conversion to mixed
alcohols (C1–8OH) as function of the temperature (a) and the effect of: WGSR (b),
methanation (c) and WGSR and methanation (d). Calculation conditions: 10 bar,
H2/CO=2, initial mass flow for CO=28 g/h and for H2=4 g/h. Method based on the
minimization of Gibbs free energy using a PSRK equation of state
(From Paper I). Adapted from [11] with permission from The Royal Society of
Chemistry.
4.2. Types of catalysts
Several catalysts have been proposed and tested for the synthesis
of ethanol and higher alcohols [11, 32, 33]. They can roughly be
classified as Rh-based, Cu-based, Co-based and Mo-based
catalysts. Among them, the Rh-based catalysts present the highest
selectivity to ethanol. The rest of the catalysts have similar
selectivity to ethanol, but higher activity (conversion of syngas per
catalyst volume). In the present work, the attention was focused on
the study of Rh and Cu based catalysts.
24
4.2.1. Rh-based catalysts
Several metal promoters have been tested with Rh in order to

increase both the selectivity and activity to ethanol. Among the
most promising metal promoters are Fe, La, V, Zr, Ce, and Mn [11].
Typically, they are combined in multi-promoted Rh-based
catalysts, for example, the Rh-La-V/SiO2 catalyst is able to increase
the ethanol selectivity from 16.7 % to 39 %, as compared to
unpromoted Rh/SiO2 [34]. Rh-Mn/SiO2 catalyst has shown a high
syngas conversion (42 %), but low ethanol selectivity (<9 %) [35].
Rh-Ce-Zr/SiO2 catalyst has showed both a high ethanol selectivity
and a high syngas conversion, that is 35 % and 27 %, respectively
[36]. Similar results were reported using a Rh-CeO2/TiO2 catalyst
showing a selectivity to ethanol of 33 % and a syngas conversion of
32 % [37].
4.2.2. Cu-based catalysts
Previous work has shown that Cu-based catalysts are less selective
for ethanol formation, and can produce a mixture of alcohols at
high syngas conversion. In this case, ethanol could be extracted
from the produced alcohols. Metal promoters such as Fe, Co, Ni,
La, Mn or Pd are active for increasing the yield to alcohols [11]. For
example, a catalyst containing Cu-Pd-Fe-Co metals, has shown a
syngas conversion as high as 84 % and an alcohol selectivity of 37
% with the following alcohol distribution: 26 % methanol, 38 %
ethanol, 27 % propanol and 9 % butanol [38].
4.2.3. Role of the catalyst’s support
The main role of the catalyst support is to increase and maintain

the dispersion of the metal active sites. The catalyst support should
be thermally stable and not suffer alterations during the catalytic
testing. Ideally, the catalyst support should not interact or affect
chemically the course of a reaction. However, it is know that a
25
catalyst support can affect the product distribution by different
mechanisms, such as increasing the acidity (e.g. aluminas or
zeolites), basicity (e.g. MgO or TiO2) or generating strong metal-
support interactions. Thus, it is desirable to have an inert catalyst
with no effect on the active sites of a catalyst. Among the typical
catalyst supports, silica (SiO2) is one of the most inert supports and
is widely used in different catalytic processes. In our work, we have
chosen a typical SiO2 and a novel mesoporous silica (MCM-41,
described in the following section) as catalyst supports.
4.2.3.1. Ordered Mesoporous Silica (MCM-41):

The “Atrane Route”
Ordered mesoporous silica was reported in the early of 1990 [39].

At that time, various kinds of mesoporous materials were originally
reported by Mobil Corporation scientists such as MCM-41 (Mobil
Composition of Matter No. 41), which exhibits 1D-cylindrical
hexagonal pores with amorphous walls; other related phases were
cubic (MCM-48) and lamellar (MCM-50). These structures are
known as the M41S family. Afterward, modified and new
mesoporous materials have been obtained by both academy and
industry [40]. Moreover, ordered mesoporous materials are being
applied with promising results in different fields [40-42];
chemistry, engineering, catalysis, health and others.
Generally, ordered mesoporous materials are obtained via the sol-

gel processes, with hydrolysis and condensation as main reactions
[43]. The novelty of the Mobil Corporation scientists was in the use
of assemblies of surfactant molecules as framework templates [44].
Surfactants are large organic molecules, such as
cetyltrimethylammonium bromide (C16H33)N(CH3)3Br (CTAB),
which have a hydrophilic head and a long hydrophobic tail of
variable length. In aqueous solutions, these species can form
different forms of micelles (spherical, cylindrical or higher–order)
depending on the solution conditions (pH, temperature, others). In
26
case of MCM-41, the surfactant (CTAB) packs together to form
cylindrical micelles.
Further Beck et al. [45] proposed two mechanisms for the

formation of MCM-41; „„liquid-crystal templating‟‟ (LCT) and self-
assembly (Figure 4.2). In the first mechanism, the structure is
defined by the organization of surfactant molecules into LC phases
and this serves as templates for the building of the MCM-41
structure. The inorganic silicate species would occupy the space
between a preformed hexagonal lyotropic crystal phase, and are
deposited on the micellar rods of the LC phase as shown in Figure
4.2, pathway 1. However, since the LC structures are very sensitive
to the characteristics of the solution, the same authors proposed
that the addition of inorganics could mediate the ordering of the
surfactants into specific mesophases (pathway 2). In both cases,
the inorganic species interact electrostatically with the charged
surfactant head groups and condense into a hexagonal array of
surfactant micellar rods embedded in an inorganic matrix.
Figure 4.2. MCM-41 formation via possible mechanistic pathways: (1) liquid
crystal phase initiated and (2) silicate anion initiated. Reprinted with permission
from Beck et al. [45], Copyright (1992) American Chemical Society.
Ordered mesoporous materials have some remarkable properties

[46] such as: i) well-defined pore structure, ii) high thermal
stability, iii) large pore volume, and iv) high specific surface area.
Since these properties are desirable for a catalyst support, it has
27
been used in different catalytic reactions with interesting results
[41].
The “Atrane Route”
The hydrolysis and condensation of transition metals are generally

so fast that their control is difficult. This is due to the high
reactivity of the metal precursor either in the form of inorganic salt
or metal alkoxides [43]. In order to reduce the reactivity of the
metal precursor, an intermediate with low tendency to hydrolyse
and condense is required.
The atrane compounds are formed by two bridgehead atoms linked

by three three-atom moieties, with the general chemical formula of
EN(YCH2CH2)3R [47], where: E=metal; Y=”an element like
oxygen” and; R=an organic substituent or water molecule. A
schematic of an atrane compound (silatrane) is presented in Figure
4.3. This particular structure of atrane compounds makes it
possible to regulate the hydrolysis rate and thus the packing with
surfactant molecules is improved.
28
a)
b)
Figure 4.3. Schematic drawing of silica precursors for the synthesis of MCM-41:
a) silatrane like compound (R= organic substituent or water molecule) and, b)
tetraethyl orthosilicate (TEOS). In the right part in both a) and b), the surface total
charge density (calculated by the Chem3D software [48]) is shown.
The synthesis of mesoporous materials using atrane compounds as

metal precursors basically involves five steps:
1. Preparation of atrane compound by transesterification of

a metal alkoxide with triethanolamine (TEA):
( ) ( ) ( ) ( )( ) (4.1)
Where M is metal (Si, Al, Ti, etc.). Various forms of atrane-like

compounds may be present in aqueous solution. For example, in
basic aqueous solution the following compounds have been found
for silatrane: SiNa(TEA)2H2+, Si(TEA)2H2, Si2Na(TEA)3H+,
Si3Na(TEA)4+ [49].
29
2. Surfactant (e.g. CTAB) addition to the mixture of atrane
(e.g. silatrane) and TEA. TEA acts as a co-solvent which
enhances the solubility of the CTAB.
3. Hydrolysis and condensation by addition of water to the
mixture of silatrane + CTAB + TEA. Cabrera et al. [49]
have studied the stability of the atrane compounds in
aqueous media; in the case of the siliatrane, the main
specie has been characterized as [Si(TEA)2(H3O)H2]+.
4. Aging in order to favor condensation reactions and thus
consolidate the meso-structures at long range
(gelification).
5. Elimination of the surfactant and TEA by thermal
treatment (calcination), leaving a solid mesoporous
structure (e.g. MCM-41).
Thus, silica mesoporous materials can be obtained via the atrane

route and most importantly, mesoporous material containing
several metals can be formed, corresponding to the following
formula: Mx-MCM-41 [49]. The latter is successfully achieved
because of the low reactivity of the atrane complexes towards
hydrolysis and condensation.
4.3 Reaction mechanisms
The reaction mechanism for ethanol and higher alcohols formation

is still under investigation. Regarding the Rh-based catalysts, some
mechanistic steps have been generally accepted [33, 50, 51],
schematically shown in Figure 4.4. The rate-limiting step of the
overall syngas conversion is the hydrogenation of surface CO* to
formyl species (HCO*) which is further hydrogenated to CH3O*. At
this point, this methoxy specie may either dissociate to CH3* and
O* or may be hydrogenated to form methanol (CH3OH). Methane
(CH4) is formed from the hydrogenation of CH3*. Ethanol
(CH3CH2OH) is formed from the CO insertion to CH3* and
subsequent hydrogenation steps.
30
+ H*
CH4
CH3*+O* + CO* + 3H*
dissociation CH3CO* CH3CH2OH
insertion
CO+1/2H2 CO*+H* HCO*+2H* CH3O*
+ H*
CH3OH
non-dissociation
Figure 4.4. Schematic mechanism for ethanol synthesis and main byproducts
formation (methanol and methane) over Rh-based catalysts, elaborated from
references [33, 50, 51].
Similar reaction pathways have been discussed for the formation of

ethanol and higher alcohols over Cu-based catalysts [11, 52, 53].
The higher alcohols (C2+-OH) are formed from consecutive C-C
coupling between formyl species and methyl species (CHx*) and/or
CO insertion. The higher alcohols distribution follows the
Anderson-Shultz-Flory (ASF) model. The ASF model is defined by
equation (4.2) [54]:
( ) (4.2)
( )
( ) ( ) (4.3)
where Sn is the selectivity to molecules with n carbon atoms and 

is the chain growth propagation probability (independent of n).
The  is obtained by least-squares linear regression of the
logarithmic form of the ASF equation (4.3). The  is directly
related to the rate of chain propagation and inversely to the rate of
chain termination.
31
CHAPTER 5
Experimental methods
5.1. Catalyst preparation

5.1.1. Mesoporous Silica MCM-41
The “Atrane Route” was used to prepare mesoporous silica MCM-

41 [49]. This method uses cetyltrimethylammonium bromide
(CTAB) as a structural directing agent, and 2,2′,2″-nitriletriethanol
(triethanolamine, TEA) as a complexing polyalcohol which
regulate the hydrolysis rate. The synthetic procedure is described
elsewhere [49, 55, 56]. The main steps for the preparation of
MCM-41 are shown in Figure 5.1. The atomic ratios are
4TEA:1Si:1Na:0.1CTAB:90H2O.
Tetraethyl orthosilicate
(TEOS) Triethanolamine
(TEA)
- NaOH
- 130 ºC
SILATRANE
- 60 ºC
- Surfactant CTAB
- H2O
- Aging
(48h at 20ºC)
- Washing/filtration
- Calcination
(6h at 550ºC)
MCM-41
Figure 5.1. Main steps for the preparation of MCM-41 via the “Atrane Route”.
Elaborated from references [49, 55, 56].
33
A commercial hexagonal MCM-41 was purchased from Sigma
Aldrich which was indistinctly used with the MCM-41 obtained
from the “Atrane Route”.
5.1.2. Metal impregnation
Rh/MCM-41 and Rh/SiO2 catalysts

The Rh/MCM-41 and Rh/SiO2 catalysts were prepared by
successive incipient wetness impregnation, using an aqueous
solution of RhCl3·nH2O. After impregnation, the catalysts were
dried at 120 °C for 6 h and then calcined at 500 °C for 5 h. The
total metal loading was 3 wt.% Rh for both the Rh/MCM-41 and
the Rh/SiO2 catalysts.
Cu-promoters/MCM-41 catalysts
Copper (from the precursor Cu(NO3)2·3H2O ) was incorporated
into MCM-41 by aqueous wetness impregnation using an excess of
water under constant stirring for 3 h. After impregnation, the solid
was dried at 120 °C for 3 h and then calcined at 500 °C for5 h to
obtain the Cu/MCM-41 catalyst. Then, potassium (from the
precursor K2CO3) was added to the Cu/MCM-41 catalyst following
the same procedure as for Cu addition and using the same thermal
treatment as described above. Iron (from the precursor
Fe(NO3)3·9H2O) was added to the Cu-K/MCM-41 catalyst also
following the same procedure as for the Cu addition.
5.2. Catalyst characterization

5.2.1. N2-Physisorption
N2-physisorption analyses were carried out using a Micromeritics

ASAP 2000 instrument and the Brunauer-Emmett-Teller (BET)
method was used to calculate the surface area and the Barrett-
Joyner-Halenda (BJH) method was used to calculate the pore size
and pore volume from the desorption isotherm.
34
5.2.2. X-Ray Diffraction (XRD)
Powder X-ray diffraction was performed using a Siemens D5000
instrument with Cu K-alpha radiation (2θ = 10°–90°, step size =
0.04°) equipped with a Ni filter and operated at 40 kV and 30 mA.
5.2.3. H2-Chemisorption
H2-chemisorption was carried out on a Micromeritics ASAP 2020
instrument. Prior to the analysis, the catalyst sample was reduced
with hydrogen. Repeated analyses were made in order to
discriminate between the amounts of hydrogen adsorbed via
physisorption and chemisorption.
5.2.4. Transmission Electron Microscopy (TEM)

TEM images were obtained using a JEOL JEM 1400 microscope.
Samples were mounted on 3 mm holey carbon copper grids. The
particle size and distribution were estimated after examination of
more than 100 metal particles.
5.2.5. Temperature Programmed Reduction (TPR)

TPR analysis was carried out in a Micromeritics Autochem 2910
instrument, a reducing gas mixture (5 % H2 in Ar) at a flow of 50
mL/min passed through the catalyst sample while the temperature
was increased by 5 °C/min up to 900 °C.
5.2.6. X-Ray Photoelectron Spectroscopy (XPS)

For XPS analysis, the data were recorded on 4 mm × 4 mm pellets
of 0.5 mm thickness, outgassed to a pressure below 2×10−8 torr at
150 °C in the instrument pre-chamber. The main chamber of a
Leybold-Heraeus LHS10 spectrometer is equipped with an EA-
200MCD hemispherical electron analyzer and a dual X-ray source
using AlKα (hv = 1486.6eV) at 120 W, 30 mA, with C(1s) as energy
reference (284.6 eV).
35
5.2.7. Thermogravimetric analysis (TGA)
TGA was carried out using a SETARAM (TG-DTA-DSC 1600 °C).
The sample was heated up to 400 °C at a rate of 5 °C/min in a
continuous flow of He. The differential thermo-gravimetric (DTG)
curves were estimates from the TGA data.
5.3. Catalytic testing

5.3.1. Reactor set-up and procedures
The catalytic testing was carried out in a stainless-steel, down-flow

fixed bed reactor. The internal diameter of the reactor was 8.3 mm,
into which about 300 mg of catalyst was charged with a particle
size between 160 and 250 μm. Prior to the testing, the catalyst was
reduced with H2. After reduction, the reactor was cooled to 280 °C
and pressurized with syngas. The gas hourly space velocity (GHSV)
was varied between 3 000 and 19 000 mLsyngas/gcath. Premixed
syngas bottles with a H2/CO ratio of 2:1 and 1:1 were used. Water
addition was regulated by means of a Gilson 307 pump, and joined
to the syngas feed stream. In all the experiments, the axial
temperature gradient through the catalyst bed (measured by a
mobile thermocouple introduced in a thermowell inside the
catalyst bed) was always less than 1 °C. The catalytic set-up has
been described elsewhere by Andersson et al. [57], from which a
schematic drawing is shown in Figure 5.2.
36
Figure 5.2. Schematic overview of the gas feed, high pressure reactor and
analysis system connections. Main parts are from left to right: gas bottles, mass
flow controllers, hot box preheating (and post heating), high-temperature reactor,
pressure controller, and heated line 1, GC1. Reprinted from Andersson at al. [57],
Preliminary estimations were carried out to ascertain transport

effects on the mesoporous catalyst (Rh/MCM-41). The results
indicated that, at the experimental conditions used in this study,
intraparticle diffusion limitation might begin to occur at high
syngas conversion (>70 % in terms of CO conversion), according to
the Weisz-Prater‟s criterion [58]. An additional experiment was
carried out at 230 °C, 20 bar and 40 000 mLsyngas/gcat h (H2/CO =
2/1) using a catalyst sample with a fixed number of active sites (3
wt.% Rh and a metal dispersion of H/Rh = 22 %, Paper III). A
fraction of this sample was diluted with pure MCM-41 support, at a
ratio of 1:3, resulting in a catalyst with nominal composition 0.75
wt.% Rh and a metal dispersion of H/Rh = 22 %. The results
indicate a minor variation (<10 %) between the TOFs of the non-
diluted catalyst and the diluted catalyst, suggesting that the
37
reaction operates in the kinetic regime according to the Koros-
Nowak criterion [58].
5.3.2. Product analysis and data treatment
An on-line GC, Agilent 7890A, was used to quantify the reaction

products. A detailed description of the GC configuration and the
analytical procedure has been published previously by Andersson
et al. [57]. N2 was added to the syngas mixture and used as internal
standard to quantify CH4, CO and CO2 in a thermal conductivity
detector. The hydrocarbon and oxygenated compounds were
analyzed in a flame ionization detector using the internal
normalization of corrected peak areas method. In all the
experiments the carbon balance was between 99.1-100 %.
The expressions used to evaluate the results are the following [57]:
- Syngas conversion (in terms of CO conversion):

( ) ( ) (5.1)
- Selectivity to CO2:
( )
( ) (5.2)
( ) ( )
Because CH4 is detected by both FID and TCD detectors, but CO2
only by the TCD detector, the CH4 in the FID is equivalent to the
CH4 in the TCD without CO2 (CO2-free).
- Selectivity to CH4 (CO2-free) by FID:
( ) ∑
(5.3)
( )
38
Where Rij is the corrected response factor (relative to methane or a
hydrocarbon compound). The selectivity to the other organic
compounds measured by FID is calculated using the above
equation replacing CH4 by an organic compound (SCorg, FID).
- Selectivity to CH4 (CO2-free) by TCD:
( )
(5.4)
( ) ( )
⁄ ⁄
( ) ( )
- Material Balance:
The total flow (in terms of carbon moles) that enters the reactor
should be equal to the total flow that leaves the reactor, assuming
no carbon accumulation inside the reactor. This relation is given
below and measures the carbon material balance (MB) for each
catalytic testing.
( )
(5.5)
39
CHAPTER 6
Catalytic performance of a typical Rh/SiO2 catalyst

and a mesoporous Rh/MCM-41 catalyst
6.1. Product distribution and selectivity to C2-oxygenated
compounds
An examination study of the catalytic performance of the

mesoporous Rh/MCM-41 catalyst shows a different product
distribution as compared to a typical Rh/SiO2 catalyst, Figure 6.1.
In addition to the selectivity to each compound is being different,
the total selectivity to the main groups of compounds, i.e.
hydrocarbons (methane and higher hydrocarbons) and oxygenated
compounds (methanol, carbon dioxide, ethanol, acetaldehyde,
acetic acid, methyl acetate and ethyl acetate), is also different.
Thus, for the mesoporous Rh/MCM-41 catalyst the total selectivity
to hydrocarbon and oxygenated compounds is 43.4 % and 56.6 %,
respectively. For the Rh/SiO2 catalyst the total selectivity to
hydrocarbon compounds (58.2 %) is higher than the selectivity to
oxygenated compounds (41.8 %). The higher selectivity to
hydrocarbons than to oxygenated compounds is characteristic for
the Rh/SiO2 catalyst [59] and, for that reason the addition of metal
promoters was investigated in order to increase the selectivity
towards oxygenated compounds [32, 33].
41
45
42
39
Rh/SiOcatalyst
Rh/SiO2 2
36 Rh/MCM-41
Rh/MCM-41 catalyst
33
30
Selectivity (%)
27
24
21
18
15
12
9
6
3
0
Methane Higher Carbon Methanol Ethanol Acetaldehyde Acetic acid Acetate
hydrocarbons dioxide compounds
Figure 6.1. Product selectivities obtained from the Rh/SiO2 and Rh/MCM-41
catalysts. Higher hydrocarbons: ethane, propane and butane. Acetate
compounds: methyl acetate and ethyl acetate. Reac. Cond.: 280 °C, 20 bar,
GHSV=12000 mlsyngas/gcat h for Rh/SiO2 and GHSV=3000 mlsyngas/gcat h for
Rh/MCM-41 (From Paper III).
An interesting result was obtained regarding the selectivity to the

C2-oxygenated compounds (ethanol, acetaldehyde and acetic acid),
where the selectivity to ethanol for the mesoporous Rh/MCM-41
catalyst is three times that of the typical Rh/SiO2 catalyst, that is
24 % and 8 %, respectively. Still, the total selectivity to C2-
oxygenated compounds has a similar value for both catalysts; 34 %
for Rh/SiO2 and 32 % for Rh/MCM-41. This result suggests a
different catalytic performance of the mesoporous Rh/MCM-41
catalyst. In order to verify this observation, additional experiments
were conducted changing the reaction conditions for the
Rh/MCM-41 catalyst: i) syngas conversion, ii) pre-reduction
treatments, iii) water addition and iv) hydrogen partial pressure.
42
6.1.1. Effect of syngas conversion
It is known that the product distribution depends, in some degree,

on the syngas conversion [32, 33]. Thus, both Rh/MCM-41 and
Rh/SiO2 catalysts have been tested in a large range of syngas
conversion, as can be seen in Figure 6.2. The range of syngas
conversion has been obtained by varying the reaction conditions
(temperature, pressure and gas hourly space velocity). At low
syngas conversions, the selectivity to oxygenated compounds for
Rh/MCM-41 is higher than for Rh/SiO2, in agreement with
previous results. At high syngas conversion, the hydrocarbon
compounds dominate, in agreement with thermodynamic
equilibrium at high temperature (see section 4.1). The most
notable difference in the product distribution obtained from
Rh/MCM-41 and Rh/SiO2 catalysts, is the selectivity to CO2.
Almost zero selectivity to CO2 is found over the Rh/SiO2 catalyst
while for the Rh/MCM-41 catalyst the CO2 selectivity varies from
16 % (at low syngas conversion) up to 57 % (at high syngas
conversion). It is known that the formation of CO2 is
thermodynamically possible and favored at high temperatures (see
section 4.1).
Rh/MCM-41 Rh/SiO2
90
90
80
80
70
70
Selectivity (%)
Selectivity (%)
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50
syngas conversion (%) Syngas conversion (%)
Hydrocarbons CO2 Oxygenates
Figure 6.2. Effect of the catalyst reduction temperature on the product selectivity
over Rh/MCM-41 and Rh/SiO2 catalysts. Catalysts pre-reduced at 200 °C (solid
lines) and nonreduced catalysts (segmented lines) (From Paper IV). Reprinted
from Lopez at al. [60], Copyright (2015), with permission from Elsevier.
43
6.1.2. Effect of the catalyst reduction temperature
As can be seen in Figure 6.2, different product distributions are

found as the catalyst reduction temperatures are changed, in both
Rh/MCM-41 and Rh/SiO2 catalysts. This again evidences the
different reactivity of the mesoporous Rh/MCM-41 catalyst
compared to the typical Rh/SiO2 catalyst. Regarding the selectivity
to the C2-oxygenated compounds, the ethanol selectivity is much
higher in the mesoporous Rh/MCM-41 catalyst than in the typical
Rh/SiO2 catalyst, independently of the syngas conversion and the
catalyst reduction temperature, Table 6.1.
Table 6.1. Distribution of C2-oxygenates for Rh/MCM-41 and Rh/SiO2 catalysts as

function of the catalyst reduction temperature and syngas conversion (From
Paper IV). Reprinted from Lopez at al. [60], Copyright (2015), with permission
from Elsevier.
C2-oxygenate ratio
Reduction Range of syngas
Catalyst Ethanol / Ethanol /
Temperature conversion (%)
Acetaldehyde Acetic Acid
Not reduced 1.5 - 68% 6 – 17 1 – 12
Rh/MCM-41 200°C 0.8 - 58% 5 – 11 10 – 27
500°C 0.6 - 64% 7 – 13 4 – 13
Not reduced 0.9 - 33% 0.7 – 2 1–2
Rh/SiO2 200°C 5.9 - 45% 0.6 – 2 1 – 22
500°C 4.4 - 28% 0.5 – 1 1–4
6.1.3. Effect of hydrogen partial pressure
The partial pressures of the syngas feed stream (PH2 and PCO) can
modify the product distribution [32, 33]. Thus, the evaluation of
the syngas composition (H2/CO) is important in order to elucidate
the reactivity of the mesoporous Rh/MCM-41 catalyst. In Figure
6.3, the product distribution obtained at low syngas ratio
(H2/CO=1) is compared to the results obtained at higher syngas
ratio (H2/CO=2). The lowering of the syngas ratio decreases the
selectivity to methane and methanol, while in contrast, the
selectivities to higher hydrocarbons, carbon dioxide, and acetate
increases. The latter indicates that compounds with high H/C
44
ratios (like methane or methanol) are favored at high syngas ratios
(high hydrogen partial pressure), possibly by increasing the
occurrence of hydrogenation reactions.
Among the C2-oxygenated compounds, the selectivity to the more

oxidized compound (i.e. acetic acid) is decreased at high syngas
ratio (i.e. high hydrogen partial pressure). In the Rh/MCM-41
catalyst ethanol and acetaldehyde are favored by increasing the
syngas ratio.
48
45
Rh/SiO2 (H
Rh/SiO2, syngas ratio: 2
2/CO=2)
42
39
Rh/SiO2, syngas
Rh/SiO2 (H ratio: 1
2/CO=1)
36 Rh/MCM-41catalyst
Rh/MCM-41 (H2/CO=2)
33
Rh/MCM-41syngas
Rh/MCM-41, ratio: 1
(H2/CO=1)
30
Selectivity (%)
27
24
21
18
15
12
9
6
3
0
catalysts. Reac. Cond. (syngas H2/CO=1): 280 °C, 20 bar, GHSV=6000
mlsyngas/gcat h for Rh/SiO2 and GHSV=3000 mlsyngas/gcat h for Rh/MCM-41. Reac.
Cond. for the experiments with syngas H2/CO=2 as indicated in Figure 6.1 (From
Paper III).
6.1.4. Effect of water addition
Typically, Rh-based catalysts do not form CO2 as a main product

[32, 33]. However, the mesoporous Rh/MCM-41 has shown a
high selectivity to CO2 as reported in section 6.1.1. An additional
45
reaction taking place during many catalytic processes, is the
water gas shift reaction (WGS) which consumes CO and H2O to
generate CO2 and H2 [32, 33]. If the WGS reaction would occur
over the Rh active sites in the mesoporous Rh/MCM-41 catalyst,
it should also occur in the Rh/SiO2 if water is added to the syngas
feed stream. Figure 6.4 shows the obtained product distributions
found when water is added to the syngas feed stream in both
catalysts. It can be observed that CO2 is produced for the typical
Rh/SiO2 catalyst by water addition. Interestingly, the selectivity
to methanol is also increased by water addition. The latter may be
related to the conversion of CO2 to methanol, as known in
literature [61].
90
Rh/SiO2, feedsyngas)
Rh/SiO2 (only stream: syngas
80 Rh/SiO2, feed stream: syngas + water
Rh/SiO2 (syngas+water)
70 Rh/MCM-41catalyst
Rh/MCM-41 (only syngas)
Rh/MCM-41feed
Rh/MCM-41, stream: syngas + water
(syngas+water)
60
Selectivity (%)
50
40
30
20
10
0
catalysts. Reac. Cond. (with addition of water): 280 °C, 20 bar, GHSV=6000
mlsyngas/gcat h (H2:CO:H2O=2:1:2.7) for Rh/ SiO2 and GHSV=3000 mlsyngas/gcat h
(H2:CO:H2O=2:1:1.5) for Rh/MCM-41. Reac. Cond. for the experiments without
addition of water as indicated in Figure 6.1 (From Paper III).
46
6.2. Catalyst characterization before and after catalytic testing
Extensive catalyst characterization has been performed for both

the mesoporous Rh/MCM-41 and the typical Rh/SiO2 catalysts in
order to understand the catalytic results. Particular attention was
given to the characterization after the catalytic testing.
6.2.1. Specific surface area and pore size distribution
The surface area of the mesoporous Rh/MCM-41 catalyst is almost

four times the surface area of the typical Rh/SiO2 catalyst. The
high surface area of the mesoporous catalysts is due to the small
1D-porous structure. In the case of Rh/MCM-41 the average pore
size is 2.5 nm. In contrast, the typical Rh/SiO2 catalyst does not
present any structural ordering. When both catalysts were tested
without water addition to the syngas feed stream, their surface
areas were not really affected. The surface area decreased by 9.0 %
in the Rh/MCM-41 catalyst and by 3.7 % in the Rh/SiO2 catalyst
(Table 6.2). More significant changes in the surface area values
were observed when the catalytic tests were carried out with water
addition in the syngas feed stream. In this case, the surface area
values decreased by 19.3 % for the Rh/MCM-41 catalyst and by
10.3 % for the Rh/SiO2 catalyst. Partial structure degradation may
occur in the Rh/MCM-41 catalyst in presence of an excess of water;
possibly the hydration of the siloxane structure and siloxane
hydrolysis-hydroxylation [62]. This could result in the collapse of
some 1D-channels into a single one.
47
48
Table 6.2 . N2-physisorption and XPS analyses of the Rh/SiO2 and Rh/MCM-41 catalysts, before and after the catalytic testing
(From Paper III).
Surface Change in Pore volume Rh0 Rh3+
Catalyst Condition
area (m2/g) surface area (cm3/g) % B.E. (eV) % B.E. (eV) Rh/Si
Rh/SiO2 Pure support 238 - 0.87 - - - - -
Before catalytic testing 236 0.5 %* 0.90 86.5 307.3 13.4 309.7 0.0057
After catalytic testing 228 3.7 %** 0.90 82.4 307.3 17.6 309.7 0.0064
(280 °C, 20 bar, 12000
ml/gh):
only syngas
After catalytic testing 212 10.3 %** 0.88 100 307.2 - - 0.0079
(280 °C, 20 bar, 6000
ml/gh):
syngas and water
Rh/MCM-41 Pure support 970 - 1.08 - - - - -

Before catalytic testing 961 0.9 %* 1.15 80.6 307.1 19.4 308.6 0.0079
After catalytic testing 875 9.0 %** 1.04 90.8 307.4 9.2 309.3 0.0087
(280 °C, 20 bar, 3000
ml/gh):
only syngas
After catalytic testing 776 19.3 %** 0.94 100 307.1 - - 0.0100
(280 °C, 20bar, 3000
ml/gh):
syngas and water
* Compared to the pure support. ** Compared to the catalyst before catalytic testing.
6.2.2. Surface composition: Rh0 and Rh3+
The catalytic surface of the Rh/MCM-41 and Rh/SiO2 catalysts

consists of metallic Rh (Rh0) and tri-valent Rh (Rh3+). In both
catalysts, before and after the catalytic testing the proportion of
Rh0 to Rh3+ was kept in the same range as can be seen in Table 6.2.
Moreover, after the catalytic testing the increased Rh/Si atomic
ratio indicates that Rh species migrate to the outer surface in both
catalysts.
6.2.3. Porous ordering by XRD and TEM
The long-range periodic structure of the mesoporous Rh/MCM-41

catalyst is evidenced by its characteristic reflections (100), (110),
and (200) in the XRD diffractogram at low angles (Figure 6.5),
which corresponds to a hexagonal structure [39]. Both Rh/MCM-
41 and Rh/SiO2 catalysts are amorphous materials with no
segregation of rhodium oxide species. After the catalytic testing
(with no addition of water to the syngas feed stream) no changes in
the surface area values were observed in either catalysts. However,
when the catalytic testing was done in presence of excess water, a
peak at around 2θ=35–40, is observed. This peak can be
attributable to the growth of Rh0 clusters in accordance with the
XPS results (section 6.2.2.).
49
Rh/SiO2
(100)
MCM-41
Rh/MCM-41
A
Rh/MCM-41 A
15 30 45 60 75 90
Rh/MCM-41 B 2 (degrees)
Rh/MCM-41 C
(110)
(200)
SiO2
1 2 3 4 5 6 7 8 9 10
2 (degrees)
Figure 6.5. Small and wide angle XRD patterns of pure SiO2 and MCM-41
supports, impregnated with Rh A, after catalytic testing B, and after catalytic
testing with addition of water C (From Paper III).
In the case of the mesoporous Rh/MCM-41 catalyst, Rh species are

dispersed within the 1D-channel pores as observed by TEM (Figure
6.6). The average Rh particle size for the Rh/MCM-41 catalyst and
the Rh/SiO2 catalyst is around 3 and 4 nm, respectively. These
results are in agreement with the particle size estimated from H2-
chemisorption, which gives an average particle size of 3 nm for
both catalysts (metal dispersion H/Rh=22 %) assuming an
icosahedral particle shape [63].
50
Figure 6.6. TEM images of Rh/SiO2 and Rh/MCM-41 catalysts; reduced A,
after catalytic testing B, and after catalytic testing with addition of water C
(From Paper III).
6.2.4. Metal support interactions
According to previous work, metal support interactions can occur

in both mesoporous and other types of catalysts [41, 64]. In our
case, the broad signal found in the TPR profile from the
Rh/MCM-41 catalyst, Figure 6.7, suggests some metal support
interaction. In contrast, the typical Rh/SiO2 catalyst shows a well-
defined signal in its TPR profile, suggesting a minor or negligible
metal support interactions.
51
G
Rh/SiO
H2 - Consumption
2
Rh/MCM-41
C
30 60 90 120 150 180 210 240

Temperature (°C)
Figure 6.7. Temperature-programmed reduction profiles of the Rh/SiO2 and
Rh/MCM-41 catalysts (From Paper III).
6.3. Interpretation of the catalytic performance of Rh/MCM-41

compared to Rh/SiO2
The novel mesoporous Rh/MCM-41 catalyst has shown a different

reactivity in the conversion of syngas, as compared to typical a
Rh/SiO2 catalyst. In this section, an explanation for the different
product selectivity obtained from the Rh/MCM-41 catalyst is
proposed. This explanation has been based on; i) additional
catalytic experiments (effect of hydrogen partial pressure and
addition of water to the syngas feed stream), and ii) the exhaustive
characterization before and after the catalytic testing.
6.3.1. Water vapor concentration in mesoporous

Rh/MCM-41 catalyst
The following aspects must to be considered in order to interpret

the product distribution obtained in the mesoporous Rh/MCM-41
catalyst:
52
 Some metal-support interactions seem to be present in the
Rh/MCM-41 catalyst, but not in the Rh/SiO2 catalyst (as
suggested from TPR analysis). However, the Rh surface
composition (in terms of Rh0 and Rh3+) is similar in both
catalysts (as indicated from XPS analysis), which could
result in similar reactivity for both catalysts. Thus, a minor
or negligible effect of the metal-support interactions could
be related to the different product selectivity obtained in
the Rh/MCM-41 catalyst.
 In both catalysts, the Rh particle size is kept around the
same value (3-4 nm); as obtained from H2-chemisorption
and confirmed by TEM, thus no effect of particle size on the
product distribution should be expect.
 The 1D-channels with small pore diameter of the
mesoporous MCM-41 seem to be retained in the Rh/MCM-
41 catalyst (as suggested from N2-physisorption, XRD and
TEM analyses), which is an important and different
characteristic as compared to the typical Rh/SiO2 catalyst.
This aspect may possibly be mainly responsible the
different product distribution found for the Rh/MCM-41
catalyst. The proposed role of the 1D-channels of Rh/MCM-
41 in the product distribution is further discussed in the
following paragraphs.
During the preparation of mesoporous catalysts some metal-

support interactions are favored by the concentration of water
vapor in the mesopores [41, 65]. Consequently, for the reactions
involved in the catalytic conversion of syngas producing water as a
main product [32, 33], reactions (6.1-6.4), some water vapor can
be concentrated in the mesopores of the Rh/MCM-41 catalyst.
Ethanol generation (6.1)
Methanation (6.2)
53
Hydrocarbons formation (6.3)
Methanol synthesis
(6.4)
This environment rich in water vapor in the mesopores of

Rh/MCM-41 may induce some reactions, such as the water-gas-
shift-reaction (WGSR).
Water gas shift reaction (6.5)
WGSR generates extra carbon dioxide and hydrogen (reaction 6.5).

In agreement, the selectivity to CO2 is much higher in Rh/MCM-41
than in Rh/SiO2, independently of the syngas conversion and
catalyst reduction temperature (section 6.1.1.). Furthermore, when
water is added to the syngas feed stream the selectivity to CO2 is
notably increased in both catalysts; from almost zero to 20 % in
Rh/SiO2 and90 % in Rh/MCM-41.
It is generally accepted that methanol synthesis from syngas take

places via the hydrogenation of CO2 [61]. So, if CO2 is generated in
Rh/MCM-41, methanol can be part of the products, which is true
(Figure 6.1). In agreement, methanol is also produced by the
Rh/SiO2 catalyst when water is added to the syngas feed stream.
6.3.2. Higher ethanol selectivity as consequence of the

water vapor concentration in mesoporous Rh/MCM-41
catalyst
According to the proposed WGSR occurrence in the mesoporous

Rh/MCM-41 catalyst, more H2 can be produced. Which, in
addition to the H2 from the syngas feed stream may induce some
hydrogenation reactions. It may explain the distribution between
the C2-oxygenated compounds, where a higher selectivity to the
54
more hydrogenated compounds, i.e. ethanol and acetaldehyde, is
found in the Rh/MCM-41 catalyst (92 %) than in the Rh/SiO2
catalyst (75 %). The hydrogenation reactions in Rh/MCM-41 may
convert acetic acid or a C2-oxygenated intermediary, perhaps an
acetyl intermediate [35], to acetaldehyde and ethanol. Moreover,
the selectivity to ethanol is higher than the selectivity to
acetaldehyde (Figure 6.1 and Table 6.1). The latter may occur via
the hydrogenation of acetaldehyde to ethanol, as suggested in the
literature [66]. A schematic representation of the hydrogenation
steps is shown in Figure 6.8.
O O H H
H3C + H2 H3C + H2 H O
OH H H H H
Acetic acid Acetaldehyde Ethanol
Figure 6.8. Schematic representation of the hydrogenation of the C2-oxygenated

compounds. Author’s own elaboration.
The hydrogen partial pressure affects the distribution between the

C2-oxygenated compounds. The selectivities to ethanol and
acetaldehyde have been favored at high hydrogen partial pressure
(varying H2/CO2), while the selectivity to acetic acid is increased
at low hydrogen partial pressure as shown in Figure 6.3 for the
Rh/MCM-41 catalyst. Indeed, the selectivity between the C2-
oxygenated compounds over the Rh/MCM-41 catalyst can be
related to the degree of oxidation: ethanol > acetaldehyde > acetic
acid.
Regarding the selectivity to hydrocarbons and acetate compounds

(Figure 6.1), they may be understood by exploring the reaction
mechanism proposed by Bowker [50], where acetate compounds
are formed by the reaction of CO2 with CHx* species. Following this
reaction mechanism, the additional CO2 formed via WGSR would
consume much more CHx* species in the Rh/MCM-41 catalyst than
in the Rh/SiO2 catalyst. This means that a lower number of CHx*
55
species would be available for conversion into hydrocarbon
compounds and more acetate compounds should be expected from
the Rh/MCM-41 catalyst. In fact, lower selectivity to hydrocarbon
and higher selectivity to acetate compounds are found over
Rh/MCM-41 as compared to Rh/SiO2 (Figure 6.1).
56
CHAPTER 7
Effect of Fe and K promoters on Cu/MCM-41 catalyst
In this chapter, a mesoporous Cu/MCM-41 catalyst has been

studied for the synthesis of ethanol. In addition to the
mesoporosity of the catalyst the effect of metal promoters such as
Fe and K, have also been studied.
7.1. Catalyst characterization: XRD, TGA, N2 physisorption,

TEM, XPS and TPR
CuO is present in all catalysts; Cu/MCM-41, Cu-Fe/MCM-41, Cu-

K/MCM-41 and Cu-Fe-K/MCM-41 (XRD pattern in Fig. 1., Paper
V). The Fe and K promoters have not been detected by XRD,
indicating low metal segregation of these promoters. Minor mass
loss in the all catalysts (1.5-2.5 wt.% up to 400 °C) has been
ascribed to dehydroxylation reactions (TGA profiles in Fig. 6.,
Paper V), which indicates that the catalysts are thermally stables.
The Cu/MCM-41 catalyst keeps the mesoporous structure of the

MCM-41 support (as suggested from the N2 physisorption
isotherms in Figure 7.1. and TEM analysis in Paper V). However,
in presence of the Fe or K promoters, the mesoporosity of the
support disappears due to collapsing of the pores, which results in
the reduction of the surface area as can be seen in Table 7.1.
Further degradation of the pores occurs when both Fe and K are
impregnated simultaneously and, as a consequence there is a
further decrease of the surface area to 72 m2/g.
57
500
Volume adsorbed (cm3/g)

1.8
400
dV/dlogD (cm3/g nm)
1.5
300
1.2 200
100
0.9
0
0.6 0.0 0.2 0.4 0.6 0.8 1.0
P/Po
0.3
0.0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
Pore diameter (nm)
MCM-41 Cu/MCM-41 Cu-K/MCM-41
Cu-Fe/MCM-41 Cu-Fe-K/MCM-41
Figure 7.1. BJH pore size distribution and (inset) N2-isotherm of the prepared
catalysts (From Paper V). Reprinted from Lopez at al. [67], Copyright (2016), with
permission from Elsevier.
For all the catalysts, the surface composition consists of Cu0 and
Cu+1 sites as indicated by XPS analysis (Table 7.1). By adding the
metal promoters, the surface atomic ratios are changed (Table 7.1).
When Fe is added to the Cu/MCM-41 catalyst, the ratio Si/Cu is
increased, which indicates that either Fe atoms cover some Cu
particles or some Cu atoms migrate from the outside to the core of
the catalyst particle. While when K is added the Si/Cu ratio is kept
low, suggesting a better Cu dispersion. The latter may be related to
the literature suggesting that K stabilizes some Cu sites,
presumably Cu+ species [68, 69].
58
Table 7.1. Physico-chemical properties of the prepared catalysts (From Paper V). Reprinted from Lopez at al. [67], Copyright
(2016), with permission from Elsevier.
BET Average Metal loading (%) by
Pore Average metal Atomic ratios by XPS
surface pore AAS
Catalyst volume particle size by
area size
(cm3/g) TEM (nm) Cu K Fe Si/Cu Cu/K Cu/Fe Fe/K
(m2/g) (nm)
MCM-41 710 0.49 2.9 - - - - - - - -
Cu/MCM-41 375 0.24 3.2 4.8 28.89 - - 2.8 - - -
Cu-K/MCM-41 208 0.26 5.1** 5.0* 29.79 1.53 - 2.9 13.0 - -
Cu-Fe/MCM-41 200 0.32 6.6** 5.0* 26.82 - 2.28 7.0 - 4.3 -
Cu-Fe-K/MCM-41 72 0.27 14.8** 6.1* 29.30 1.65 2.07 2.9 11.7 5.3 2.2
* Average of all the metals. ** Average of the interparticle space.

59
The potential metal-support interactions in the Cu/MCM-41
catalyst are partially eliminated or weakened by the presence of K,
as deduced from the reduction temperature shift from 245 °C to
210 °C observed in the TPR prolife of this catalyst (Figure 7.2.). For
Fe (Cu-Fe/MCM-41 and Cu-Fe-K/MCM-41) the resulting catalysts
show a new peak between 335 °C and 350 °C: that can be attributed
to the reduction of Fe2O3→Fe3O4 [70]. For these catalysts, CuO is
reduced at higher temperatures than in the Cu/MCM-41 and Cu-
K/MCM-41 catalysts, which indicates some electronic effects
induced by Fe.
Cu-Fe/MCM-41
Cu-K/MCM-41
Cu/MCM-41
Cu-Fe-K/
MCM-41
130 170 210 250 290 330 370 410 450

Temperature (°C)
Figure 7.2. TPR profiles of the prepared catalysts (From Paper V). Reprinted
from Lopez at al. [67], Copyright (2016), with permission from Elsevier.
7.2. Catalytic testing: product selectivity trends
The mesoporosity of the Cu/MCM-41 catalyst could induce the

increased concentration of water vapor as occured in the
Rh/MCM-41 catalyst (Chapter 6). This phenomenon is supported
by the results obtained from the product distribution. This
distribution shows that the selectivity to oxygenated compounds is
higher than the selectivity to hydrocarbon compounds. The
opposite selectivity trend for hydrocarbon and oxygenated
60
compounds is found in typical Cu-based catalysts [71, 72]. The
concentration of water vapor can promote the occurrence of the
Cu Cu-K WGSR which in turn
Cu-Fe promotes secondary reactions such as
Cu-Fe-K
hydrogenation reactions (as explained in Chapter 6 in the case of
Rh-based catalysts).
CuCu/MCM-41 Cu-K Cu-K/MCM-41

Cu-Fe Cu-Fe-K
Cu-Fe/MCM-41 Cu-Fe-K/MCM-41
100 100
Selectivity and conversion (%)
90 90
80 80
70 70
Cu Cu-K Cu-Fe Cu-Fe-K
100 60 60 Hydrocarbons
Oxygenates
90 50 50 Conversion
80 40 40
5 10 7015 035305 40 1045

15 020 5 25 1030 30 0
50 5
55 10
60 15
65 20
70 25
75
60 Time20on stream
20 (h)
50 10 10
40 0 0
0 05 510 10
1015 2501030
1515020205 25 305 035
10 54015
35 1045050 50
40 45 5055 105 15
60
55 65 0 70
10
60 155 7570
65 10 8075
20 158520
25
30
Time
Time on on stream
stream (h) (h)
20
10 Figure 7.3. Product selectivity trends obtained from the prepared catalysts. Reac.
Cond.: syngas H2/CO ratio: 2/1, 300 °C, 20 bar and a GHSV of 1500 mlsyngas/gcat
0 h for the Cu/MCM-41 and Cu-K/MCM-41 catalysts and 30000 mlsyngas/gcat h for
0 5 10 15 020
15the 5 25 1030 035 and
Cu-Fe/MCM-41 5 40 Cu-Fe-K/MCM-41
1045 50 0 55 5 6010catalysts
15 70
65 20(From
25 Paper V). Reprinted
75
Time on
from Lopez stream
at al. [67], (h)
Due to the pores collapsing of the Cu/MCM-41 catalyst when K and

Fe are added (Figure 7.1., Table 7.1.), minor or negligible water
vapor concentration may be expected. For future work, another
method of catalyst preparation could be used in order to keep the
structure of mesoporous MCM-41. It is known that a narrow metal
particle size distribution (2 nm) can be obtained by novel
techniques such as the so-called microemulsion [73]. This
technique could be used to introduce the metal promoters inside
the mesoporous (2.9 nm) of MCM-41.
61
7.2.1. Effect of K as promoter
The addition of K to the Cu/MCM-41 catalyst results in a notable

increase of the selectivity to oxygenated compounds, with a value
equal to 92 % for all the products (Figure 7.3). The effect of the K
promoter can be related to two main actions: i) stabilizing the
active sites, presumably the Cu+ species [68, 69], which can be
related to the lower reduction temperature of the Cu-K/MCM-41
catalyst compared to the Cu/MCM-41 one (Figure 7.2) and ii)
blocking some acid sites thus decreasing the selectivity to
hydrocarbons [74]. Moreover, some metal-support interactions are
present in the Cu/MCM-41 catalyst, which are weakened or
eliminated by the presence of K (Figure 7.2). This suggests that the
metal-support interactions have a minor effect on the formation of
oxygenated compounds.
7.2.2. Effect of Fe as promoter
As opposed to the action of the K promoter, the addition of Fe to

Cu/MCM-41 catalyst promotes the selectivity towards hydrocarbon
compounds (Figure 7.3). The effect of Fe can be related to its
action in the Fischer-Tropsch synthesis. There the formation of
hydrocarbons is believed to occur via CO dissociation to produce
C* (or *CH) radicals, which react to form C-C bonds and are
subsequently hydrogenated [11].
7.2.3. Effect of K and Fe addition
When both K and Fe promoters are added to the Cu/MCM-41

catalyst, the selectivity to hydrocarbons and oxygenated
compounds become similar: 52 % and 48 %, respectively. This
suggests that both kinds of mechanisms could take place: CO
dissociation and CO non-dissociation. In addition, the CO
insertion mechanism could also take place over the Fe promoter,
62
which may produce oxygenated compounds via the so-called enol
route [11].
7.3. Selectivities to alcohols and other oxygenated

compounds
Among the alcohols and oxygenated compounds (acetates,

aldehyde and acetic acid), methanol is the dominant product (>98
%) on both Cu/MCM-41 and Cu-K/MCM-41 catalysts, Figure 7.4.
When Fe is incorporated, the methanol selectivity decreases to 45
% and, at the same time, the selectivity to the higher alcohols is
increased to about 33 %. When both K and Fe promoters are
Cu-K Cu-Fe incorporated,
Cu-Fe-K the selectivity to the higher alcohols increased to 49
Cu-K Cu-Fe Cu-Fe-K
Cu Cu-K %.Cu-Fe
The latter indicates
Cu-Fe-K that the combination of these promoters is
favorable for the formation of higher alcohols.
Methanol
Cu-K Cu-Fe Cu-Fe-K C2+-Alcohols
Acetates
Cu/MCM-41
Others Cu-K/MCM-41 Cu-Fe/MCM-41 Cu-Fe-K/MCM-41
100
90
80
70 Methanol
Selectivity (%)
60 C2+-Alcohols
Acetates
50 Others
20 5 25 1030 0 35 5 40 1045 0
50 540 10
55 60 15
65 20
70 25
75
20 5 25Time
1030 on
0 35stream
5 40 10(h)
45 0
50 555 10
30 60 15
65 20
70 25
75
10 Time
15
15 020on5 stream
25 1030 (h)
0 35 5 40 10
20
45 50
0 55
5 60
10 65
15 70
20 75
25
Time on stream10(h)
0 5 25 1030 0 35 5 40 1045 0
50 5
55 10
60 15
65 20
70 25
75
0
Time on stream (h)
0 55 10
10 15 20 250 30
5 35
10 40
15 45 0 50 5 5510 6015650 705 75
10 80
15 85
20
Time on stream (h)
Figure 7.4. Oxygenates and alcohol selectivities obtained from the prepared
catalysts. Reac. Cond. as specified in Figure 7.3 (From Paper V). Reprinted from
Lopez at al. [67], Copyright (2016), with permission from Elsevier.
The selectivity to ethanol related to all other alcohol products (C1–

5OH) changes notably in presence of the metal promoters. While
63
ethanol selectivity is 1-2 % on the Cu/MCM-41 and Cu-K/MCM-41
catalysts, this increases to 30 % with the Cu-Fe/MCM-41 catalyst.
By combining Fe and K promoters (Cu-Fe-K/MCM-41 catalyst) the
ethanol selectivity is even boosted up to 41 %.
Besides the fact that the ethanol selectivity is enhanced by action of

the metal promoters, the syngas conversion and reaction yield are
also increased as reported in Table 7.2. The ethanol yield in the
non-promoted Cu/MCM-41 catalyst is 0.3×10−5 Cmol/gcath, which is
enhanced to 165.5×10−5Cmol/ gcath in the Cu-Fe-K/MCM-41
catalyst. For the latter catalyst, the surface atomic composition,
estimated from XPS analysis is Cu0.34Fe0.08K0.08Si1.00. Further
studies may be made in order to modulate the surface composition
of the Cu-Fe-K/MCM-41 catalyst and, thus boost the ethanol yield.
Table 7.2. Space time yield (STY) of alcohols and other oxygenated compounds
over the mesoporous catalysts. Reac. Cond. as indicated in Figure 7 (From
Paper V). Reprinted from Lopez at al. [67], Copyright (2016), with permission
from Elsevier.
Conv. STY (10-5 C mol/ gcat h)
Catalyst
(%) C1OH C2OH C3-C4OH Acetates* Others**
Cu/MCM-41 2.2 27.3 0.3 0.0 0.0 0.2
Cu-K/MCM-41 2.8 42.9 0.8 0.1 0.0 0.0
Cu-Fe/MCM-41 10.0 307.2 159.2 61.4 46.4 101.8
Cu-Fe-K/MCM-41 4.9 145.4 165.5 83.3 53.0 59.4
* Methyl acetate and ethyl acetate. ** Propanal, acetaldehyde and acetic acid.
7.4. Anderson–Schulz–Flory (ASF) distribution
The plotting of product distribution in the form of ASF distribution

(Fig. 9 in Paper V) indicates that the hydrocarbon distribution
from the Cu/MCM-41 catalyst is quite similar to the one from the
Cu-K/MCM-41 catalyst, suggesting that a similar reaction
mechanism occurs in both catalysts. This mechanism may be
related to formation of oxygenated compounds, especially
64
methanol, as observed from the selectivity trends (Figure 7.4).
Thus, this may be initially related to the CO non-dissociation
and/or CO insertion mechanisms. In the same way, the
hydrocarbon distribution obtained from the Cu-Fe/MCM-41 and
Cu-Fe-K/MCM-41 catalysts are similar (Figure 9 in Paper V). This
can be associated to the formation of hydrocarbon compounds
(Figure 7.4) and thus to the CO dissociation mechanism.
Further and detailed studies are needed to clarify the reaction

mechanism over the Cu-Fe-K/MCM-41 catalyst. We believe that a
synergic combination of CO non-dissociation, CO dissociation and
CO insertion takes place which boosts the alcohol formation, in
particular the ethanol formation.
65
CHAPTER 8
Conclusions
8.1. Main results of this work
Large efforts are being carried out in order to diversify fuel sources
in the transportation sector, specially the generation of renewable
biofuels. This aims to reduce the fossil fuel dependency and the
abatement of GHG emissions. First-generation biofuels, obtained
from food-related biomass (e.g. corn, sugar cane or vegetable oils)
have some disadvantages for larger production in terms of land
and water availability. As an alternative source of biomass, in
recent years, forest and agricultural biomass as well as municipal
solid waste and different industrial waste products are being
evaluated for producing the so-called second-generation biofuels.
One route for biomass manufacturing is the thermochemical

process, in which biomass resources are converted into syngas
which is subsequently catalytically converted into liquid and
gaseous fuels. One of the most commercialized biofuels is
bioethanol, which is used as a pure fuel or blended with gasoline.
During the last years, some thermochemical plants for bioethanol
production were launched and another is under construction. A
total of about 290 million liters of ethanol are expected to be
processed per year via the thermochemical route, mostly using
municipal solid waste. Some critical parameters for ethanol
manufacturing are the biomass cost and the plant capacity (volume
production of >200x103 ton of ethanol/year is desired in order to
obtain a favorable economy of scale).
An essential stage in the ethanol production from biomass is the

final catalytic conversion of syngas to ethanol. In this stage,
considerable effort has been made in order to find a catalyst
selective for the desired product, i.e. ethanol. A novel type of
67
catalysts is the mesoporous catalysts based on mesoporous support
which have a 1D-porous ordering with pore diameters of around 2-
10nm. Few studies have been made using this kind of catalysts for
the conversion of syngas to fuels. The first part of the work
presented is focused on the performance evaluation of mesoporous
Rh/MCM-41 catalyst (MCM-41 is a hexagonal mesoporous silica).
Under identical reaction conditions (level of syngas conversion,

metal dispersion, pressure and temperature) the mesoporous
Rh/MCM-41 has shown different product distribution as compared
to typical Rh/SiO2 catalyst. Additional experiments were made in
order to clarify the results obtained; i) water was added to the
syngas feed-stream, ii) the hydrogen partial pressure was modified
by changing the syngas feed-stream ratio (H2/CO), iii) testing for a
wide range of conversion levels (1-68 %) and iv) different catalyst
reduction temperatures (no-reduction, reduction at 200 °C and
reduction at 500 °C). Also, the catalysts were characterized (XRD,
BET, XPS, chemisorption, TEM and TPR) before and after the
catalytic testing. So, analyzing these results we conclude that the
different product selectivities obtained over the mesoporous
Rh/MCM-41 is mainly due to the porous ordering of the catalyst,
in which water vapor can be concentrated and then the water-gas-
shift reaction promoted. Water vapor is the main by-product
generated in most of the catalytic reactions of syngas. The
occurrence of the water gas shift reaction in turn induces side
reactions thus changing the product distribution, as compared to a
typical Rh/SiO2 catalyst which does not have porous ordering. The
extra hydrogen generated from the water-gas-shift reaction could
facilitate the hydrogenation of acetic acid and/or acetaldehyde (or
some C2-oxygenated intermediary) to ethanol and, this could be
related to the higher selectivity to ethanol observed in Rh/MCM-41
(24 %) compared to Rh/SiO2 (8 %).
The second part of the work was focused on the evaluation of the
effect of metal promoters such as Fe and K on the catalytic
68
performance of a Cu/MCM-41 catalyst. Firstly, the non-promoted
Cu/MCM-41 catalyst produces more oxygenated products than
hydrocarbons; this result is the opposite of that obtained from
typical Cu/SiO2 catalyst. The suggested explanation is that some
water vapour could concentrate in the 1D-pores of this catalyst,
Cu/MCM-41, affecting the product distribution. The addition of
both K and Fe to the Cu/MCM-41 catalyst causes a large
deterioration of the pore structure, resulting in a minor or
negligible water vapor concentration in these catalysts. The most
interesting result obtained from the Cu-Fe-K/MCM-41 catalyst,
was the noticeable increase of the reaction rate to ethanol as
compared to the non-promoted Cu/MCM-41 catalyst; in terms of
space time yield 0.3×10−5 carbon-mol/gcath and 165.5×10−5carbon-
mol/gcath, respectively. This result could be ascribed to a synergic
action of both K and Fe promoters, favoring the CO non-
dissociation and CO dissociation mechanism, respectively. From
XPS analysis, the atomic surface composition in this catalyst has
been found equal to Cu0.34Fe0.08K0.08Si1.00. Further studies are
needed in order to boost the yield to ethanol even more by
modulating the surface composition in the Cu-Fe-K/MCM-41
catalyst.
8.2. Final remarks and future work
The work presented in this thesis has contributed to increasing the

knowledge concerning the syngas conversion using mesoporous
catalysts. The findings concerning water vapor concentration in the
pores of mesoporous catalysts have not been extensively reported
in the literature. Nor, more importantly, the effect of the water
vapor concentration over the product distribution. Although
several experimental techniques have been used to evaluate the
catalytic performance of the mesoporous catalysts, further and
more detailed characterization is desirable. For example, in-situ
techniques such as FT-IR spectroscopy can give greater insight
concerning the water vapor concentration in the mesopores of the
69
catalysts. Also, the results obtained in this work can be further
evaluated by theoretical approaches (computational catalysis) and
if possible by a micro-kinetic model. Specially, the occurrence of
the water gas shift reaction in the mesoporous catalysts and its
effect on the product distribution.
Another aspect that deserves further study is the incorporation of

nano-metal particles, with a diameter of about 2nm or smaller,
inside the 1D-pore of mesoporous catalysts, which have a pore
diameter of about 3 nm. Moreover, the incorporation of multi-
metal promoters inside the pores would result in a synergic
combination of; i) CO dissociation activity (e.g. Fe promoter), ii)
CO non-dissociation activity (e.g. Cu and Cu-K promoters) and iii)
water vapor concentration which promotes the water gas shift
reaction. The microemulsion method could be exploited for the
incorporation of multi-metal promoters, allowing the preparation
of monodispersed nanoparticles with controlled size.
70
Nomenclature
1D 1-Dimensional
AAS Atomic Absorption Spectroscopy
ASF Anderson-Schulz-Flory
BE Binding energy
BET Brunauer-Emmett-Teller
C1-8OH Mixture of alcohols from methanol to octanol
CTAB Cetyltrimethylammonium bromide
CTL Carbon to Liquids
DME Di-Methyl Ether
DTG Differential thermogravimetric analysis
E10 A blend of 10 % ethanol and 90 % gasoline by volume
E85 A blend of 85 percent ethanol and 15 % by volume
gasoline
FFV Flexible fuel vehicle
FID Flame ionization detector
FTS Fischer-Tropsch Synthesis
GC Gas chromatograph
GoBiGas Gothenburg Biomass Gasification Project
GTL Gas to Liquids
GHSV Gas hourly space velocity
HTFT High temperature Fischer-Tropsch synthesis
ktons Thousands of tons
LCT Liquid crystal templating
LTFT Low temperature Fischer-Tropsch synthesis
MFC Mass flow controller
MSR Methane steam reforming
MSW Municipal solid waste
PSRK Predictive Soave-Redlich-Kwong (equation of state)
SEM Scanning electron microscopy
SNG Synthetic natural gas
STY Space time yield
TEA Triethanolamine
TCD Thermal conductivity detector
71
TEOS Tetraethyl orthosilicate
TEM Transmission electron microscopy
TGA Thermogravimetric analysis
TPR Temperature programmed reduction
vt.% Percentage in terms of volume
XRD X-ray diffraction
wt.% Percentage in terms of mass
WGSR Water-gas shift reaction
XPS X-Ray Photoelectron Spectroscopy
72
Acknowledgements
First and foremost, I would like to thank my supervisors Associate
Professor Magali Boutonnet and Professor Sven Järås for giving
me the opportunity to carry out doctoral studies at the division of
Chemical Technology. I appreciate their patience, support,
confidence in me and my work and, the possibilities you gave me
to participate in conferences. I want to acknowledge to Dr. Saul
Cabrera for his supervision, support and friendship. Thanks also to
Associate Professor Henrik Kušar for his interest and supervision
during the last years of my studies.
I would also like to acknowledge the Swedish International

Development Cooperation Agency (SIDA) for financial support,
and thus making this work possible.
I would like to thank Professor Lars J. Pettersson for his cordiality

and good humor. I am indebted to Robert Andersson for guidance
with experimental work and friendship. Also, I want to express my
sincere gratitude to Rolando Zanzi for his help and friendship
during all these years. Thanks to Yohannes Kiros for his kindness
and support.
Thanks to all colleagues at Chemical Technology for making the

department a stimulating and friendly workplace. I learned a lot
from the formal discussions at the Catalysis Meetings, as well as
after, in the informal discussions in the coffee room.
The largest thank you goes to Jorge Velasco, Mauricio Ormachea

and Adhemar Araoz for sharing with me the experience of being a
“sandwich” doctoral student. I will remember the discussions that
had did about almost everything (academy, science-technology,
politics, life...) and of course the great moments doing sports; wa-
sáá at the “international football matches”, volleyball and
swimming.
73
I had the opportunity to meet very nice people from different
countries at Chemical Technology. Special thanks to Robert
Andersson, Sara Lögdberg, Mattelo Lualdi, Francesco Regali,
Xanthias Karatzas, Moa Ziethén Granlund, Vera Nemanova, and
Angelica González for good times and fruitful experiences. Thanks
to Fatima Pardo, Rodrigo (Rodri) Suárez, Javier (Barri) Barrientos,
Pouya Haghighi, Francesco Montecchio, Jonas Granestrand,
Alagar Raj Paulraj, Jerry Solis, Sandra Dahlin, Lina Norberg
Samuelsson and Zari Musavi for your kindness and good humor.
Special thanks to Otto von Krusenstierna for being an inspiration
of scientific enthusiasm and charisma at social events. I am also
grateful to Christina Hörnell for correcting and improving the
linguistic quality of this thesis and appended papers.
I would like to thank Oscar Laguna and Mariarosa Brundu who

were source of enthusiasm while doing their research stay at
Chemical Technology. Thanks to Vicente Montes for collaborating
in TEM and XPS analyses and interpretation.
Furthermore, I am grateful to Avelino Corma, Susana Valencia and

Urbano Díaz from the Instituto de Tecnología Química (ITQ) in
Valencia, Spain for receiving me for a short research stay. Special
thanks to Raquel Simancas, Diego Cómbita and Yannick Mathieu
for your support and friendship.
Many thanks to my colleagues at the Natural Gas Institute (IGN-

UMSA) and Chemical Research Institute (IIQ-UMSA) in La Paz,
Bolivia, for their support and friendship. Special thanks to Ronald
Escobar, Cristhian Fernández and Pedro Limachi for their
enthusiasm, good work and friendship. Thanks to all the persons
who made their research project (graduate and postgraduate
scholarship holders) at IGN and IIQ during these years, for sharing
not only work, but also nice social activities.
The deepest thanks go to the memory of mom (mamá Silvia) for all
the love and support. Finally, I would like to thank all my family,
74
especially my wife Hemilse and my son Matias for your patience,
understanding and love.
75
References
[1] Key World Energy Statistics, International Energy Agency, Paris,
France, 2016, p. 80.
[2] Population Estimates and Projections, The World Bank
(http://datatopics.worldbank.org/hnp/popestimates#), Accessed
06/10/2016.
[3] Renewable Energy: bioenergy, International Energy Agency,
https://www.iea.org/topics/renewables/subtopics/bioenergy/, Accessed
20/09/2016.
[4] Global Bioenergy Supply and Demand Projections: A working paper
for REmap 2030, International Renewable Energy Agency, 2014, p. 80.
[5] S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva, An overview of
the chemical composition of biomass, Fuel, 89 (2010) 913-933.
[6] R.C. Brown, Thermochemical processing of biomass conversion into
fuels, chemicals and power, Chichester, West Sussex, Wiley, 2011.
[7] K.R. Cummer, R.C. Brown, Ancillary equipment for biomass
gasification, Biomass and Bioenergy, 23 (2002) 113-128.
[8] R. Warnecke, Gasification of biomass: comparison of fixed bed and
fluidized bed gasifier, Biomass and Bioenergy, 18 (2000) 489-497.
[9] S.Q. Turn, C.M. Kinoshita, D.M. Ishimura, T.T. Hiraki, J. Zhou, S.M.
Masutani, An Experimental Investigation of Alkali Removal from Biomass
Producer Gas Using a Fixed Bed of Solid Sorbent, Industrial &
Engineering Chemistry Research, 40 (2001) 1960-1967.
[10] L. Devi, K.J. Ptasinski, F.J.J.G. Janssen, A review of the primary
measures for tar elimination in biomass gasification processes, Biomass
and Bioenergy, 24 (2003) 125-140.
[11] R. Suarez Paris, L. Lopez, J. Barrientos, F. Pardo, M. Boutonnet, S.
Jaras, Chapter 3 Catalytic conversion of biomass-derived synthesis gas to
fuels, Catalysis: Volume 27, The Royal Society of Chemistry, 2015, p. 62-
143.
[12] J.A. Velasco, L. Lopez, M. Velásquez, M. Boutonnet, S. Cabrera, S.
Järås, Gas to liquids: A technology for natural gas industrialization in
Bolivia, Journal of Natural Gas Science and Engineering, 2 (2010) 222-
228.
76
[13] Database on facilities for the production of advanced liquid and
gaseous biofuels for transport, BIOENERGY 2020+: International Energy
Agency, Accessed 26/09/2016 (http://demoplants.bioenergy2020.eu/).
[14] Gothenburg Biomass Gasification Project, GoBiGas, Göteborg
Energi (Sweden), Accessed 30/09/2016
(http://www.goteborgenergi.se/English/Projects/GoBiGas__Gothenburg
_Biomass_Gasification_Project).
[15] R.C. Brown, Thermochemical processing of biomass: conversion into
fuels, chemicals and power, Wiley, Chichester, Wiley, 2011.
[16] R. Sims, M. Taylor, J. Saddler, W. Mabee, From 1st- and 2nd-
Generation Biofuels Technologies: An Overview of Current Industry and
RD&D Activities, International Energy Agency Bioenergy, Paris, 2008.
[17] R.E.H. Sims, W. Mabee, J.N. Saddler, M. Taylor, An overview of
second generation biofuel technologies, Bioresource Technology, 101
(2010) 1570-1580.
[18] J. He, W. Zhang, Techno-economic evaluation of thermo-chemical
biomass-to-ethanol, Applied Energy, 88 (2011) 1224-1232.
[19] M.D. Jackson, C.B. Moyer, Alcohol Fuels, Kirk-Othmer Encyclopedia
of Chemical Technology, John Wiley & Sons Inc., 2000.
[20] C. Wix, Process for synthesis of alcohols, Patent: WO 2013/120548
A1, Haldor Topsoe, 2013.
[21] E. Chornet, B. Valsecchi, Y. Avila, B. Nguyen, J.M. Lavoie, Production
of ethanol from methanol, Patent US 2009/0221725 A1, Enerkem, Inc.,
2009.
[22] Enerkem, Introduction to Enerkem, October 2014, p. 1-23.
[23] Coskata; Process Overview
(http://www.coskata.com/process/index.asp?source=7E352957-657F-
44D4-8CEC-3FCA8BBB2D7C), Accessed 21/05/2015.
[24] INEOS Bio; Technology Platform
(http://www.ineos.com/businesses/ineos-bio/technology/#gasification),
Accessed 21/05/2015.
[25] G.F.T. Orías, J.A. Lordemann, L.F. Buch, A.B. Lanchez, J.C.G. Salinas,
M.F. Fuentes, R.O. Lafuente, R.R. Zurita, E.G. D’Angelo, Perspectivas de
la Matriz Energética Boliviana, Fundación Hanns Seidel, 2011.
[26] Ley para el manejo y tratamiento de la basura, Ministerio de Medio
Ambiente y Agua de Bolivia, Accessed 07/10/2016
(http://www.mmaya.gob.bo/index.php/noticias/0,1434.html).
77
[27] L.F. Vincenti, Estado del Arte y Novedades de la Bioenergía en
Bolivia, Organización de las Naciones Unidas para la Alimentación y la
Agricultura (FAO), 2011.
[28] L. Lopez, Evaluación de la tecnología disponible para la producción
de etanol y alcoholes superiores, in Ciencia y Tecnología en Bolivia:
Estado del arte de procesos industriales para el sector de hidrocarburos
y petroquimico, Editors: S. Cabrera and L. Lopez, Instituto del Gas
Natural - Universidad Mayor de San Andrés, La Paz, Bolivia, 2016, p. 52.
[29] A. Dutta, M. Talmadge, J. Hensley, M. Worley, D. Dudgeon, D.
Barton, P. Groenendijk, D. Ferrari, B. Stears, E. Searcy, C. Wright, J.R.
Hess, Techno-economics for conversion of lignocellulosic biomass to
ethanol by indirect gasification and mixed alcohol synthesis,
Environmental Progress & Sustainable Energy, 31 (2012) 182-190.
[30] S. Chovau, D. Degrauwe, B. Van der Bruggen, Critical analysis of
techno-economic estimates for the production cost of lignocellulosic
bio-ethanol, Renewable and Sustainable Energy Reviews, 26 (2013) 307-
321.
[31] Reglamento de Calidad de Carburante y Lubricantes, Gaceta Oficial
de Bolivia, Decreto Supremo No. 1499, 2013.
[32] J.J. Spivey, A. Egbebi, Heterogeneous catalytic synthesis of ethanol
from biomass-derived syngas, Chemical Society Reviews, 36 (2007)
1514-1528.
[33] V. Subramani, S.K. Gangwal, A review of recent literature to search
for an efficient catalytic process for the conversion of syngas to ethanol,
Energy & Fuels, 22 (2008) 814-839.
[34] N.D. Subramanian, J. Gao, X. Mo, J.G. Goodwin Jr, W. Torres, J.J.
Spivey, La and/or V oxide promoted Rh/SiO2 catalysts: Effect of
temperature, H2/CO ratio, space velocity, and pressure on ethanol
selectivity from syngas, Journal of Catalysis, 272 (2010) 204-209.
[35] D. Mei, R. Rousseau, S.M. Kathmann, V.-A. Glezakou, M.H.
Engelhard, W. Jiang, C. Wang, M.A. Gerber, J.F. White, D.J. Stevens,
Ethanol synthesis from syngas over Rh-based/SiO2 catalysts: A combined
experimental and theoretical modeling study, Journal of Catalysis, 271
(2010) 325-342.
[36] Y. Liu, K. Murata, M. Inaba, I. Takahara, K. Okabe, Synthesis of
ethanol from syngas over Rh/Ce1-xZrxO2 catalysts, Catal. Today, 164
(2011) 308-314.
78
[37] C. Li, J. Liu, W. Gao, Y. Zhao, M. Wei, Ce-Promoted Rh/TiO2
Heterogeneous Catalysts Towards Ethanol Production from Syngas,
Catal. Lett., 143 (2013) 1247-1254.
[38] X. Yang, X. Zhu, R. Hou, L. Zhou, Y. Su, The promotion effects of Pd
on Fe-Cu-Co based catalyst for higher alcohols synthesis, Fuel Process.
Technol., 92 (2011) 1876-1880.
[39] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck,
Ordered mesoporous molecular sieves synthesized by a liquid-crystal
template mechanism, Nature, 359 (1992) 710-712.
[40] G. Ertl, H. Knözinger, J. Weitkamp, Handbook of Heterogeneous
Catalysis, VCH, Weinheim, 1997.
[41] A. Martínez, G. Prieto, The Application of Zeolites and Periodic
Mesoporous Silicas in the Catalytic Conversion of Synthesis Gas, Topics
in Catalysis, 52 (2009) 75-90.
[42] A. Wingen, F. Kleitz, F. Schüth, Ordered Mesoporous Materials:
Preparation and Application in Catalysis, in: M. Baerns (Ed.) Basic
Principles in Applied Catalysis, Springer, Berlin, Heidelberg, 2004, p. 281-
319.
[43] C.J. Brinker, G.W. Scherer, CHAPTER 3 - Hydrolysis and
Condensation II: Silicates, Sol-Gel Science, Academic Press, San Diego,
1990, p. 96-233.
[44] S. Biz, M.L. Occelli, Synthesis and Characterization of
Mesostructured Materials, Catalysis Reviews, 40 (1998) 329-407.
[45] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D.
Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B.
Higgins, J.L. Schlenker, A new family of mesoporous molecular sieves
prepared with liquid crystal templates, Journal of the American Chemical
Society, 114 (1992) 10834-10843.
[46] X.S. Zhao, G.Q. Lu, G.J. Millar, Advances in Mesoporous Molecular
Sieve MCM-41, Industrial & Engineering Chemistry Research, 35 (1996)
2075-2090.
[47] J.G. Verkade, Main group atranes: chemical and structural features,
Coordination Chemistry Reviews, 137 (1994) 233-295.
[48] Perkin Elmer Informatic Inc., Chem3D Professional, 2016.
[49] S. Cabrera, J. El Haskouri, C. Guillem, J. Latorre, A. Beltrán-Porter, D.
Beltrán-Porter, M.D. Marcos, P. Amorós, Generalised syntheses of
79
ordered mesoporous oxides: The atrane route, Solid State Sci, 2 (2000)
405-420.
[50] M. Bowker, On the mechanism of ethanol synthesis on rhodium,
Catal. Today, 15 (1992) 77-100.
[51] Y.M. Choi, P. Liu, Mechanism of Ethanol Synthesis from Syngas on
Rh(111), J. Am. Chem. Soc., 131 (2009) 13054-13061.
[52] R. Zhang, X. Sun, B. Wang, Insight into the Preference Mechanism of
CHx (x=1-3) and C-C Chain Formation Involved in C2 Oxygenate Formation
from Syngas on the Cu(110) Surface, J. Phys. Chem. C, 117 (2013) 6594-
6606.
[53] M. Gupta, M.L. Smith, J.J. Spivey, Heterogeneous Catalytic
Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based
Catalysts, ACS Catal., 1 (2011) 641-656.
[54] C.H. Bartholomew, R.J. Farrauto, Fundamentals of Industrial
Catalytic Processes, New Jersey, Second ed., Wiley-Interscience, 2006.
[55] J. El Haskouri, S. Cabrera, C. Guillem, J. Latorre, A. Beltrán, D.
Beltrán, M.D. Marcos, P. Amorós, Atrane Precursors in the One-Pot
Surfactant-Assisted Synthesis of High Zirconium Content Porous Silicas,
Chemistry of Materials, 14 (2002) 5015-5022.
[56] M.S. Cabrera, Química en medios organizados para la obtención de
nuevas alúminas, aluminosilicatos y ALPOs mesoporosos con tamaño de
poro modulable. PhD thesis, Instituto Universitario de Ciencia de los
Materiales, Universitat de Valencia, Valencia, Spain, 1999.
[57] R. Andersson, M. Boutonnet, S. Järås, On-line gas chromatographic
analysis of higher alcohol synthesis products from syngas, Journal of
Chromatography A, 1247 (2012) 134-145.
[58] R.J. Madon, M. Boudart, Experimental criterion for the absence of
artifacts in the measurement of rates of heterogeneous catalytic
reactions, Industrial & Engineering Chemistry Fundamentals, 21 (1982)
438-447.
[59] R.P. Underwood, A.T. Bell, Influence of particle size on carbon
monoxide hydrogenation over silica- and lanthana-supported rhodium,
Applied Catalysis, 34 (1987) 289-310.
[60] L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås, Effect of
syngas conversion and catalyst reduction temperature in the synthesis
of ethanol: concentration of water vapor in mesoporous Rh/MCM-41
catalyst, Catalysis Communications, 69 (2015) 183-187.
80
[61] J.B. Hansen, P.E. Højlund Nielsen, Methanol Synthesis, in: G. Ertl, H.
Knözinger, J. Weitkamp (Eds.) Handbook of Heterogeneous Catalysis,
VCH, Weinheim, 2008.
[62] M.V. Landau, S.P. Varkey, M. Herskowitz, O. Regev, S. Pevzner, T.
Sen, Z. Luz, Wetting stability of Si-MCM-41 mesoporous material in
neutral, acidic and basic aqueous solutions, Microporous and
Mesoporous Materials, 33 (1999) 149-163.
[63] A. Borodziński, M. Bonarowska, Relation between Crystallite Size
and Dispersion on Supported Metal Catalysts, Langmuir, 13 (1997) 5613-
5620.
[64] S.D. Robertson, B.D. McNicol, J.H. De Baas, S.C. Kloet, J.W. Jenkins,
Determination of reducibility and identification of alloying in copper-
nickel-on-silica catalysts by temperature-programmed reduction, Journal
of Catalysis, 37 (1975) 424-431.
[65] J. Panpranot, J.G. Goodwin Jr, A. Sayari, Synthesis and
characteristics of MCM-41 supported CoRu catalysts, Catalysis Today, 77
(2002) 269-284.
[66] A. Egbebi, J.J. Spivey, Effect of H2/CO ratio and temperature on
methane selectivity in the synthesis of ethanol on Rh-based catalysts,
Catalysis Communications, 9 (2008) 2308-2311.
[67] L. Lopez, V. Montes, H. Kušar, S. Cabrera, M. Boutonnet, S. Järås,
Syngas conversion to ethanol over a mesoporous Cu/MCM-41 catalyst:
Effect of K and Fe promoters, Applied Catalysis A: General, 526 (2016)
77-83.
[68] G.R. Sheffer, T.S. King, Potassium's promotional effect of
unsupported copper catalysts for methanol synthesis, Journal of
Catalysis, 115 (1989) 376-387.
[69] L.E.Y. Nonneman, V. Ponec, On the problem of the activity in
methanol synthesis of supported, unpromoted copper catalysts,
Catalysis Letters, 7 (1990) 213-217.
[70] S.V. Sirotin, I.F. Moskovskaya, B.V. Romanovsky, Synthetic strategy
for Fe-MCM-41 catalyst: a key factor for homogeneous or
heterogeneous phenol oxidation, Catalysis Science & Technology, 1
(2011) 971-980.
[71] L.E.Y. Nonneman, V. Ponec, Promotion and support effects in
syngas reactions, Catalysis Letters, 7 (1990) 197-203.
81
[72] A. Gotti, R. Prins, Basic Metal Oxides as Cocatalysts for Cu/SiO2
Catalysts in the Conversion of Synthesis Gas to Methanol, Journal of
Catalysis, 178 (1998) 511-519.
[73] M. Boutonnet, S. Lögdberg, E. Elm Svensson, Recent developments
in the application of nanoparticles prepared from w/o microemulsions in
heterogeneous catalysis, Curr. Opin. Colloid Interface Sci., 13 (2008) 270-
286.
[74] A.-M. Hilmen, M. Xu, M.J.L. Gines, E. Iglesia, Synthesis of higher
alcohols on copper catalysts supported on alkali-promoted basic oxides,
Applied Catalysis A: General, 169 (1998) 355-372.
82

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Catalytic conversion of

syngas to ethanol and higher

Doctoral Thesis in Chemical Engineering

TRITA-CHE Report 2017:2

Akademisk avhandling som med tillstånd av Kungliga Tekniska

© Luis Gagarin Lopez Nina 2017

Tryck: Universitetsservice US-AB

The thesis is the summary of five publications. The first two

Keywords: thermochemical process, ethanol, higher alcohols,

Avhandlingen är en sammanfattning av fem publikationer. De två

Nyckelord: termokemisk process, etanol, högre alkoholer,

I. R. Suárez, L. Lopez, J. Barrientos, F. Pardo, M. Boutonnet,

II. J.A. Velasco, L. Lopez, M. Velasquez, M. Boutonnet, S.

III. L. Lopez, J. Velasco, V. Montes, A. Marinas, S. Cabrera, M.

IV. L. Lopez, Jorge Velasco, Saul Cabrera, Magali Boutonnet,

Contribution to appended papers

I. I have contributed to all sections by discussion with the all

II. J. Velasco is the main author of this paper and I had

III. I am the main author of this paper. J. Velasco helped in TPR

IV. I am the main author of this paper. J. Velasco helped with

V. I am the main author of this paper. V. Montes performed the

J.A. Velasco, L. Lopez, S. Cabrera, M. Boutonnet, S. Järås

J.A. Velasco, C. Fernandez, L. Lopez, S. Cabrera, M.

L. Lopez, L. Quispe, P. Crespo, M. Litter, S. Cabrera.

L. Quispe, L. Lopez, V. Teixeira, S. Cabrera

M. Alacama, L. Lopez, J. Velasco, F. Gracia, W. Yapu, S.

S. Cabrera, L. Lopez (editors)

L. Lopez, L. Quispe, P. Crespo, M. Boutonnet, S. Järås, M. Litter, S.

L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

L. Lopez, J. Velasco, S. Cabrera, M. Boutonnet, S. Järås

1.1 Setting the scene

Biofuels are produced from renewable organic material (obtained

The work included in this thesis was mostly conducted at the

Thermochemical processing of biomass: fuels for

The composition of biomass depends on its origin. Proximate

i) Pretreatment and ii) Cleaning and

iii) Catalytic Synthesis and

- Synthetic Natural Gas

Figure 2.1: Fuels obtained from the thermochemical processing of biomass.

2.1 Biomass pre-treatment and gasification

Raw biomass must be pretreated and converted into a suitable

− Size reduction, smaller particles have larger surface area

After the pretreatment step, the biomass is thermally processed via

The product composition, obtained from the gasification, depends

- Type of gasifier. Various kinds of gasifiers have been

The gasification product needs further processing in order to

2.3 Catalytic synthesis of fuels

Traditional fuels such as gasoline and diesel as well as alternative

The simplest reaction that converts syngas into a fuel is the

2.3.2 Gasoline and Diesel

The Fischer-Tropsch Synthesis (FTS) refers to the conversion of

Considerable efforts have been made by several institutions in

2.3.3 Di-Methyl Ether

DME is an alternative fuel for compression-ignition engines

2.3.4 Ethanol and Higher Alcohols

Currently, ethanol grade fuel is being obtained from biochemical

The production of ethanol, and also higher alcohols, via the

Ethanol and Higher Alcohols Synthesis

3.1 Alcohols as motor fuels

Table 3.1 summarizes the basic properties of alcohols as compared

MW (g/mol) 16.80 32.04 46.07 41.68 46.07 100-105 200

CO+1/2H2 CO+H HCO+2H CH3O*