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Department of
Chemical Engineering,
DIPONEGORO
UNIVERSITY
Bulletin of Chemical Reaction
Engineering & Catalysis
ISSN 1978-2993
Chemical Reaction
(CREC) Group
Bull. Chem. React.
Eng. Catal.
Vol. 3 No. 1-3 1 62
Semarang
December 2008
ISSN
1978-2993
Masyarakat Katalisis
IndonesiaIndonesian
Catalyst Society
(MKICS)
Secondar yStor y He adlin e
Volume 6, Number 2, Year 2011, 1 November 2011
Bulletin of Chemical Reaction
ISSN 1978-2993
An Electronic Journal. Available online at: http://bcrec.undip.ac.id/
Bull. Chem. React.
Eng. Catal.
Vol. 6 No. 2 63 152
Semarang
December 2011
ISSN
1978 -2993
Department of Chemical Engineering,
DIPONEGORO UNIVERSITY
Masyarakat Katalis Indonesia
Indonesian Catalyst Society (MKICS)

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Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, i
BULLETIN OF CHEMICAL REACTION ENGINEERING and CATALYSIS (ISSN 1978-2993), an
electronic journal, provides a forum for publishing the novel technology related to chemical reaction engi-
neering and catalysis engineering.

Scientific articles dealing with chemical reaction engineering, catalysis engineering, catalyst characteriza-
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articles, original research report, review articles, short communications, and scientific commentaries in
chemical reaction engineering and catalysis, including: fundamental of catalysis, fundamental of chemical
reaction engineering, chemistry of catalyst, applied chemical reaction engineering, applied catalysis, ap-
plied bio-catalysis, applied bio-reactor, chemical reactor design, catalyst regeneration, and industrial prac-
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AIMS AND SCOPE
ABSTRACTING & INDEXING

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For detail please visit BCREC website: http://bcrec.undip.ac.id
PUBLICATION INFORMATION

Bulletin of Chemical Reaction Engineering and Catalysis (ISSN 1978-2993)
Short journal title: Bull. Chem. React. Eng. Catal.
For year 2012, Volume 7, Number 1 2 are scheduled for publication.
Bulletin of Chemical Reaction Engineering and Catalysis is electronically published via journal website
(http://bcrec.undip.ac.id). The BCREC journal has been distributed by EBSCO PUBLISHING
(ACADEMIC SEARCH COMPLETEhttp://search.ebscohost.com) started from Volume 4 Number 1
Year 2009 to present.

The BCREC journal is published by Department of Chemical Engineering, Diponegoro University, and
Masyarakat Katalis IndonesiaIndonesian Catalyst Society (MKICS)

Commencement of publication: January 2006
Copyright 2011, BCREC, ISSN 1978-2993

Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, ii
EDITOR-IN-CHIEF:
Assoc. Prof. Dr. I. Istadi
Department of Chemical Engineering, Diponegoro University, Jln. Prof. Sudharto, Kampus UNDIP Tembalang, Semarang, Central
Java, INDONESIA 50239; E-mail: bcrec@undip.ac.id

Editorial Member:
Prof. Dr. P. Purwanto, Department of Chemical Engineering, Diponegoro University, Jln. Prof. Sudharto, Kampus UNDIP
Tembalang, Semarang, INDONESIA 50239, E-mail: purwanto@undip.ac.id

Dr. Didi Dwi Anggoro, Department of Chemical Engineering, Diponegoro University, Jln. Prof. Sudharto, Kampus UNDIP
Tembalang, Semarang, INDONESIA 50239, E-mail: anggoro_phd@yahoo.com

Dr. Mohammad Djaeni , Department of Chemical Engineering, Diponegoro University, Jln. Prof. Sudharto, Kampus UNDIP
Tembalang, Semarang, Central Java, INDONESIA 50239, E-mail: mzaini98@yahoo.com
EDITORIAL BOARD
Prof. Dr. Mostafa Barigou
School of Chemical Engineering, University of Birmingham,
Edgbaston, Birmingham B15 2TT, United Kingdom, Tel: +44 (0) 121
414 5277, Fax: +44 (0) 121 414 5324 , Email: m.barigou@bham.ac.uk

Prof. Dr. Raghunath V. Chaudhari
Center for Environmental Beneficial Catalysis, Department of
Chemical and Petroleum Engineering, The University of Kansas,
1501 Wakarusa Dr., Building B-Room 112B, Lawrence, KS 66047-
1803, USA, Phone: 785 864 1634; Fax: 785 864 6051

Prof. Dr. Dmitry Yu. Murzin
Laboratory of Industrial Chemistry and Reaction Engineering, Abo
Akademi University, Biskopsgatan 8, 20500, Turku/bo, Finland, ph:
+ 358 2 215 4985 fax:+ 358 2 215 4479,
e-mail: dmurzin[at]abo.fi

Dr. Yibo Zhou
2351 Gilman Hall, Department of Chemistry, Iowa State University,
USA, Phone: 1-515-294-6986,
Email: yibozhou[at]iastate.edu

Assoc. Prof. Dr. Sibudjing Kawi
Department of Chemical and Biochemical Engineering, National
University of Singapore, Singapore, E-mail:chekawis@nus.edu.sg

Prof. Dr. Ram Prasad
Department of Chemical Engineering and Technology, Institute of
Technology, Banaras Hindu University, India,
E-mail: rprasad.che[at]itbhu.ac.in

Assoc. Prof. Dr. Subagjo
Department of Chemical Engineering, Institut Teknologi Bandung, Jl.
Ganesha 10, Bandung, Indonesia,
E-mail: subagjo@che.itb.ac.id

Prof. Dr. Abdullah M. Busyairi
Department of Chemical Engineering, Diponegoro , University,
Semarang, Indonesia, E-mail: abd_busairi@yahoo.com
Prof. Dr. Nor Aishah Saidina Amin
Chemical Reaction Engineering Group (CREG), Faculty of Chemical
and Natural Resources Engineering, Universiti Teknologi Malaysia,
81310 UTM Skudai, Johor, Malaysia ,
E-mail: profnoraishah@yahoo.com

Prof. Dr. Y. H. Taufiq-Yap
Putra Centre for Catalysis Science and Technology, Department of
Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM
Serdang, Selangor, Malaysia, E-mail: yap@fsas.upm.edu.my

Prof. Dr. Hadi Nur
Ibnu Sina Institute for Fundamental Science Studies, Universiti
Teknologi Malaysia , 81310 UTM Skudai, Johor, Malaysia, E-mail:
hadi@kimia.fs.utm.my

Prof. Dr. Abdul Rahman Mohamed
School of Chemical Engineering, Universiti Sains , Malaysia, 14300
Nibong Tebal, Pulau Penang, Malaysia,
E-mail: chrahman@eng.usm.my

Dr. Hery Haerudin
Research Center for Chemistry, Indonesian Institute Of Sciences (PP
Kimia LIPI), Kawasan PUSPIPTEK, Tangerang, Banten, Indonesia;
E-mail: h.haerudin@katalisis.org ; h_haerudin@yahoo.com

Dr. Yang Hong
Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
457 Zhongshan Road, Dalian 116023, China; E-mail:
yanghong@dicp.ac.cn

Dr. Oki Muraza
CENT & Department of Chemical Engineering, King Fahd University
of Petroleum and Minerals (KFUPM), PO Box 5040 Dhahran 31261
KSA, Saudi Arabia , E-mail: omuraza@kfupm.edu.sa

Prof. Dr. Liu Yan
School of Chemical Engineering , Qinghai University, Xining, China
Email: liuyan_qhu@163.com
INTERNATIONAL ADVISORY EDITORIAL BOARDS

BULLETIN OF CHEMICAL REACTION ENGINEERING & CATALYSIS (ISSN 1978-2993), Volume
6, Number 2, Year 2011 is an electronic journal as a media for communicating all research activities in
Chemical Reaction Engineering and Catalysis fields, and disseminating the novel technology and news
related to chemical reaction engineering, catalyst engineering and science, and catalytic reactor
engineering.

In this issue, articles related to: Applications and Preparation Methods of Copper Chromite Catalysts;
Pressure Drop Hysteresis of Hydrodynamic States in Packed Tower for Foaming Systems; Impeller
Submergence Depth for Stirred Tanks; Catalyst Deactivation Simulation Through Carbon Deposition in
Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst; and System Identification for Experimental Study
for Polymerization Catalyst Reaction in Fluidized Bed are highlighted.

Currently, BCREC journal is an open access electronic journal. Visitors can read and download any full-
text articles for free of charge. However, Authors may pay some processing fees once their articles has
been accepted. The research articles submitted to the BCREC journal will be peer-reviewed by at least two
reviewers. Accepted research articles will be available online (free download) following the journal peer-
reviewing process. Language used in this bulletin is English.

Website address of BCREC journal is: http://bcrec.undip.ac.id, while website address for Online
Submission System is: http://ejournal.undip.ac.id/index.php/bcrec.

Editor would like to appreciate all researchers, academicians, industrial practitioners focused on chemical
reaction engineering and catalysis to contribute to this online journal. This journal is also expected to be a
reputable international journal.

The BCREC journal has been distributed by EBSCO PUBLISHING (ACADEMIC SEARCH
COMPLETEhttp://search.ebscohost.com) started from Volume 4 Number 1 Year 2009 to present.

Assoc. Prof. Dr. I. Istadi (Editor-in-Chief)
Chemical Reaction Engineering & Catalysis Group, Department
of Chemical Engineering, Diponegoro University
E-mail: bcrec@undip.ac.id

PREFACE
Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, iii

TABLE OF CONTENTS
Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, iv
1. Aims and Scope ... (i)
2. Indexing and Abstracting ...(i)
3. Editorial Board .(ii)
4. Preface .. (iii)
5. Table of Content . (iv)
6. Applications and Preparation Methods of Copper Chromite Catalysts: A Review
(R. Prasad, & P. Singh) ......... (63 - 113)
7. Pressure Drop Hysteresis of Hydrodynamic States in Packed Tower for Foaming Systems
(V. Sodhi, & R. Gupta ) ................ (115 - 122)
8. Impeller Submergence Depth for Stirred Tanks
(T. T. Devi, A.P. Sinha, M. Thakre, & B. Kumar ) ......... .(123 - 128)
9. Catalyst Deactivation Simulation Through Carbon Deposition in Carbon Dioxide Reforming over Ni/
CaO-Al2O3 Catalyst
(I. Istadi, D.D. Anggoro, N.A.S. Amin, & D.H.W. Ling ) .................................... (129 - 136)
10. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed
(A. S. Ibrehem) ................................... . (137 - 146)
11. Author Guidelines (2011 version) ........ (147 - 149)
12. Copyright Transfer Agreement ....... . (61 - 62)
13. Submission Information

Applications and Preparation Methods of Copper Chromite
Catalysts: A Review
Ram Prasad
*
, and Pratichi Singh

Department of Chemical Engineering & Technology, Banaras Hindu University, Varanasi 221005, India
* Corresponding Author, E-mail: rprasad.che@itbhu.ac.in (R. Prasad)
Tel.: +91 542 2367323, fax: +91 542 2368092.
Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, 63 - 113
Received: 19th March 2011, Revised: 03rd May 2011, Accepted: 23rd May 2011
Abstract

In this review article various applications and preparation methods of copper chromite catalysts have been
discussed. While discussing it is concluded that copper chromite is a versatile catalyst which not only ca-
talyses numerous processes of commercial importance and national program related to defence and space
research but also finds applications in the most concerned problem worldwide i.e. environmental pollution
control. Several other very useful applications of copper chromite catalysts are in production of clean en-
ergy, drugs and agro chemicals, etc. Various preparation methods about 15 have been discussed which de-
picts clear idea about the dependence of catalytic activity and selectivity on way of preparation of catalyst.
In view of the globally increasing interest towards copper chromite catalysis, reexamination on the impor-
tant applications of such catalysts and their useful preparation methods is thus the need of the time. This
review paper encloses 369 references including a well-conceivable tabulation of the newer state of the art.
Copyright 2011 by BCREC UNDIP. All rights reserved.

Keywords: Copper chromite, Applications, Preparation methods, Review

Citation Guide: R. Prasad, and P. Singh. (2011). Applications and Preparation Methods of Copper Chro-
mite Catalysts: A Review. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2): 63-113

bcrec_829_2011 Copyright 2011, BCREC, ISSN 1978-2993
Available online at BCREC Website: http://bcrec.undip.ac.id
Review Article
Contents
1. Introduction
2. Applications of copper chromite catalysts
2.1 Commercial applications
2.2 Hydrogen production
2.3 Clean energy production
2.4 Vehicular Pollution control
2.5 Desulphurization of hot coal gas
2.6 Mercury capture from hot coal gas
2.7 Removal of aqueous organic waste
2.8 Burning rate catalyst for solid propellants
2.9 Electrodes and Sensors
2.10 Semiconductors
2.11 Drugs and agrochemicals
3. Preparation methods of copper chromite catalyst
3.1 Co-precipitation method
3.2 Co-impregnation method
3.3 Solid state reaction (ceramic method)
3.4 Thermal decomposition of ACOC
3.5 Hydrothermal method
3.6 Nanocasting method (Template technique)
3.7 Hydrolysis of Some soluble salts
3.8 Microemulsion method
3.9 Combustion synthesis
3.10 Flame spray pyrolysis method
3.11 Electroless method
3.12 Sonochemical method
3.13 Metal organic chemical vapour deposition
3.14 Chemical reduction method
3.15 Sol-gel process
4. Conclusion
Acknowledgement
References

1. Introduction
The copper chromite (CuCr2O4) is one of the
most efficient materials, has wide commercial
application as catalysts being used in the unit
processes of organic synthesis such as
hydrogenation [1], dehydrogenation [2],
hydrogenolysis [3], oxidation [4], alkylation [5],
cyclization [6], etc. It can be used in the pollution
abatement as the catalyst to remove aqueous
organic wastes [7], volatile organic compound
(VOC) [8] and vehicular primary emissions [9]
such as CO, unburned hydrocarbon, NOx and
soot. In addition it has been used in various
composite solid propellants as one of the efficient
combustion supporting catalysts [10] in the
domain of space vehicles (rockets) and weapon
industries (high explosives, ballistic missiles).
Furthermore, copper chromite has been proved as
promising catalyst for the production of H2 a
clean energy carrier, by photo-catalytic
phenomena [11-13], conversion of alcohols [14],
water gas shift reaction [15], through sulphur
based thermo-chemical water splitting cycles [16],
etc. The next application of CuCr2O4 is catalyst
for alternative fuels preparations, synthesizing
methanol [17], an important hydrogen carrier;
high alcohol synthesis (HAS) by hydrogenation of
CO or CO2, and fast pyrolysis of biomass [18] to
bio-oil products. The catalyst is also helpful in the
production of drugs and agro chemicals [19]. In
fine chemicals industry for perfumery and
synthesis of fragrances [20] CuCr2O4 is used as
catalysts. The CuCr2O4 catalyst is useful in
desulphurization sorbents for hot coal gas in
integrated gasification combined cycle (IGCC)
power plants [21,22]. Several other uses of
CuCr2O4 are electrodes and sensors [23],
semiconductors [24], heat-resistant pigment [25],
etc.
Many research projects sanctioned [12, 26-29],
several Ph.D. theses approved [30-34], a number
of patents granted [35-39] and numerous studies
[14,15,17,19,40-42] have been conducted on
innovative preparation methods and utilizations
of the copper chromite catalysts. However,
preparation methods and utilizations of such
catalysts have hardly been reviewed so far. Owing
to the recurrently expanding interest the world
over on the application of copper-chromite
catalysts, this brief article is an attempt to
summarise the applications of the copper
chromite catalytic systems and to review their
various useful preparation methods. This review
paper will be beneficial to the research
community as well as industries and national
programs related to defence and space research in
understanding the progress of preparation
methods and applications of copper chromite
catalysts.

2. Application of copper chromite catalysts
2.1 Commercial application
2.1.1 Hydrogenation
Catalytic hydrogenation is undoubtedly the
most useful and widely applicable method for the
reduction of chemical substances, and has found
numerous applications in organic synthesis in
research laboratories and industrial processes
[42]. Copper chromite is an industrially important
catalyst because of its ability to hydrogenate
functional groups in aliphatic and aromatic
compounds selectively. It is employed in both
vapour-phase (e.g. hydrogenation of nitrobenzene
and nitrotoluenes to their corresponding amines)
and liquid phase (e.g. hydrogenation of carbonyl
group in aldehydes, ketones and esters to the
corresponding alcohol) commercial processes [43].
Copper chromite catalyst was first reported by
Adkins et al. [44] to be active for the
hydrogenation of a wide range of organic
compounds. They tested the catalyst in the
hydrogenation of a group of twenty-one organic
compounds in the liquid state at temperature
varying between 150-220
0
C and pressure 100-150
atm, out of twenty-one compounds sixteen have
been successfully hydrogenated in a batch reactor
with 100% yield and 100% selectivity.
The catalysts of copper chromites (chromium
wt.% > 25) have found extensive use in industrial
processes for reducing furfural (C4H3O-CHO) to
furfuryl alcohol (C4H3O-CH2OH), butyraldehyde
or crotonaldehyde to 1-butanol, partially reducing
conjugated dienes to monoenes, and selectively
reducing carbonyl group in vegetable oils and
fatty acid with non-conjugated carbonyl and
ethylenic bonds [45].
The s e l e c t i ve hydr o ge nat i o n o f
polyunsaturated organic compounds [46] attracts
great interest from both industrial and academic
point of view. In fine chemicals industry, we often
need a semi-hydrogenation, for example with
industrial foodstuffs and partial hydrogenation of
edible oils and fatty acids [47] for perfumery and
synthesis of fragrances which require the
selective formation of allylic alcohols [48].

2.1.1.1 Hydrogenation of edible oils
Hydrogenation of edible oils is an important
process because of its wide applications to
produce margarine, frying oils, etc. Vegetable oils
Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2), 2011, 64

contain a mixture of saturated, monounsaturated,
and polyunsaturated fatty acids. The mono- and
polyunsaturated fatty acids have double bonds, all
in the normal cis formation. These bonds can
easily be broken down by oxygen. This produces
compounds that make the oil rancid. Rancidity
produces off-flavours in foods. To control this edible
oil is hydrogenated in the food industry to produce
fats and oils with desirable melting properties and
an improved shelf life.

Edible oil + H2 Margarine (1)

Beside the desired hydrogenation reaction
(eqn.1), trans-isomers of fatty acids are formed as
well [49]. The trans-isomer has been reported to be
undesirable for human diet due to adverse health
effects [50]. It has similar effects as saturated fats
increasing serum cholesterol levels in the blood,
believed to be a major cause of heart disease [51].
The reduction and/or elimination and content of
trans fatty acids in the food supply has attracted
worldwide interest [52-56]. The options to reduce
the trans levels in the hydrogenation of an edible
oil are changing process conditions and applying
selective low trans heterogeneous catalysts [57].
The copper chromite [44] has been extensively
studied due to the high selectivity shown by this
catalyst in the partial hydrogenation of vegetable
oils [58,59]. In particular, many experiments have
been done to correlate catalytic properties with
operational parameters such as temperature [60],
hydrogen pressure [60,61-63], hydrogen flow [64],
catalyst concentration [61,63], substrate
composition [62] and activation procedures [65].
Copper chromite catalysts have long been
known in edible oils hydrogenation as the most
selective for the reduction of linolenate C18:3 to
oleate C18:1 leaving unaffected linoleate C18:2,
valuable component from the nutritional point of
view [59]. The major factor responsible for the
relative instability of soybean oil and other
vegetable oils for food uses is widely recognized as
the linolenate present in the oil [66]. A particular
feature of the copper chromites is their high
selectivity which has been used to advantage in the
hydrogenation of edible oils and fats, where
stronger hydrogenation catalyst, such as nickel can
lead to excessive saturation and inferior
nutritional quality of the final product [67].
Commercially employed Ni catalysts have limited
linolenate selectivity in comparision to copper-
chromite catalyst. Consequently, soybean oil
hydrogenated over Ni catalyst to an iodine value
(IV) of 110 contains 3% linolenate, while copper-
chromite catalyst reducing it to 0.1% [66]. In room
odour evaluations, copper chromite hydrogenated
soybean oil gave higher scores and lower fishy
responses than nickel-hydrogenated soybean oil
after both had been exposed to fluorescent light
[68].
The catalysts are usually charged into the oil in
the oxidized form and are partly reduced to Cu(I)
and/or Cu(0) during use. Pre-reduced copper
chromites have found to be strongly deactivated in
soybean oil hydrogenation due to disappearance of
Cu(II) and Cu(I) species and to the decrement of
Cu/Cr ratio on the catalyst surface [69]. Capece
and co-workers [70] determined the oxidation
states and surface composition of copper chromite
at various stages of catalytic use and after
reductive pre-treatments, and they concluded that
Cu
1
is the active species for double-bond
isomerization while Cu
0
is required for
hydrogenation of conjugated dienes. According to
Rieke et al. [71], activity and selectivity correlate
well with the crystallinity of the copper chromite
surface; they increase with decreasing
crystallinity.
Szukalska and Drozdowski [72] hydrogenated
rapeseed oils with different erucic acid contents
with Adkins type copper-chromite catalyst. The
tested rapeseed oils, after the elimination of
linolenic acid by selective hydrogenation showed
several times higher oxidative stability than the
initial raw material and retained the liquid state
at ambient temperatures.

2.1.1.2 Hydrogenation of aromatic compounds
Adkins copper chromite CuO.CuCr2O4 catalyst
[73] is a rugged one commonly used in
hydrogenations of ethylenic bonds, esters amides
under high pressures and temperatures, but rarely
employed to reduce aromatic compounds. It is less
susceptible to poisons. With this catalyst
phenanthrene [74] and anthracene [75] are
converted to their dihydroderivatives, whereas
naphthalene [76] was converted to tetralin. In
general, copper chromite catalyst is employed in
hydrogenations of compounds where reducible
groups other than aromatic nucleus are to be
hydrogenated in preference, e.g. hydrogenation of
nitrobenzene to aniline [75].
Selective hydrogenation of aromatic nitrogroups
to the corresponding aromatic amines is one of the
most important reactions. There are three main
categories of aromatic nitrogroup hydrogenations
depending on the presence of other functional
groups at the aromatic ring [77]:
a) The first category includes high volume
products, such as aniline and toluene-diamines.

The largest end user of these products is the
polyurethane industry;
b) Category two includes the hydrogenation of
halonitroaromatic compounds. The corresponding
haloanilines are used in the life science and
specialty chemicals industries as intermediates
for the production of pesticides, rubber chemicals,
dyes, pigments and pharmaceuticals;
c) Category three nitrogroup hydrogenations
include the selective hydrogenation of
nitroaromatic compounds to anilines without
hydrogenation of other functional groups present
in the aromatic system [77].
Aniline is an important raw material and
intermediate for the production of dyes, medicine,
agriculture pesticides, antioxidants and
vulcanisation accelerators. It is usually
manufactured by the reduction of

C6H5NO2 + 3H2 C6H5NH2 + 2H2O (2)

Copper chromite is known for its ability to
hydrogenate functional groups in aromatic
compounds selectively without affecting the
benzene nucleus [79]. Fang et al. concluded that
hydrogenation of nitrobenzene is enhanced by
addition of Cr-Cu/SiO2 catalysts [80]. Keki et al.
[81] found that the unreduced copper chromite is
the stable active catalyst for hydrogenation of
nitrobenzene.
The hydrogenation of nitrobenzene to aniline
over reduced Cu(FexCr2x)O4 series of catalysts
(where x=0, 0.2, 0.4, 0.6, 0.8 and 1.0) has been
studied by Jebarathinam et al. [82] at 250
0
C in a
fixed bed flow type reactor. The conversion of
nitrobenzene to aniline is optimum over the
catalysts with composition x=0.4. They compared
the results of reversible and irreversible
adsorption of carbon monoxide with
hydrogenation activity and concluded that
univalent copper at octahedral sites is more
active for hydrogenation than metallic copper.
The second cations [Cr(III) or Fe(III)] develop
their catalytic activity by sharing anionic
vacancies.

2.1.1.3 Perfumery and synthesis of
fragrances
There is a continuing search for synthetic
materials having desirable fragrance properties.
Such materials are used either to replace costly
natural materials or to provide new fragrances of
perfume types which have not theretofore been
available. For perfumery and synthesis of
fragrances semihydrogenation is often needed,
which require the selective formation of allylic
alcohols [20]. During citral (I) hydrogenation at
atmospheric pressure, citronellal (II) nerol (III)
appears simultaneously at the initial stage of the
reaction (Fig. 1). The ratio of the amounts of these
two primary products is about 5 in favour of the
saturated aldehyde (II). Citronellol (IV), the
saturated alcohol appears before complete
consumption of the starting material but remains
a secondary product [46]. The higher amounts of
both primary products (II) and (III) are reached
for the same conversion value which roughly
corresponds almost to the total disappearance of
citral.
Furfuryl alcohol is an important compound in
the fragrance industry. The hydrogenation of
furfural with copper chromite is the industrial
means of producing furfuryl alcohol given by the
eqn. (3) [45].

C4H3OCHO + H2 C4H3OCH2OH (3)

It is well known, a need exists for synthetic
substances which are precious, in demand and
having limited supply such as sandalwood
substitute or extenders. It would be most
desirable to be able to synthetically provide the
major odorant compound of such natural
sandalwood oils such as, -santalol and -
santalol. Weigers et al. [83] described an
economical and novel process for preparing a
mixture containing 2-campholenylidenbutanol
Bulletin of Chemical Reaction Engineering & Catalysis, 6(2), 2011, 66
Fig.1. Hydrogenation of citral at atmospheric pressure [20]
Fig. 2. 2-campholenylidenbutanol [83]

having the structure shown in Fig. 2, by
hydrogenating the compound having structure
given in Fig. 3, in the presence of copper chromite
catalyst. Such mixtures are used in augmenting or
enhancing the aroma of perfume compositions,
colognes and perfumed articles including fabric
softener compositions, cosmetic powders and solid
or liquid anionic, cationic, non-ionic and
zwitteronic detergents.
Giersch and Ohloff [84] discovered the bicyclic
alcohol of formula as shown in the Fig. 4. The
alcohol possesses a natural woody odour with an
ambary character. The woody note is reminiscent
in particular of cedar wood without however
possessing the sawdust character of latter. The
ambary note, on the other hand, is reminiscent of
certain aspects presented by precious materials
such as grey amber. Owing to their odour
properties, the alcohols find an utilisation of wide
scope, both in alcoholic perfumery and in technical
applications such as, in the perfuming of soaps,
powder or liquid detergents, fabric softeners,
household materials, cosmetics, shampoos, beauty
creams, body deodorizers or air fresheners.
A process for the preparation of bicyclic
aliphatic alcohols comprises the following reaction
steps shown in Fig. 5 [84]:


a) the addition of ethyl methacrylate to mycrene
under the conditions of a Diels-Alder type
reaction and the treatment of the resulting
reaction mixture with an acidic cyclization
catalyst;
b) the reduction of the obtained ester by Ni-
CuCr2O4 hydrogenation, and
c) the reduction of the resulting by means of a
usual reduction reagent of the ester formation.

2.1.1.4 Hydrogenation of Alcohols
Long-chain alcohols can be converted directly to
N,N-dimethylalkylamines by the reaction with
dimethylamine at 36
0
C in the presence of of Cu-Cr
catalyst and hydrogen at elevated temperatures
and pressure as shown by eqn. (4) [85,86].

Cu-Cr
RCH
2
OH + HN(CH
3
)
2
RCH
2
N(CH
3
)
2
+ H
2
O (4)
H
2

Ethoxylated tertiary amines can be produced by
the reaction of primary or secondary amines with
ethylene oxide. The asymmetrical tertiary amines
are used exclusively as starting materials for the
manufacture of quaternary ammonium compounds,
cationic and amphoteric surfactants, and amine
oxides. Quaternary ammonium compounds used as
bactericides and algaecides are produced by the
reaction of tertiary amines with benzyl chloride,
methyl chloride, or dimethyl sulphate. Of these,
the benzyl ammonium chloride salt is the most
widely used [87].

2.1.1.5 Hydrogenation of aldehydes
Copper-chromium oxide catalyst is effective for
the hydrogenation of aldehydes [88] at a
temperature of 125-150
0
C. The hydrogenation of
benzaldehyde over copper-chromium gives a high
yield of benzyl alcohol even at 180
0
C without
hydrogenolysis [44] to give toluene (eqn. 5).

C6H5CHO + H2 C6H5CH2OH (5)

Vapour-phase hydrogenation of furfural over
copper chromite catalyst is perhaps the best
method of producing furfuryl alcohol [1,89].
Furfuryl alcohol is an important fine chemical for
polymer industry. It is widely used in production of
various synthetic fibres, rubbers, resins, e.g., dark
thermostatic resins resistant to acids, bases and
resins used for strengthening ceramics. It is also
used as solvent for furan resin, pigment, varnish
Fig. 3. Compound formed by hydrogenation of 2-
campholenylidenbutanol [83]
Fig. 4. Bicyclic alcohol [84]
Fig. 5. Preparation of bicyclic aliphatic alcohols [84]

and as rocket fuel. Pramottana et al. [39] observed
Cu
0
as the active phase in the copper chromite
particles for the selective hydrogenation of furfural
to furfuryl alcohol.

2.1.1.6 Hydrogenation of ketone
Copper-chromite catalyst is also effective for the
hydrogenation of ketones to corresponding
alcohols. Yurieva [90], reported maximum yield of
isopropanol on hydrogenation of acetone (eqn. 6)
over copper chromite catalyst at 300-350
0
C,
prepared by thermal decomposition of basic copper
ammonium chromate at 900
0
C.

CH3COCH3 + H2 C3H7OH (6)

Kang et al. [91] carried out hydrogenation of
methyl dodecanoate for the synthesis of 1-
dodecanol in the presence of a copper chromite
catalyst. The catalysts used were synthesized by
ceramic method, co-precipitation, and improved co-
precipitation method. The highest yield of
dodecanol in the hydrogenation reaction was 95.5%
when copper chromite synthesized in the PEG
solution was used as a catalyst in the optimized
reaction condition. 1-dodecanol is also known as
lauryl alcohol (C12H25OH), is a fatty alcohol. It has
a floral odour. Dodecanol is used to make
surfactants, lubricating oils, and pharmaceuticals.
In cosmetics, dodecanol is used as an emollient.

2.1.2 Dehydrogenation of alcohols
The dehydrogenation of alcohols to aldehydes or
ketones is a well-known industrial process, and
these reactions are primarily carried out on copper
catalysts because of their high selectivity to the
dehydrogenation product [27]. Catalytic
dehydrogenation of alcohols plays a key role in the
chemical industry particularly in the synthesis of
various pharmaceuticals and fine chemicals apart
from bulk chemicals. The reaction can generally be
described by the eqn. 7:

R1CHOHR2 R1COR2 + H2 (7)

where, R2 = H for primary alcohols or an alkyl or
aryl group for secondary alcohols.
Methanol dehydrogenation to formaldehyde [92]
or methyl formate over copper chromite catalysts
proceeds via successive reactions (eqn. 8 and 9)
[93]:

CH3OH HCOH + H2 (8)
HCOH + CH3OH HCOOCH3 + 2H2 (9)

Unlike other primary alcohols which are
dehydrogenated to aldehydes, the dehydrogenation
of methanol forms methyl formate over copper
chromite catalysts [94,95]. Methyl formate is used
as larvicide and fumigant. It is a starting material
in the synthesis of formic acid, acetic acid, N, N
dimethylformamide, formamide, hydrogen cynide,
methyl cellulose and high purity carbon monoxide
[96].
Ethanol dehydrogenation to acetaldehyde over
copper chromite catalysts [97,2,98] is highly
selective ( selectivity > 95%) represented by the
eqn. 10:

C2H5OH CH3CHO + H2 H
0
= 12.51 Kcal/mole
(10)

Acetaldehyde is an important intermediate for
the production of a number of industrial chemicals
such as acetic acid, acetic anhydride, n-butanol,
pentaerythritol, pyridines, peracetic acid, ethyl
acetate, 2-ethylhexanol, aldol, chloral, 1,3-butylene
glycol, trimethylolpropane, vinyl acetate, perfumes,
aniline dyes, plastics and synthetic rubber [99]. It
is used in silvering mirrors and in hardening
gelatin fibers. It is also a starting material for the
polymer paraldehyde, phenol, aldehyde
condensation products, dyes, synthetic flavouring
substance and finds its use as a hardener in
photography.
Isopropyl alcohol dehydrogenation to acetone
involves a secondary alcohol, whereas both R1 and
R2 are methyl groups in eqn. (7). Copper chromite
catalysts possess high selectivity and satisfactory
activity [27,100] for isopropyl alcohol
dehydrogenation (eqn. 11):

Iso-propanol: C3H7OH CH3COCH3 + H2 (11)

Acetone is an excellent solvent for a wide range
of gums, waxes, resins, fats, greases, oils,
dyestuffs, and cellulosics. It is used as a carrier for
acetylene, in the manufacture of a variety of
coatings and plastics, and as a raw material for the
chemical synthesis of a wide range of products
[101] such as ketene, methyl methacrylate,
bisphenol A, diacetone alcohol, methyl isobutyl
ketone, hexylene glycol (2- methyl-2,4-
pentanediol), and isophorone.
The use of dehydrogenation for obtaining
butyraldehyde from 1-butanol is of interest
because it does not allow any side reaction and
yields pure hydrogen as a by-product. The
stoichiometric equation for the dehydrogenation of
1-butanol is given by eqn. 12 [102]:

C4H9OH C3H7CHO + H2 (12)

According to Rao [1], 90% copper, 8% chromia,
and 2% carbon supported on pumice was best
catalyst for dehydrogenation of 1-butanol to
butyraldehyde, with high activity and selectivity.
The Cu-ZnO-Cr2O3/SiO2 catalysts prepared by
impregnation method, exhibits high activity for the
dehydrogenation of 2-butanol to 2-butanone [103].
A copper catalyst with chromium addition,
prepared by the electroless plating method, was
investigated by Shiau et al. [104] for
dehydrogenation of 1-butanol.
Butyraldehyde is used in organic synthesis,
mainly in the manufacture of rubber accelerators,
and as a synthetic flavouring agent in foods.
Isobutyraldehyde is an intermediate for rubber
antioxidants and accelerators. It is used in the
synthesis of amino acids and in the manufacture of
perfumes, flavourings, plasticizers and gasoline
additives.
Crivello et al. [105] prepared hydrotalcite-like
materials containing Cu
2+
, Mg
2+
and Cr
3+
cations in
the layers and carbonate in the interlayer by the co
-precipitation method with different Cu/Cr/Mg
molar ratios. The synthesized catalysts with 40% of
Cu show a high conversion of isoamylic alcohol and
selectivity to isovaleraldehyde. The authors
proposed that the presence of small percentages of
magnesium contributes in a significant extent to
the dispersion of entities of oxidized copper on the
surface of the calcined samples. Isovaleraldehyde
is an important industrial intermediary in the
manufacturing of synthetic resins, special
chemicals and isovaleric acid which is widely used
in the medical industry.

2.1.3 Hydrogenolysis of glycerol to propylene
glycol
Glycerol is a by-product from bio-diesel
industry. As the bio-diesel production is increasing
exponentially, the crude glycerol generated from
the trans-esterification of vegetables oils has also
been generated in a large quantity. For every 9 kg
of biodiesel produced, about 1 kg of a crude glycerol
by-product is formed [106]. The rapidly increased
production of biodiesel has led to a drastic surplus
of glycerol in the chemical markets. For this
reason, many catalytic processes had been reported
to convert glycerol into value-added chemicals [107
-109] by means of oxidation, hydrogenolysis,
dehydration, esterification, carboxylation and
gasification. Among those routes, selective
hydrogenolysis of glycerol to propylene glycol (PG)
is a promising route to increase the profitability of
biodiesel plant. PG is an important chemical used
to make unsaturated polyester resins, functional
fluids (antifreeze, de-icing, and heat transfer),
personal care, paints, animal feed, food industry
coolants, non-ionic detergents, pharmaceuticals,
cosmetics, flavours and fragrances, plasticisers and
hydraulic brake fluids [107,109]. It is also an
excellent solvent and extractant, and used as a
tobacco humectant. Dasari et al. [110] reported the
efficiency of pre-reduced copper chromite catalysts
for the hydrogenolysis of glycerol to PG (85.0%
selectivity, 54.8% conversion and 73% yield) at 473
K and 1.4 MPa (a mild hydrogen pressure).
The reduced Cu-Cr catalysts show significant
catalytic activity and selectivity in glycerol
hydrogenolysis, i.e. above 51% conversion of
glycerol and above 96% selectivity to 1,2-
propanediol in 4.15 MPa H2 at 210
0
C. The Cu-Cr
catalysts with low Cu/Cr molar ratio present high
conversion of glycerol, which is different from the
conventional copper-chromite catalyst [107].
Chiu et al. [111,112] performed dehydration of
glycerol in the presence of copper-chromite catalyst
to obtain acetol in a single stage semi-batch
reactive distillation unit under mild conditions.
The acetol from this reaction readily hydrogenates
to form propylene glycol providing an alternative
route for converting glycerol to propylene glycol.
They achieved high acetol selectivity levels (90%)
using copper-chromite catalyst. The conversion of
glycerol to propylene glycol is achieved through a
reactive intermediate (acetol). First, glycerol is
dehydrated to form acetol, and then, this acetol is
hydrogenated in a further reaction step to produce
propylene glycol as illustrated by reaction eqn. 13.

OH OH OH OH O OH OH
- H
2
O + H
2

CH
2
-CH-CH
2
CH
2
-C-CH
3
CH
2
-CH-CH
3
(13)
glycerol acetol propylene glycol

Kim et al. prepared copper chromite catalysts
using methods involving impregnation and
precipitation, and evaluated for the hydrogenolysis
of glycerol [28]. Catalyst (10I and 50I) prepared by
the impregnation method contained a mixed phase
of both individual copper and chromium oxide
structures, while the catalyst (50P) prepared by
precipitation showed a single phase, with a copper
chromite spinel structure (CuCr2O4). XPS data
indicated that, after the reduction step, the copper
species in the impregnated catalyst was reduced to
Cu
0
, but the catalyst prepared by the precipitation

method retained a spinel structure evidenced by
the large amount of Cu
2+
species. In hydrogenolysis
reactions, the precipitated catalyst showed a
higher catalytic activity than the impregnated
catalyst. Thus, the reduced copper chromite spinel
structure, which constitutes a single phase,
appears to be responsible for the high catalytic
activity in the hydrogenolysis of glycerol to
propylene glycol.
Copper chromite catalysts are useful for a
variety of chemical reactions in the processing of
oleo-chemical feedstocks. Major oleo-chemical
applications include hydrogenolysis of fatty esters
to fatty alcohols including both methyl ester and
wax ester processes, alkylation of alcohols with
amines and amination of fatty alcohols. The
catalysts have unique performance for selective
hydrogenation of vegetable oils and can be used in
the conversion of bio-renewable feedstocks into
industrial chemicals. Dovell and Greenfield [113]
used copper chromite as a catalyst for the
preparation of alkylaryl secondary amines by the
reductive alkylation of a primary aromatic amine
with an aliphatic ketone in the presence of
hydrogen (eqn. 14).

ArNH2 + ORCR + H2 ArNHRCHR + H2O (14)

The noble metals cause both nuclear
hydrogenation and formation of alkylamines [114]
by hydrogenolysis of the carbon-nitrogen bond
between the alkyl group and the nitrogen atom in
the secondary amine i.e.: ArNHR + H2 ArH +
RNH2. Copper chromite catalysts avoid these
undesirable side reactions, but a large amount of
ketone is reduced to the corresponding alcohol.
Fatty alcohols are an important raw material
for surfactants as well as constitute one of the
largest groups within the oleochemicals. The
fraction of natural fatty alcohols, i.e. fatty alcohols
based on natural fats and oils, is steadily growing
[115]. The fatty alcohols can be produced by
hydrogenation of fatty acid methyl esters, a
product from natural abundant coconut and palm
kernel oils, to form high alcohol in the presence of
a CuCr2O4 catalyst [116]. The hydrogenation of
methyl esters and of fatty acids to form fatty
alcohols is given by the following general eqns. (15)
and (16) respectively:
CuCr
RCOOCH + 2H2 RCH2OH + CH3OH (15)
Methyl ester Fatty alcohol

CuCr
RCOOH + 2H2 RCH2OH + H2O (16)
Fatty acid Fatty alcohol
Copper chromite catalyst also converts any
unsaturated carbon double bonds so that only
saturated fatty alcohols are formed [87]. The
hydrogenation process is carried out at 25-30 MPa
and a temperature of 250-300
0
C in a tubular
column.

2.1.4 Oxidation reactions
Oxidation of ethylbenzene (liquid phase) with t-
butyl hydroperoxide (TBHP) as an oxidant is
feasible over nickel substituted copper chromite
catalysts [4]. Effective utilization of ethylbenzene,
available in the xylene stream of the petrochemical
industry, for more value-added products is an
interesting option. Oxidation of ethylbenzene is of
much importance for the production of the
aromatic ketone, acetophenone, one of the key
products in the industries. It is used as a
component of perfumes and as an intermediate for
the manufacture of pharmaceuticals, resins,
alcohols and tear gas. The oxidation pathways of
ethylbenzene are presented in fig. 6.
Benzaldehyde is used in perfumery and
pharmaceutical industries. Choudhary et al [117]
prepared benzaldehyde in liquid phase oxidation of
benzyl alcohol by tert-butyl hydroperoxide using
Cu-Cr containing layered double hydroxides and/or
mixed hydroxides selectively. The reaction is given
by eqn. (17):

C6H5CH2OH + (CH3)3COOH C6H5CHO +
(CH3)C-OH + H2O (17)

George and Sugunan [118] prepared spinel
system with the composition of [Cu1-xZnxCr2O4] by
Fig. 6. Reaction scheme of ethylbenzene oxidation
[117].

co-precipitation method and reported cyclohexane
oxidation at 273 K using TBHP as oxidant. 69.2%
selectivity to cyclohexanol and cyclohexanone at
23% conversion of cyclohexane. Oxidation of
cyclohexane is one of the important bulk processes
for the production of polyamide fibres and plastics,
such as nylon-6 and nylon-6,6.

2.1.5 Alkylation
Alkylation reactions are of great interest in the
petrochemical industry as they lead to several
commercially important alkyl aromatics. Cumene
is one such alkyl aromatic produced by
isopropylation of benzene. The commercial
importance of cumene is felt by the worlds growing
phenol demand, 90% of which is met through
cumene. In the cumene route for the production of
phenol, acetone is produced as a low value by
product. Barman et al. [119] synthesised cumene
with 100% selectivity, by reductive alkylation of
benzene with acetone in the presence of a
bifunctional catalyst system comprising a solid
acid material, H-mordenite (HM), as alkylation
functional and nano-copper chromite as
hydrogenation functional, eqn. (18).

C6H6 + CH3COCH3 + H2 C6H5CH(CH3)2 + H2O
(18)

Copper chromite has been reported as a catalyst
for the reductive N-alkylation of aniline with
acetone [120,100]. Pillai [121] prepared different
aliphatic secondary amines by reductive alkylation
of methylamine and ethanolamine with carbonyl
compounds over copper chromite catalyst. Almost
100% selectivity was observed in all cases. Under
optimum conditions of reaction the yield of N-
isopropylaniline was 91% and that of N-benzyl-
ethanolamine was 94%.

2.1.6 Cyclization
Nitrogen-containing heterocyclic compounds are
pharmaceutically important [122,123]. Intensive
attention was concentrated on the manufacture of
this type of compounds over a half century. Bai et
al. [124] employed Cu-Cr-Fe/-Al2O3 catalysts for
the intramolecular cyclization of N-(2-
hydroxyethyl)-ethylenediamine to piperazine
which showed excellent activity, selectivity and
long service life under the optimum reaction
conditions (eqn. 19). Further they reported that
satisfactory results were obtained for cyclizations
of other alkanolamines, such as N-(2-hydroxyethyl)
-1,2-diaminopropane and 5-amino-1-pentanol.

2C2H2(NH2)2 C4H4(NH)2 (19)
Ethylene diamine Piperazine

Moss and Bell [125] used Ni-Cu-Cr-oxide for the
amination of ethanolamine to a mixture of
ethylenediamine and cyclic product, piperazine.
They found that addition of water increased the
selectivity of a Ni-Cu-Cr-oxide catalyst to the cyclic
product. Wang et al. [6] found that the Cu-Cr-Ba-
Al2O3 catalyst was suitable for highly selective
synthesis of homopiperazine. Cu
0
is believed to be
the active site of the catalyst and the addition of
Ba to the Cu-based catalyst improves the
dispersion of copper and prevents it from sintering.
The cyclization of N--hydroxyethyl-1,3-
propanediamine to homopiperazine proceeded with
more than a 90% yield under optimum reaction
conditions.

2.2 Hydrogen production
Hydrogen is used in massive quantities in the
petroleum and chemical industries [126]. In a
petrochemical plant, hydrogen is used for
hydrodealkylation, hydrodesulfurization, and
hydrocracking, all methods of refining crude oil for
wider use. Ammonia synthesis plants accounted for
40% of the world's consumption of H2 in making
fertilizer. In the food industry, hydrogen is used to
hydrogenate oils or fats, which permits the
production of margarine from liquid vegetable oil.
Hydrogen is used to produce methanol and
hydrochloric acid, as well as being used as a
reducing agent for metal ores. Since H2 is the least
dense of gases, meteorologists use hydrogen to fill
their weather balloons. The balloons carrying a
load of instruments float up into the atmosphere,
for recording information about atmospheric
conditions.
Hydrogen has the highest combustion energy
release per unit of weight of any commonly
occurring material (eqn. 20).

H2(g) + 1/2O2(g) H2O(l) H
0
= 286 kJ/mol (20)

This property makes it the fuel of choice for
upper stages of multi-stage rockets. Much has been
said about hydrogen being the "energy carrier of
the future" due to its abundance and its non-
polluting combustion products. When it is
combusted, heat and water are the only products.
The use of hydrogen as a fuel for fuel cell-powered
vehicles can greatly reduce green house gas
emissions from internal combustion engines.
Moreover, development of affordable hydrogen fuel

cells will help reduce the nations dependence on
foreign oil, leading to an increased national energy
security. Thus, hydrogen offers a potentially non-
polluting, inexhaustible, efficient, and cost
attractive cleanest fuel for todays rising energy
demands [127].
Hydrogen is not found in free state but it is
abundantly available in nature as compounds of
oxygen (water) or carbon (alcohols, hydrocarbons,
carbohydrates, etc.). Energy must be supplied to
generate hydrogen from either water or
carbonaceous materials. Thus, note that hydrogen
is not an energy source, as energy is needed to
produce it (21). As an energy carrier, hydrogen is
the most attractive option with many ways to
produce and utilize it [128].

H2O + energy H2 + 0.5O2 (21)

Processes using copper chromite as catalysts for
the production of hydrogen are as follows:
a). From water splitting
Photo-electrolysis of water
Sulphur based thermo-chemical water
splitting cycles
b). Catalytic conversion of alcohols
Dehydrogenation of alcohols
Decomposition of methanol
Reforming of alcohols
Methanol reforming
Ethanol reforming
c). Water gas shift reaction

2.2.1 From water splitting
2.2.1.1 Photo-electrolysis of water
In the past two decades, the photo-
electrochemical (PEC) processes at semiconductor
(SC)/electrolyte junctions have been intensively
investigated [11]. The search of new materials to
achieve the photo-chemical conversion has led to a
great deal of work on CuCr2O4 [11-13,129-130] and
remains the best possible way of solar energy
storage in hydrogen form. Photochemical H2
evolution based on a dispersion of CuCrO2 powder
in aqueous electrolytes containing various reducing
agents (S2, SO2
-3
and S2O2
-3
) has been studied by
Saadi [129]. The powder dispersion has the
advantage of a liquid-junction solar-cell where the
two half reactions take place simultaneously on the
same particle that behaves like a micro-photo-
electrochemical cell and it is cost effective too. It
has a long lifetime, a pH insensitive energetic and
absorbs a large part of the sun spectrum.
Schematic photocatalytic evolution of H2 is
illustrated in Fig. 7.
Yan et al. [12] synthesized CuCr2O4/TiO2 hetero
-junction via a facile citric acid assisted sol-gel
method for photocatalytic H2 evolution. The nano-
composite of CuCr2O4/TiO2 is more efficient than
their single part of CuCr2O4 or TiO2 in producing
hydrogen. CuCr2O4 is a p-type semiconductor with
a small band gap [129]. A possible reaction model
(eqns. 22,23,24) of the CuCr2O4/TiO2 hetero-
junction is proposed by Yan, et al. [12]. For both
pure CuCr2O4 and CuCr2O4/TiO2 hetero-junction,
mainly CuCr2O4 can be activated under simulated
sunlight irradiation:

CuCr2O4 + h CuCr2O4 (e
-
, h
+
) (22)

The photo-generated electrons and holes
migrate in opposite directions according to the p-
type conductivity of CuCr2O4, i.e. the electrons
migrate in the direction of the illuminated side of
the particle to react with adsorbed water and
produce H2. Meanwhile holes move in the opposite
direction (the particles dark side) to oxidize
adsorbed oxalic acid. Because of the Schottky
barrier formed between the interface of CuCr2O4
and TiO2, the hetero-junction can improve the
separation of the photo-generated electrons and
holes. When coupled with TiO2, the photo-
generated electrons are injected from excited
CuCr2O4 into the conduction band of TiO2 and
reduce adsorbed water into H2:

CuCr2O4 (e
-
) + TiO2 CuCr2O4 + TiO2 (e
-
) (23)
CuCr2O4 (e
-
, h
+
) + TiO2 CuCr2O4 (h
+
) + TiO2 (e
-
)
(24)

As a result, CuCr2O4/TiO2 hetero-junction with
appropriate CuCr2O4/TiO2 ratio can enhance the
separation of the photo-generated electrons and
Fig. 7. Schematic illustration of photocatalytic
evolution of hydrogen

holes, and therefore improve the H2 photo-catalytic
activity [130]. Boumaza et al. [13] reported that
the best catalytic performance over CuCr2O4 for H2
-photoproduction was obtained in (NaOH 0.5 M,
Na2S2O3 0.025 M) with an average rate of 0.013
cm
3
h
-1
/mg catalyst and a quantum efficiency of
0.2% under polychromatic light.

2.2.1.2 Sulphur based thermo-chemical water
splitting cycles
Thermochemical water-splitting cycle is a
promising process to produce hydrogen using solar
or nuclear energy [131]. Ginosar et al. [16]
evaluated the activity and stability of several
complex metal oxides: two ABO3 structures
(FeTiO3 and MnTiO3) and three AB2O4 structures
(NiFe2O4, CuFe2O4, and NiCr2O4) and copper
chromite (i.e., 2CuO.Cr2O3) (was also selected due
to the high activities of Cr2O3 and CuO [132]) for
the atmospheric decomposition of concentrated
sulfuric acid in sulfur-based thermochemical water
splitting cycles. Catalyst activity was determined
at temperatures from 725 to 900
0
C. Catalytic
stability was examined at 850
0
C for up to 1 week
of continuous operation. The results were
compared to a 1.0 wt% Pt/TiO2 catalyst. Over the
temperature range, the catalyst activity of the
complex oxides followed the general trend:
2CuO.Cr2O3 > CuFe2O4 > NiCr2O4.NiFe2O4 >
MnTiO3. FeTiO3. Tagawa and Endo [132] observed
the order of the activities for the decomposition of
sulfuric acid in thermochemical water splitting
process at the initial concentration of SO3 of 4.0
mol% as follows: Pt Cr2O3 > Fe2O3 > (CuO) >
CeO2 > NiO > Al2O3. The activity of Cr2O3 above
700C was nearly the same as the Pt catalyst.

2.2.2 Catalytic conversion of alcohols
In recent years, the catalytic decomposition/
reforming of alcohols has gained particular interest
due to growing environmental, economic, and
political concerns regarding energy production
[133]. Safe and efficient in situ hydrogen
generation from alcohols (i.e. methanol, ethanol,
propanol, butanol) can promote the use of fuel cells
and other clean technologies as a source of energy
for mobile applications. Alcohols can serve as H2
carriers that are compatible with current
infrastructures for liquid fuels and can be
catalytically converted on-site in order to minimize
energy input requirements and operating
temperatures [134]. Methanol and ethanol have
the highest H/C ratios among the alcohols and
gasoline-range alkanes (e.g., heptane). That is,
more hydrogen can be extracted from their
molecular frameworks [135]. Production of
hydrogen from alcohols can be accomplished by
their dehydrogenation and reforming processes.

2.2.2.1 Dehydrogenation of alcohols
Hydrogen as by-product is obtained from
dehydrogenation of alcohols over copper chromite
catalysts as discussed in section (2.1.2). The
dehydrogenation of alcohols is a reversible and an
endothermic process which implies that heat must
be supplied to the system. Of course very pure
hydrogen is obtained on dehydrogenation of
ethanol over copper chromite catalyst [136].

2.2.2.2 Decomposition of methanol
Methanol is easy to transport over long
distances and to store. The catalytic decomposition
of methanol to CO and H2 can provide a clean and
efficient fuel (eqn. 25):

CH3OH CO + 2H2 H = 90.2 kJ/mol (25)

For example, methanol decomposition on board
of a vehicle (Fig. 8) provide a fuel which is cleaner
and 60% more efficient than gasoline and up to
34% better than undecomposed methanol [137-
139]. Methanol decomposition is an endothermic
reaction. The reaction heat can be provided by the
engine coolant and exhaust gas. This recovers the
waste heat and increases the heating value of the
fuel. The decomposed methanol may also be used
as a clean fuel for gas turbines at times of peak
demand of electricity [137-140]. Lean and complete
Fig. 8. Methanol decomposition on board a vehicle

combustion will ensure low CO and formaldehyde
emissions. NOx emission will be greatly reduced
because of lower combustion temperatures.
Al though the potenti al gain from
implementation of methanol decomposition related
technology is evident, successful development of
efficient catalysts and reaction processes is crucial
for the implementation of the technology. Cu-based
catalysts such as Cu/Cr/Mn are active catalysts in
the decomposition of methanol to CO and H2.
Cheng et al. [138] concluded that Cu/Cr-based
catalysts are much more active than the
conventional Cu/Zn catalysts in methanol
decomposition. The acidic nature of the Cu/Cr-
based catalysts, which leads to the decreased
selectivity, can be greatly reduced by passivating
the catalysts with alkali metal ions such as
potassium.

2.2.2.3 Reforming of alcohols
Alcohols and more specifically methanol are
convenient storage systems for hydrogen [141].
These liquids can easily be transported through
the existing infrastructure and have lesser
constraints concerning safety than for instance
gaseous hydrogen storage. Alcohols transformation
into gaseous mixtures enriched with hydrogen can
be achieved by several reactions such as steam
reforming (SR) [142,20], partial oxidation (PO)
[135] and oxidative steam reforming (OSR) [143].

A. Methanol reforming
Catalytic reforming of methanol is a well-
established technology, mainly used for small
hydrogen plants. This technology is promising for
energy feeding in portable electronic devices, for
decentralized refuelling units for hydrogen-based
automobiles or as on-board generation systems for
hydrogen-based internal combustion engines or
PEM fuel cells [144]. Methanol is considered as an
appropriate source of hydrogen due its safe
handling, low cost and high storage density.
Moreover, it can be produced from renewable and
fossil fuels [14].
The steam reforming (SRM) of methanol can be
modelled as occurring in two stages by two
different pathways, the first one involves the
decomposition of methanol into CO and hydrogen
(eqn. 26):

CH3OH CO + 2H2 (26)

Followed by a water gas shift reaction (eqn. 27):

CO + H2O CO2 + H2 (H
0
= 41.2 kJmol
-1
) (27)

The second mechanism for methanol steam
reforming consists of the reaction of water and
methanol to CO2 and hydrogen (eqn. 28):

CH3OH + H2O CO2 + 3H2 (H
0
= 49 kJmol-1)
(28)

which can be followed by a reverse shift reaction to
establish the thermodynamic equilibrium (eqn. 29):

CO2 + H2 CO + H2O (29)

The advantage of SRM process is the amount of
CO generated along CO2 is low. This is important
since it acts as a poison for fuel cells. The accepted
levels of CO are between 10 and 100 ppm [134].
The main disadvantage of SR is its endothermicity
requiring external heating, which makes short
start-up and fast transient behaviour difficult to
achieve [143]. The schematic flow sheet for a
conventional SRM process is shown in Fig. 9.
Copper-based catalysts (CuMn2O4 and CuCr2O4
spinels or CuO/CeO2 and CuO/ZnO) exhibit a high
activity and selectivity for the steam reforming
process. Small amounts of Cr2O3 in skeletal copper
catalysts significantly enhance the copper surface
area and thus promoted the activities for SRM
[142,145]. Supported Cu-Cr on yttria-doped ceria
(YDC)/Al2O3 showed the most pronounced
enhancement of the catalyst activity in the SRM at
reaction temperatures of 200-250
0
C, the CO
concentration in the products was smaller than
0.1% [146]. Valdes-Sols et al. [14] prepared nano-
sized CuCr2O4 catalysts by nano-casting
techniques for the production of hydrogen by

Catalytic refor
ming (250
0
C)
Preferential
Oxidation
CH
3
OH
H
2
O
Air CO
2
Air + Fuel
Shift conve
rsion (200-
500
0
C)
Water
H
2

Fig. 9. Flow-sheet for a conventional SRM process

methanol steam reforming. They observed that the
activity values of the catalysts are similar to or
greater than those found in the literature for
common methanol steam reforming catalysts
including noble metal-based catalysts.
Deactivation of the catalysts seems to be
independent of the preparation method and can be
attributed to the concomitant effect of coke
deposition and sintering.
Partial oxidation of methanol (POM) is an
exothermic reaction (eqn. 30) and can be used for
fast dynamic in methanol reforming [147].

CH3OH + 0.5O2 = CO2 +2H2 H
0
= -192 kJ mol
-1

(30)

But the formation of hot-spots in the catalytic bed
is the main drawback, leading to catalyst sintering
resulting in the activity loss [148]. Cu-based
catalysts have been the most generally studied
catalysts for partial oxidation of methanol [149].
Wang et al. [150] showed that Cu60Cr40 catalyst
exhibits high CH3OH conversion and H2 selectivity
as compared with other binary catalysts and the
introduction of Zn promoter not only helps to
increase the activity of the catalyst but also
improves the stability of the catalyst, the highest of
the activity of the ternary Cu/Cr/Zn is obtained
with a relative composition of Cu/Cr (6:4)/Zn (10%).
Oxidative steam reforming of methanol (OSRM)
combined SRM and POM which gives fast
dynamics and generates high hydrogen
concentrations (eqn. 31).

CH3OH + 0.75 H2O + 0.125 O2 CO2 + 2.75 H2
H
0
= 0 kJ mol
-1
(31)

Reactors for this process operate autothermally,
i.e. it does not require any external heating or
cooling once the operational temperature is
reached. For fast transient response, the methanol/
oxygen ratio can be varied as in the case of the Hot
-Spot reformer [151]. OSRM is combination of
steam reforming and partial oxidation processes.
Reactions are balanced in such a way that net
energy requirement is zero (H
0
=0). The schematic
flow sheet for a conventional OSRM process is
shown in Fig. 10.
Horny et al. [151] developed a compact micro-
structured string reactor with catalytic brass wires
for OSRM to produce hydrogen in auto-thermal
mode for fuel cells. CuCr2O4 catalyst used in
OSRM showed high activity, and selectivity to
carbon dioxide and hydrogen. The selectivity
towards carbon dioxide was 98% for a methanol
conversion of 91.5% being higher than predicted for
the water-gas shift equilibrium. The string reactor
presents nearly isothermal profile. The reactor
presents a short start-up and a fast transient
behaviour showing a rapid temperature change
when adjusting the oxygen amount introduced into
the reactor.

B. Ethanol reforming
Hydrogen is essentially produced by steam
reforming (SR) of hydrocarbon fractions (natural
gas, naphtha,) on an industrial scale. Replacing
fossil fuels by biofuels for H2 production has
attracted much attention with an increased
interest for bioethanol reforming [152]. Reforming
of ethanol is a potential way to generate renewable
hydrogen. Bioethanol can be easily produced in
renewable form from several biomass sources,
including plants, waste materials from agro-
industries (molasses, corn, bole, etc.) or forest
residue materials [153]. Moreover, a bioethanol-to-
H2 system has the advantage of being CO2 neutral
[154]. Steam reforming, partial oxidation and auto-
thermal reforming of ethanol can be illustrated by
eqns. 32, 33 and 35 respectively.
Steam reforming is an endothermic process and
requires energy input to initiate reactions [155]:

C2H5OH + 3H2O 2CO2 + 6H2 H
0
= 174 kJ mol
-1

(32)

Alternatively, hydrogen can be obtained by partial
oxidation of ethanol at a temperature of about 500

Partial oxidation,
catalytic reforming
(250
0
C)
Preferential
Oxidation H
2

CH
3
OH
H
2
O
Air CO
2
Air
Fig. 10. Flow-sheet for a conventional OSRM process

0
C according to the following reaction [156]:

C2H5OH + 1.5O2 = 2CO2 +3H2 H
0
= - 552 kJ mol
-1

(33)

However, hydrogen selectivity of ethanol partial
oxidation is generally low. In order to enhance
hydrogen production, autothermal reforming can
be applied. Autothermal reforming, also called
oxidative steam reforming, is a combination of
ethanol oxidation and steam reforming. The total
reaction of autothermal reforming of ethanol can
be written as eqn. 34 [157,158]:

C2H5OH + 2.25 H2O + 0.375 O2 = 2CO2 + 5.25 H2
H
0
= -30 kJ mol
-1
(34)

This reaction indicates that the autothermal
reforming not only attains thermally sustained
operation, but also maximizes hydrogen
production.
Dolgykh et al. [159] investigated the catalytic
activity of copper chromite catalysts in the process
of ethanol steam reforming at low temperatures
using 12 wt.% C2H5OH in water mixtures. They
found that without catalyst appreciable hydrogen
production starts at the temperatures above 300
0
C
and reaches hydrogen yield 0.3 g 2 (kg cat)
-1
(h)
-1

at 400
0
C. Use of catalysts allows reaching the
hydrogen productivity 9-25 g 2
/
(kg cat.)/(h) at 250-
300
0
C.

2.2.3 Water gas shift reaction
The production of hydrogen mainly relies on the
liquid fuels reforming processes. Reformate gas
(CO/H2 mixture) contains significant amount of
CO (10-15%) [160-162]. Water gas shift (WGS)
reaction (eqn. 35) is used to enrich hydrogen in the
reformate stream and decrease the CO content.
The water gas shift reaction is presented by:

CO + H2O CO2 + H2 H = - 41.1 kJ/mol (35)

is mildly exothermic, with an adiabatic
temperature rise of 8-10
0
C per percent (wet gas)
CO converted to CO2 and H2. Industrial WGS
reaction is carried out using two different catalysts
in two stages (high temperature WGS and low
temperature WGS) with inter-bed cooling [162] as
shown in Fig. 11.
Recently, low-temperature WGS reaction has
attracted renewed interest due to the increasing
demands for high-purity hydrogen for application
in fuel-cell systems [162]. Cu-based spinel-type
oxides [163,14-15] have received much attention in
the last years owing to their high catalytic activity
and durability at low temperatures to that of
conventional, Cu/ZnO/Al2O3 for WGS reaction.
Boumaza et al. [15] prepared a series of AB2O4
spinel catalysts by the co-precipitation method
where B is commonly Al, Zn, Mn, Co, Cr and Fe.
The catalysts were tested in the water gas shift
reaction at atmospheric pressure. They ranked the
oxide systems in the following order follows: Cu-
Cr>Cu-Fe>>Zn-Al>Cu-Co at 250
0
C. Significant
improvements to the activity of skeletal copper
catalysts for the water gas shift reaction were
achieved by adding small amounts of Cr2O3 to the
surface of copper [145].

2.3 Clean energy production
In the last few years new extremely stringent
standards in emission legislation have required the
development of new technologies for both clean
energy production and emission control, either for
industrial or for household appliances. Among the
processes of energy production, high temperature
combustion of fossil fuels is the most
conventionally used [164-165]. During combustion,
the formation of pollutants, in particular NOx, is
favoured due to the high temperatures attained
[164,166]. Catalysis can offer the possibility to
realize clean combustion in an interval of
temperature in which the formation of given
pollutants, e.g. NOx, is depressed [164,165,167].
The choice of the appropriate catalyst is a
fundamental step for improving the combustion, in
terms of both activity and selectivity, limiting the
formation of hazardous by-products [164,165].
The performances of Pt or Pd with respect to
hydrocarbons combustion, in particular methane,
have been largely studied by many authors
[168,169]. The use of noble metals has stringent
effects on the commercial cost of the whole
catalyst, so that a great interest has turned to
oxide-based catalysts [170]. Various oxides
containing Co, Cr, Mn, Fe, Cu, and Ni are
potentially interesting for catalytic combustion
Fig. 11. Water gas shift reaction process

appliances [171]. Mixed oxide compositions show
better activity than the single oxide ones [164]. The
copper chromite catalyst offered interesting
performances for CH4 combustion [170] in view of
such application. Comino et al. [170] studied
complete oxidation of methane over two
unsupported over copper chromite (CuO-Cr2O3)
and alumina-supported one (CuO-Cr2O3/Al2O3).
The unsupported catalyst showed better activity
while supported one was very stable. Kinetic study
provided a value of the activation energy about110
kJ/mol.
To increase the combustion efficiency of
gasoline, several additives such as antioxidants,
oxygenates and other functionalities are added.
Most prominent additives among them are
oxygenates, which are a class of oxygen containing
compounds used as blending components to
improve the combustion efficiency of the fuel [172].
Blending of oxygenates with the gasoline results in
complete combustion, thereby reducing the CO and
hydrocarbon (HC) emissions to a large extent
under full load operating conditions [172]. Alcohols
such as ethanol and methanol were recognized as
octane boosters in 1920. Tertiary alkyl ether based
oxygenates such as methyl tertiary butyl ether
(MTBE), ethyl tertiary butyl ether (ETBE), tertiary
amyl ethyl ether (TAEE), tertiary amyl methyl
ether (TAME), isopropyl tertiary butyl ether
(IPTBE) and diisopropyl ether (DIPE) are other
possible candidates for gasoline blending [173].
Methyl-tertbutyl-ether or isooctane (MTBE) is a
clean energy resource and an alternative fuel. The
selective synthesis of isobutyl alcohol (iBuOH) has
recently gained an increasing interest because this
substrate is a potential precursor of gasoline
additives such as methyl-tertbutyl-ether or
isooctane. iBuOH may be directly synthesized from
syngas through the higher-molecular-weight
alcohols synthesis carried out at high temperature
and pressure over copper chromite catalysts [174].
Another most promising clean energy source is
methanol. Methanol decomposition or reforming
can provide clean fuel for fuel cells, automobiles,
power generation, chemical processes and material
processing (see section 2.3.1 and 2.3.3.1). The use
of methanol as a fuel additive and in MTBE
production has renewed interest in the search for
improved methanol processes.

2.3.1 Methanol synthesis
Commercially methanol is synthesized from
synthesis-gas using Cu/ZnO/Al2O3 catalysts (eqn.
36) [164]:

CO + 2H2 CH3OH (36)

The stability of Cu/ZnO catalysts has been
discussed in view of the sintering of Cu via brass
formation [175-178]. It is suggested that the
sintering of Cu via brass formation could be
prevented in Cu-ZnO-Cr2O3 catalysts obtained
from Cu-Zn-Cr hydrotalcite-like precursor [179].
Venugopal et al. [180] synthesized a series of Cu-
ZnO-Cr2O3-Al2O3 (Zn/Cr = 1.2-6.8) catalysts using
hydrotalcite like layered double hydroxide
precursors for conversions of synthesis gas to
dimethyl ether in a single step process. Single step
dimethyl ether (DME) synthesis from syngas has
technological advantages over the two step process
of methanol synthesis (eqn. 37) and dehydration of
the methanol (eqn. 37).

2CH3OH CH3OCH3 + H2O (37)

The advantages being high one-through
conversion in thermodynamic point of view [181]
and low operating cost in the economic point of
view [182]. Venugopal et al. [180] concluded that
the high syngas conversion over Cu:Zn:Cr =
7:6:1.88 (mol ratios) catalyst was attributed to the
high copper metal surface area as compared to the
other catalysts and higher yields of DME was
obtained in single step over a Cu-Zn-Cr (Zn/Cr =
3.3) with -Al2O3.
Ohyama and Kishida [183] prepared slurry-
phase methanol via methyl formate at 100 0C and
an initial pressure of 5 MPa using alkoxide and a
physical mixture of CuO and Cr2O3 as a catalyst.
Methanol synthesis is a highly exothermic reaction
and thermodynamically favourable at lower
temperatures. Thus, if a catalyst which is highly
active at low temperatures is available and the
heat of reaction is efficiently removed, methanol
production with high per-pass conversion could be
achieved. Slurry-phase methanol synthesis using
alkali metal alkoxide and copper-based compound
as a catalyst has been investigated by several
researchers [184-188]. In this system, methanol is
considered to be formed through the formation of
methyl formate by the following two reactions
(eqns. 38 and 39) which occur concurrently:

CH3OH + CO HCOOCH3 (38)
HCOOCH3 + 2H2 2CH3OH (39)

Here, the alkali metal alkoxide is a well-known
catalyst for carbonylation of methanol to methyl
formate (reaction 3.2) [189-190], whereas copper-

based materials such as copper chromite reported
to function as catalysts in the hydrogenolysis of
methyl formate to methanol (reaction 3.3).
Therefore, employing a mixture of both catalysts,
methanol can be produced in a single reactor from
H2 and CO according to the above sequence of
reactions [190-195]. Ohyama [196] reported
excellent activities of copper chromite catalyst for
the production of methanol in liquid phase in
presence of potassium methoxide, which involves
carbonylation of methanol to methyl formate and
consecutive hydrogenation of methyl formate to
methanol. The effects of reaction variables on the
catalytic performance are investigated under the
conditions of 373-423K temperature and 1.5-
5.0Mpa pressure. Huang and Wainwright [145]
observed significant improvements to the activity
of skeletal copper catalysts for the methanol
synthesis achieved by adding small amounts of
Cr2O3 to the surface of copper. Slurry phase
concurrent synthesis of methanol has also been
described by Palekar [192] using a potassium
methoxide/copper chromite mixed catalyst which
operates under relatively mild conditions (100-180
0
C, 30-65 atm).

2.3.2 Fast pyrolysis of biomass
Biomass, a form of renewable sources, can be
transformed via thermochemical processing such
as fast pyrolysis into liquid bio-oil, which is a
storable and transportable fuel as well as a
potential source of a number of valuable chemicals
that offer the attraction of much higher added
value than fuels. Bio-oil is successfully used as
boiler fuel and also showed promise in diesel
engine and gas turbine applications. Upgrading bio
-oil to a quality of transport liquid fuel still poses
several technical challenges and is not currently
economically attractive. Some chemicals, especially
those produced from the whole bio-oil or its major
fractions offer more interesting commercial
opportunities. The main properties and
applications of bio-oil have been reviewed by
Czernik and Bridgwater [197].
Bio-oils are complex hydrocarbon mixtures
known to contain significant amount of oxygenated
compounds including lignin derivates which
ultimately lead to low heating values, low
stabilities, high viscosity, low volatility and low
pH. Therefore, in order to improve the quality of
the bio-oils in terms of heating values, viscosity
and storage stability, the oxygenates and the large
molecules derived from lignin need to be reformed
into more useful products. Catalytic pyrolysis is a
promising approach for upgrading bio-oil involves
direct catalytic conversion in the vapour phase at
low pressure via vapour cracking and reforming.
Incorporating a catalyst into the pyrolysis unit is
expected to enhance deoxygenation, cracking and
reforming reactions. The selection of appropriate
catalysts plays a vital part in bio-oil upgrading.
The severity of these catalytic reactions often
influences the liquid product distribution and
depends largely on types of catalyst and other
processing parameters. Pattiya et al. [198] used
copper chromite catalyst for cassava rhizome as
the biomass feedstock for upgrading bio-oil. They
observed that the copper chromite was selective to
the reduction of most oxygenated lignin
derivatives.

2.3.3 Preferential oxidation of CO
The preferential oxidation (PROX) process is
one of the most effective methods for the removal
of CO trace from the reformate stream. PROX of
CO is a reaction to convert CO in a H2-rich gas
mixture to CO2 with minimal H2 consumption.
Therefore, preferential oxidation process is an
indispensable step to reduce the concentration of
CO to 10 ppm level in a H2 generation process
[199]. The flow diagram of hydrogen purification by
CO-PROX is shown in Fig. 12.
The following reactions (eqns. 40 and 41) can
occur in the PROX system.

CO + O2 CO2 H
0
= -282.98 kJ/mol (40)

H2 + O2 H2O H0 = -241.82 kJ/mol (41)

CO is a typical by-product in the production of
hydrogen by reforming of alcohols or hydrocarbons
and must be reduced down to ppm levels in order
to be used as feed for proton-exchange membrane
fuel cells. Up to date, several options for CO
removal have been studied and the selective
oxidation (CO-PROX) is considered one of the most
Fig.12. Flow diagram of H2 purification by CO-
PROX

straightforward and cost-effective methods to
achieve acceptable CO concentrations (eqn. 42).

H2 + CO + O2 (air) CO2 + H2 (42)

Many industrial applications using H2 as a
feedstock require a H2 stream containing a little
CO. These include ammonium synthesis, fuel cell
and semiconductor processing etc. because CO is a
poison in these processes. Cu/Cr/Ba based catalysts
were found to be non-precious metal catalysts that
can selectively oxidize CO in a H2-containing
stream [200].

2.4 Vehicular Pollution control
Vehicles play a very important role in the
development of a nation since they are widely used
to transport goods, services and people. But there
is a major negative effect of the emissions of
pollutants from the exhaust of the vehicle engines
[201]. The complex reactions occurring in the
internal combustion engine can be represented by
eqn. 43:

Fuel (HC) + Air (O2+N2) CO2 + H2O + N2 + O2 +
CO + HC (unburned) + NOx (43)

Engine exhausts consist of a complex mixture,
the composition depending on a variety of factors
such as: type of engine (two- or four-stroke, spark-
or compression -ignited), driving conditions, e.g.
urban or extra-urban, vehicle speed, acceleration/
deceleration, etc. Table 1 reports typical
compositions of exhaust gases for some common
engine types [202].
It is clear from the table 1 that there are three
main primary pollutants, CO, HC and NOx from
the spark ignited engines while NOx and
particulate matter (PM) are the major composition
of the diesel engine exhausts. Because of the large
vehicle population, significant amounts of HC, CO,
NOx and PM are emitted in the atmosphere. These
pollutants have harmful effects [203-205] on living
beings, materials, environment and climate
change. Morover once emitted into the atmosphere,
primary pollutants could be the precursors for the
formation of more dangerous secondary pollutants
such as smog, aerosol, ground level ozone, peroxy-
acetyl-nitrate (PAN), polycyclic aromatic
hydrocarbon (PAH) etc. by photochemical reactions
[206].
The catalytic control of these pollutants has
been proposed as an end of the pipe treatment
technology. The benefits of catalytic purification of
primary pollutants to atmospheric gases (CO2, N2,
O2 and H2O) using three way catalyst (TWC) for
spark ignited engine [207] and catalytic filter for
diesel engine [41] exhaust have been documented.

2.4.1 Purification of spark ignited engine
exhaust
Automotive catalytic converters having TWCs
consisting of noble metals (Pt, Pd, Rh) are used for
purification of exhaust gases of gasoline driven
vehicles [208]. Catalysts simultaneous carry out
both reduction and oxidation reactions that convert
exhaust pollutant to normal atmospheric gases.
The reactions can be presented by following eqns.
44, 45 and 46:
The oxidation of CO and HC :

2CO + O2 2CO2 (44)
HC + O2 CO2 + H2O (45)
The reduction of NOx with CO :

NOx + xCO 1/2N2 + xCO2 (46)

Because of the abatement of all the three
primary pollutants catalyst used is known as TWC.
Although noble metal-based catalysts have
dominated this area, efforts were always put in
towards development of low cost non-noble metal-
based catalysts [209] and modification of TWC to
decrease precious metal percentages by means of
nanotechnologies [210] and in combination with
base metals [211]. Among such catalysts copper
chromite has been observed to be an attractive
alternative to presently used noble metals in view
of availability, lower cost and comparable activity
[212-216,9] for purification of vehicular exhaust.
Cu-Cr catalyst system has been studied
extensively for reactions such as the oxidation of
CO [217], hydrocarbons [213], alcohols and
aldehydes [218], sulfurated hydrocarbons [219],
and chlorinated hydrocarbons [220] as well as NO
reduction [214]. Kapteijn et al. [214] reported that
Cu-Cr catalysts showed higher CO oxidation and
NO reduction activity than single oxide catalysts
based on Cu, Ni, Co, Fe, Mn, Cr. Stegenga et al.
[212] have found that a monolith-supported 10
wt% Cu.Cr/Al2O3 catalyst showed a three-way
catalytic activity comparable to that of noble metal
catalysts operated under the same conditions.

2.4.1.1 Oxidation of carbon monoxide
Carbon monoxide (CO) can prove perilous
without giving any physical indication because it is
a colorless, tasteless and odourless gas. It is
chemically inert under normal conditions with
estimated atmospheric mean life of about 2.5
months [221]. This, poisonous gas can seriously

affect human aerobic metabolism because of its
affinity to haemoglobin being 210 times greater
than that of oxygen and so, if its concentration
becomes higher than 0.0998% by volume in
atmosphere, it can lead to the failure of the process
of combination of oxygen with the haemoglobin
resulting ultimately in respiratory failure and
consequent death. It forms a very stable compound
called carboxyhaemoglobin (COHb) in blood whose
1-2% concentration can cause headache, fatigue,
drowsiness and may have effect on human
behavioural performance, 2-5% concentration may
cause impairment of time interval discrimination,
visual acuity, brightness discrimination and
certain other psychomotor functions which may
lead to accident on roads. 5-10% concentration can
lead to changes in cardiac and pulmonary
functions and 10-80% can cause coma, respiratory
failure and death [222]. It not only affects human
beings but also vegetations by interfering with
plant respiration and nitrogen fixation. The
vehicle emission is the major source of CO in urban
air, accounting for slightly over half of all the
anthropogenic air pollutants.
The catalytic oxidation of carbon monoxide with
the object of reducing air pollution is actually an
important consideration when one thinks in terms
of automobile emission control [223]. Copper
chromite is found to be most promising among non-
noble metal catalysts and exhibits comparable
activity for CO oxidation to that of precious metals
based auto exhaust purification catalyst [224]. The
catalyst converts CO to harmless product CO2,
found in the atmosphere which is useful to the
plants. Copper chromite catalysts have been
studied in detail for CO oxidation. The studies
have been attributed to the catalytic activity and
stability tests [225,226], postulating mechanisms
[227], characterization of catalysts [228,229], rapid
evaluation of the catalysts [230], search for the
active sites on the catalysts [231,232], kinetics of
the reaction [228,233], catalysts deactivation
[229,234], etc. Pantaleo et al. [235] reported the
catalytic tests in CO oxidation indicated a
synergetic effect between copper and chromium in
the mixed oxides supported on silica and calcined
at 500
0
C. Xavier et al [236] found that Cu-Cr
based catalysts are effective for CO oxidation at
lower temperatures. Park and Ledford [228]
reported that the Cu/Cr/Al2O3 catalyst of Cr/Al =
0.054 showed the highest CO oxidation activity due
to the formation of CuCr2O4 which was more active
than the CuO phase. Higher loadings yielded
higher activities per amount of catalyst, but above
10 wt.% Cu+Cr the intrinsic activity per metal
atom decreased. Li et al. [229] synthesized
monodi spersed spheri cal CuCr2O4. CuO
Table 1. Exam ple of exhaust conditions for two- and four-stroke, diesel and lean-four-stroke engines [202]
-----------------------------------------------------------------------------------------------------------------------------------------------------------
Exhaust components Diesel engine Four-stroke spark Four-stroke lean-burn Two-stroke spark
and conditions
a
ignited-engine spark ignited-engine ignited-engine
-----------------------------------------------------------------------------------------------------------------------------------------------------------
NOx 350-1000 ppm 100-4000 ppm 1200 ppm 100-200 ppm
HC 50-330 ppmC 500-5000 ppmC 1300 ppm C 20,000-30,000 ppmC
CO 300-1200 ppm 0.1-6% 1300 ppm 1-3%
O2 10-15% 0.2-2% 4-12% 0.2-2%
H2O 1.4-7% 10-12% 12% 10-12%
CO2 7% 10-13.5% 11% 10-13%
SOx 10100 ppm
b
15-60 ppm 20 ppm 20 ppm
PM 65 mg/m
3

Temperatures r.t.-650
0
C(r.t.420
0
C) r.t.-1100
0
C
c
r.t.-850
0
C r.t.-1000
0
C
(test cycle)
GHSV (h
1
) 30,000100,000 30,000100,000 30,000100,000 30,000100,000
(A/F)
d
1.8 (26) 1 (14.7) 1.16 (17) 1 (14.7)
e

---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
a N2 is remainder.
b For comparison: diesel fuels with 500 ppm of sulphur produce about 20 ppm of SO
2
.
c Close-coupled catalyst.
d defined as ratio of actual A/F to stoichiometric A/F, = 1 at stoichiometry (A/F = 14.7).
e Part of the fuel is employed for scavenging of the exhaust, which does not allow to define a precise definition of the A/F.

encapsulated Bi2O3 nanoparticles with a
homogeneous core/shell structure by using
monodispersed Bi2O3 nanospheres as templates
with a pre-coating of NH4
+
on the surfaces of Bi2O3
nanoparticles. The prepared core/shell nano-
particles exhibit promising catalytic activities
towards the oxidation of CO. Therefore, the Bi2O3/
CuCr2O4-CuO core/shell nanomaterials provide
promising for pollution treatment in car exhaust
purification.
Pre-reduced copper chromite catalysts have
been shown to be more active than unreduced ones
[232]. Pre-reduction with H2 produced higher
activity than prereduction with CO, which can be
attributed to a higher surface concentration of
active species after the former treatment. Activity
results, together with TPR and XPS
characterization point out that both Cu
0
and Cu
+

species are the primary active sites of CO oxidation
while surrounding Cr2O3 phase can prevent Cu
0

and Cu
+
from being oxidized to Cu(II), which will
limit the catalytic activity. The activated carbon
impregnated with Cu/Cr/Ag is a good catalyst for
CO oxidation at low temperature (<70
0
C) [234].
Stegenga et al. [235] reported that Cu-Cr oxide
based converters are superior to precious metal
based device for CO oxidation.
Hertl and Farrauto [227] employing infrared
spectroscopic, gravimetric, and kinetic techniques
studied the mechanism of oxidation of CO on a
copper chromite catalyst. They showed that surface
species involved in reaction are either a copper
carbonyl, at temperatures above 80
0
C or a
carbonate associated with chromium at higher
temperatures above 200
0
C. A thorough kinetic
study [228] of the two reactions, including the
phenomena of N2O formation and the reduction of
N2O with CO, provided a kinetic model that
accounts for the observed reaction behaviour of the
catalyst, and which can serve to model a converter
based on the Cu/Cr catalyst. The experimental
results indicate that these oxidic Cu/Cr catalysts
have a three way performance and that they may
find application in the purification of exhaust gases
of low sulphur contents. Prasad and Rattan [233]
studied kinetics of oxidation of CO over a novel
copper chromite catalyst in a compact bench scale
reactor. Preparation details of the catalyst are
given elsewhere [232]. On the basis of the
experimental findings they proposed the following
empirical rate expression (eqn. 47):

Rate = 2.02x10
4
exp(-12290/RT)(CCO)
0.7
(47)

Phosphorous and sulphor originating from fuel
and engine oil may lead to degradation of
automotive exhaust purification catalysts. Shelef
et al. [236] have documented the effects of various
poisons on the durability of various catalysts.
Mechanisms of catalyst deactivation have been
reviewed by Bartholomew [237]. SO2 can be severe
inhibitor for the oxidation of CO and hydrocarbons
[238] in the temperature range (400-600
0
C) of use
of base metal catalysts in automobiles. Kim et al.
[239] studied the deactivation of supported copper
chromite catalyst by SO2 and water vapour and
found that the degree of deactivation of the
catalyst due to SO2 was more severe than water
vapour. Lauder [240] reported that small amounts
of noble metals present in base metal perovskites
significantly improve their resistance to poison.
General Motors company preferred copper
chromite catalyst for exhaust emission control in
the beginning due to its much lower cost in
comparision to platinum [208]. It was later shown
to have inferior activity and was susceptible
poisoning by sulphur present in the fuel. By the
time catalysts were introduced in 1974, all car
companies had adopted platinum based systems
for emission control.
The main reason for withdrawal of base metals
from catalytic converter formulations was their
undesirable behavior in cycled transient conditions
and their high susceptibility to deactivation by
lead, sulphur and water [207]. The huge decrease
in sulphur content in the lead free fuels and
progress in oxide catalyst synthesis, have allowed
copper chromite to be reconsidered for practical
applications [241] in the catalytic converter.

2.4.1.2 Oxidation of hydrocarbon
Hydrocarbons such as benzene, formaldehyde,
hazardous polycyclic aromatic hydrocarbons
(PAHs), and nitropolycyclic aromatic hydrocarbons
(NPAHs), methane, butane, hexane, soot, propene,
decane, toluene etc. are mainly originated from
imperfect combustion of fossil fuels such as
petroleum and coal [242]. (PAHs) and (NPAHs)
have been identified as potent mutagens and
possible carcinogens. Both PAHs having 4 rings or
more and NPAHs are detected in particulates
exhausted from diesel and gasoline-engine
vehicles, while PAHs of lower molecular weights (3
rings or below) were detected in the gaseous phase
in the atmosphere and unburned diesel fuel [243-
245]. Copper chrmomite is the active catalyst for
the pyridine oxidation and NOx control [246].
Methane is a potent greenhouse gas. It has a
global warming potential (GWP) 23 times greater
than carbon dioxide. Reducing methane emissions
would lead to substantial economic and

environmental benefits. Methane is emitted from
a variety of anthropogenic activities, such as fossil
fuel production, biomass combustion, operation of
natural gas vehicles (NGVs), and waste
management [247]. For example, in mine
ventilation air, the methane concentration is 0.1-
1vol% [248]. In natural-gas-fuelled vehicles, which
are increasingly popular in some countries because
of their low emissions of NOx and particulates [249
-251], the unburned methane concentration in the
exhaust is around 0.3 vol.% [252]. It is estimated
that 60% of global methane emissions are related
to human-related activities [253]. Catalytic
combustion (eqn. 48) is considered to be an
effective approach to methane emissions
abatement [254].

CH4 + 2O2CO2 + 2H2O (48)

Hui et al. [255] showed that multi-transition-
metal-(Cu, Cr, Ni, and Co)-ion-exchanged zeolite
13X catalysts outperformed single-ion-exchanged
and acidified 13X catalysts and that lengthening
the residence time led up to 100% conversion at a
relatively low temperature of 500
0
C. The enhanced
catalytic activity in the multi-ion-exchanged
catalysts was attributed to the presence of
exchanged transition ions instead of acid sites in
the catalyst.
Comino et al. [170] found higher activity of
CuCr2O4 for CH4 combustion in the temperature
range 300-700
0
C at constant CH4/air ratio of 1:30
and constant methane content, 1.2%. Ismagilov et
al. [256] reported higher catalytic activity of Cu-Cr-
O catalyst for complete oxidation of n-butane in a
micro-channel reactor. According to Solovev [41]
the catalysts for n-hexane conversion are arranged
in the order of activities are expressed as follows:
CuCr2O4 > CuCo3O5 > CuMnO3 > Co3MnO6. Chien
et al. [213] repoted that the Cu-Cr/-Al2O3 catalyst
is highly active for oxidation of CO as well as for
propene also (eqn. 49).

2C3H6 + 9O2 6CO2 + 6H2O (49)

The activity of propene oxidation over Cu-Cr/-
Al2O3 catalysts increases with increasing heat-
treatment temperature in an oxidizing
atmosphere. The activity of propene oxidation on
the CuO catalyst reaches a maximum at a copper
content of about 10 wt.-% and that on the Cr2O3
catalyst reaches a maximum at a chromium
content of about 25 wt.-%. Harrison et al [257]
studied the preparation, characterization, and
catalytic activity of Cr(VI)-and Cu(II)-doped tin(IV)
oxide catalysts. The catalysts, particularly the
mixed Sn-Cu-Cr-O catalysts, exhibit comparable
activity to conventional platinum catalysts for CO
and hydrocarbon oxidation.

2.4.1.3 NOX abatement
Oxides of nitrogen (NOx) consist of N2O, NO and
NO2 pollutants which are emitted from both
natural and anthropogenic sources in large
quantities. Enormous concern over the role of NOx,
as one of the primary pollutants for the green
house effect, on ozone formation and depletion in
stratosphere, on formation of photochemical smog,
and acidic precipitation has received increasing
attention since 1970s because of its detrimental
effect on life on earth in general [258]. If NOx is
prevented from entering the atmosphere, most of
the down-stream effects of pollution can be
eliminated. Copper chromite has been recognised
as the active catalyst for the NOx pollution control
[259,260].
Nitrous oxide (N2O) is a compound that during
the last decade has been recognized as a potential
contributor to the destruction of the ozone in the
stratosphere and acknowledged as a relatively
strong greenhouse gas [261,262]. The continuous
increase of its concentration, both due to natural
and anthropogenic sources (adipic acid production,
nitric acid production, fossil fuels, biomass
burning) and longer atmospheric residence time
(150 years), entails the need of developing efficient
catalysts for its decomposition (into nitrogen and
oxygen). In recent years, spinel-type oxides such as
CuCr2O4 have been the subject of increasing
fundamental and applied research because of their
good stability and intrinsic catalytic activity [259].
The two most toxic oxide gases of nitrogen are NO
and NO2 of which NO2 is known to be more toxic.
NOx are These oxides produced by the high
temperature combustion of fuels that use air as an
oxidant, through endothermic oxidation of N2 by
O2. Automotive vehicles as well as industries are
also the major sources of NOx emission [263,264].
NO plays a major role in the photochemistry of
the troposphere and the stratosphere [265]. The
photochemical complex HC-NOx-Ox is formed
during the HC interactions in the photolytic cycle
of NO; the mixture of products generated is called
photochemical smog and contains O3, CO,
peroxyacetyl nitrates (PAN), alkyl nitrates,
ketones, etc [265]. The chemical depletion of ozone,
in an important part due to nitrogen oxide species,
is a prolonged phenomenon [266]. Carcinogenic
products are also formed during these reactions.
NO2 is linked to causing bronchitis, pneumonia,

susceptibility to viral infection, and alterations to
the immune system [267]. It also contributes to
acid rain, urban smog, and ozone [268]. Therefore,
it is important to control the emission of such gases
to comply with stringent emission standards. The
three way catalytic (TWC) reduction of NO in the
presence of CO, HC and/or hydrogen is typical of
automotive pollution control [265]. Shelef and
Gandhi [269] first investigated the reduction of NO
with hydrogen on copper chromite catalysts. NO
reduction by CO has been examined over
supported Cu-Cr systems by sevaral workers
[209,235,270]. Lee at al. [271] observed maximum
activity for NO decomposition over co-impregnated
copper chromite on mordenites at 450
0
C. For the
NO + CO reaction, the catalytic performance of
copper-supported catalyst was significantly
affected by the addition of Cr. The Cu-Cr system
exhibited an overall better performance than the
single metal catalytic system (Cu, Co, and Ni) and
three-way catalytic converter [209,235]. The
characteristics of CO and NO molecules at Cu
2+

and Cr
3+
ion sites on the CuCr2O4 (100) surface
have been studied by Xu et al. [272]. They found
that CO/NO mixture adsorb selectively at the Cu
2+
ion site and simultaneously at the Cr
3+
ion site,
respectively. Stegenga et al. [235] investigated a Zr
-stabilized Degussa monolith prepared by using
washcoats corresponding to 10 wt% Cu-Cr loading
on Al2O3 or 2.5 wt% La-stabilized Al2O3. These
monoliths had behaviour typical of three-way
catalysts.

2.4.1.4 Volatile organic compounds abatement
Volatile organic compounds (VOCs) are the
carbon containing compounds which have
significant vaporization due to high vapour
pressure at ambient conditions [273]. Being
volatile they enter the atmosphere and are harmful
to human beings and environment because of their
toxicity and malodorous nature. These are emitted
from many industrial processes, transportation
and house-hold activities and are considered as an
important class of air pollutants [274]. Many VOCs
have been proved to be carcinogenic and mutagenic
and contribute to stratospheric ozone depletion
[275]. Moreover, once emitted into the atmosphere,
VOCs could be the precursors for the formation of
secondary pollutants such as smog, aerosol, ground
level ozone, peroxy-acetyl-nitrate (PAN), and
polycyclic aromatic hydrocarbon (PAH) etc. by
photochemical reaction [276]. Because of these
negative effects, legislation has been introduced in
many countries setting very low emission limits for
VOCs in process exhaust e.g. Occupational Safety
and Health Administration Permissible Exposure
Level (OSHA PEL) for toluene is 100 ppm in the
workplace [277]. Therefore, the proper control,
removal, and reduction of the emission of VOCs are
the crucial tasks for the protection of the
environment.
Catalytic combustion is a promising way to
control the emissions of the VOCs [278]. Catalytic
combustion processes (Fig.13), typically achieve
complete destruction at temperatures around 350-
500
0
C, which are much lower than those used in
thermal combustion (800-1200
0
C) [279]. The
lowering of reaction temperatures leads to several
advantages in terms of environmental impact as
well as energy saving: very low production of
secondary pollutants (i.e., NOx and micropollutants
such as dioxins from chlorinated compounds) and
reduction of fuel costs [275]. Moreover catalytic
combustion exhibits advantages such as high
efficiency, ultra low pollutant emissions, stable
combustion, and so on [280]. The coupling of a low-
temperature oxidation catalyst with an improved
combustion technology can lead to further decrease
of reaction temperatures at which the complete
destruction of VOCs is obtained [280].
Among VOC, ethyl acetate is a key component
in ink manufacture. The catalytic combustion of
ethyl acetate has been investigated by Mazzocchia
and Kaddouri [9] using undoped and Mn- or Ba-
doped copper chromite catalysts. Good conversion
reported even at low temperatures (180-240
0
C).
While in the presence of molecular oxygen the only
product observed was CO2, when the reaction has
been carried out in the absence of oxygen (with
lattice oxygen alone) noticeable amounts of CO
were also detected [281]. The synergic effects of the
combustion catalyst Ba-CuO-Cr2O3/Al203 and
ozone, used as strong oxidant species in the
combustion of various VOCs such as, acrylonitrile,
Fig. 13. Schematic drawing of catalytic oxidation
of VOCs

methanol, styrene, toluene and 1,2-dichloroethane
[278] .
With the Clean Air Act amendments requiring
increased use of oxygenated compounds such as
alcohols and ethers in motor fuels, the problem of
effectively controlling the emissions caused by
burning these substances has become a more
pressing issue. Alcohols, both ethanol and
methanol, are currently in use. Supported catalysts
containing mixed oxides of copper and chromium
prepared by a wet impregnation technique and
supported on -alumina shows activity for complete
oxidation of ethanol, acetaldehyde, and methanol-
ethanol mixture [213].
Driven by the need for decreasing
manufacturing cost and increasing resistance to
poisoning of commercial catalysts for volatile
organic compounds (VOCs) elimination, efforts
have been made to develop metal oxide catalysts,
which can exhibit activity similar or higher than of
noble metal catalysts [281]. Among these catalysts
the copper-chromite seems to be promising for the
VOCs total combustion and it was also
comparatively tested with noble metal catalysts
[278,281]. Ismagilov et al. [256] fabricated
microreactors with alumina coating impregnated
with an aqueous solution of copper dichromate
followed by drying and calcination at 450
0
C to
produce active copper chromite catalysts. They
studied the effect of a copper dichromate
concentration, number of impregnation cycles (1 or
2), and different after-treatments on catalytic
activity and stability in complete oxidation of n-
butane. They observed that even at much lower
loadings of active metals, the catalytic activity of
the prepared coatings, related to the volume of the
alumina layer, is superior to that of pelletized
catalysts. They concluded that the microreactors
made according to their procedures can be used for
a variety of small-scale total oxidation processes
involving combustion of toxic and hazardous
chemicals.
The industrial formaldehyde production all over
the world produce huge amount of dusts and
exhaust gases, which contains CO, dimethyl ether
and methanol as main components. Therefore,
their complete oxidation is of high importance for
environmental protection. Cherkezova-Zheleva et
al. [282] reported total oxidation of CO, dimethyl
ether and methanol over copper chromite catalysts
supported on -Al2O3. Copper chromite catalysts
were evaluated by Heyes et al. [214] for the control
of organic air pollutants responsible for
malodorous process emissions. In laboratory tests,
catalyst shows the ability to achieve and maintain
high efficiency for the complete oxidation of n-
butanal and methyl mercaptan [100 ppm in air].
The life of copper chromite could be extended by
washing after partial deactivation by retained
sulphur. Odour removal efficiencies (measured by
olfactometry in terms of dilution to detection
threshold values) at 340-415
0
C was found mostly
in the range 98.5-99.5%.
Organic Ion Exchange (IX) resins used to purify
primary coolant of nuclear power plants contain
high 137 Cesium and 60 Cobalt radioactivities.
Direct fixation of spent IX resin wastes in polymer
or slag cement matrices leads to increase in waste
form volumes. For organic wastes, incineration
appears to be most logical route to reduce waste
form volumes. Pyrolysis of IX resins leads to
release of radioactivity, SO2, styrene, toluene, ethyl
benzene and trimethyl amine to the off gases. The
organic matter in off gases could be successfully
oxidised by using CuO.CuCr2O4 catalysts at
temperature above 475
0
C and 22500 hr-
1
space
velocity [283].

2.4.2 Diesel exhaust gas purification
It is expected that the world market for diesel
engines will grow significantly in the near future
because of their superior thermal efficiency,
durability, and reliability in comparison to the
gasoline-powered engine. Exhausts of gasoline-
fueled engines operated near stoichiometric air/fuel
ratio have been successfully cleaned up by three-
way catalytic systems, while the pollution by diesel
-engine exhausts has become more and more
serious in the last decade. For diesel emission
control, three possibilities, i.e., oxidation, soot
trapping and NOx reduction, have been
investigated [284]. Nitrogen oxides (NOx) and
particulate matters (PM) are main objectives to be
removed from diesel exhausts. Since
concentrations of CO and hydrocarbons are lower
and that of O2 is higher in diesel exhausts than in
gasoline-engine exhausts, three-way catalysts
cannot remove NOx from the diesel exhausts [285].
The ever-increasingly stringent exhaust
emissions legislation requires an ever-increasing
degree of efficiency of a catalytic converter.
CuCr2O4 catalysts are found active for
simultaneous catalytic removal of NO and diesel
soot particulates [286]. Catalytic performance of
CuCr2O4 for the simultaneous NOx-soot removal
reaction was investigated by Teraoka and Kagawa
[285]. Selective catalytic reduction of NOx with
hydrocarbons (SCR-HC) has the potential in
eliminating NOx emission from the oxygen rich
(lean conditions) exhaust. CuCr2O4 is identified as
one such catalyst active for SCR-HC [287]. The

conversion of NO over Cu-Cr/-Al2O3 catalyst in the
SCR of NO by NH3 in the presence of sulfur dioxide
was reported to be very high (95-100%) [288].
Recent studies have demonstrated a positive
effect on the reduction of diesel emissions by
adding oxygenated compounds [289]. Light
catalytic gas oil (LCO) hydrotreating was
performed by Tailleur and Caris [290] on a
laboratory-scale trickle bed reactor to obtain a 15
ppm sulfur fuel. The fuel was then selectively
oxidized using a CuCr/IP(4-PVP) catalyst in air at
different operating conditions on a laboratory-scale
continuously stirred tank reactor. The oxygenated
and polyoxygenated compounds formed were
measured and fuel stability was also measured.
The results show a decrease in emissions by low-
sulfur diesel oxidation, as well as the benefits of
having a high selectivity toward ketone formation
when using a CuCr/IP(4-PVP) catalyst [290].

2.4.2.1 Diesel soot oxidation
The diesel engines find widespread applications
as power source in both automotive and stationary
applications but their emissions of particulate
matter (soot) and NOx are responsible of severe
environmental and health problems. Therefore,
special attention has been paid to the reduction of
soot particulate emitted from diesel engines. Soot
can be effectively trapped by diesel particulate
filters [291]. Traditional soot filters are made from
metallic wires, ceramic foams, inorganic fibers,
etc., which have a number of unsatisfactory
features connected, in the first place with the
complexity of regenerating the filters. The most
effective solution to the problem is the combination
in a single element of the functions of the soot filter
and soot oxidant [292].
In recent years there have been attempts to
develop catalytic coatings for soot filters, capable of
improving their effectiveness and of oxidizing
carbon particles directly in the soot filters. Solovev
et al. [41,292] showed that the most reactive
catalyst both in the model reaction of oxidising CO
and hexane and in the burning of diesel soot
present in the gaseous exhaust of internal
combustion engines is copper chromite. Further
they reported that regeneration of soot filters with
catalytic coatings of copper chromite is possible
even at the temperatures of exhaust gases from
internal combustion engine.

2.5 Desulphurization of hot coal gas
The energy demand of the world, which
increases in accordance with the rise in economic
development, will have to be met by the prevalent
energy sources, such as coal, new sources, as well
as improvement of the efficiency of energy
production technologies. However, the growth in
energy production need not take place to the
detriment of the environment, so that strict
regulations on pollutant emissions have been
imposed around the world. An integrated
gasification combined cycle (IGCC) systems are
being advanced today, due to their higher thermal
efficiency and superior environmental performance
and economics, compared to conventional plants
[293]. The development of these systems depends
on the ability to remove sulphur compounds,
mainly H2S, from the coal gas. During gasification
process, about 95% of the sulphur contained in the
coal is turned into H2S and rest of them are
converted into SO2 [294]. The produced H2S should
be lowered from the typical gasifier output of 5000
ppm to the tolerable limit of 150 ppm [295]. H2S
being a very corrosive gas, could be damaging to
the mechanical parts and the construction material
at high temperatures and pressures under IGCC
system conditions.
Although thermal efficiencies of 30-35% are
typical for conventional pulverized coal plants,
efficiencies of 43-46% may be easily attainable by
IGCC with HGC. This improvement in efficiency
would represent a significant decrease in the cost
of electricity along with a reduction in emissions of
sulphur compounds [296]. In addition, the method
offers potential improvements for hydrogen fuelled
solid oxide fuel cells (SOFC) and molten carbonate
fuel cells (MCFC) technologies [297].
In order to have high efficiency in the IGCC
system, removal of H2S without cooling the coal
gas is a very important task. These facts
emphasises the importance of hot gas
desulphurization. Hot gas desulphurization may be
accomplished by using sorbents such as metal
oxides that forms stable sulphides. Typically, these
metal oxides are converted to sulphides during a
sulphur-loading stage under reducing hot fuel gas
conditions [298]. This reaction is represented
generically by the following equation 50:

Sulfidation: MO + H2S MS + H2O (50)

The ultimate capability of removing H2S
depends on the thermodynamic properties of the
metal oxide. In addition, H2S capacity, which is
defined as grams of sulphur removed by 100 grams
of sorbent, is an important parameter. Economic
considerations require that the sulphided sorbent
be regenerable according to the following generic
reaction (eqn. 51):

Regeneration: MS + 1.5O2 MO + SO2 (51)

SO2 must be captured and ultimately be
converted to elemental sulphur or sulphuric acid.
Copper oxide is able to achieve low levels of H2S in
the clean fuel gas provided the sorbent is not
reduced to elemental copper. This is because
copper oxide readily reduces in high temperature
reducing atmospheres, and elemental copper is an
order of magnitude less active for sulfidation than
Cu2O and CuO [299].
Binary Cu-Cr-O oxides were studied as
regenerable sorbents for high temperature fuel gas
desulphurization by Li and Stephanopoulos [21].
CuO-Cr2O3 sorbents can remove H2S from
simulated coal-derived fuel gas to less than 5-10
ppmv in the temperature range of 650-850
0
C. The
presence of stable CuCr2O4 in CuO-Cr2O3 solids
retains some copper in the Cu
+2
or Cu
+1
oxidation
state, which can account for the high H2S removal
efficiency. A regenerable copper chromite sorbent
with superior hot fuel gas desulfurization
performance has been developed for IGCC
applications by Abbasian and Slimane [300] in the
temperature range of 550-650
0
C. This sorbent is
capable of achieving less than 5 ppmv H2S
concentration in the cleaned fuel gas.

2.6 Mercury capture from hot coal gas
Coal-fired utilities are the largest source of
anthropogenic mercury emissions. Because of its
high volatility, almost all the mercury present in
coal is transformed into gas phase during
combustion or gasification of coal. Control of
mercury emissions from coal-fired power plants is
a difficult task, in part due to its high volatility
and its much lower concentration (5-20 g/m3) in a
large volume of flue gas. In addition, depending on
the type of coal and combustion conditions, a
majority of mercury in the flue gas can exist in the
elemental form (Hg
0
), which is more difficult to
capture than its oxidized (Hg
2+
) or particulate
(Hgp) forms. Jadhav [301] evaluated Nano Active
sorbents (CuO-Cr2O3) for Hg capture. He
explained the role of Cr, which would suppress the
reduction of Cu in the presence of H2 and would
maintain Cu in Cu
2+
state [4], which would have
enhanced reactivity towards Hg. This experimental
study has demonstrated that supported forms of
binary oxides of Cu and Cr have showed their
potential as effective Hg sorbents.
2.7 Removal of aqueous organic waste
The main polluting branches of industry are
refineries, coke ovens, organic compounds
production plants, pharmaceuticals factories, pulp
and paper mills, textile, leather industries, etc.
Waste water from these industrial and agricultural
activities contains refractory organic pollutants
such as plaguicides, organochloride compounds,
phenols, detergents, polycyclic aromatic
hydrocarbons, etc. that must be treated before
discharge to comply with the environmental
regulations. Water treatment technologies require
revision, modernization and enriching by utilizing
more effective methods and catalyst to achieve
required standards for drinking water along with
keeping in mind the conomic aspects [302].
Therefore, it is important to have efficient catalyst
at our disposal for removal and oxidation of
pollutants present in wastewater in reduced forms
- NO
2-
, NH
4+
, phenols etc.

2.7.1 Wet oxidation of phenol
Among the harmful organic compounds in
industrial wastewaters, phenol and phenolic
substances have deserved more attention in the
last two decades, because of their toxicity and the
frequency of industrial processes producing waters
contaminated by phenol. Moreover, phenol is
considered to be an intermediate product in the
oxidation pathway of higher molecular weight
aromatic hydrocarbons, thus it is usually taken as
a model compound for advanced wastewater
treatments [303]. The conventional process of
biological oxidation fails to destroy toxic and
rec al c i t r ant pol l ut ant s l i ke phenol .
Santos et al. [304] have reported the high
detoxification of phenolic wastewater about 77%
using a heterogeneous catalyst based on
CuO.Cr2O3 at basic pH, obtained by adding sodium
bicarbonate as buffer reactive (pH 8). Further, they
observed that the catalyst was chemically and
mechanically stable during long periods of time on
stream, this point being of great importance for its
industrial application. The oxidation of phenol in
water over 26% CuO + 74% Cu-Chromite in a
batch autoclave was investigated by Akyurtlu et al.
[305]. They found copper chromite to be most
active catalyst and concluded that depending on
the operating conditions, the catalyst can facilitate
complete phenol conversion within 90 min.

2.7.2 Ammonia removal
The formation of ammonia is inevitable during
industrial-scale wet oxidation of wastewater if
nitrogen-containing compounds (like: production of
soda, nitric acid, urea; metallurgical industry; coal

or biomass gasification) are present. The major
source of ammonia emission has been attributed to
the intensive farming areas and notably to
livestock manure [306]. Ammonia is toxic for fishes
and other marine organisms. It causes
eutrophication in ponds and lakes. It has been
recently studied for its role in the formation of a
rural version of urban smog [307]. The ammonia-
containing waste produced in industries is usually
characterized by high concentration and high
temperature, and is not treatable by biological
methods directly [308]. Huang et al. [308]
suggested wet oxidation as a promising means of
pretreating wastewater containing ammonia at
concentrations of up to 600 mg/L.
As most of the wet oxidation processes run at
elevated pressure and temperature, running the
heterogeneously catalysed oxidation of ammonia in
the gas phase in a downstream reactor could
protect the catalysts mainly from leaching and
offers an economic alternative by avoiding loss of
unused oxygen after depressurisation. Noble metal
-containing catalysts [309] are used for wet
oxidation processes, but they are very costly and
insufficient stability against hydrothermal impact.
Martin et al [310] reported oxidation of ammonia
with air in steam atmosphere using Cu,Cr-
containing supported and bulk copper chromite
catalysts at 235-305
0
C and 30-60 bar. Bulk copper
chromite catalyst gave the best performance (86%
conversion) at 305
0
C, 45 bar and contact time of 1
second. It shows only slight changes in their
structural phase composition, high contents of Cr
(III) in a CuCr2O4 spinel phase and higher
stability.

2.7.3 Nitrite Removal
Nitrite is a common pollutant in water whose
principal source arises from fertilizers and
industrial rejects causing ecological problems
[311]. The world health organization guidelines
required the levels of NO
2-
and NO
3-
in drinking
water less than or equal to 3.3 and 44 mg L
-1

respectively. The nitrite removal from water is a
topic of great concern owing to its toxicity to the
environment and detrimental to human health.
NO
2-
coming from industrial activities disturbs the
ecological system and beyond a threshold
concentration, it becomes an increasing problem
[312]. High concentrations of nitrates in drinking
water are harmful due to their reduction to nitrites
(NO
2-
) that combine with haemoglobin in the
human blood to form the toxic compound of
methaemoglobin [313]. The photoactive CuCrO2 is
low cost, easy to synthesize and exhibits a long
term chemical stability in the nitrite conversion
almost complete in less than 5 h [314]. CuCrO2
exhibits a long term chemical stability with a
corrosion rate of 0.34 mol m
-2
year
-1
in KCl (0.5
M).

2.8. Burning rate catalyst for solid
propellants
In recent years the Cu-Cr-O composites are
found great promising in application as burning
rate catalysts (ballistic modifier) for solid
propellants used in defence (high explosives,
ballistic missiles) [315] and space vehicles (rocket
propellants) [316-318]. Solid composite propellants
are mixtures of prepolymer (binder), aluminum
fuel, oxidizer salts (e.g. ammonium perchlorate),
and other components, including curatives,
plasticizers, bonding agents, stabilizers and
catalysts [319]. Even though added at few percent
of the propellant binder, the catalysts used to
control the burn rate are of high importance, since
they allow improving the ballistics of rockets.
Combustion of this system involves the
decomposition of AP(ammonium perchlorate) and
the binder and mixing and oxidation-reduction of
the decomposition products.
Rajeev et al. [316] prepared Cu-Cr-O composite
oxides via thermal decomposition of copper
ammonium chromate and found that the
propellant burning rate is enhanced by the
addition of Cu-Cr-O composite oxides. Li et al. [10]
used Cu-Cr-O nanocomposites as additives for the
catalytic combustion of AP-based solid-state
propellants, synthesized via a citric acid (CA)
complexing approach. They showed that well-
crystallized Cu-Cr-O nanocomposites could be
produced after the CA-Cu-Cr precursors are
calcined at 500
0
C for 3 h. Addition of the as-
synthesized Cu-Cr-O nanocomposites as catalysts
enhances the burning rate as well as lowers the
pressure exponent of the AP-based solid-state
propellants considerably. Noticeably, catalyst with
a Cu/Cr molar ratio of 0.7 exhibited promising
catalytic activity with high burning rate and low
pressure exponent at all pressures, due to the
effective phase interaction between the spinel
CuCr2O4 and delafossite CuCrO2 contained in the
as-synthesized Cu-Cr-O nanocomposites. Patil, et
al. [320] synthesized p-type nano-CuO and
CuCr2O4 by an electrochemical method and
investigated the catalytic effect on the thermal
decomposition behaviour of ammonium perchlorate
(AP) as a function of catalyst concentration using
differential scanning calorimetry. The nano-copper
chromite (CuCr2O4) showed best catalytic effects as

compared to nano-cupric oxide (CuO) in lowering
the high temperature decomposition by 118
0
C at 2
wt.%. They observed high heat released of 5.430
and 3.921 kJ g
-1
in the presence of nano-CuO and
CuCr2O4, respectively. The decrease in the
activation energy and the increase in the rate
constant for both the oxides confirmed the
enhancement in catalytic activity of AP. They
proposed a mechanism based on an electron
transfer process for AP in the presence of nano-
metal oxides.

2.9. Electrodes and Sensors
NOx, are the primary pollutants produced by
the high temperature combustion processes,
automotive vehicles as well as industries. There is
a need to detect NOx in the concentration range
between 10 and 2000 ppm for a greater control of
fuel combustion processes and for monitoring
automobile exhaust gases [321]. NOx
electrochemical sensors based on ceramic materials
are suitable in high temperature application and in
chemically harsh environment since they are
mainly based on semi-conducting oxides and solid
electrolytes. Xiong et al. [322,323] studied a mixed-
potential sensor based on CuO + CuCr2O4 which
exhibited high selectivity and sensitivity toward
NO2. They found the open-circuit electromotive
force (EMF) of the NO2 sensor to be stable,
reproducible and, the sensor responded rapidly
(t90 < 8 s) to change in the NO2 concentration
between 100 and 500 ppm at 659
0
C [323]. Porous
Pt reference electrode was used in the research
[321,322]. Recently, the same workers [23] tested a
solid-state planar sensor consisting of scandia-
stabilised zirconia (8 mol% Sc2O3-ZrO2) solid
electrolyte sandwiched between CuO + CuCr2O4
mixed-oxide and Au foil reference electrodes in
NO2 containing gaseous atmosphere in the range of
100-500 ppm NO2 at 611 and 658
0
C. They found
that the response time of the sensor was less than
6 s and the recovery time was approximately 6 s at
658
0
C, respectively. The response of the sensor
was found to be logarithmically dependent on the
concentration of NO2 between 100 and 500 ppm at
611
0
C whereas it was found to vary linearly with
the concentration of NO2 at 658
0
C. The response of
the sensor was highly reproducible to change in
concentration of NO2 and also showed negligible
cross-sensitivity to O2, CO and CH4 in the gas
stream.

2.10. Semiconductors
Diluted magnetic semiconductors (DMSs)
involve charge and spin degrees of freedom in a
single substance and therefore have attracted
much interest owing to their unique magnetic,
magneto-optical and magneto-electrical effects.
Possible spintronic devices are spin-valve
transistors, spin light-emitting diodes and
nonvolatile logic devices [24]. Generally, oxide
semiconductors have wide band gaps, i.e.
transparent for visible light. This feature serves an
important role as transparent conducting oxides
(TCOs) that are used for various applications such
as transparent electrodes in flat panel displays and
window layers in solar cells. Li et al. [24]
successfully prepared Mn-doped CuCrO2
polycrystalline semiconductors by the sol-gel
method which exhibit FM transitions at about 120
K.
Among the physical properties of solid materials
which have been used as heterogeneous catalysts
in a variety of chemical industries, the electrical
conductivity and thermoelectric power are of
fundamental importance [324]. The electrical
transport of catalysts is of basic importance in the
determination of the relationship between
electronic structures and catalytic properties of
semiconductors. The electrical conductivity and
thermoelectric power of CuCr2O4 are reported in
the temperature range 295 to 815 K [325].

2.11. Drugs and agrochemicals
Nitrogen-containing heterocyclic compounds,
such as quinoline, indoles, pyrroles, pyrrolidines
(and their alkylated homologues), piperazine and
pyrazine are of high industrial interest, for
applications as intermediates to produce
pharmaceuticals, agro chemicals (herbicides,
fungicides), dyes, etc. [326-328]. Pyrazine is
synthesized by passing ethylene-diamine (ED)
vapor over a copper oxide/copper chromite catalysts
in the temperature range of 340-440
0
C with a very
high selectivity (98-100%) [19]. The reaction
proceeds by intermolecular deamination and
cyclization of ED to form piperazine, which
undergoes subsequent dehydrogenation to form
pyrazine (Fig. 14).
Propylene glycol (PG) is used in
pharmaceuticals, such as: a carrier of active
ingredients in vaccines, cough relief syrups or gel
capsules to help deliver these substances within
the body for treatment and prevention of diseases.
It is also used as a solvent in many
pharmaceuticals, including oral, injectable and
topical formulations. Notably, diazepam, which is
insoluble in water, uses PG as its solvent in its
clinical, injectable form [329]. PG is synthesized
efficiently by hydrogenolysis of glycerol over copper

chromite catalysts [110].
A novel environment-friendly vapour phase
synthesis of different classes of nitrogen-containing
heterocyclic compounds was developed by
Campanati et al. [330] using non-hazardous,
commercially available and low cost feeds. 2-
Methyl-8-ethylquinoline (MEQUI) was synthesized
from 2-ethylaniline (2-ETAN) and ethylene glycol
(EG) or chloro-ethanol (CE), operating at high
temperature in the presence of acid-treated K10
montmorillonite or ZnCl2/K10 montmorillonite. At
lower temperatures and using copper chromite
catalysts, 7-ethylindole (7-ETI) or 5-ethylindole (5-
ETI) were obtained from 2-ETAN or 4-ethylaniline
(4-ETAN), respectively, and EG; excess of alkyl-
aniline was required to avoid the formation of
polyalkylated by-products. Mixing SiO2 with the
best copper chromite, made it possible to operate
with higher LHSV values, thus improving the yield
in alkylindoles. Finally, N-(2-ethylphenyl) pyrrole
(EPP) and N-(2-ethylphenyl) pyrrolidine (EPD)
were synthesised using a commercial copper
chromite catalyst and feeding 2-ETAN and 2,3-
dihydrofuran (DHF), EPP being favoured by high
temperatures and absence of water in the feed
(Fig. 15).

3. Preparation methods of copper chromite
catalyst
Catalysts, when prepared via different routes,
would demonstrate different properties, even with
the same starting compositions. Crystallinity,
surface properties, and specific surface area, three
of the most important parameters determining the
catalytic activity of the product are highly
dependent on the synthesizing routes [14]. Several
preparation methods have been established to
prepare CuCr2O4, for instance chromium and
copper doubly promoted ceria catalysts have been
prepared by Harrison et al. [331] by three routes:
(A) coprecipitation from aqueous solutions
containing cerium(IV), copper(II), and chromium
(III) ions, (B) sequential impregnation of CeO2 by
using an aqueous CrO3 solution followed by an
aqueous solution of copper(II) nitrate, and (C)
impregnation of Cu(II)/CeO2 prepared by
coprecipitation by using an aqueous CrO3 solution.
They found that at low processing temperatures,
copper is present as (polymeric) Cu(OH)2 in both
the Cu/Cr/CeO2-cop and Cu/Cr/CeO2-cop/imp
materials. Chromium is present as adsorbed
(Cr2O7
2-
) ions in the Cu/Cr/CeO2-imp/imp and Cu/
Cr/CeO2-cop/imp materials, but a variety of
chromium species in oxidation states +III, +V and
+VI are present in the Cu/Cr/CeO2-cop material.
Brief descriptions of synthesis principles,
typical processes, important aspects that influence
the characteristics, specific advantages and some
experimental data are presented for the following
methods for the preparation of CuCr2O4 catalysts:

Co-precipitation method
Adkins method
Complexing-coprecipitation method
Co-impregnation method
Thermal decomposition (ACOC)
Thermal decomposition of ammoniacal
copper oxalate chromate (ACOC)
Hydrothermal method
Non-Casting method: Template technique
Hydrolysis of some soluble salts
Microemulsion method
Fig. 14. A generalized reaction pathway for the for-
mation of pyrazine and other products.
Fig. 15. Reaction pathway for the synthesis of
N-(2-ethylphenyl) pyrrole (EPP) and N-
(ethylphenyl) pyrrolidine (EPD) using CuCr2O4
catalysts [331]

Combustion synthesis
Self-propagating high-temperature
synthesis
Solution combustion synthesis
Electroless method
Sonochemical method
Metal organic chemical vapour deposition
(MOCVD)
Flame Synthesis of Nanostructured
Chemical reduction method
Sol-gel process
Citric acid (CA) complexing approach
Pechini Method
Non-alkoxide sol-gel route

3. 1 Co-precipitation method
3.1.1 Adkins method
The preparation procedure [44] is as follows:
Ammonium hydroxide was added to a solution of
126 g. (0.5 mole) of ammonium dichromate in 500
ml. of water until the colour of the solution
changed from orange to yellow. The volume of the
solution was now 653 ml. The solution was allowed
to come to room temperature and a solution of
241.6 g. (1.0 mole) of cupric nitrate tri-hydrate in
300 ml. of water was added with stirring. The red-
brown precipitate of basic copper ammonium
chromate (BCAC) was filtered with suction and
dried overnight in an oven at 100-110
0
C. It was
then finely powdered, transferred to a porcelain
casserole, and decomposed by heating the casserole
in the flame of a Bunsen burner. After
decomposition had begun, the heat of reaction was
sufficient almost completely to decompose the
chromate. When spontaneous decomposition had
ceased, the casserole was heated with the free
flame until fumes ceased to be evolved and the
contents was black and so finely powdered as to be
almost like a liquid. During this heating, care was
taken to keep the material well stirred and to
rotate the flame in order to avoid local
superheating. The product was allowed to cool and
then suspended in 200 ml. of a 10% solution of
acetic acid. The suspension was filtered with
suction, washed thoroughly with water, dried for
twelve hours in an oven at 100-110
0
C, and finely
powdered. The yield of catalyst was 113 g. The
reactions involved can be represented by the
following equation 52-55:

(NH4)2Cr2O7 + 2NH4OH 2(NH4)2CrO4 + H2O
(52)
(NH4)2CrO4 + Cu(NO3)2 + NH4OH Cu
(OH).NH4CrO4 + 2NH4NO3 (53)
2Cu(OH)NH4CrO4 CuO.CuCr2O4 + N2 + 5H2O
(54)
CuO.CuCr2O4 + 2CH3COOH CuCr2O4 +
(CH3COO)2Cu + H2O (55)

Adkins et al. [44] have hydrogenated a group of
21 organic compounds using above prepared
catalyst and reported that 16 have been
successfully hydrogenated with 100% yield and
100% selectivity.
Kawamoto et al. [315] prepared the catalyst
following the co-precipitation method from aqueous
solution of K2Cr2O7 and CuSO4.5H2O in the
presence of ammonia at Cu/Cr molar ratios of 0.3
and 0.5. The fine precipitates of BCAC were
filtered, washed with distilled water and dried at
110
0
C to a constant weight. Then, they were
powdered to a 250 mesh and heated at 500
0
C for 2
hours. The formation of the catalyst can be
represented by equations 56 and 57:

2CuSO4 + K2Cr2O7 + 4 NH3 + 3H2O K2SO4 +
2Cu(OH)NH4CrO4 + (NH4)2SO4 (56)

110-500
o
C
2Cu(OH)NH4CrO4 CuO.CuCr2O4 + 5H2O
(57)

They concluded that the samples synthesized by
the co-precipitation method present a better
granulometric distribution than solid state
reaction and this has led to propellants with higher
burning rate and higher pressure exponent.

3.1.2 Complexing-coprecipitation method
The most common method for mixed-oxide
catalyst preparation is crystallization or
precipitation or co-precipitation in solution of a
precursor form (hydroxide, oxide, insoluble salt) of
the catalyst [332]. Other specific steps, for example
either addition of an extra component or its
removal by partial extraction, may sometimes be
necessary to adjust the final catalyst composition
and ensure homogeneity [333]. Adkins et al. [44]
described for the first time preparation of copper
chromite catalyst for hydrogenation of organic
compounds following this method. Subsequently,
several workers used this method for the
preparation of copper chromite catalysts using
different compounds of copper and chromium with
aqueous ammonia solution as precipitating agent.

3.2. Co-impregnation method
Co-impregnation method is the easiest method

of preparation of copper chromite catalysts. In this
method catalysts are obtained [291,334] by mixing
of support (-Al2O3) with an aqueous solution of
chromium anhydride and copper nitrate in
required proportion. The amount of solution taken
is sufficient for incipient wetness to be observed.
The samples are dried and calcinated at
appropriate temperatures to get the catalysts.

3.3 Solid state reaction (ceramic method)
The vast majority of the powder synthesis of
high temperature superconducting oxides to date
has been carried out using the traditional solid-
state reaction route [335]. Copper chromite
spinels are usually synthesized by the conventional
high temperature method of solid state reaction
(eqn. 58):
900
o
C
CuO(s) + Cr2O3(s) CuCr2O4 (s) (58)
6h
Kawamoto et al. [315] prepared copper chromite
by ceramic method, mixing copper (II) and
chromium (III) oxides at 3 different ratios Cu/Cr =
0.61; Cu/Cr = 1.0; Cu/Cr = 1.5. The mixtures of
oxides were homogenized with acetone followed by
subsequent calcination at 900
0
C for 6 hours. This
method results in spinel particles with low surface
areas. In order to synthesize spinels with high
surface area, they attempted different wet
chemistry techniques.

3.4 Thermal decomposition of ammoniac
copper oxalate chromate
Prasad [2] synthesized a novel precursor,
ammoniac copper oxalate chromate (ACOC) and
suggested the stoichiometric formula of the
p r e c u r s o r c l o s e l y a p p r o x i ma t i n g ,
CuNH3C2O4NH4CrO4. ACOC was used for the
production of active copper chromite catalysts. The
precursor, ACOC was prepared by mixing
ammoniacal solutions of copper oxalate and
ammonium chromate in a Cu/Cr atomic ratio of 1:1
followed by evaporation on a steam bath and
finally dried at 378 K in an oven for 5 h. No
precipitation occurred during mixing. The dried
greenish colored complex was stored in a desiccator
over anhydrous calcium chloride. The
homogeneous complex precursor is soluble in
aqueous ammonia. The catalysts were prepared by
calcination of the prepared complex precursor in
air and in argon atmosphere around 623 K. The
overall decomposition of ACOC in air was highly
exothermic and can be exemplified by the following
equation 59:

2CuNH3C2O4NH4CrO4 + 2O2 CuO.CuCr2O4 +
4CO2 + 2N2 + 7H2O (highly exo.) (59)

The overall decomposition of ACOC in argon was
mild exothermic, can be represented as follows
(eqn. 60):

2CuNH3C2O4.NH4CrO4 Cu.CuCr2O4 + 2NH3 +
4CO2 + N2 + 4H2O (mild exo.) (60)

The environments of calcinations of ACOC have
strong influence on mechanism of decomposition
and also on the chemical composition and physico-
chemical properties of the resulting Adkins
catalysts. Violent exothermic oxidative-
decomposition of ACOC in air leads to bi-dispersed
bigger particles and consequently lowers specific
surface area of resulting catalyst, CuO.CuCr2O4 in
comparison to finely-divided mono-dispersed
particles of active catalyst, Cu.CuCr2O4 obtained
through mild exothermic decomposition in argon
environment. Thus, decomposition of ACOC in
argon produces novel active catalyst directly,
minimizing a process step of catalyst reduction,
leading to saving of not only reduction time but
also reducing and diluents gases.

3.5 Hydrothermal method
George and Sugunan [4] prepared the catalysts
as follows: a mixture consisting of 10% solutions of
copper nitrate, nickel nitrate and chromium
nitrate for Cu1-xNixCr2O4 (x = 0, 0.25, 0.5, 0.75 and
1) series were taken in appropriate mole ratios and
the mixture was heated to 343-353 K. To this hot
mixture a 15% ammonia solution was added drop
wise with constant and uniform stirring to
maintain a constant pH of 6.5-8. The precipitate
was maintained at this temperature for 2 h and
aged for one day. The precipitate was filtered,
washed and dried at 353 K for 24 h and calcined at
923 K for 8 h.
Arboleda et al. [336] synthesized a new single-
phase copper chromate compound, (NH4)
1.5Cu2Cr2O8(OH)1.5H2O by the hydrothermal
method. The synthesized compound decomposed
into CuCr2O4 and CuO after being calcined at 600
0
C. The Cu-Zn-Cr catalysts derived from
hydrotalcite (HT) structures were prepared by the
hydrothermal method by Venugopal et al. [337].
Catalyst precursors were prepared by the co-
precipitation method with mol% ratios of Cu:Zn:Cr
= 44:44:12 and Cu:Zn:Cr = 47:38:15 with
hydrothermal treatment. About 0.6 L aqueous
solution of copper, zinc, chromium nitrates

(solution A) and a solution B containing 2 M NaOH
and 1 M Na2CO3 (1:1 = v/v) were added
simultaneously to 2.0 L of distilled water under
vigorous stirring. The rate of addition of solution A
was approximately 0.5 L/h while maintaining a
constant pH ~8.0 0.1 by adjusting the flows of
solutions A and B. The co-precipitation is carried
out at room temperature. The precipitate was kept
at 70
0
C for 1 h subsequently washed several times
until the pH of the gel reached the pH of the
distilled water that has been used for the
preparation. The precipitates were oven dried at
100
0
C for 24 h and calcined in static air at 400
0
C
for 3 h. They found the presence of hydrotalcite
structure and the finely dispersed copper species in
the calcined form.

3.6 Nanocasting method (Template
technique)
The common preparation methods of mixed
oxides and mixtures of oxides usually require the
unconfined precursors to be subjected to high
temperature calcinations steps. This provokes the
sintering of the resulting particles, with the
concomitant reduction of active surface area,
typically in the range of a few square meters (<10)
per gram. Thermal treatments can be avoided by
the use of chimie douce-based nanotechnological
approaches, such as microemulsion techniques
[338], but these are expensive procedures which,
moreover, must integrate stages for the separation
of the organic solvents and surfactants. These
disadvantages, when using thermal methods for
unconfined precursors or liquid phase
preparations, have been recently overcome by
means of nanocasting procedures, such as template
methods with hard templates (porous solids such
as silica gel and active carbon) [339-341]. Using
this method the synthesis of the nanoparticles
takes place in a confined space formed by the
porosity of the template. The attraction of these
methods is the confined calcination process that
allows an effective control of the particle size of the
resulting materials by adjusting the conditions of
synthesis, thus favouring the formation of
nanostructures [341].
Generally, the nanocasting methods involve two
main steps: (a) preparation of a nanostructured
template; and (b) filling the template nanopores
with the desired precursor, followed by
crystallization in the voids of the template and
then removing the template framework. Liang et
al. [106] firstly demonstrated that the carbon
template route allows synthesizing high-surface
area Cu-Cr catalysts, which show high activity and
selectivity to 1,2-propanediol in glycerol
hydrogenolysis. The method is as follows: about 3 g
of the carbon materials were impregnated at room
temperature with about 15 ml aqueous solution of
copper nitrate and chromium nitrate mixture of
different molar ratios for 30 min. Alternatively,
impregnation was performed with a slight excess of
solution. The slurry was then filtered and squeezed
to remove the liquid on the carbon surface that
could cause the formation of large oxide particles.
After drying in air at 70
0
C overnight, the resulting
sample was transferred to a quartz reactor inside a
tubular resistance furnace. The furnace was then
ramped at 1
0
C/min to final temperature and was
held for 120 min. The atmosphere was of argon
before 300
0
C, and then shifted into a mixture gas
of 20% O2 in Ar at a flow rate of 120 ml/min.
Finally, carbon template was removed at 550
0
C in
air for 8 h. The conversion is almost 100% from
copper nitrate and chromium nitrate to final
copper and chromium oxide catalyst, and the ratio
of Cu to Cr was obtained from the initial molar
ratio of copper nitrate to chromium nitrate.
Valds-Sols, et al. [14] prepared high surface-
area spinel-type complex oxides using a porous
silica xerogel as template. To synthesize the metal
oxides, a solution of the hydrated metal nitrates in
the appropriate ratio was prepared in ethanol (0.4-
0.6 M). The silica xerogel was stirred with this
solution at moderate temperature (60
0
C) until
complete removal of the solvent. The impregnated
sample was dried at 80
0
C overnight and calcined
in air at 5
0
C/min up to the temperature required
for the formation of the oxide and then left for 4 h.
The mixed oxides were obtained after the
dissolution of the silica framework in a NaOH
solution (2 M) and final washing with distilled
water to remove impurities. Copper-based
catalysts (CuMn2O4 and CuCr2O4 spinels or CuO/
CeO2 and CuO/ZnO) exhibit a high activity and
selectivity for the methanol-steam reforming
process.

3.7 Hydrolysis of some soluble salts
Patron et al. [317] developed the hydrolysis
method for obtaining chromium based oxides. It
consists in the hydrolysis of the metal salts in
presence/or absence of a complexant agent. The
potential advantages of this synthesis route lies in
the accessibility and moderate costs of the starting
materials, in the low temperatures required by the
procedure and the enhanced homogeneity and
purity of the end products. They obtained a pure
tetragonal CuCr2O4 with mean crystallite sizes

varying in the range 133-210 between the
temperatures limits 823 K-1073 K. The precursors
were prepared by hydrolysis of Cr(NO3)3.9H2O and
Cu(NO3)2.3H2O and Cu(CH3COO)2.H2O. Working
in different conditions two polynuclear
coordination precursors [Cr2Cu(NH3)2(OH)6](NO3)2
and [Cr2Cu(OH)8].4H2O were obtained. The
following reaction equations 61 and 62 may be
written for precursors synthesis:
NH4
Cu
2+
[Cu(NH3)4]
2+
[Cr2Cu(NH3)2(OH)6](NO3)2]
~10-11 (Precursor A) (61)

Cr
3+
Cr(OH)3 [Cr2Cu(OH)8].4H2O
(Precursor B) (62)

Copper chromite was obtained through thermal
decomposition of the precursors. Following
decomposition mechanism (eqns. 63 and 64) has
been predicted for the two compounds:

Precursor A :
[Cr2Cu(NH3)2(OH)6](NO3)2 [Cr2Cu(OH)6](NO3)2
Cr2CuO(OH)6 Cr2O2(OH)2.CuO
Cr2O8/3.CuO Cr2O3.CuO CuCr2O4 (63)

Precursor B:
[Cr2Cu(OH)8].4H2O Cr2Cu(OH)8 Cr2O2(OH)2
CuO Cr2O3.CuO CuCr2O4 (64)

3.8 Microemulsion method
The use of an inorganic phase in water-in-oil
microemulsions has received considerable
attention for preparing metal particles. This is a
new technique, which allows preparation of
ultrafine metal particles within the size range 5-50
nm particle diameter [342].
Nanoparticles of copper chromium hexacyanide
with varying particle-size are prepared by Kumar
et al. [343] using the micro-emulsion method and
Poly (vinylpyrrolidone) (PVP) as a protecting
polymer. Two separate microemulsions of Cu(NO3)2
and K3Cr(CN)6 with PVP are prepared and
subsequently mixed together to get the precipitate
of copper-chromium hexacyanide nanoparticles.
The nanoparticles are separated out by adding
acetone in the resultant mixture and are washed
many times with acetone and demineralized water.
The different mixing ratios of PVP to Cu ion
concentration (20 to 200) are used to control the
size of the nanoparticles.

3.9 Combustion synthesis
Combustion synthesis (CS) [344] has emerged
as important technique for the synthesis and
processing of advanced ceramics (structural and
functional), catalysts, composites, alloys,
intermetallics and nanomaterials. In CS, the
exothermicity of the redox (reduction-oxidation or
electron transfer) chemical reaction is used to
produce useful materials [345]. Depending upon
the nature of reactants: elements or compounds
(solid, liquid or gas); and the exothermicity
(adiabatic temperature, T), CS is described as: self-
propagating high temperature synthesis (SHS);
low-temperature CS, solution combustion synthesis
(SCS), gel-combustion, sol-gel combustion,
emulsion combustion, volume combustion (thermal
explosion), etc. Combustion synthesis processes are
characterised by high-temperatures, fast heating
rates and short reaction times. These features
make CS an attractive method for the manufacture
of technologically useful materials at lower costs
compared to conventional ceramic processes. Some
other advantages [346] of CS are:
(i) Use of relatively simple equipment
(ii) Formation of high-purity products
(iii) Stabilization of metastable phases and
(iv) Formation of virtually any size and shape
products.
Combustion synthesis has been extensively
used to prepare a variety of catalysts. Patil et al.
[346] reviewed the recent developments in the field
with special emphasis on the preparation of
Catalysts and Nanomaterials by solid state
combustion and solution combustion.

3.9.1 Self-propagating high-temperature
synthesis (SHS)
The SHS method is being developed for the low-
cost production of engineering and other functional
materials, such as advanced ceramics,
intermetallics, catalysts and magnetic materials.
The method exploits self-sustaining solid-flame
combustion reactions which develop very high
internal material temperatures over very short
periods. It therefore offers many advantages over
traditional methods, such as much lower energy
costs, lower environmental impact, ease of
manufacture and capability for producing
materials with unique properties and
characteristics [347].
Xanthopoulou and Vekinis [348] prepared the
SHS catalysts and carriers from initial batch
mixtures consisting of nitrates and sulphates,
metals and oxides, compacted under a pressure of 5
-10 MPa in the form of rods of diameter 1-5 cm
and, in some cases, by extrusion as honeycomb
carrier blocks with diameter 1-5 cm and channel

size of about 5 mm. The samples were preheated in
an electric furnace at temperatures of 700-900
0
C
for a few minutes prior to initiation of SHS. The
specific area was increased by depositing a second
oxide layer (wash-coat) on the surface of SHS
carriers of about 0.9-4.9% aluminium oxynitrate
(denoted as OX, 3.2% for the Cu-Cr-O catalyst). Pd
was then deposited on the SHS carriers using
standard aqueous impregnation followed by
calcination and reduction. Standard 0.05% or 0.5%
Pd/Al(NO3)3/Al2O3 catalyst systems produced by a
conventional impregnation/ calcination/ reduction
process were used for comparison [348] . The
author reported that the Cu-Cr-O catalyst
prepared by SHS is resistant to fuel impurity
poisoning and used as carrier for 0.05% Pd,
achieved 50% conversion (light-off) at
temperatures about 50
0
C lower than conventional
0.5% Pd/Al2O3 catalysts for CO oxidation [348].

3.9.2 Solution combustion synthesis
A highly exothermic and self-sustaining
reaction, the so-called solution combustion
synthesis method is described by Russo et al.
[349]. Particularly, a concentrated aqueous
solution of various precursors (metal nitrates and
urea) was located in an oven at 600
0
C for a few
minutes in a crucible, so as to ignite the very fast
reaction. Under these conditions nucleation of
metal oxide crystals is induced, their growth is
limited and nano-sized grains can be obtained. The
innovative solution combustion synthesis
technique was adopted successfully because it was
possible to produce in an easy and low-cost one
shot way catalysts [259] with a rather high
surface area and pureness. The same technique
could be used to deposit the catalyst on ceramic
carriers with a very high surface area. They
studied the catalytic decomposition of N2O to N2
and O2 over CuCr2O4 and reported that the
conversion of N2O reached 50% in the absence and
in the presence of oxygen at 630
0
C and 745
0
C
respectively.

3.10 Flame spray pyrolysis method
Flame synthesis is an easy, single step method
for the preparation of CuCr2O4 powder. The
process is shorter than most wet chemical methods
and is cost efficient [350]. The flame-synthesized
sorbents have higher surface areas than particles
synthesized by co-precipitation.
Akhuemonkhan et al. [351] produced high
surface area CuCr2O4 sorbent for desulfurization in
fuel cells using the flame spray pyrolysis method.
They described the procedure as follows: The
precursors used for making the sorbents are copper
(II) nitrate trihydrate, chromium (III) acetate,
copper (II) acetate monohydrate, chromium (III)
nitrate nonahydrate. A series of 0.3 molar aqueous
precursor solutions have been made with deionized
water and mixed in the stoichiometric ratio. The
solutions are then atomized with the help of
compressed air in a medical nebulizer. The
droplets from the nebulizer are then sent directly
into a flame rector. The flame in the reactor is
generated with methane, oxygen and nitrogen
gases. The total flow rates for each gas including
the contributions from the air used to atomize the
precursor were methane 0.90 l/min, oxygen 2.61 l/
min and nitrogen 5.95 l/min. The maximum
temperature of the flame using these flow rates
was in the range of 1400-1500
0
C, which was
measured by using S-type (Pt/10%Rh-Pt)
thermocouple. In the reactor, the droplets undergo
a series of physical and chemical steps including
solvent evaporation and precipitation, intraparticle
reaction and densification, to form the final
product, a dense particle. The particles move from
the reactor to a water-cooled surface placed
directly over the reactor. The temperature gradient
caused by placing the cooled surface above the
flame reactor causes the particles to move from a
hotter region to the cooler surface a
thermophoresis process. The authors reported that
the flame-synthesized sorbent has higher sulfur
loading capacities than one synthesized by co-
precipitation.

3.11 Electroless method
A critical comparison of those methods is
needed to make the best choice for given boundary
conditions of targeted eventual material properties,
raw materials, investment, processing and waste
disposal costs. Preparing catalysts using different
methods also abet to compare the suitability of
catalysts for specific applications for instance,
Shiau and Tsai [352] showed that the electroless
deposition method provides more uniform copper
distribution than the impregnation method. The
electroless method is an oxidation-reduction
chemical deposition reaction, which can deposit
certain metals on a substrate without an external
electrical source [352].
Shiau and lee [104] prepared copper chromite
catalyst via electroless plating process using Al2O3
as substrate. Before conducting electroless
deposition, Al2O3 was pretreated with nitric acid to
remove any impurities, and activated by palladium

chloride solution to provide palladium nucleating
centres on surface of Al2O3. The activated Al2O3
was finally contacted with copper solution for
copper plating. In the copper solution,
formaldehyde was added as reducing agent for the
oxidation-reduction reaction. The plating bath was
maintained at 70
0
C and the pH was adjusted to
12.5. The plated Al2O3 was filtered and washed
with distilled water, then dried at 110
0
C for 24 h.
The copper content was controlled at 15%.
Chromium was then added on the catalyst by a
traditional incipient wet impregnation method.
Chromium contents varied from 1 to 5%. They
reported that n-butanol dehydrogenation activity
reaches a maximum at 2 wt. % of chromium
addition, which corresponds to the saturated
chromium loading that can penetrate into the bulk
of copper layer. This penetrated chromium can
reduce the particle size of copper crystallites and
therefore can enhance the copper dispersion on -
Al2O3.

3.12 Sonochemical method
Sonochemistry is a very useful process for
preparing novel materials with unusual properties
[353], and its utilization in the synthesis of
catalysts has been reported [354,355]. The
prominent advantages of catalysts prepared by
sonochemistry are their high activity and
nanosized particles. The driving force for
sonochemistry is acoustic cavitation that is formed
in liquid. During cavitation, bubble collapse
produces intense localized hot spots (5000 K) and
high pressure (1000 atm). The microjets of liquid
and shockwave created by ultrasound can make
great effect on solids in liquid.
Huang et al. [89] studied selective
hydrogenation of furfural to furfuryl alcohol over
CuCr2O4 catalysts prepared via sonochemical
method. The method of preparation described is as
follows: Preparation of catalyst S1: K2Cr2O7 (6 g)
and CuAc2.H2O (6 g) is dissolved in NH3.H2O (30
ml) solution. The solution is kept in a thermostatic
bath (65
0
C) under stirring. After NH3 is removed
completely, the formed precipitate is centrifuged
and washed two times with water and once with
acetone, and then dried at room temperature under
vacuum. Preparation of catalyst S2: K2Cr2O7 (6 g)
and CuAc2.H2O (6 g) are dissolved in water (20 ml),
respectively. Then 1 ml of NH3.H2O is added into
the solution of K2Cr2O7. Two solutions are mixed
up and the mixture is sonicated for 3 h by
employing a direct immersion titanium horn
(Sonics and Materials model VCX-600, 20 kHz,
100W/cm
2
). The reaction cell is cooled by water at
ambient temperature during the sonication
process. The mixture is centrifuged after
sonication. The product is washed two times with
water and once with acetone, and then dried at
room temperature under vacuum. Samples S3, S4
and S5 are prepared in the same way of preparing
S2 besides that 10, 15 and 20 ml of titanium (IV)
isopropoxide (Me2CHO)4Ti are injected into the
mixture as soon as the sonication starts,
respectively. They concluded that comparision with
Adkins catalyst (S1) prepared by convenient
method, the Adkins catalyst (S2) prepared via
ultrasound has higher catalytic activity for
hydrogenation of furfural.

3.13 Metal organic chemical vapour
deposition (MOCVD)
Chemical vapor deposition (CVD) is a chemical
process used to produce high-purity, high-
performance solid materials. The process is often
used in the semiconductor industry to produce thin
films. In a typical CVD process, the wafer
(substrate) is exposed to one or more volatile
precursors, which react and/or decompose on the
substrate surface to produce the desired deposit.
Frequently, volatile by-products are also produced,
which are removed by gas flow through the
reaction chamber [356].
Chang et al. [22] prepared for the first time
copper chromite films by metal organic chemical
vapour deposition (MOCVD) with temperature
below 500
0
C. The processing window was:
deposition temperature above 420
0
C, partial
pressures of oxygen, above 190 torr, copper
acetylacetonate(Cu(acac)2), 0.21 torr, and
chromium acetylacetonate (Cr(acac)3), 0.4 torr,
respectively. Keeping the more volatile reactants
as Cr(acac)3 in excess amount is essential for
depositing stoichiometric films. Higher deposition
temperature is essential for depositing oxide films
with complex crystalline structure. SEM results
showed CuCr2O4 films exhibited different
morphologies such as equiaxed fine grain,
truncated polyhedron, and hillocks, depending on
the process condition. Both substrate temperature
and precursor partial pressures have significant
impact on film morphology and reflect the basic
natures of film growth mechanism. XRD patterns
indicate that CVD films are polycrystalline, which
exhibit highly textured, normal spinel structure.

3.14 Chemical reduction method
The chemical reduction is a convenient method
with simple procedures for preparing amorphous

nano-size metal particles for catalysis [357]. The
ultrafine copper chromite catalyst is obtained
using this method [45]. Liaw and Chen [45]
prepared the catalyst by reducing copper nitrate
(0.1 M) in an aqueous solution with sodium
borohydride (1 M). The aqueous sodium
borohydride solution was added into the copper
nitrate solution by a micropump under a flow of
nitrogen. Cr introduced to copper by reducing/co-
precipitating with sodium borohydride in an
aqueous solution of copper nitrate and an
appropriate amount of Cr salt. The resulting black
precipitate was thoroughly washed with distilled
water three times to remove the residual ions and
then washed with ethanol to remove water. The
precipitate are then dried and calcined. They
studied catalytic properties of catalyst prepared by
this method for hydrogenation on monofunctional
(olefinic and carbonyl) and bifunctional (conjugated
and nonconjugated) compounds and compared with
those of a commercial catalyst of copper chromite.
The ultrafine catalysts of Cr-CuB containing a
much lower content of chromium (Cr<5mol%) were
more active than the commercial copper chromite
(Cr > 50mol%). The authors proposed that these Cr
-CuB catalysts are highly promising for replacing
copper chromite for liquid-phase hydrogenation
reactions.

3.15 Sol-gel method
The sol-gel methods show promising potential
for the synthesis of mixed oxides catalysts. The
versatility of the sol-gel techniques allows control
of the texture, composition, homogeneity, low
calcination temperatures (minimizing the
undesired aggregation of the particles), and
structural properties of solids, and makes possible
production of tailored materials such as dispersed
metals, oxidic catalysts and chemically modified
supports [358].
Such methods are used primarily for the
fabrication of materials (typically a metal oxide)
starting from a chemical solution (sol) which acts
as the precursor for an integrated network (or gel)
of either discrete particles or network polymers
[359]. Typical precursors are metal alkoxides and
metal nitrates, which undergo hydrolysis and
polycondensation reactions to form either a
network elastic solid or a colloidal suspension (or
dispersion) - a system composed of discrete (often
amorphous) submicrometer particles dispersed to
various degrees in a host fluid.
The hydrolysis of precursor molecules and the
condensation between the resulting reactive
species, are the essential reactions of the sol-gel
process [360]. The resulting processes involved and
the properties of the precursor molecules have a
decisive influence on the resulting material
properties [360]. On addition of water, the metal
alkoxides [M(OR)n] readily hydrolyze as
represented by Eqn. 65.

M(OR)n + H2O M(OR)n-1OH + ROH (65)

Hydrolysis is followed by condensation to form -
M-O-M- bonds via either dehydration or
dealcoholation as described in Eqs. (66) and (67),
respectively:

(RO)mM-OH + HO-M(OR)m (RO)mM-O-M(OR)m
+ H2O (66)
-M-OH + RO-M- -M-O-M- + ROH (67)

In this manner, inorganic polymeric oxide
networks are built up progressively. The
hydrolysis, condensation and polymerization
reactions are governed by several factors, including
the molar ratio of water to alkoxides, choice of
solvents, temperature and pH (or concentration of
acid or base catalysts). There are essentially three
different kinds of sol-gel or gel technology for
preparation of catalysts.

3.15.1 Citric acid complexing method
Citric acid (CA)-assisted sol-gel method (namely
Pechini approach) is a facile synthesis for
producing homogeneous nanocomposites [10], in
which the use of citric acid as chelating agent
ensures the formation of homogeneous transparent
metal-citrate gels, and the intimate mixing of
components ensures homogeneity of the final
product. Li et al.[10] have prepared Cu-Cr-O
nanocomposites by citric acid (CA) complexing
approach in which 0.01 mol Cu(NO3)2 and 0.02 mol
Cr(NO3)3 are dissolved in 100 mL deionized water
to obtain a mixed metal nitrate solution. Then
citric acid is added to this solution and the molar
ratio of citric acid to the total metal ions is fixed to
be 2:1. After stirring for 30 min, the solution is
heated at 95
0
C for several hours to evaporate the
water solvent to produce dark brown transparent
viscous gels. The gels are then dried at 160
0
C for 2
h to obtain the foamy dark powders, which are
denoted as precursors of Cu-Cr-O nanocomposites
(CA-Cu-Cr). After grinding, the precursors are
successively heated at 600
0
C for 3 h to obtain the
final black Cu-Cr-O nanocomposites.
Li and cheng [229] have prepared Bi2O3/
CuCr2O4 core/shell nanomaterials following the

facile synthesis and show that the nanomaterials
demonstrate high catalytic activities towards the
oxidation of CO. Yan et al. [12] also synthesized
CuCr2O4/TiO2 heterojunction via a facile CA-
assisted sol-gel method for photocatalytic H2
evolution. The optimized composition of the
nanocomposites has been found to be
CuCr2O4.0.7TiO2. And the optimized calcination
temperature and photocatalyst mass concentration
are 500
0
C and 0.8 g/l, respectively.

3.15.2 Alkoxide sol-gel method (Pechini
Method)
The Pechini method [361,362] based on
polymeric precursors, is used to prepare spinels
and it does not require high temperature
calcinations and permits good stoichiometric
control as well as reproducibility. This method
consists of the formation of a polymeric resin
between a metallic acid chelate and polyhydroxide
alcohol by polyesterification. The metal nitrate
solution is mixed with a stoichiometric amount of
citric acid. The resulting solution is stirred for
about 1 hour on a hot plate and the temperature is
stabilized at 70
0
C. The mixture is heated to 900
0
C, at which point ethylene glycol is added at a
mass ratio of 40:60 with respect to citric acid. The
temperature is maintained constant up to resin
formation, which polymerizes at 300
0
C. The
precursor powders are then calcined for 4 hours at
various temperatures, ranging from 500 to 900
0
C,
or at 900
0
C for 8 hours [363]. The crystallization of
the spinel structure starts upon calcining at 700
0
C. Cu0.8Ni0.2Cr2O4 is the only phase present upon
calcination at 900
0
C. The process of the Pechini
method is almost the same as that of the citrate gel
method, except that metal nitrates are dissolved in
alcohols, instead of water [364].
The major disadvantages of using the metal
alkoxide based sol-gel process are its moisture
sensitivity and the unavailability of suitable
commercial precursors especially for mixed-metal
oxides. The sol-gel synthesis of mixed oxides from
alkoxide mixture usually suffers from the different
hydrolysis susceptibilities of the individual
components and the benefits of improved
homogeneity can be lost during the hydrolysis of
the alkoxides, which may ultimately lead to
component segregation and mixed phases in the
final materials. To achieve homogeneous mixed
oxides with predetermined compositions, the
difference in reactivity has been minimized by
controlled prehydrolysis of the less reactive
precursor [365], by chemical modification of the
precursors [366], by using single-source
heterobimetallic alkoxide precursors [367], or by
non-hydrolytic sol-gel processes [368].

3.15.3 Non-alkoxide sol-gel method
Non-alkoxide sol-gel process, involving
hydrolysis and condensation of metal salts, avoids
the disadvantage of alkoxide sol-gel process (high
sensitivity to moist environment), however, has
still the disadvantage of different hydrolysis
susceptibilities of the individual components [25].
One of the advantages of this method is the
important reduction of the required calcination
temperatures, minimizing the undesired
aggregation of the particles. This method was
found to be an effective route to synthesize mixed
oxide nanoparticles with narrow size distribution
[25]. Ma et al. [369] presented a non-alkoxide sol-
gel route to synthesised highly active and selective
Cu-Cr catalysts for glycerol conversion. The
synthesis involves dissolving 3.3 g of Cr
(NO3.3.9H2O and 1.0 g of Cu(NO3)2.3H2O in 16 mL
of ethanol at 60
0
C to give a clear dark blue
solution. After adding 5.0 mL of propylene oxide, a
dark green transparent gel is formed within a few
minutes under stirring. After drying overnight in
air at 70
0
C, the resulting xerogel is transferred to
a quartz reactor inside a tubular resistance
furnace. The furnace is then ramped at 1
0
C/min to
a final temperature and is held for 120 min under
20% O2 in Ar at a flow rate of 120 ml/min. The
yield of copper and chromium in the oxide catalyst
is about to 100%, and the ratio of Cu to Cr could be
varied by the initial molar ratio of copper nitrate
and chromium nitrate.
The results show that the surface area of the Cu
-Cr catalyst is adjusted by the hydrolysis
conditions, Cu/Cr molar ratio, and treatment
conditions (such as gas atmosphere and final
temperature). For the sample with Cu/Cr = 0.5, the
surface area of Cu-Cr xerogel can reach 94 m
2
/g
and decreased to only 31 m
2
/g after calcination at
500
0
C. The catalysts show significant catalytic
activity and selectivity in glycerol conversion, i.e.
above 52% conversion of glycerol and above 88%
selectivity to 1,2-propanediol at 210
0
C and 4.15
MPa H
2
pressure. CuCr2O4 supported Cu catalysts
are much more active than Cr2O3 supported Cu
catalysts. This indicates a strong interaction
between Cu and CuCr2O4 that is significantly
improving the effectiveness of the catalyst for
glycerol conversion.


4. Conclusions
Depending on the ratio of oxides of Cu-Cr and
preparation technique the final products are
usually called copper chromite (CuCr2O4) and
Adkins catalyst (CuO.CuCr2O4). This review
summarized the potential applications of
unsupported and supported Cu-Cr catalysts and
advances in their preparation methods. The Cu-Cr
catalysts exhibit versatile applications as catalysts
being used in the unit processes of organic
synthesis, pollution abatement, ballistic modifier
for composite solid propellants, production of H2
and clean energy carrier, drugs and agro
chemicals, electrodes and sensors, etc. In addition
to these applications recently, Cu-Cr catalysts
finds use in hydrogenolysis of bio-glycerol to
produce value added product such as propylene
glycol.
A properly designed Cu-Cr catalyst should have
the essential attributes of activity, stability,
selectivity, and regenerability. These can be
related to the physical and chemical properties of
the catalyst, which in turn can be related to the
variable parameters inherent in the method used
for the preparation of the catalyst. The various
methods used for preparation of Cu-Cr catalysts
have their own importance and limitations. The sol
-gel methods show promising potential for the
synthesis of mixed oxides of homogeneous
nanocomposite catalysts. The versatility of the sol-
gel techniques allows control of the texture,
composition, homogeneity, low calcination
temperatures, and structural properties of solids,
and makes possible production of tailored
materials such as dispersed metals, oxidic
catalysts and chemically modified supports. There
is a significant increase in the thermal stability of
the material by the addition of chromia with other
refractory materials like alumina, silica gel, etc.;
because of the formation of copper chromite and
higher dispersion, inhibiting the sintering at high
temperature.

Acknowledgement
The authors are gratefully acknowledging the
financial support given for the project by the
Department of Science and Technology, India.

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Table 2: Recent literature review at a glance on Cu-Cr catalysts development for various reactions
Ref.
No
Catalyst prepn.
method
Expmnt. Operating conditions Remarks
1. Hydrogenation
a) Hydrogenation of edible oils
69 CuCr2O4 Soybean oil hydrogenation, 200
0
C
and 6 atm
Pre-reduced catalyst deactivates due to disappearance of
Cu(II) and Cu(I) species and to the decrement of Cu/Cr
ratio on the catalyst surface
b) Hydrogenation of polyunsaturated organic compounds
20 Cu-Cr O, co-ppt. of
hydroxide, caln 370
0
C
Citral hydrogenation, 300 mg of
catal, 0.5 mL of substrate in 5 mL of
decalin at 140
0
C, atm & subatm
pressure, batch reactor
At high pressure, unsaturated alcohol competes with
initial reagent on hydro-genation site; at low pressure,
this comp-etition decreases, but the allylic alcohol is
isomerized on another active site.
c) Hydrogenation of allylic alcohol
20 Cu-Cr/Al, co-ppt. of
Cu and Al hydroxides
Crotyl alcohol, -methallyl alcohol,
flow apparatus, reagent-constant pp-
20 Torr, atm. pressure
Allylic alcohols react with H2 and lead to several primary
products, Cu
+1
promote hydrogenation, Cr
+3
/Al
+3
- isomeri-
sation and hydrodeoxygenation
d) Hydrogenation of fatty acids
71 CuCr2O4 Fatty methyl ester hydrog. to fatty
alcohol, semibatch reactor, low H2
press elevated temp.
Both activity and selectivity correlate well with the crys-
tallinity of the copper chromite surface; they increase
with decreasing crystallinity.
e) Hydrogenation of Furfural
1

CuCr2O4 pre-reduced
cat at 473, 573, or
673 K for 4 h
Furfural/ crotonaldehyde , fixed bed,
15 g cat, temp. 423 & 473 K, press
730 Torr H2 & 10 Torr furfural
Both activity & TOF for furfural and crotonaldehyde
hydrogenation reached their highest values after reduc-
tion at 573 K, compared to 473 and 673 K,
f) Selective hydrogenation of furfural
3 9
89
CuCr2O4 Selective hydrogenation of furfural to
furfuryl alcohol
Cu
0
is the active phase, reduction with H2 at 573 K for 4
h produced the highest specific activity of catalyst due to
the existence of maximum accessible Cu
0
species
g) Selective hydrogenation of nitrobenzene to aniline
82 Cu(FexCr2x)O4 250
0
C, fixed bed flow reactor Optimum composition, x=0.4, Cu
+1
at octahedral sites is
more active than Cu
0

h) Perfumery and synthesis of fragrances
84 CuCr2O4 Partial hydrogenation of vegetable
oils & fatty acids
Selective formation of allylic alcohols for perfumery &
synthesis of fragrances
i) Hydrogenation of ketones
91 CuCr2O4 Treatment of CuCr2O4 in H2 at 180-
370
0
C
Exhibit activity in hydrogenation reactions including
ketone & olefin

2. Cyclization
124 Cu-Cr-Fe/ Al2O3, sol-
gel
Cyclization of alkanolamines, fixed-bed
reactor
Excellent activity, selectivity & long life Modified sol-
gel method > common impregn. or co-ppt. method
6 Cu-Cr-Ba-Al2O3 Cyclization of N--hydroxy-ethyl-1,3-
propanediamine to homopiperazine,
fixed-bed
Ba improved the dispersion of Cu and prevented it
from sintering, conversion-93.2%-100%, selectivity-
90%

3. Dehydrocyclisation
329 CuCr2O4, CuCr2O4/SiO2 Low temperature, 2-ETAN/ EG molar
ratios 10.0
Dehydrogenation of EG to 2-hydroxy acetaldehyde,
followed by N-alkylation of 2-ETAN to form a Schiffs
base, that cyclises to 7-ETI

Table 2: (contd)
4. Dehydrogenation
a) Dehydrogenation of Methanol
92 CuCr2O4, CuO-
75%, CuCr2O4-
25%
CH3OH dehydrog. to HCOH, slurry
reactor, temp. 598-673 K
CuCr2O4 deactivate slowly than Cu-catalyst at 673 K
40 CuCr2O4 Dehydrog. of CH3OH to HCOOCH3,
micro-reactor operated at atm. press.
Order half with respect to the partial pressure of CH3OH,
follow L-H model

b) Dehydrogenation of Ethanol
93 CuCr2O4, thermal
decomp. of co-ppt.
Cu-Cr hydroxyl
carbonate
Methanol dehydrogenation to for-
maldehyde or methyl formate
Highly selective to methyl formate ( > 95%)

c) Dehydrogenation of Iso-propanol
27 CuCr2O4, wet im-
pregnation
Isopropanol dehydro-genation to
acetone
High selectivity and satisfactory activity

d) Dehydrogenation of butanol
104 CuCr2O4/electroless
plating method
Dehydrogenation
of n-butanol
5 wt.% addition of chromium to Cu have higher activity
than the 2 wt.% Cr, especially at higher chromium loading.

e) Dehydrogenation of isoamylic alcohol
105 CrCuMg layered
double hydroxides
with hydro -talcite
structure, co-ppt.
Dehydrogenation of isoamyl alcohol
to isovaleraldehyde
Show a high conversion and selectivity, catalytic activity
attributed to copper content,

5. Dehydration
a) Dehydration of Glycerol
32 CuCr2O4 Dehydration of glycerol, semibatch
reactive distillation
> 90 % acetol selectivity, hydrogenation of acetol to propyl-
ene glycol
106 Cu-Cr catalyst,
carbon materials as
templates & ni-
trates precursors
High surface area Cu-Cr catalysts Reduced Cu-Cr, selectivity- 51% in glycerol conversion,
96% to 1,2- propanediol

6. Hydrogenolysis
a) Hydrogenolysis of glycerol to propylene glycol
110 CuCr2O4, Temperature 200
0
C, Pressure 200 psi,
specially designed stainless steel multi
clave reactor capable of performing
eight reactions simultaneously
Yield >73% achieved at moderate reaction conditions. Cu
+1

as active sites for hydrogenation
111 CuCr2O4 Convert glycerol to PG, Low-pressure
vapour-phase processing, Semibatch
reactive distillation
At lower temp. & pressures, 50-100% conversion, little
selectivity towards ethylene glycol and other by-products,
Acetol as transient intermediate with selectivity levels
90%
28 CuCr2O4, Co-
ppt., impregn.
method
Hydrogenolysis of glycerol to propylene
glycol, Pre-reduced cat at 320
0
C, flow
reactor
Precipitated catalyst >impregnated catalyst
3 Cu-Cr, non-
alkoxide sol-gel
route, Cal 500
0
C
Temp. 210
0
C, H2 Press 4.15 MPa, Glycerol conversion > 52%, 88% selectivity to 1,2-
propanediol, CuCr2O4 supported Cu catalysts are much
more active than Cr2O3 supported Cu catalysts, highly
active and selective for glycerol conversion

7. Alkylation
a) Alkylation of amines
119

BaO promoted
CuCr2O4 & un-
promoted
CuCr2O4
The red. alkyl. of C6H5NH2 with
(CH3)2CO to C9H13N, CuO44%,
CrO45%, BaO9%, catalyst-10 g, pre-
reduced
The active sites of CuCr2O4 used for red. alkyl. of amines
are Cu(I) species, catalyst reduced at 573 K showed the
highest activity

Table 2: (contd)
8. Hydrogen Production
a) Sulphur based thermo-chemical water splitting cycles
16

AB2O4 structures H2 production, through S-base
thermo-chemical water split-ing cy-
cles, temp.725-900
0
C
Highest activity at temp. >850
0
C, Activity order:
CuCr2O4> CuFe2O4 > NiCr2O4NiFe2O4 > MnTiO3FeTiO3.
16 Nanocomposit
CuCrO, Pechini
method,
5 wt% catalyst, burning rate cata-
lysts for AP solid propellants
Cu/Cr molar ratio of 0.7 exhibits the most stable combus-
tion at all pressures

b) Photocatalytic H2 evolution
12 CuCr2O4 /TiO2,
facile CA-solgel
method
CuCr2O4/TiO2- 0.7, calc.-500
0
C catalyst
mass conc.0.8 g/l
H2 evolution from oxalic acid solution under simulated
sunlight irradiation, consistent with the Langmuir model
13 CuCr2O4, co-ppt. H2 evolution, solutions containing
NaOH-0.5 M, Na2S2O3-0.025 M with an
average rate of 0.013 cm
3
h
-1
(mg cata-
lyst)
-1
and a quantum efficiency of 0.2%
Thiosulfate gives best performance, excellent chemical sta-
bility, corrosion potential of -0.775 VSCE and an exchange
current density of 16 A cm
-2
, exhibits p-type extrinsic con-
ductivity.
129 CuCr2O4, solid
state reaction,
delafossite
CuCr2O4,
H2 evolution based on a dis-persion of
CuCrO2 powder in aq. electrolytes con-
taining various reducing agents (S
-2
,
SO3
-2
& S2O3
-2
)
Low cost H2 photocathode, inertness to corrosion, prolonged
irradiation (>80 min) leads to a pronounced decrease of the
photoactivity

c) Water Gas Shift Reaction and Methanol Steam Reforming
145 skeletal copper
catalysts+ Cr2O3
Role of additives in MSR and WGSR Enhance the activity for the WGSR, MSR and methanol
synthesis reactions

d) Water Gas Shift Reaction
15 Different cats. co-
ppt. method
Production of H2 via WGSR, 150 & 250
0
C
Cu-Zn-Al>Cu-Al>Cu-Mn, Cu-Cr>Cu-Fe>>Zn-Al>Cu-Co

e) Reforming of alcohols
Methanol Steam Reforming
14 CuCr2O4 nano-
particulate ternary
oxides
Using template technique - silica xero-
gel , 250
0
C, WHSV = 52-57 h
-1

High activity and selectivity
Partial oxidation of methanol
150 Cu/M/Cr (M = Zn,
Ce, Fe, etc), co-ppt.
method
Production of hydrogen by Partial oxi-
dation of methanol
Exhibits high CH3OH conversion and H2 selectivity
Oxidative steam reforming of methanol
151 Cr/Cu-spinel Compact micro-structured string reac-
tor
High activity, and selectivity to carbon dioxide (98%) and
hydrogen, methanol conversion 91.5%
Steam reforming of ethanol
159 CuCr2O4 Ethanol steam reforming at low temps
using 12 wt.% C2H5OH in water mixtures
H2 productivity 9-25 g 2 (kg cat.)
-1
(h)
-1
at 250-300
0
C.

9. Pollution Abatement
a) Abatement of CO/Soot
280 CuCr2O4/ Al2O3
Impregn. method
CO-n-C6H14 air-oxid: CO 1.6% ,n-C6H14
1.1%; reduction : 0.8% NO and 0.9 %
CO in a flow reactor; S.V. 20000 h
-1

CuCr2O4 most active catalyst coating of soot filters in CO
and n-hexane oxidation and in combustion of soot.
229 Bi2O3/CuCr2O4-
CuO, comple-xing-
coppt. method
Oxidation of CO, pre-coating of NH4
+
on
the surfaces of Bi2O3 nano-particles
High catalytic activities

b) Hydrocarbon abatement
213 CuCr2O4/Al2O3, Co-
impregn, metal
20%; Cu/Cr=1 calc.
500
0
C
CO-propene oxidation, Temp. 300-
900
0
C; prereduced cat.
Mech.: adsorbed propene transforms to a unidentate CO3
2-

and liberates H2O vapour
170 CuCr2O4, impre-
method, calc. 600
0
C
CH4 oxidation, Temp. range 300-700
0
C
at constant, CH4 : air ratio of 1 : 30,
constant CH4 1.2%.
Activation energy- 110 kJ/mol, reaction rates between 10
-3

and 10
-4
(molCH4 )/(g h)
254 CuCr2O4/ Al2O3 CH4 oxidn. Mechn.: adsorb. O2 on active sites, oxid.red. form R-E or
L-H model

c) Abatement of Volatile organic matter(VOC)
273 Ba doped CuCr2O4 VOC, Presence/absence of molecular oxygen Total combustion of ethyl acetate occurs in a range of temps. which is
compatible with the industrial requirements.
170 Ba-CuO-
Cr2O3/Al2O3
Flow rate:201/h SV: 10000 h
1
, Catalyst 2 cm
3
,
reactor (700 mm long, 15 mm id).
Complete oxidation of volatile organic compounds

213 Cu- Cr oxides, and
supported on -
Al2O3, wet impreg.
Complete oxidation of
ethanol, acetaldehyde, and methanol-ethanol
mixture
Cu-Cr increase CO2 yield in ethanol oxidation, Cu-containing cata-
lysts give higher CO2 yields in case of ethanol-methanol mixture
d) Nitrogen oxides (NOx) abatement
259 CuCr2O4,CuCr2O4/
Al2O3 Impregn.
method
CO & HC oxidation; O-xylene
NOx reduction
CuCr2O4>MnCr2O4>CoCr2O4>Zn Cr2O4>Mg Cr2O4
CuCr2O4>MnCr2O4>CoCr2O4> Mg Cr2O4>Zn Cr2O4>
e) Desulphuriastion of hot coal gas in (igcc) power plants
21 Cu-Cr-O Remove H2Sfrom coal derived fuel gas to less
than 5-10 ppmv, temp. 650-850
0
C
The regeneration temperature affects the reaction pathway and the
regenerability of the solid composition
294 CuCr2O4 Good thermodynamic stability and slow reduc-
tion kinetics
Remove H2S to less than 5-10 ppm at 650-850
0
C
Table 2: (contd)
10. Clean energy Production
a) Synthesis of alcohol
Methanol Synthesis
17 Ag-Cu/CrAl3O6, wet
impreg.
synthesis from H2, CO and CO2 mixture un-
der atm press, gradientless reactor
Most active catalyst- 20%Cu/CrAl3O6 and 1%Ag to 5%Cu/Cr Al3O6
catalysts.
196 CuCr2O4 and
CH3OK
Low-temperature methanol synthesis in liq-
uid phases, 373-423K, 1.5-5.0Mpa
Synergistic effect exhibit CuCr2O4 and CH3OK, excellent activities for
the production of methanol
Synthesis of iso-butyl alcohol
174 CuCr2O4, Cu-
36wt.%, Cr-33%,
Mn-3%
MeOH + PrOH BuOH, Guerbet condensa-
tion, 200
0
C, inert atm.-3.0MPa of N2
Catalysts tolerant of the co-produced water, no deactivation during
the course of reaction
Higher alcohols Synthesis (HAS)
310 Cu-Zn-Cr Production of HAS from syngas High selectivity of HAS at low Cr content, at high reduction
temp.673K
Fast pyrolysis
198,
197
CuCr2O4 Fast pyrolysis of biomass into liquid bio-oil Selective to the reduction of most oxygenated lignin derivatives
e) Removal of Ammonia from effluent streams
310 CuCr2O4, impregn. Temp 305
0
C, 45 bar, contact time 1s 86% removal of ammonia
11. Synthesis of nitrogen-containing heterocyclic compounds
a) Synthesis of Indoles
330 CuCr2O4,
CuCr2O4/SiO2
mixtures
Aniline/alkylanilines + diols indoles or
alkylindoles, at lower temp. + catalysts, weak-
acid sites (Lewis-type) are present
Economically synthesised, simple and safe reaction conditions, use of
non-toxic, low cost and widely available commercial feeds, simple
catalyst recovery, easy set-up or work-up, minimum waste produc-
tion.
12. Drugs and Agrochemicals
19 CuO/ CuCr2O4, co-
ppt. method
340-440
0
C, intermolecular deamination and
cyclization of ED to form piperazine, dehy-
drogn to form pyrazine
High selectivity (98-100%),
13. Combustion supporting Catalysts
315 CuCr2O4 ceramic &
co-precipitation
methods
Burning rate catalysts for solid propellants:
HTPB binder 14%, amm. perchlorate 72%, Al
12% and catalyst 2%
Burning rate order:
Co-precipitation > ceramic method
319 Cu-Cr-O nano-
composites, ce-
ramic & sol-gel
Additives for the catalytic combustion of AP-
based solid state propellants, temp. 600
0
C
Enhances the burning rate as well as lowers the pressure exponent,
Cu/Cr molar ratio of 0.7 exhibits the most stable combustion at all
pressures
320 CuCr2O4 Propellants modifier Increase the combustion rates
230 Bi2O3/CuCr2O4-
CuO, comple-xing-
coppt.
Oxidation of CO, pre-coating of NH4
+
on the
surfaces of Bi2O3 nanoparticles
Solid-state propellant addictives
14. Electrodes and Sensors
321 CuO + CuCr2O4 Detect NOx in the conc. range between 10 and
2000 ppm
High selectivity and sensitivity toward NO2, Sensor responds rapidly
(t90 < 8 s) to change in the NO2 conc. between 100 and 500 ppm at 659
0
C
15. Semiconductors
24 Mn-doped CuCrO2 poly-
crystalline semicon-ductors,
sol-gel method
Magnetic and electrical properties

Exhibit clear ferromagnetic transitions at about 120 K


1. Introduction
Trickle bed reactors are randomly packed
columns in which reactant-carrying gas and liquid
phases flow co-currently downwards. In petroleum
refining industry, processing fluids in multiphase
reactors or in trickle bed reactors may display
foaming (especially products like alcohols, diesel,
kerosene, gas oils and other products resulting
from the reforming process). Conventionally most
of the industries rely on frequently used gas
continuous flow (GCF) where operational output is
Pressure Drop Hysteresis of Hydrodynamic States in
Packed Tower for Foaming Systems

Vijay Sodhi
1

*
and Renu Gupta
2

1
Department of Chemical and Biotechnology Engineering
Beant College of Engineering and Technology, Gurdaspur, Punjab 143521 , INDIA

2
Department of Chemical Engineering
Dr. B. R. Ambedkar National Institute of Technology, Jalandhar 144011, INDIA
* Corresponding Author.
E-mail: vijaysodhi10@gmail.com, Telp/Fax.: +91-9888035540 / +91-181-2491877
Received: 14
th
March 2011, Revised: 29
th
June 2011; Accepted: 4
th
July 2011
Abstract

An experimental investigation was carried out to determine the effects of gas and liquid flow velocities and
surface tension on the two-phase phase pressure drop a in a downflow trickle bed reactor. Water and non-
Newtonian foaming solutions were employed as liquid phase. More than 240 experimental points for the
trickle flow (GCF) and foaming pulsing flow (PF/FPF) regime were obtained for present study.
Hydrodynamic characteristics involving two-phase pressure drop significantly influenced by gas and liquid
flow rates. For 15 and 30 ppm air-aqueous surfactant solutions, two-phase pressure drop increases with
higher liquid and gas flow velocities in trickle flow and foaming/pulsing flow regimes. With decrease in
surface tension i.e. for 45 and 60 ppm air-aqueous surfactant systems, two-phase pressure drop increases
very sharply during change in regime transition at significantly low liquid and gas velocities. Copyright
2011 BCREC UNDIP. All rights reserved.

Keywords: Trickle Bed Reactor, Foaming, Hydrodynamics, Pressure Drop

How to Cite: V. Sodhi, and R. Gupta. (2011). Pressure Drop Hysteresis of Hydrodynamic States in Packed
Tower for Foaming Systems. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2): 115-122
satisfactory but not efficient as compare to pulsing
flow (PF) and foaming pulsing flow (FPF) [1].
These three phase reactors (reactions) are widely
used in industrial practice of treatment of foaming
petroleum products [2], [3]. Foams play an
important role in productivity and petroleum
recovery and processing [4]. In actual practice foam
formation is inhibited by adding antifoaming
agents or defoamers, this may increases overall
production cost.
Experimental evidence of two-phase pressure
Research Article

drop for foaming liquids was first presented by
Midoux [5]. They suggest the existence of
multiple hydrodynamic states to various non
uniform flow rates of gas and liquid showed
pulsing due to strong interaction of gas and
liquid. Value of pressure drop for foaming
systems, differs such an extent for these for non-
foaming systems that seems necessary to
elaborate separate correlation equation based on
experimental data Saroha and Nigam [6] and
Bansal [ 2], [3] . Therefore parameters
characterization for both GCF and PF are
different for both Newtonian and non Newtonian
fluids.
Grandjean [7] and Muthanna [8] has shown
that the gas flow has a considerable influence on
the hydrodynamics of TBR. Especially at high
operating pressure and the .interactions between
the gas and liquid phases are not negligence with
regard to the momentum transfer mechanisms.
Iliuta and Thyrion [9] investigated the
pressure drop for different CMC concentrations.
Sai and Varma [10] and Larachi [11] presented
different correlation in terms of Lockhart-
Martinelli parameters, flow variables and packing
characteristics. Liquid holdup and two-phase
pressure drop are the two basic hydrodynamic
parameters that are often inter-linked with
reaction conversion and selectivity, power
consumption and interfacial mass transfer that
take place in a trickle-bed reactor [12]. The
systems on which work has been already done
experimentally, would enables to prior
information to those fluids display foaming and
aims significantly to what type of systems must
need further researches. Therefore several
attempts done to solve this problem, found in
literature are listed below in Table 1. These
authors reported that the values of two-phase
pressure drop for foaming systems are much
lower than those prevailing with non-foaming
systems of close physicochemical properties under
identical flow rates of both phases.
Past researches shows the dependence of
decreasing surface tension with increasing
foaming nature of listed systems. The Sodium
Lauryl Sulphate used for present study produces
a moderate to extensive foam formation ability
depend upon concentration used and other
parameters. Bansal [2], [3] produced very good
correlation to predict foaming/pulsing transition
regime by experimentation of 6 ppm and 12 ppm
Sodium Lauryl Sulphate. Therefore to consider
observations of past researches in a better
manner and predict a more accurate correlation,
we used higher concentration of Sodium Lauryl
Sulphate which also exhibits a similar
physiochemical properties to chemicals listed in
literature. During preliminary tests,
concentrations over 60 ppm showed a very
intensive foaming and resulted into blockage,
clogging and over flow within the reactor.
Therefore present study is limited to four
concentrations of 15, 30, 45 and 60 ppm aqueous
solutions of Sodium Lauryl Sulphate along with
water have been investigated in the form of more
than 240 experiments. The impact of liquid and
gas flow velocities, surface tension, gas density,
solution concentration and particle diameter on
the transition from trickle to pulse flow analyzed
by change in two phase pressure drop and liquid
hold up.

2. Experimental set-up
A schematic of the experimental setup is
shown in Figure 1 and 2. The experimental
section mainly consists of a packed column, the
movement of phases being concurrent down flow
over the spherical glass packing. Liquid was
pumped from a liquid feed tank through a
rotameter to the top of the column and fed to the
distributor. Experiments were carried out on a 10
Type of Liquid

L
(Kg/m
3
)

L x 10
-3

(Kg/m.s)
x 10
-3

(N/m)

Ref:
Kerosene
Cyclohexane
790.8
780.1
0.99
0.93
25.3
25
[16]

0.5 % CMC
1.0% CMC
1001.40
1004.67
17.78
55.99
54
51.9
[9]

59 % Ethanol
24 % Methanol
43 % Methanol
891.5
956.1
912.7
2.45
1.67
1.67
29.78
45.35
35.90
[17]

6-ppm Surfactant
56 % I-propanol
34 % I-propanol
993
895.5
947.8
1.13
3.74
3.02
54.25
24.18
27.43
[13]

60 % Glycerol
77 % Glycerol
6 ppm SLS*
12 ppm SLS
1148.0
1192.7
999.5
999.5
5.93
27.04
1.13
1.13
64.53
63.24
59.10
55.0
[2,3]

0.25 % CMC +
CTAB
1001.2

6.66

56.16

[18]

Table 1: Description of foaming systems listed in
literature on which work already has been done

cm diameter glass column, packed with spherical
glass beads of size 7.12 mm were provided at the
top of the column. Air coming from the
compressor via air surge tank was first saturated
with process liquid in a saturator before
introducing into the packed bed. This would avoid
the effect of mass transfer between the gas and
liquid phase inside the column. For the even
distribution of liquid, a distributor was provided
at the top of the packed section.
The liquid was introduced into the column at
the desired air rate. Air is drawn from compressor
trough pressure regulator. Solenoid valve in the
air flow is provided so as to cut the supply of air
instantly for the measurement of dynamic liquid
saturation, air and liquid phase after transverse
the length of the packing were discharged at the
bottom of the column through a conical
separator/discharger. Two quick closing solenoid
valve provided at the top of the column, one each
in the air and liquid flow line facilitated in
simultaneous cut-off the phases when desired for
holdup measurement. After start process, liquid
concurrently down flow over packing. To check
any leakage in the reactor the column exists at
the bottom were closed. Manometer valve was
also closed and air supply at 0.0312 kg/m
2
s
pressure was introduced. Now the setup was left
in position for 30 minutes. The liquid flow was
run for 20 minutes for complete wetting of the
packing. Small quantity of air was now
introduced into the column and slowly the airflow
rate was brought to its desired rate within 2-3
minutes. Both the phases were allowed to flow
downward over the packing for 20-25 minutes,
which is necessary for the flow to attain a steady
state. The flow pattern across the glass column
was visually observed. The dynamic liquid
saturation of the system was studied by drainage
method. The inlet and outlet valve of the system
were closed simultaneously. The liquid was
collected in the column for 30-45 minutes till
formation for stable foaming/pulsing flow at high
flow rates.

3. Results and Discussion
Each set corresponds to reading at same air
flow velocity whereas liquid flow rate is varied
over a wide range of points in low as well as high-
interaction regimes. Solid packing of 7.12 mm
glass beads, air flows of 0.0512 0.2559 kg/m
2
s
were used to investigate 15 ppm , 30 ppm, 45 ppm
and 60 ppm Sodium Lauryl Sulphate tap water
solution (Table 2).

3.1. Effect of Liquid Flow Rate
On decreasing liquid flow rate, a uniform
distribution persists in the form of trickle flow

1 Control valve for gas
stream
3 Rotameter
5 Air exit for packed bed
7 Liquid outlet valve
9 Drain valve for Hold-up
11 Transparent glass column
13 Air compressor
15 Air Saturator
17 Mesh to control drop solid

2 Control valve for liquid
stream
4 Tracer inlet valve
6 Air out valve for trickle
8 Liquid collector for RTD
10 Liquid collector
12 Solid catalyst packing
14 Air ON/OFF valve
16 Air flow meter
18 Liquid distributor

Figure 1: Experimental set-up for present study
of foaming liquids in trickle bed reactor
Figure 2: Schematic of liquid distributor situated on
top of column

(GCF) is Figure 3. It maintains the continuous
flow of film on the wetted and dry surface formed
a uniform contact between liquid-gas and solid
particles for foaming liquids. This uneven flow of
liquid and gas produces two low and high contact
surfaces over packed bed in the form of two-phase
pressure drop during change of regime transition.
High liquid-side shear stress at the gas-liquid and
liquid-solid interface leads to increases pressure
drop with increase in surfactant concentration
For 15 and 30 ppm aqueous surfactant
solution, the influence of liquid flow velocities on
two-phase pressure drop is more prominent at
corresponding high gas flow rates. Further Figure
4 shows, for 60 ppm aqueous surfactant solution,
observed a significant increase in two-phase
pressure drop especially at low liquid flow rates.
Further, Figure 5 presents the change in two-
phase pressure drop for different values of liquid
flow velocities while comparing with past
researches. The trends of high two-phase

Type of Liq-
uid Used
L
(kg/m
3
)

L x 10
-3

(kg/m.s)
x 10
-3

(N/m)

Water
15 ppm SLS
*

30 ppm SLS
45 ppm SLS
60 ppm SLS
997.8
999.1
999.2
999.4
999.9

1.01
1.13
1.13
1.15
1.19
70.1
58.3
51.8
47.2
44.1

Table 2: Physical properties of chemicals used in
study.
* SLS Sodium Lauryl Sulphate
Figure 3: Effect of liquid flow rate on two-phase
pressure drop for 30 ppm Sodium Lauryl Sul-
phate
Figure 4: Effect of liquid flow rate on two-phase
pressure drop for 60 ppm Sodium Lauryl Sulphate
Figure 5: Full points are isoprpanol-nitrogen sys-
tem at at = 27.43 N/m and G = 0.175 kg/m
2
s [13]
and 6 ppm surfactant-air system at = 59.10 N/m
and G = 0.225 kg/m
2
s [2], [3]. Empty points are
aqueous solution of Sodium Lauryl Sulphate for
present study at various liquid flow velocities.

100
1000
10000
100000
1 10 100
Ser
ies

100
1000
10000
100000
1 10 100

100
1000
10000
100000
1 10 100

pressure drop in high interaction regime are
similar to that reported by Wang [13] but lie
significantly higher than the observations of
Bansal [2], [3] in both low and high interaction
regimes. From Figure 5, It is cleared that liquid
flow rate have a strong effect on two-phase
pressure drop, and found 10-15% higher two-
phase pressure drop values than observations
reported in literature. These fluctuations in
results are possibly due to impact of foam
formation during change of regime transition.
Here more noticeable thing is effect of foam
concentration is more prominent and significantly
controls/changes the value of pressure drop in
both trickle flow and foaming pulsing flow regime.

3.2. Effect of Gas Flow Rate
The dependence is not much similar to that
observed for non-foaming air-water system (at 30
C) corresponds to low liquid and high air flow
rates and vice-versa (Figure 6). Surprisingly, the
results observed are completely different to the
foaming systems. Figure 7 confirms that the
interaction between gas and liquid phases is
small which leads to less prominent change in
two-phase pressure drop as compared to high gas
flow rates. For 15 ppm aqueous surfactant
solution, effect of gas flow rate is less prominent
as compared to corresponding high gas flow
velocities. It is observed that from Figure 8, at
high gas flow rate of 0.2559 kg/m
2
s, two-phase
pressure drop significantly increases in both low
and high interaction regimes. The effect of gas
flow rate on two-phase pressure drop is highly
pronounced than that of liquid flow rates.
For present study, it is observed that the
presence of the gas phase only reduces the
available space for the flowing liquid.
Investigation of 45 ppm and 60 ppm Sodium
Lauryl Sulphate showed, at gas flow velocity of
more than 0.1024 kg/m
2
s liquid flow may be
assumed uniform in each flow zone. Further with
Figure 6: Effect of liquid flow rate on pressure drop
on non-foaming water at gas flow velocities of
0.0512 0.2559 kg/m
2
s
Figure 8: Comparison of foaming aqueous solu-
tion of Sodium Lauryl Sulphate with non-foaming
water at air flow rate of 0.2559 kg/m
2
s
Figure 7: Comparison of foaming aqueous solu-
tion of Sodium Lauryl Sulphate with non-
foaming water at air flow rate of 0.0512 kg/m
2
s.

100
1000
10000
1 10 100

100
1000
10000
100000
1 10 100

100
1000
10000
100000
1 10 100

increase in liquid flow rate it behaved non-
uniformly in the form of pulsation and foaming
over packed bed surface.
Figure 9 presents the comparison between the
present investigations of 30 ppm aqueous solution
of surfactant with literature listed researches. For
foaming liquids, at a given liquid flow rates, the
two phase pressure drop increased when the gas
velocity was increased. Similar kinds of
trendlines are observed by Wang [13] on gas flow
rate of 0.208 kg/m
2
s and by Bansal [2], [3] at gas
flow rate of 0.104 kg/m
2
s and 0.175 kg/m
2
s for low
concentrations of surfactant-nitrogen and
surfactant-air systems respectively. The trends
observed by [2], [3] lies prominently lower than
present investigation. Now it is crystal clear that,
two phase pressure drop increases drastically
with increase in gas flow rate during transition to
trickle flow to pulsing-foaming regime and impact
is much pronounced as compare to liquid flow
rate in downflow packed bed reactors.

3.3. Effect of Surface Tension
Trends from observations indicates, increase
in pressure drop corresponding to excessive foam
formation. Whereas for water, trends shows less
prominent change in two-phase pressure drop as
compared to foaming aqueous surfactant system
was observed. The solution of low surface tension
in the foaming pulsing flow regime produced
much higher two-phase pressure drop in
Figure 9: Full points are observations of 6 ppm sur-
factant-air system at G = 0.104 kg/m
2
s and G =
0.175 kg/m
2
s by Bansal [2], [3]. Another full points
at G = 0.208 kg/m
2
s signifies the 6 ppm surfactant-
nitrogen system by Wang [13]. Empty points are
aqueous solution of 30 ppm surfactant-air system at
different gas flow velocities for present investigation
Figure 11: Full points are trends for 34% Isopro-
panol nitrogen system with = 27.43 N/m and
40% Ethanol argon system with = 31.88 N/m
observed by Bartelmus [14], [15]. Trends with
other full points signifies 6ppm surfactant air
system with = 59.12 N/m. Empty points are
aqueous solution of surfactant air system of
different surface tensions at G = 0.204 kg/m
2
s
Figure 10: Effect of surface tension on two-phase
pressure drop at air flow rate of 0.2047 kg/m
2
s.

100
1000
10000
100000
1 10 100

100
1000
10000
100000
1 10 100 1000

100
1000
10000
100000
1 10 100 1000

comparison to for non-foaming water systems. It is
observed that from present trends, at gas flow
rates of 0.2047 kg/m
2
s and 0.2559 kg/m
2
s, the effect
of lowered surface tension on two phase pressure
drop is much significant (Figure 10). At these
particular gas flow rates, an early increase in
pressure drop was observed in high interaction
regime at corresponding low liquid flow rates.
This clearly indicated that the decrease in
surface tension results in higher two-phase
pressure drop both in low and high interaction
regimes. It is worth mentioning that high two-
phase pressure drop was observed for aqueous 45
ppm and 60 ppm surfactant solution in both low
and high interaction regimes.
For present investigation it is believed that the
decrease in surface tension is associated with
better spreading of the fluid. In trickle bed reactor
lower surface tension or better spreading is
expected to increased pressure drop. Figure 11
confirmed that, the influence of surface tension on
pressure drop corresponds to different liquid
Reynolds number is very significant while
comparing high foaming liquids. The experimental
points of present study lies lower than the
trendline proposed by Bartelmus and Janecki [13],
[14] which confirms that two-phase pressure drop
increases with increase in gas flow rate and
decrease in surface tension.
For present study, foam generally starts
occurred at liquid flow rate L = 4.022 kg/m
2
s.
Aqueous solution of 60 ppm surfactant produced
heavy foam even at low liquid flow rate of L =
2.550 kg/m
2
s g which simultaneously leads to
heavy pressure drops values. This heavy change in
two-phase pressure drop values is depends upon
concentration of foam (i.e. lowering of surface
tension). It is verified by comparing results
observed for presently studied air-aqueous
surfactant and air-water systems.

4. Conclusions
For surfactant-air systems, two-phase pressure
drop increases with an increase in liquid and gas
flow rates. Change in gas flow velocities leads to
significantly rapid increase in high interaction
regime (FPF) as compare to low interaction regime
(GCF). Studies of aqueous solution 60 ppm
surfactant showed surprised results with sharp
increase in reactor pressure drop even at very low
liquid flow rate of 3.274 kg/m
2
s corresponds to gas
flow rate of more than 0.102 kg/m
2
se. The
possibility of foam formation in low surface tension
solutions like 60 ppm aqueous surfactant solution
under trickle flow conditions can not be ruled out.
Effect of surface tension on two phase pressure
drop is more pronounced in high interaction
regimes at corresponding low and high gas
velocities.

Abbreviations / Acronyms
Z packed bed height/ column, m
L liquid superficial mass, kg/m
2
s
G gas superficial, kg/m
2
s
P two-phase pressure, N/m
2

PG pressure drop based on gas, N/m
2

PL pressure drop based on liquid, N/m
2

ReL Liquid Reynolds Number
liquid surface tension
density of liquid, kg/m
3

density of water, kg/m
3

density of gas, kg/m
3

viscosity of liquid, kg/m.s
viscosity of water, kg/m.s

References
[1] Burghardt, A.; Bartelmus, G.; Szlemp, A. 1995.
Hydrodynamics of pulsing flow in three-phase fixed-bed
reactor operating at an elevated pressure, Industrial
and Engineering Chemistry Research 43: 45114521.
[2] Bansal, Ajay, 2003. Hydrodynamics of trickle bed
reactor, Ph.d Thesis. Engineering and Technology
Faculty, Punjab University, Patiala, Punjab, India.
[3] Bansal, A.; Wanchoo, R. K.; and Sharma, S. K. 2008.
Flow regime transition in a trickle bed reactor,
Chemical Engineering Communication 58:111-118.
[4] Prudhomme. R.K.; Khan, S.A. Foams, Theory,
Measurements, and Applications, CRC Press, 1996.
[5] Midoux, N.; Favier, M.; Charpentier, J.C. 1976. Flow
pattern, Pressure Loss and Liquid Holdup Data in Gas
Liquid Downflow Packed Beds with Foaming and Non-
foaming Hydrocarbons, Journal of Chemical
Engineering of Japan, 9: 350356
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mechanistic model for pressure drop and liquid holdup
in trickle flow reactors, Chemical Engineering Science
57: 3359 3371.
[8] Muthanna, A.; Dudukovic, M. 1995. Pressure drop and
liquid holdup in high pressure trickle bed reactors.
Chemical Engineering Science 49: 56815698.
[9] Iliuta, I.; Thyrion, F.C.; Muntean, O. 1996. Residence
time distribution of the liquid in two-phase cocurrent
downflow in packed beds: air/Newtonian and non-
Newtonian liquid systems, Canadian Journal of
Chemical Engineering 74: 783-796.
L

[10] Sai, P.S.T.; Varma, Y.B.G. 1987. Pressure drop in gas
liquid downflow through packed beds, American
Institute of Chemical Engineering. Journal 33: 2027
2035.
[11] Larachi, F.; Laurent, A.; Midoux, N.; Wild, G. 1991.
Experimental study of a trickle bed reactor operating at
high pressure: two-phase pressure drop and liquid
saturation. Chemical Engineering Science 46: 1233
1246.
[12] Aydin, B.; Larachi, F. 2008. Trickle bed hydrodynamics
for (non-)Newtonian foaming liquids in non-ambient
conditions, Chemical Engineering Journal 143: 236243.
[13] Wang, R.; Zai-sha, M.; and Jiayong, C. 1995.
Experimental and Theoretical Studies on Pressure Drop
Hysteresis in Trickle Bed Reactors, Chemical
Engineering Science, 50(14): 2321-2328 .
[14] Bartelmus, G.; Janecki, D. 2004. Hydrodynamics of the
cocurrent downflow of a gas and a foaming liquid
through a packed bed. Part I. Estimation of the
transition boundary between the hydrodynamic regimes
from the gas continuous flow to the pulsing flow,
Chemical Engineering and Processing 43: 169179.
[15] Bartelmus G.; Janecki, D. 2003. Hydrodynamics of a
cocurrent downflow of gas and foaming liquid through
the packed bed. Part II. Liquid holdup and gas pressure
drop, Chemical Engineering Processing 42: 9931005.
[16] Charpentier, J. C.; and Favier, M. 1975. Some liquid
holdup experimental data in trickle-bed reactors for
foaming and non-foaming hydrocarbons. American
Institute of Chemical Engineering Journal 21: 1213-
1218.
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Hydrodynamics of a co-current three-phase solid-bed
reactor for foaming systems, Chemical Engineering
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[18] Aydin, B.; Larachi, F. 2008. Trickle bed hydrodynamics
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on a Trickle Bed Reactor for Foaming Liquids. Bulletin
of Chemical Reaction Engineering & Catalysis, 5 (1): 31
37.


1. Introduction
Stirred tanks are among the most commonly
used pieces of equipment in the chemical and
biochemical processes. Oxygen transfer rate and
the corresponding power requirement to operate
the impeller are vital for design of stirred tanks.
The physical and chemical processes taking place
in the stirred tank are complex and closely coupled
to the underlying transport processes, in
particular-the flow field. Therefore, a detailed
understanding of the hydrodynamics of stirred
tank (velocity field, turbulence, stress field etc.) is
useful for optimum design [1-2].
Knowledge about the mixing processes is also
important when scaling up a process from
laboratory scale to industrial plant scale. The
experimental studies of mixing phenomena are
usually concentrated around a standard geometry
stirred tank where the phases are agitated with
some kind of impeller. The study of mixing
Impeller Submergence Depth for Stirred Tanks
Thiyam Thamphasana Devi
1
, Annu Priya Sinha
2
, Meena Thakre
2
, and Bimlesh Kumar
1*

1
Department of Civil Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India
2
Agriculture Engineering, JNKVV, Jabalpur, India
* Corresponding Author
E-mail: bimk@iitg.ernet.in, Tel: +91-361-2582420, Fax: +91-361-2582440
Received: 4
th
March 2011; Revised: 12
nd
July 2011; Accepted: 14
th
July 2011
Abstract

Impeller submergence governs the performance of mixing tanks employed in oxygen transfer operation.
Present work experimentally investigates the effect of impeller submergence depths on oxygen transfer and
corresponding power consumption. It has been found that at higher range of impeller submergence, mixing
tanks consume less power and gives higher values of oxygen transfer coefficient. Optimal range of submer-
gence depth is 0.7 to 0.9 times the impeller diameter. Copyright 2011 BCREC UNDIP. All rights reserved.
.
Keywords: oxygen transfer; power consumption; rotational speed; submerged depth; stirred tanks; two-film
theory

How to Cite: T.T. Devi, A.P. Sinha, M. Thakre, and B. Kumar. (2011). Impeller Submergence Depth for
Stirred Tanks. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2): 123-128
includes understanding of how gas and liquid
phases are transported in the tank, and how this
transport is affected by the tank and the
impeller(s) geometry, as well as the operational
conditions such as stirring rate and pumping
capacity. Flow behavior and mixing characteristics
in stirred tanks has been studied extensively [1, 3-
11]. The performance of surface aerators is known
to depend on the impeller submergence, which
indicates the position of impeller in stirred tank
[10, 12]. According to Oldshue [1], there is not only
one optimal or unique design for each kind of
process. Several designs may satisfy the process
specifications [1]. In order to simplify design and
minimize costs, standard reactor designs are
usually good enough for most processes. Even
though the role of impeller submergence has been
identified as an important parameter, it has not
been systematically investigated. Generally
impeller position has been fixed at 1/6 to 1/2 of
Research Article

tank diameter [7]. Zlokarnik [13] has found
relatively greater effect of the impeller
submergence on the oxygen transfer rate than on
the power consumption. Backhurst et al [14] has
found that the oxygen-transfer rate per unit
power consumption was optimum at an impeller
clearance of twice the impeller diameter and that,
with a further increase in impeller clearance, the
value of oxygen-transfer rate per unit power
consumption decreased. Takase et al [15] has
reported different effects of impeller clearance.
Patil et al [10] has conformed the observations
reported by Backhurst et al [14]. For a pitched
blade down flow turbine (PBTD) and standard
disk turbine (DT), optimality has been observed
when an impeller clearance is twice the impeller
diameter [10].
The economics of stirred tanks, particularly
operating costs, are contributing much more
heavily to system selection [16-17]. Because of the
widespread applications of stirred tanks in the
process industry, even a small reduction in the
operational costs of these vessels can result in
major cost savings. It is essential that the design
and operation of stirred tank must be as near as
is possible or practicable. The design guideline on
Rushton turbine (generally called as standard
turbine) is well documented in the literature,
whereas in case of non-standard impeller such as
curved blade, arrowhead impeller are not always
easy to find in the open literature. Present work
tries to find out the optimal impeller submergence
for non-standard impeller (curved blade impeller).
The effect of impeller position has been
investigated in the present work for optimal
oxygen transfer and power consumption.

2. Materials and Method
Experiment has been carried out with an
objective of finding the effect of impeller position
on oxygen transfer coefficient and power
consumption. Two sizes of unbaffled stirred tanks
(A = 0.0314 m
2
and 0.01766 m
2
) have been used in
the experimentation. Fig. 1 shows schematic
diagram of the setup used in the present study.
The various geometric dimensions of the aerator
are: D (tank diameter), H (water depth), h
(impeller submergence or distance between the
horizontal bottom of the tank and the top of the
blades) and d (diameter of the impeller). Diameter
of the tanks (D) is 200 mm and 150 mm,
respectively. Standard geometry of impeller
(Rushton turbine) has been documented well in
the literature [11]. Thus the impeller used in the
present study is six curved blade impeller
Given the same conditions of power per unit
volume, curved blade impeller is having higher
value of mass transfer (www.chemineer.com) than
conventional flat blades disc impeller (Rushton
turbine). When a single impeller is to be used, a
liquid level equal to the diameter is optimum,
with the impeller located at the center for an all-
liquid system [7, 18].
Generally unbaffled tanks are being employed
for surface aerators, because unbaffled tanks give
rise to higher fluid-particle mass transfer rates
for a given power consumption [4], which is the
paramount importance in designing aeration
system. Baffled tanks are also giving rise to dead
zones, actually worsening the mixing performance
of an aeration system [7]. It has been also
recognized that the local value of the mass
transfer rates would probably vary from one
region to another in baffled tanks [19]. There are
regions in the tanks where the surface renewal
rate is high and the other parts where the liquid
is relatively stationary [19]. This non-uniformity
of local value of mass transfer rates is the
fundamental disadvantage of the use of baffled
tank in mass transfer process.

2.1 Power Consumption
Power consumption is a basic integral quantity

Motor
H

h
b
l
d
Shaft
Rotor blades
D
N
Figure 1. Experimental setup and Schematic dia-
gram

in an aerator, which determines the other
processes involved in aeration phenomena such as
mass transfer rates, gas hold up etc [20-21]. The
power usage in mass transfer operations is very
important in judging the aeration performance of
the aerator. Power draw is defined as the amount
of energy necessary in a period of time, in order to
generate the movement of the fluid within a
container (e.g. bioreactor, mixing tank, chemical
reactor etc.) by means of mechanical or pneumatic
agitation [22]. Power draw in systems has been
measured by means of a wattmeter. The power
available at the shaft was calculated as follows
[22]. Let P1 and P2 are the power requirements
under no load and loading conditions at the same
speed of rotation. Then the effective power
available to the shaft is Peff = P2 P1 Losses.
Reproducibility of measurements has been found
to be 5%. The main advantages of the estimation
of power draw by electrical measurements are: (1)
It is a simple method, (2) little instrumentation is
required and (3) high investment is not required.

2.2 Oxygen Transfer Rate
According to two-film theory [23], the oxygen
transfer coefficient at T
o
C, KLaT may be expressed
as follows (Eq. 1):

KLaT = [ln(Cs - C0) - ln(Cs - Ct)]/t (1)

where, ln represents natural logarithm and Cs, C0
and Ct are dissolved oxygen (DO) concentrations
in parts per million (ppm), Cs = the saturation DO
at time tending to very large values, C0 is at the
beginning of time t=0 and Ct is at time t = t. The
value of KLaT can be obtained as slope of the
linear plot between ln(Cs - Ct) and time t. The
value of KLaT can be corrected for a temperature
other than the standard temperature of 20
o
C as
KLa20, using the Vant- Hoff Arrhenius, Eq. (2):

KLaT = KLa20 q
(T - 20)
(2)

where q is the temperature coefficient equal to
1.02 for pure water. Once the impeller starts
rotating, DO meter (Thermo-Orion) reading is
noted at regular interval up to the point when the
DO values reaches 80% of the saturation value or
above. Thus the known values of DO
measurements in terms of Ct at regular intervals
of time t (including the known value of C0 at t = 0)
a line is fitted, by linear regression analysis of
Eq.1, between the logarithm of (Cs - Ct) and t, by
assuming different but appropriate values of Cs
such that the regression that gives the minimum
"standard error of estimate" is taken and thus the
values of KLaT and Cs has been obtained
simultaneously. Oxygen transfer modeling by
two-film theory assumes that a single and
constant value of Cs is adequately representative
of the equilibrium DO for the liquid phase oxygen
mass transfer for the entire aeration systems and
the transfer process is predominately liquid phase
mass transfer controlled and the gas phase
resistance to transfer can be ignored. Now by
fixing the value of Cs, the value of KLaT has been
determined by the best fit straight line, semi-
logarithmic plot of (Cs - Ct) and t. It may be noted
that the value of Cs used in the log-deficit
approach can be based on field measurement,
published value, or simple assumption [24]. It is a
common practice to fix the value of Cs around the
maximum DO value with some increment in it, as
long as it gives the best fit. The slope of such a
straight line, semi-logarithmic is equal to - KLaT.
It is worth noting that selection of a particular
value for Cs will influence the resultant value for
KLaT determined by this approach. The oxygen
transfer coefficient calculated using this method
may have errors, because the method used
Figure 2. Impeller Used in the Experiments
Impeller
diameter
(d) (mm)
Blade
length
(mm)
Blade
width
(mm)
Blade
thickness
(mm)
80 20 16 0.8
60 15 12 0.6
45 11.25 9 0.45
40 10 8 0.4
30 7.5 6 0.3
Table 1. Impeller geometrical properties

requires a straight line to fit the data, the error
could be reduced if the linear regression
coefficient of the chosen line is high. In that case
the slope of the line would accurately represent
the oxygen transferred to the water.

The performance of stirred tank is known to
depend on the impeller submergence. Therefore,
the effect of impeller submergence has been
investigated systematically. Fig. 3 illustrates
observations made on power consumption with
different submergence depths of impeller. The
value of h/d varies from 0.3 to 0.9. Power
consumption is strongly dependent on the gas
holdup near the impeller i.e., the local gas hold-up
in the vicinity of the impeller [25]. As the size of
this region increases, impeller rotates in
progressively increasing liquid free region thereby
decreasing the power consumption. The less
power consumption at higher value of h/d can be
also attributed to the fact that blades are exposed
to the air. Exposure of blades decreases the drag
d/D=0.2
0
5
10
15
20
25
30
0 500 1000 1500
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
d/D=0.3
0
5
10
15
20
25
0 200 400 600 800 1000 1200
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
d/D=0.4
0
5
10
15
20
25
30
0 200 400 600 800
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
Figure 3a. Influence of submergence depth at
power consumption (200mm tank)
d/D=0.2
0
2
4
6
8
10
12
14
16
0 500 1000 1500 2000
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
d/D=0.3
0
2
4
6
8
10
12
14
16
0 500 1000 1500
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
d/D=0.4
0
2
4
6
8
10
12
14
16
18
20
0 200 400 600 800 1000 1200
N (rpm)
P
e
f
f

(
W
a
t
t
)
h/d=0.3
h/d=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
Figure 3b. Influence of submergence depth at
power consumption (150 mm tank)

resistance. This decrease in drag results in lower
power draw or consumption. This fact can be seen
from the Fig. 3. It can be seen from the Fig. 3, the
value of h/d = 0.9 consumes less power in most of
the cases. Overall these observations suggest that
a range of 0.7 to 0.9 is optimal as far as power
consumption is concerned.
With increasing submergence, the number of
eddies at gas-liquid interface are decreased. A
decrease in impeller submergence results in
stronger surface waves and/or forceful liquid jets.
However, the liquid circulation velocity increases
with increasing submergence. The centrifugal
force due to the strong tangential velocity is the
cause for jet formation from the impeller. A vortex
is also formed as shown in the Fig. 4. The vortex
size increases as the impeller approaches the
liquid surface.
The combined effect of bubble entrapment,
vortex size and liquid circulation results in a
maximum value of oxygen transfer as shown in
the Fig. 5. At low submergence depth, momentum
of the impeller is not transferred properly to the
liquid. In this case, overall liquid velocity is low
and thus reducing the oxygen transfer rates. Fig.
5 also suggests that range of 0.7 to 0.9 is optimal
for oxygen transfer process.

4. Conclusion
General l y standard gui deli nes for
submergence are being followed for designing the
stirred tanks for desired process, which can far
from being an optimal point. Slight change in
submergence depth can cost much when optimal
performance is required. There is practically no
published information, which explicitly stipulates
the optimal submergence depth of impeller.
Present work experimentally investigates the
influence of submergence depth on power
consumption and oxygen transfer process. The
range of h/d = 0.7 to 0.9 is found to be optimal,
however for design purpose h/d=0.9 can be taken
as optimal point.

Acknowledgments
This work was supported by a research grant
from Indian Institute of Technology Guwahati,
Guwahati (SG/CE/P/BK/01)

References
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0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0 200 400 600 800 1000
N (rpm)
K
L
a
2
0

(
1
/
m
i
n
)
h/d=0.3
h/D=0.4
h/d=0.5
h/d=0.6
h/d=0.7
h/d=0.8
h/d=0.9
Figure 5. Oxygen transfer at different submergence
depth

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16.

1. Introduction
CO2 reforming of methane (CORM) to produce
synthesis gas has drawn much interest in recent
years because it consumes methane and carbon
dioxide which are both major contributors to the
green house gases. Moreover, the availability of
methane (which is the major component in natural
gas) has also encouraged development of this
process [1]. The CORM is a catalytic process which
Catalyst Deactivation Simulation Through Carbon Deposition
in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst

I. Istadi
1) *)
, Didi D. Anggoro
1)
, Nor Aishah Saidina Amin
2)
,
and Dorothy Hoo Wei Ling
2)

1)
Laboratory of Chemical and Process Engineering, Department of Chemical Engineering, Diponegoro
University, Jl. Prof. Soedarto, Kampus Undip Tembalang, Semarang, Indonesia 50275
2)
Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM
Skudai Campus, Malaysia
*
Corresponding Author.
Telp: (+62-24-7460058); Fax.: (+62-24-76480675);
Email: istadi@undip.ac.id (I. Istadi)
Received: 10th May 2011; Revised: 16th August 2011; Accepted: 27th August 2011
Abstract

Major problem in CO2 reforming of methane (CORM) process is coke formation which is a carbonaceous
residue that can physically cover active sites of a catalyst surface and leads to catalyst deactivation. A key
to develop a more coke-resistant catalyst lies in a better understanding of the methane reforming mecha-
nism at a molecular level. Therefore, this paper is aimed to simulate a micro-kinetic approach in order to
calculate coking rate in CORM reaction. Rates of encapsulating and filamentous carbon formation are also
included. The simulation results show that the studied catalyst has a high activity, and the rate of carbon
formation is relatively low. This micro-kinetic modeling approach can be used as a tool to better understand
the catalyst deactivation phenomena in reaction via carbon deposition. Copyright 2011 BCREC UNDIP.
All rights reserved.

Keywords: CO2 reforming of methane; CORM; Ni/CaO-Al2O3; coke formation; micro-kinetic modeling;
simulation

How to Cite: I. Istadi, D.D. Anggoro, N.A.S. Amin, and D.H.W. Ling. (2011). Catalyst Deactivation Simula-
tion Through Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 Catalyst. Bulletin of
Chemical Reaction Engineering & Catalysis, 6 (2): 129-136
involves the indirect utilization of methane and
carbon dioxide to produce valuable synthesis gas.
Utilization of this process will bring both economic
and environmental benefits.
The main reaction for the production of
synthesis gas via CORM reaction is given in
Equation 1. The CORM reaction is usually
accompanied by the simultaneous occurrence of the
Reverse Water-Gas Shift reaction (RWGS) as
written in Equation 2. However, the critical
problem in this process is catalyst deactivation
caused by carbon deposition (coking). Basically,
there are two types of carbon formation in this
reaction, i.e. encapsulating carbon and filamentous
Research Article

carbon (Figure 1). Therefore, in order to create a
more stable catalyst for CORM, great attention
has been focused on development of coke-resistant
catalysts. Besides that, cost factor is also
important to be considered if the catalyst will be
applied industrially.

CH4 + CO2 2CO + 2H2 (H
0
298K = +247 kJ/mol)
(1)
CO2 + H2 CO + H2O (H
0
298K = +41 kJ/mol)
(2)

During last several years, great efforts have
been focused on development of catalysts for this
process incorporating a kinetic inhibition of
carbon formation under conditions where
deposition is thermodynamically favorable.
Nickel-based catalysts and noble metal-supported
catalysts such as Rh, Ru, Pd, Pt and Ir were
found to have promising catalytic performance in
terms of conversion and selectivity for the CORM
process. According to results by Wang et al. [3],
noble metal-based catalysts have shown to have
high activity and less sensitive to coking
compared to the Ni-based catalysts for the CORM
process. In spite of this, high cost and limited
availability of noble metals prevent the
commercial use for this reaction. Therefore, it is
more practical to develop improved Ni-based
catalysts which exhibit stable operation for a long
period of time.
In order to increase the stability of supported
Ni catalysts, some elements were added acting as
support modifiers or promoters. According to
some experimental researches, it has been proven
that the support type and presence of the
modifiers greatly affect the coking tendency.
According to Ferreira-Aparicio et al. [4] who
prepared and tested two series of transition
metals (Co, Ni, Ru, Rh, Ir, Pt)-based catalysts
using silica and alumina in the CORM reaction, it
was shown that alumina-based catalysts show
higher specific activity than their respective
counterparts dispersed on silica. According to
Quincoces et al. [5], CaO-modified Ni catalysts
present high stability and good activity with
respect to Ni/Al2O3. When CaO is added to the
support, the formation of filamentous carbon
decreases and favors the formation of more
reactive carbonaceous species. Recent simulation
on catalyst deactivation due to coke formation
was done by Chigada and co-workers [6]. They
suggested that long-range heterogeneities in the
pore structure of the catalyst are important for
determining deactivation behavior, and the
experimental system involved a series deactivation
scheme for the reaction under supercritical
conditions. A comparison of simulation with
experiment has enabled a validation of the
structural model and particular reaction scheme
used in the simulations.
In actual fact, the key to develop a more coke-
resistant catalyst lies in a better understanding of
the methane reforming mechanism at a molecular
level [7]. Micro-kinetic analysis is an examination
of catalytic reactions in terms of elementary
chemical reactions that occur on the catalytic
surface and their relation with each other and with
the surface during a catalytic cycle. Micro-kinetics
has, for the most part, focused on analysis for
understanding the reaction mechanism. It has
been shown that micro-kinetic modeling based on
knowledge about elementary steps and their
energetics, is a very powerful tool for a detailed
understanding of catalytic processes [8]. This paper
is aimed to simulate a micro-kinetic approach in
order to calculate coking rate in CORM reaction.
Rates of encapsulating and filamentous carbon
formation are also included in this study.

2. Modeling and Simulation Methods
First step in this research was to study the
micro-kinetic model of methane reforming on Ni
catalysts developed by Aparicio [9]. The micro-
kinetic model consists of adsorption and desorption
steps of all reactants and products and the surface
elementary reaction steps. The combined reaction
for the main CORM reaction and the side RWGS
Figure 1. Schematic of encapsulating and fila-
mentous carbon on nickel catalyst [1]

reaction is:

2 CO2 + CH4 3 CO + H2 + H2O (3)

The reactions steps for both main and RWGS
reactions are combined and they are presented in
Table 1 [9]. For each step in the model, the
reaction rates for forward and backward reactions
are written. It is assumed that the reaction steps
are elementary, and the rates are written in terms
of partial pressure and surface species. This rate is
calculated as turnover frequency. Table 2 shows
the reaction rates for all the steps (Equations 4 -
24). The next step in this research was to write the
mathematical models in terms of rate of reaction
for all the ten surface species and five gaseous
species. The differential equations against time is
written for each of the surface species namely
*CH3, *CH2, *CH, *C, *H2O, *OH, *CHO, *CO, *H
and *, and also the partial pressures for five
gaseous species CH4, CO2, H2O, H2 and CO. The
fifteen differential equations of surface species are
then solved simultaneously to obtain the fraction of
sites occupied by each surface species. The site
coverage of adsorbed carbon would then be used to
calculate the rate of coking. The fifteen differential
equations are presented in Table 3 (Equations 25 -
39).
In this model, it is assumed that the atomic
carbon on the surface is a common intermediate in
both the main reaction and the carbon formation
including filamentous and encapsulating carbon.
According to Chen et al. [7], the reaction between
the adsorbed carbon on the surface is assumed to
be reversible and the sole pathway for
encapsulating carbon formation, as shown in
Equation 40 [6].

n **C n Cp (40)

Therefore, the rate for encapsulating carbon
formation is given in Equation 41 [7].

rcp = kp cn (41)

The weight of encapsulating carbon is given in
Equation 42:

Cp = rcp . dt . 12 (42)

The site coverage of encapsulating carbon is
calculated from Equation 43 [8]:

(43)

According to Froment [9], the filamentous carbon
formation involves the following process:

(a) Dissolution of adsorbed-carbon through Ni:
**C CNi,f (44)
(b) Diffusion of carbon through Ni:
CNi,f CNi,r (45)
(c) Precipitation / Dissolution of carbon:
CNi,r Cf (46)

The adsorbed surface carbon, **C, at first
dissolves in the Ni particle, therefore it diffuses
and precipitates at rear of the nickel crystallite.
The continuous precipitation of this adsorbed
carbon will form filamentous carbon. For this
process to take place, the carbon concentration in
the layer just below the Ni surface, CNi,f must
exceed the carbon solubility in Ni, Csat. The higher
the difference between CNi,f and Csat, the bigger
the driving force for this process of filamentous
carbon formation.
A simple Langmuir equation was used to
estimate the concentration of carbon in the
segregation layer is given in Equation 47 [7].

(47)

This equation is used to calculate the weight
fraction of carbon in the segregation layer, xb. The
values of c are obtained from the simulation
results. The value of c needs to be divided by 2, as
one carbon atom occupies two active sites on the
catalyst.
Equation 48 is used to calculate the Gibbs
energy for the segregation layer in this process [7]:

Gseg = -10800 3.4T (cal/mol) (48)

The rate of carbon diffusion through Ni, which is
also the rate of filamentous carbon formation, is
given in Equation 49 [8].

(49)

where CNi,f is calculated based on xb in Equation
46 by multiplying xb with a Ni density of 8900
kg/m
3
.
All values for constant parameters are obtained
from Chen et al. [7]. The values are presented in
Table 4. All the necessary equations were solved
using MATLAB

c Ni
Ni p
cp
M Df
M C
=
|
|
\
|
=
RT
G -
exp
x - 1
x

- 1
seg
b
b
c
c
|
\
|
=
sat
C
f Ni,
C
Ni
a
Ni
d
C
D
r

Table 1. Reaction steps for the combined reaction [9]
Reaction Steps k E
CH4 + 2* *CH3 + *H 2.02 x 10
6
53. 9
*CH3 + *H CH4 + 2* 2.50 x 10
10
95.9
*CH3 + * *CH2 + *H 1 x 10
13
115.4
*CH2 + *H *CH3 + * 2 x 10
12
75.4
*CH2 + * *CH + *H 1 x 10
13
102.9
*CH + *H *CH2 + * 2 x 10
12
75.4
*CH + 2* **C + *H 1 x 10
13
0
**C + *H *CH + 2* 1.54 x 10
11
64.4
2 [ CO2 + 2*H + 2* **CHO + OH* + * ] 9.97x10
6
(1/T)
0.968
-50.0
2 [ **CHO + OH* + * CO2 + 2*H + 2* ] 2.9 x 10
15
0
3 [ **CHO + * **CO + *H ] 5.14 x 1019 0
3 [ **CO + *H **CHO + * ] 1 x 10
7
23.0
3 [ **CO CO + 2* ] 5 x 1012 115.0
3 [ CO + 2* **CO ] 1 x 10
8
0
2*H H2 + 2* 1 x 10
13
95.0
H2 + 2* 2*H 3 x 10
8
0
**C + *OH **CHO + * 3 x 10
14
65.5
**CHO + * **C + *OH 1.13x10
21
(1/T)
3.03
90.3
*H + *OH *H2O + * 3.08 x 10
11
32.2
*H2O + * *H + *OH 4.15 x 10
7
0
*H2O H2O + * 1 x 10
13
64.4
H2O + * *H2O 1.78 x 10
6
0
Table 2. Reaction rates for all the steps
Step Reaction Rates Equation Num-
ber
1 CH4 + 2* *CH3 + *H R1 = k1PCH4 *
2
(4)
2 *CH3 + *H CH4 + 2* R2 = k2CH3H (5)
3 *CH3 + * *CH2 + *H R3 = k3CH3 * (6)
4 *CH2 + *H *CH3 + * R4 = k4CH2H (7)
5 *CH2 + * *CH + *H R5 = k5CH2* (8)
6 *CH + *H *CH2 + * R6 = k6CHH (9)
7 *CH + 2* **C + *H R7 = k7CH*
2
(10)
8 **C + *H *CH + 2* R8 = k8CH (11)
9 2 [ CO2 + 2*H + 2*. **CHO + OH* + *] R9 = k9PCO2H2*
2
(12)
10 2 [ **CHO + OH* + * CO2 + 2*H + 2* ] R10=k10CHOOH* (13)
11 3 [ **CHO + * **CO + *H ] R11 = k11CHO* (14)
12 3 [ **CO + * H **CHO + * ] R12 = k12COH
13 3 [ **CO CO + 2* ] R13 = k13CO (15)
14 3 [ CO + 2* **CO ] R14 = k14PCO*
2
(16)
15 2*H H2 + 2* R15 = k15H2 (17)
16 H2 + 2* 2*H R16 = k16PH2*
2
(18)
17 **C + *OH **CHO + * R17 = k17COH (19)
18 **CHO + * **C + *OH R18 = k18CHO* (20)
19 *H + *OH *H2O + * R19 = k19HOH (21)
20 *H2O + * *H + *OH R20 = k20H2O* (22)
21 *H2O H2O + * R21 = k21H20 (23)
22 H2O + * *H2O R22 = k22PH2O* (24)


Table 3. Rate equations for surface species and gaseous species
Species Term in rates Equation Num-
ber

/dt d
H
R1-R2+R3-R4+R5-R6+R7-R8-4(R9)+4(R10)+3(R11)
-3(R12)-(R15)+2(R16)-R19+R20
(25)

/dt d
3
CH
R1-R2-R3+R4 (26)

/dt d
2
CH
R3-R4-R5+R6 (27)

/dt d
CH
R5-R6-R7+R8 (28)

/dt d
C
R7-R8-R17+R18 (29)

/dt d
O H
2
R19-R20-R21+R22 (30)

/dt d
OH
2(R9)-2(R10)-R17+R18-R19+R20 (31)

/dt d
CHO
2(R9)-2(R10)-3(R11)+3(R12)+R17-R18 (32)

/dt d
CO
3(R11)-3(R12)-3(R13)+3(R14) (33)

/dt d
*
2(R2)-2(R1)-R3+R4-R5+R6-2(R7)+2(R8)-
4(R9)+4(R10)-3(R11)+3(R12)+6(R13)-6(R14)+2(R15)-
2(R16)+R17-R18+R19-R20+R21-R22
(34)

/dt dP
4
CH
R2-R1 (35)

/dt dP
2
CO
2(R10)-2(R9) (36)

/dt dP
O H
2
R21-R22 (37)

/dt dP
2
H
R15-R16 (38)

/dt dP
CO
3(R13)-3(R14) (39)
Table 4. Constant parameters used in the simulation [7]
Parameter Value Unit
aNi 0.33 m
3
/g cat
Csat 1.45 mol C/m
3
Ni
dNi 7.467 x 10
-8
m
D 0.0046 surface Ni atoms/ total Ni atoms
Dc 5.32 x 10
-10
cm
2
/s
fNi 0.11 g Ni/g cat
kp 605 mol C/mol of site,s
MC 12.01 g C/mol C
MNi 58.69 g Ni/mol Ni
R 1.987 cal/mol K
T 923.15 K

According to Wang and Lu [11] who evaluated
the catalyst performance of various Ni catalysts
with different supports, it was discovered that
both types of Ni/Al2O3 catalysts, namely Ni/-
Al2O3 and Ni/-Al2O3, give very high CO2 and CH4
conversions. Figure 2 indicates that the fraction
of vacant sites decrease drastically at beginning
of the reaction. This result shows that the
catalyst has a high activity. The fraction of vacant
sites becomes stagnant after a short time in the
reaction. Theoretically, the fraction of vacant sites
should be decreasing to zero, meaning that all
active sites are participating in the reaction.
However, this result cannot be achieved in
practical. There are certain numbers of sites
which are not functioning in the reaction. Some of
these sites are hidden in the catalyst pores, and
due to diffusional limitations, they are not
reachable by the reacting species. Ding and Yan
[12] who conducted their research on MgO and
CeO2 promoters on Ni/Al2O3 catalysts suggested
that this phenomenon happened because of the
blockage and coverage of active Ni sites by species
originating from the promoters. Therefore, it is
assumed that the CaO promoter used in this
model could also lead to the same consequences.
In this model, the maximum amount of
encapsulating carbon is treated as a monolayer of
carbon on the Ni surface, and this monolayer is
sufficient to block the active sites and
consequently deactivate the catalyst. Any
multiple layers of carbon are treated as
filamentous carbon in this model. From Figure 3,
it is observed that the rate of encapsulating
carbon formation increases initially at the
reaction. This is because the reaction takes place
very fast in the beginning, and the site coverage
of adsorbed carbon is high. Therefore, this will
increase the rate of encapsulating carbon
formation. However, after a certain period of
time, the rate starts to decrease until the end of
the simulation time. According to Mieville [13]
who studied the kinetics of coking for a reforming
process, there is an inverse relationship between
the coking rate and the amount of coke formed.
This is similar to the Voorhies equation originally
derived for catalytic cracking.

0 0.5 1 1.5 2
0
0.2
0.4
0.6
0.8
1
Time (h)
F
r
a
c
t
i
o
n

o
f

v
a
c
a
n
t

s
i
t
e
s
Figure 2. Fraction of vacant sites of the catalyst
0 0.5 1 1.5 2
0
1
2
3
4
5
6
x 10
-10
Time (h)
R
a
t
e

o
f

e
n
c
a
p
s
u
l
a
t
i
n
g

C

f
o
r
m
a
t
i
o
n

(
m
o
l

C

/

g

c
a
t
.
h
)
Figure 3. Rate of encapsulating carbon formation
0 0.5 1 1.5 2
0
1
2
3
4
5
x 10
-5
Time (h)
S
i
t
e

c
o
v
e
r
a
g
e

o
f

e
n
c
a
p
s
u
l
a
t
i
n
g

C
Figure 4. Site coverage of encapsulating carbon

Site coverage and weight of encapsulating
carbon simulations are depicted in Figure 4 and
Figure 5, respectively. Figure 4 shows that the site
coverage of encapsulating carbon increases quite
fast at the beginning of the reaction, and becomes
stagnant at the end of simulation time. This can be
explained by saying that at the beginning, there
are a lot of vacant sites on the catalyst, meaning
that there is a potentially higher possibility of the
formation of encapsulating carbon. As the reaction
proceeds, most of the active sites are already being
occupied, therefore there are fewer sites to be
covered, and subsequently the site of encapsulating
carbon becomes stagnant. In an overall view, the
site coverage of encapsulating carbon is relatively
low, only at about 10-5 from the total active sites.
Figure 6 depicts the rate of filamentous carbon
formation in which the negative values indicate
that filamentous carbon is not formed in our
model. Many reviews have been done regarding the
formation on filamentous carbon. It has been
proposed that catalyst deactivation by carbon
deposition depends on the amount, type and
location of carbon formed. Quincoces et al. [5]
suggested that catalyst promoted with 3% of Ca
presents lesser amount of whisker (filamentous)
carbon with respect to Ni/Al2O3 catalyst. The CaO
addition inhibits the whisker carbon formation and
is therefore more stable. This stability is related to
the formation of more reactive carbonaceous
residues that act as reaction intermediate during
methane reforming. According to Kim et al. (2000)
[14], the minimum metal particle diameter needed
to form filamentous carbon is 6 nm. The Ni particle
size used in the simulation is 112 nm.
Theoretically, filamentous carbon should be formed
in this model based on this criterion. However, this
phenomenon did not happen, and can be attributed
to the inappropriate equations used in the model.

4. Conclusions
From the simulation results, the rate of
encapsulating carbon formation and the site
coverage of encapsulating carbon is relatively low.
The catalyst used in this model also presented a
high activity which attributed to the effect of Al2O3
which serves as a good support for Ni. The
simulation results also showed that filamentous
carbon is not formed in this model. Although the
addition of CaO promoter has been proven to
inhibit the filamentous carbon formation, the
factor of Ni particle size has shown that there
should be a significant amount of filamentous
carbon formed. This could be due to the
inappropriate equations used to calculate the rate
of filamentous carbon formation. However, this
research serves as a good starting point for the
subsequent studies in micro-kinetic modeling.

Nomenclature
aNi - Ni surface area in catalyst (m
2
/g cat)
A - Stoichiometric matrix
CNi,f - Carbon concentration below the Ni
surface (mol C/m
3
Ni)
CNi,r - Carbon concentration on the support side
(mol C/m
3
Ni)
0 0.5 1 1.5 2
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
x 10
-9
Time(h)
W
e
i
g
h
t

o
f

e
n
c
a
p
s
u
l
a
t
i
n
g

C

(
g

C

/

g

c
a
t

)
Figure 5. Weight of encapsulating carbon
0 0.5 1 1.5 2
-1.25
-1.2
-1.15
-1.1
-1.05
-1
-0.95
-0.9
x 10
-3
Time(h)
R
a
t
e

o
f

f
i
l
a
m
e
n
t
o
u
s

C

f
o
r
m
a
t
i
o
n

(
m
o
l

C

/

g

c
a
t
.
h
)
Figure 6. Rate of filamentous carbon formation

Cp - Weight of encapsulating carbon (g C/g
cat)
Cf - Weight of filamentous carbon (g C/g
cat)
Csat - Carbon solubility in Ni (mol C/m
3
Ni)
dNi - Diffusion path length of carbon in Ni
(m)
D - Dispersion of Ni in catalyst (surface Ni
atoms/total Ni atoms)
Dc - Effective diffusivity for carbon in Ni
(cm
2
/s)
E - Activation energy for reaction (kJ/mol)
fNi - Weight fraction of Ni in catalyst (g Ni/g
cat)
k - Preexponential factor in Arrhenius
equation (mol/site.s)
kp - Turnover frequency for encapsulating
carbon (mol C/site.s)
m - Number of elementary reaction steps
MC - Molecular weight of carbon (g C/ mol C)
MNi - Molecular weight of Ni (g Ni/mol Ni)
Pi - Partial pressure of species (bar)
rcp - Rate of encapsulating carbon formation
(mol C/g cat.h)
r - Rate of filamentous carbon formation
(mol C/g cat.h)
R - Gas constant (cal/mol K)
Ri - Rate of reaction (s
-1
)
t - Time of reaction
T - Reaction temperature (K)
xb - Weight fraction of carbon in
segregation layer (g C/g Ni)
i - Fraction of sites covered by surface
species
* - Active sites on catalyst
b - Stoichiometric number of reaction
Gseg - Gibbs energy for segregation layer of Ni
(cal/mol)
H298 - Standard enthalpy-change of reaction
(J mol
-1
)

5. References

[1] Lunsford, J. H. (2000). Catalytic Conversion of
Methane to More Useful Chemical and Fuels, a
Challenge for the 21st Century. Catalysis
Today. 63: 165-174.
[2] Ito, M., Tagawa, T. and Goto, S. (1999).
Suppression of Carbonaceous Depositions on
Nickel Catalyst for the Carbon Dioxide
Reforming of Methane. Applied Catalysis A:
General. 177: 15-23.
[3] Wang, S. and Lu, G.Q.M. (1996). Carbon Dioxide
Reforming of Methane to Produce Synthesis Gas
Over Metal-Supported Catalysts: State of the
Art. Energy and Fuels. 10: 896-904.
[4] Ferreira-Aparicio, P., Guerrero-Ruiz, A. and
Rodriguez-Ramos, I. (1998). Comparative Study
at Low and Medium Reaction Temperatures of
Syngas Production by Methane Reforming with
Carbon Dioxide over Silica and Alumina
Supported Catalysts. Applied Catalysis A:
General. 170: 177-187.
[5] Quincoces, C.E., Dicundo, S., Alvarez, A. M., and
Gonzalez, M.G. (2001). Effect of Addition of CaO
on Ni/Al2O3 Catalysts over CO2 Reforming of
Methane. Materials Letters. 50: 21-27.
[6] Chigada, P.I., Wang, J., Al-Duri, B., Wood, J.,
Rigby, S.P. (2010). Modelling of pore structure
evolution during catalyst deactivation and
comparison with experiment. Chemical
Engineering Science. 65: 5550-5558.
[7] Chen, D., Ldeng, R., Anundskas, A., Olsvik, O.,
and Holmen, A. (2001). Deactivation during
Carbon Dioxide Reforming of Methane over Ni
Catalyst: Microkinetic Analysis. Chemical
Engineering Science. 56: 1371-1379.
[8] Chen, D. (2002). Personal Communication.
[9] Aparicio, L. M. (1997). Transient Isotopic Studies
and Microkinetic Modeling of Methane Reforming
over Nickel Catalysts. Journal of Catalysis. 165:
262-274.
[10] Froment, G.F. (2000). Production of Synthesis
Gas by Steam-and CO2 Reforming of Natural
Gas. Journal of Molecular Catalysis A: Chemical.
163: 147-156.
[11] Wang, S. and Lu, G.Q.M. (1998). CO2 Reforming
of Methane on Ni Catalysts: Effects of the
Support Phase and Preparation Technique.
Applied Catalysis B: Environmental. 16: 269-277.
[12] Ding, R. G., and Yan, Z. F. (2001). Structure
Characterization of the Co and Ni Catalysts for
Carbon Dioxide Reforming of Methane. Catalysis
Today. 68: 135-143.
[13] Mieville, R. L. (1991). Coking Kinetics of
Reforming. Catalyst Deactivation. 68: 151-167.
[14] Kim, J. H., Suh, D. J., Park, T. J., and Kim, K. L.
(2000). Effect of Metal Particle Size on Coking
during CO2 Reforming of Methane over Ni-
alumina Aerogel Catalysts. Applied Catalysis A:
General. 197: 191-200 .


1. Introduction
Fluidized catalytic bed continuous reactors
(FCR) entail very complex flow behavior (Ibrehem
et al., 2008). Moreover, the presence of four phases
in the reaction media complicates the transport
phenomena involved which dictates the need for a
thorough understanding of parameters effect on
production rate and crystallization characteristics.
System identification method (Ibrahem &
Hikamt, 2009) should have sufficient accuracy of
prediction, wide applicability, the minimum
assumption about the most parameters effects like
System Identification for Experimental Study for
Polymerization Catalyst Reaction in Fluidized Bed

Ahmmed S. Ibrehem

Department of Chemical Engineering, UiTM University of Technologi Mara, 40450,
Shah Alam MALAYSIA
* Corresponding Author.
E-mail address: ahmadsaadi1@yahoo.com (A.S. Ibrehem)

Received: 13rd May 2011; Revised: 27th July 2011; Accepted: 22th September 2011
Abstract

In this work, system identification method is used to capture the reactor characteristics of production rate
of polyethylene (PE) based on published experimental data. The identification method is used to measure
the percentage effect on the production rate of PE by measuring the effect of input factors of temperature of
reaction, hydrogen concentration, and [Al]/[Ti] molar catalyst ratio. Temperature of reaction has big effects
equal 52.4 % on the output of the system and 47.6 % on interaction of the system's parameters compare to
other two factors. Also, hydrogen concentration has big effect equal 45.66 % on the output of the system and
14.7 % on interaction of the system's parameters. [Al]/[Ti] molar catalyst ratio has big effect on interaction
of the system equal 28.6 and 1.94 % on the output of the system but less than the reaction temperature and
hydrogen concentration. All these results depend on experiment results and these results are very
important in industrial plants. 2011 BCREC UNDIP. All rights reserved

Keywords: Catalysts, Co-catalyst, System identification, reaction temperature, hydrogen concentration

How to Cite: Ahmmed S. Ibrehem. (2011). System Identification for Experimental Study for
Polymerization Catalyst Reaction in Fluidized Bed. Bulletin of Chemical Reaction Engineering & Catalysis,
6 (2): 137-146
temperature of reaction, hydrogen concentration,
and [Al]:[Ti] molar ratio. In the area of production
rate for polyethylene system and identify which is
most input variable effects on the production rate
by using experiment work was very little. In 2009,
Zohuri group made a very good experiment work
design techniques for polymerization process based
on experimental data only. We depend on this
important work to specify which is the most active
input parameters whose effect on the system
depends on experimental results and new
identification method to specify the percentage
effect of production of high molecular weight of
Research Article

polyethylene.
High molecular weight polymers and their
morphological development are the most important
achievements of heterogeneous catalyst
polymerization of the Ziegler-Natta type (Peacock,
2000; Jamjah et al., 2008; Dasilva & Defigueiredo,
2002; Shiraishi et al.,1990). MgCl2 and SiO2 are the
most common bisupports used to heterogenize
olefin polymerization catalysts (Pater et al., 2003;
Jamjah et al., 2006; Zohuri et al., 2006; Moore,
2005), and SiO2 is also used to support metallocene
and late transition metal catalysts (Galli &
Vecellio, 2004; Barbe et al., 1986). The
morphological development of the catalyst
originally obtained from its support could replicate
the polymer in controlled conditions.
Heterogeneous catalyst particles break up during
the early stages of the polymerization, possibly due
to the chemical reaction of the catalyst component,
mechanical stress and also polymer growth,
respectively [Silva et al., 2005; Shaotian et al.,
2001). In Ziegler-Natta polymerization, the
rate/time profiles are mainly a decay type with
very high polymerization activity at the early stage
of the reaction. Therefore, the fast growth of the
polymer into the pore and channel of the catalyst
could fragmentize the catalyst particles. To achieve
a reasonable morphology, the fragmentation must
be controlled, since uncontrolled fragmentation
may produce fine particles. Using SiO2 and MgCl2
components of a solid, support not only raised the
activity of the catalyst but also improved its
morphology. SiO2 also improved the mechanical
and thermal stability of the catalyst (Kono et al.,
2001; Yamahiro et al., 1999). Interaction between
co catalyst (TEA) and catalyst are very important
and explained very well in Ibrahem et al. (2009)
and Hatzantonis et al. (2000).
Morphological development of support, catalyst
and polymer is the major area of study nowadays.
Ultra high molecular weight polyethylene has
many desirable physical and mechanical
characteristics comparable to some engineering
plastics (Fukuda et al., 2003; Zohuri et al., 2003;
Zohuri et al., 2001). The present work studies the
effect of co catalyst Al/Ti flow rate, temperature
input and hydrogen concentration on production
rate of polyethylene.

2. Dynamic analysis and identification for
mathematical model
System identification involves building a
dynamical model from an input/output data and
without use of any laws concerning the
fundamental nature and properties of the
nonlinear system. The batch reactor process
involves many variables, which contribute to its
operation, and this makes it a Single-Input Single-
Output (SISO) process. These variables are
classified as follows: Input or manipulated
variables (MVs) are chosen from those variables
that have direct effect on the process performance,
and practically easy to actuate. In our case, these
are: percent ratio of Al/Ti as a co catalyst (Qc),
temperature input and concentration of hydrogen.
The controlled variables (CVs) are selected from
the process outlet streams that are usually of
foremost importance such as the production
polyethylene (PE). A schematic diagram
representing the previously mentioned variables is
shown in Figure (1).New knowledge in this work
shows effects of three important inputs variables of
polymerization system on the rate of production
compared to other works.
So, the identification steps can be defined for
PASA as follows (Ibrahem & Hikamt, 2009):
1. To make actual calculations for the system
from nominal conditions xn,i to calculate yn,i.
2. To repeat step one with +H% perturbed
parameter input vector (H xn,i) to produce
the + H % perturbed output yi matrix.
3. To subtract each element from matrix in first
step from the corresponding element in matrix
in second step and divide the difference by
yn,i. (yi- yn,i) / yn,i.
4. Similarly calculate the change in parameters
(xi- xn,i) / xn,i.
5. Divide each element in third step by fourth
step to produce the sensitivity matrix k that
depends completely on scale matrix without
using any a proper factor.
6. Calculate k matrix for negative direction
which mean calculate k+ H % and k- H % so
as, we can check the effect of each parameters
on output as seen in Table (2) .
7. Then find kaverage slope to find average angle
() that is represented overall effect of each
parameters on the measured output (1
represents the effects of Al/Ti, 2 represents
the effects of reaction temperature and 3
represents the effects of hydrogen
concentration on the system as shown in
Figure 9 . From parameters average slope
analysis, we can see a preliminary partitioning
of estimating into different groups that depend
on slope angle () of kaverage and these groups
can be specified as follows:

() 20
o
: Large effects on the system.
20
o
> () > 15
o
: Middle effects on the system.

15
o
() 10
o
: Weak effects on the system.
10
o
< (): Cannot be established.

total= in the system + interaction (1)

total= 1 + 2 + 3

3 Reaction Kinetics
In the present study, a comprehensive
mechanism is considered to describe the
copolymerization kinetics of ethylene and 1-butane
over a Ziegler-Natta catalyst with two different
catalyst porosity and rigid catalyst sites based on
the kinetic model proposed by Mc-Auley et al.
(1990). Rates of formation, initiation, propagation
and chain transfer are different for each site type.
This mechanism comprises of series and parallel
elementary reactions as listed in Table 1. The rate
constants used in this study are those given by
Kinetic and Pseudokinetic (Mc-Auley et al., 1990)
and the activation energies are taken from for
porous catalysts the effects of adsorption,
desorption and surface reaction are included in the
rate of chemical reaction. The reactions are listed
in Table 1. From the kinetic mechanism, the rate
expression for the active sites (ra) for each species
can be written as follows:

ra = Active site formation Active site
consumption

(2)

The derivation of the rate expressions based on the
kinetic mechanism for rigid catalyst is given in
Table 2. The over all rate expression for live and
dead moment is represented in equation (3) and (4)
respectively, as seen below. Rate expressions for
live moments is given as:

(3)

where (n) is the Kroneckers delta function (e.g.,
(n)=1 for n=1 and (n)=0 for n 1). Rate
expressions for dead moments is given as:

(4)

The dynamic mass balance for the catalyst is given
as:

(5)

Similarly, the mass balance for the potential active
sites and active sites are:

(6)

and

(7)

The rate expression for each species of porous
catalyst can be written and the rate expression for
the active sites ra can be written as follows:

(8)

From the kinetic mechanism, the rate expression
for the active sites ra can be written as follows:

ra = Active site formation Active site consumption

=

= (9)


Fluidized bed
reactor
Al/ Ti
H
2
Polyethylene
Manipulated
Variables
Out put
T
re
Figure 1. Representation of variables in polym-
erization system as a MISO system
2
0
0
1
[ ] [ ][ ]
n i
j j
j
k P k P M
=
, 0 2 ,
, , , 0
1
1, ,
1 1
( ) ( ) ( )( )
(1 ( ))
n i n i
n
k k h i
P n i H n i P n i i i
j
n n
P P
j i n j j j n j
j j
R r P r P r P n k M k M
n k M P k M P
= =
= + +

,
2
( [ ] [ ])
n i
k f h
v n
R k M k H = +
0 c a t c a t c a t c a t
s s
d C F Q C
d t W W
=
0
0 0 0
0
[ ]
c a t i n c a t
P
S S
d P F P Q P
r
d t W W
=
0
0 0 0 0
[ ]
c a t c a t
P
S S
d P F P Q P
r
d t W W
=
,
/
1
T n i D
j A A
A A
m P K
M P K
P K
(
=
(
+

2
, 0
0
1
/
1
T n i D n i
j A A
j
A A
M P k
k P k P P k
P k
=
(
(
+

2
0
0
1
n i
j j
j
k P k P M
=

4. Experimental study
SiO2 (PQ3050) was acquired from PQ
Corporation (USA). The compound was calcinated
at about 400 C for nearly 5 h before use [19].
Spherical adducted MgCl2.nC2H5OH was prepared
according to literature (Shiraishi et al., 1990).
Slurry polymerization of ethylene was carried out
in a 1-L stainless-steel reactor of Buchi (BDS300),
a semibatch type, equipped with a stirrer speed
control, temperature and pressure control. The
reactor was purged with nitrogen. A volume of 400
mL heptane was charged into the reactor and
degassed at least three times. When the
polymerization temperature reached the required
temperature, the catalyst components were added
in the following order; TEA, the solid catalyst, and
hydrogen (if any). All the reagents were added as
slurry in n-heptane or a gas. The pressure inside
the reactor was maintained constant with the
monomer gas. Therefore, the required amount of
the monomer to feed into the reactor is equal to the
consumption of the monomer. At the end of the
reaction time, mainly one hour, the monomer feed
was stopped. The polymerization waste ruminated
by draining the slurry polymer into a small volume
of acidified methanol. The polymer obtained was
filtered and dried at 70C for overnight (Zohuri et
al., 2001).

5. Catalyst preparation
The SiO2/MgCl2/TiCl4 catalyst was prepared
using the adducted spherical MgCl2.nC2H5OH. The
ethanol was chemically removed during the
catalyst preparation procedure. The calcinated
SiO2 (2.5 g) and MgCl2.nC2H5OH (2.5 g) were
added to a catalyst preparation reactor containing
a sinter glass heated with a jacket. The chemicals
were suspended in toluene (100 mL), and then
TiCl4 (40 mL) was added dropwise, while, the
contents of the reactor were stirred at 5 C. The
temperature was raised to 115 C in increments of
20 C, while stirring at each step for at least one
hour. The product was filtered, and washed with n-
heptane (100 mL). Toluene (100 mL) and TiCl4 (40
mL) were added at 40 C. The temperature was
raised to 115 C incrementally, as before. The final
catalyst was filtered, washed with n-heptane to
completely remove unreacted TiCl4, and dried. All
the steps were carried out under an atmosphere of
dried N2 (Zohuri et al., 2001). Co catalyst is very
important to be added with catalyst as particular
ratio 2 g of catalyst per 0.8-1 gm of co catalyst as
can be shown in the Figure 2.

6. Results and discussion
Figure 3 shows the relation between Al/Ti and
production rate of PE. The optimum value for Al/Ti
=770/1 molar ratio gives production rate of PE =
1845 at constant reaction temperature = 60
o
C.
Depend on paragraph 2, can see all calculations in
Table 3. The average slope = 0.52 and average =
27.49
o
, that is, mean Al/Ti ratio has large effects on
the system = 30.54%. Figure 4 shows the relation
between hydrogen concentration and production
rate of PE which is an inverse relation; when the
concentration of hydrogen increase, the production
rate will be decreased because addition of H2
closes the rate of live reaction and make dead
polymer to stop polymerization by competing with
monomer in adsorption on active center that
reduce polymerization. Also, in Table 4 average
slope = 1.3929 and average = 54.32
o
, that is, mean
H2 concentration has large effects on the system =
60.36%. Figure 5 shows the relation between
reaction temperature and production rate of PE.
The optimum value for reaction temperature = 60
o
C. gives production rate of PE = 1845 at Al/Ti
=770/1 molar ratio. In Table 5 the average slope =
1.4885 and average = 89.99
o
, that is, mean
reaction temperature has largest effects on the
system = 99.9%. Figure 6 represents all three
effects inside the system that are represented by
average angle slope. From equation (1):

total=89.99
o
+ 54.32
o
+ 27.49
o
= 171.8
o

in the system = 90
o

interaction = total - in the system
interaction = 171.8
o
90
o
= 81.8
o

interaction / total 2 / 1

Figure 2. Side view for experimental study

Table 6 shows the percentage effects of a
temperature, hydrogen concentration and catalyst
ratio in the system and interaction between these
inputs variables. Al/Ti has a big interaction effect
28.6 % on the temperature and hydrogen
concentration because co catalyst enters as a
protect catalyst from poison that leads to increase
temperature of reaction that effects on rate of site
activation reactions as can be explained in
paragraph 2.

0
200
400
600
800
1000
1200
1400
1600
1800
2000
300 400 500 600 700 800 900 1000
Al/Ti
P
E
(
g
)
Figure 3. Effect of Al/Ti molar ratio on production
rate of polyethylene, temperature 60 C
0
200
400
600
800
1000
1200
1400
0 20 40 60 80 100
Concentration of Hydrogen (ml)
P
E

(
g
)
Figure 4. Effect of H2 concentration on production
rate of polyethylene, temperature 60C, Al/Ti =
770:1
0
200
400
600
800
1000
1200
1400
1600
1800
2000
40 45 50 55 60 65 70 75
Temperature (c)
P
E
(
g
)
Figure 5. Effect of temperature on production
rate of polyethylene, Al/Ti = 770:1
1=54.32
o
3 =27.49
o

2 =89.99
o
Figure 6. Representation of the average angle
slope
Table 1. Numerical values of the kinetic rate
constants for adsorption, surface and desorption
reactions inside the catalyst layers
Rate constant (s Rate constant (s Rate constant (s Rate constant (s
- -- -1 11 1
) ) ) ) Site type Site type Site type Site type
Activation energy (E) Activation energy (E) Activation energy (E) Activation energy (E)
(kcal/mol) (kcal/mol) (kcal/mol) (kcal/mol)
1 11 1 2 22 2
Reactant-adsorption (KA) 0.001 0.001
E 9 9
Surface reaction (Ks) 0.001 0.001
E 9 9
Product desorption (KD) 0.00047 0.00047
E 9 9

, j j s
M s M
Reactant
adsorption

, , , j s n i s
M P
surface re-
action

, , , n i s n i
P P s +
product de-
sorption

Table 2. Kinetic mechanism of olefin copolymerization for rigid Ziegler-Natta catalyst
Spontaneous activation:
0
0
n
k
P P
Initiation: j=1,2
0 1, ,
i
j
k
j j
P M P +
(Formation of i=1,2)
1, 0 1, ,
:
i
i
k
i i i
P P M P +
Propagation:
,
, 1, ,
, 1, 2, 1, 2,...,
P
i j
k
n i j n j
P M P i j n
+
+ = =
(Consumption of )
,
1, 1, 2, ,
: , 1, 2, 1, 2,...,
P
i j
k
i i i j
P P M P i j n + = =
(Formation of )
/
,
/
/
, , ,
1,
: , 1, 2, 1, 2,...,
P
i i
k
n i i n i
n i
P P M P i i n
+ = =
Chain transfer:
,
, 1, ,
, 1, 2, 1, 2,...,
f
i j
k
n i j j n
P M P Q i j n + + = =

*
, 2 0 ,
, 1, 2, 1, 2,...,
h
i
k
n i n
P H P Q i j n + + = =
(Formation of )
/
,
/
/
1, 1, ,
,
: , 1, 2, 1, 2,...,
f
i i
k
i i i n
n i
P P M P Q i j n + + = =
(Consumption of )
,
1, 1, 1, 1,
: , 1, 2
f
i i
k
i i j j
P P M P Q i j + + =
(Consumption of )
*
1, 1, 2 0 1,
: , 1, 2
h
i
k
i i
P P H P Q i j + + =
Table 3. Calculation of the percent difference for catalyst ratio against output profile
Ratio AlTi (xi) (xi - xn,i) / xn,i PE-mmol(yi- yn,i) / yn,i Slope (k)
300 0.538 0.117 0.217
350 0.461 0.096 0.208
400 0.384 0.088 0.229
450 0.307 0.074 0.241
500 0.23 0.071 0.308
550 0.153 0.065 0.424
700 0.076 0.053 0.697
750 0.153 0.292 1.908
800 0.23 0.289 1.256
850 0.307 0.205 0.667
900 0.384 0.107 0.278
950 0.461 0.086 0.186
1000 0.538 0.079 0.146
Kaverage 0.52
Average 27.49o
% effect( Aver-
age100)/90
o

30.54

very flexible analysis of polymerization system to
reach to important results that can be used and
which depend in industry. The most active input
parameter is reaction temperature compare to
other factors because it is effected 52.4% in the
system for production PE and 47.6% for interaction
effects between the two factors. Also, hydrogen
input factor has big effect on the system because it
is effected 45.66% directly in the rate of live and
dead polymer for production PE and 14.7% for
interaction effects between the two factors. Al/Ti
ratio has small effect 1.94% in the system but it is
big effect 28.6% in interaction sides between the
two factors (reaction temperature and hydrogen
concentration). Reaction temperature and
hydrogen concentration mainly effect for all active
sites of catalyst surface reaction. All these results
are very important in industrials of polymerization
system. The initial stage of the polymerization,
including the reaction of the catalyst with the co-
catalyst and the high polymerization activity,
broke up the catalyst particles into smaller
particles of irregular shape and size. The
morphology of the polymer particles was almost
the same as that of the catalyst, which reacted
Table 4. Calculation the percent difference for hydrogen concentration against output profile
Hydrogen concentration (ml) (xi - xn,i) / xn,i PE-mmol(yi- yn,i) / yn,i Slope (k)
0 1 1.275 1.275
10 0.8 1.225 1.531
20 0.6 1.125 1.875
30 0.4 0.9 2.25
40 0.2 0.5 2.5
60 0.2 0.3 1.5
70 0.4 0.4 1
80 0.6 0.5 0.833
90 0.8 0.512 0.64
100 1 0.525 0.525
Kaverage 1.3929
Average 54.32o
% effect( Average100)/90o 60.36%
Table 5. Calculation of the percent difference for reaction temperature against output profile
Temperature (co) (xi - xn,i) / xn,i PE-mmol(yi- yn,i) / yn,i Slope (k)
40 0.272 0.512 1.882
45 0.181 0.489 2.701
50 0.09 0.368 4.088
60 0.09 0.022 0.244
65 0.181 0.001 0.005
70 0.272 0.003 0.011
Kaverage 1.4885
Average 89.99o
% effect( Average100)/90o 99.9%
Table 6. Calculation of the percent effects for in the system and interaction between the inputs
variables
Action Temperature Hydrogen concentration

Ratio AL/Ti
Percentage effects
inside the system
52.4 45.66 1.94
Percentage
interaction effects
47.6 14.7 28.6

with the cocatalyst at the early stage of the
polymerization. In addition, the morphology of the
particles may be affected by polymerization
conditions, such as temperature and monomer
pressure. However, the parameters of the initial
stages may also be critical.

Nomenclatures

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i
k
Rate constant of reaction,1/s

A
k
Thermal conductivity between layers of
catalyst particles, J/m
2
/s/k
k
n
Rate constant of spontaneous reaction 1/s
k
f
Rate constant of chain transfer 1/s
K
h
Rate constant of chain transfer to hydro-
gen 1/s

[ ]
e
M
Active metal concentration, mol Me/m
3

[ ]
i
M
Imonomer concentration, mol Me/m
3

A
P
Partial pressure of A in gas phase
P
O
Potential active sites kmol/m
3

Po Active sites concentration kmol/m
3

K
P
S
Concentration of potential k catalyst
active sites, mol/m
3

ra Rate expression for the active sites
kmol/kg.catalyst
R
k
n,i Rate expression for live moments
R
k
vn,i Rate expression for dead moments

K
X
R
Reaction rate of species X at k catalyst
activesites,mol/m
3
/s

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Bulletin of Chemical Reaction Engineering & Catalysis
SUBMISSION INFORMATION
All manuscripts should be submitted to BCREC Editorial Office by Online Submission
and Tracking Interface at: http://ejournal.undip.ac.id/index.php/bcrec

The following materials should accompany manuscripts submitted to the editorial office:
signed copyright status form (a copy reproduced from the website),
a covering letter, outlines the basic findings of the paper and their significance.
which is uploaded as Supplementary Materials in submission interface.

However, if for any reason authors are unable to use the above methods, authors may also contact
to Editorial Office according to the following address:

Assoc. Prof. Dr. I. Istadi (Editor-in-Chief)
Editorial Office of Bulletin of Chemical Reaction Engineering & Catalysis
Department of Chemical Engineering, Diponegoro University
Jl. Prof. Soedarto, Kampus UNDIP Tembalang, Semarang, Central Java, Indonesia
50275; Telp.: +62-24-7460058, Fax.: +62-24-76480675
Email: bcrec@undip.ac.id

Four types of manuscripts are acceptable for publication: Research articles, Review articles, and
Short Communication.

Preparation of manuscripts
Manuscript of research article or reviews should be prepared in camera ready as above templates,
according to the guidelines in the website: http://bcrec.undip.ac.id/author-guidelines

Reviewing of manuscripts
Every submitted paper is independently reviewed by at least two peers. Decision for publication,
amendment, or rejection is based upon their reports. If two or more reviewers consider a manuscript
unsuitable for publication in this Journal, a statement explaining the basis for the decision will be
sent to the authors within three months of the submission date. Manuscripts rejected will not be
returned to the authors.

Revision of manuscripts
Manuscripts sent back to the authors for revision should be returned to the editor without delay.
The revised manuscripts can be sent to editorial office by e-mail ( bcrec@undip.ac.id ) or preferably
through Online Submission Interface (http://ejournal.undip.ac.id/index.php/bcrec). The revised
manuscripts returned later than three months will be considered as new submissions.

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Available online at: http://www.undip.ac.

Copyright 2011, BCREC, ISSN 1978-2993

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