ENVIRONMENTAL ENGINEERING SCIENCE

Volume 23, Number 6, 2006

© Mary Ann Liebert, Inc.

Catalytic Oxidation of CO Over a Catalyst

Produced in the Ferrite Process

Jie-Chung Lou* and Chien-Kuei Chang

Institute of Environmental Engineering

National Sun Yat-Sen University
Kaohsiung, Taiwan, ROC

ABSTRACT

Ferrite process has been established to be of a powerful method for treating heavy metal wastewater. Al-
though the process can be used extensively, its application is limited by its high cost. This work explores
the performance of a catalyst for CO conversion, which is generated from the sludge of the ferrite pro-
cess. Accordingly, the value of the ferrite process is increased, and heavy metals in wastewater are used
as valuable raw materials of catalysts. Experimental results indicate that the Cu–ferrite catalyst can com-
pletely convert CO to CO2 at an inlet CO concentration of 4,000 ppm and a space velocity of 6,000 h1
were held at 140°C. The catalytic performance of Cu–ferrite did not reduce even when the concentration
of O2 was just 1%. The process in this work has good potential for use in environmental technology.

Key words: ferrite process; ferrite catalyst; CO conversion; catalytic oxidation; concentration of O2

INTRODUCTION Yoshiaki, 2002). The FP has numerous advantages over

M OST CONVENTIONAL TECHNOLOGIES for treating
heavy metals in a solution are based on the prin-
ciple of chemical precipitation. The sludge generated by
chemical precipitation has a loose structure, precipitates
slowly, is difficult to filter, and dissolves easily in acid.
Hence, it must be further solidified before it can be de-
posited in a landfill. However, solidification increases the
volume of the landfill by a large factor, and is particu-
larly wasteful in areas in which landfills are difficult to
obtain.
The ferrite process (FP), which is currently used in
Japan, is another effective approach (Kaneko et al., 1979;
Kanzaki et al., 1981; Tamaura et al., 1991; Oscar and
chemical precipitation. It can directly treat anions that
contain heavy metals, such as Cr2O72, CrO42, MnO4,
and others. (All chemical precipitation methods involve
reductive pretreatment step.) It can simultaneously re-
move various heavy metals, leaving a low concentration
of each. Its sludge is compact, easily precipitated, and fil-
tered, and can meet the Toxicity Characteristic Leaching
Procedure (TCLP) standards without requiring further so-
lidification.
The FP was originally developed for producing mag-
netite (Fe3O4) using wet synthesis. The reaction equation
is,
3Fe2  6 OH  1/2 O2  Fe3O4  3H2O (1)

*Corresponding author: Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung, Taiwan, ROC.
Fax: 886-7-5254411; E-mail: loujc@mail.nsysu.edu.tw

1024
CATALYTIC OXIDATION OF CO 1025

This reaction equation changes to Equation (2) when the Ferrite belongs to a spinel structure, which is a well-
solution contains other metal ions (such as divalent known structure for a catalyst. The ferrite catalyst is typ-
cations). ically produced in dry synthesis (Tsuji et al., 1996;
Sreekumar et al., 2000; Hwang and Wang, 2004; Mathew
xM2  (3  x)Fe2  6OH
et al., 2004). Although the FP is a form of wet synthe-
 1/2 O2  MxFe(3-x)O4  3H2O (2) sis, ferrite from the FP should have the same potential as
that from dry synthesis to be used as a catalyst. A cata-
The treatment of heavy metal wastewater by FP involves
lyst is an expensive commodity, so, if the sludge from
this reaction to insert heavy metal ions into the spinel
the FP can be transformed into a catalyst, then the FP
structure formed from iron and oxygen.
will be highly competitive.
As well as having the advantages outlined above,
Formed from incomplete combustion, carbon monox-
the FP produces a sludge that is stable and exhibits
ide is very detrimental to human health. Exposure to high
soft magnetism. It can be recycled as a magnetic
concentrations of carbon monoxide (4,000 ppm or above)
material, such as blind guide bricks, magnetic sym-
can cause coma even death (Smith and Brandon, 1973;
bols, and electric wave absorbents. The use of waste
Thom and Keim, 1989; McCammon et al., 1996). In this
as a resource is increasing. In particular, heavy metal
study, carbon monoxide is the treatment target, which is
sludge can be recycled. Hence, the FP has a great po-
converted into carbon dioxide on a catalyst obtained from
tential.
the sludge of the FP. This process has two purposes—to
However, the FP must use a large quantity of FeSO4
evaluate the feasibility of using the FP sludge as a cata-
and the reaction solution heated to over 70°C so its cost
lyst, and to develop a method for eliminating the hazard
exceeds that of chemical precipitation. Although the
of carbon monoxide.
sludge from the FP can be recycled as a magnetic mate-
rial, it is of inferior quality so it has little value. The FP
cannot compete with conventional precipitation–solidifi- EXPERIMENTAL PROTOCOLS
cation landfill unless the price per unit area is very high.
Therefore, only when the sludge can be used to manu- Apparatus of the FP reaction
facture high-price products can the FP be extensively ap- The FP reactor is a 2-L stainless steel tank. The sys-
plied. tem has an automatic temperature controller and a pH

Figure 1. The schematic diagram of the catalytic reaction apparatus.

ENVIRON ENG SCI, VOL. 23, NO. 6, 2006

1026
monitor. The reaction temperature can be maintained in
a range of 0.5°C. An agitator ensures thorough mixing.
An air supply tube provides oxygen for the reaction from
the bottom of the reactor. The maximum air supply rate
is 4 L/min. The pH can be maintained in a range of 0.2
by adding NaOH or HNO3.
Preparing the catalyst using the FP
Consider a Cu–ferrite catalyst (CuxFe(3-x)O4). The pro-
cedure for producing the catalyst is as follows. The
amounts of Cu(NO3)2 and FeSO4 added to the FP reac-
tor are determined by the molar ratio of Cu/Fe. One liter
of deionized water is added to reactor to dissolve the
Cu(NO3)2 and FeSO4 completely. The pH of the solution
is adjusted to 9 by adding NaOH, and then the solution
is heated to 85°C. The air supply rate is maintained at 3
L/min. The reaction time then begins. After 120 min, aer-
ation is stopped. The sediment is oven dried at 105°C,
then ground and sieved. The powder with a particle size
of between 65 and 150 mesh is selected to form a cata-
lyst in the subsequent experiment.
Catalytic reaction apparatus and procedure
Figure 1 presents the setup for the catalytic reaction.
The reaction gases are mixed with standard gases 10%-
100
80
CO Conversion, %
60
40
20
40 80 120
Reaction Temperature, °C
Figure 2. CO conversion over various ferrite catalysts (Reaction conditions: O2  6 %, inlet concentration of CO  4,000 ppm,
space velocity  6000 h1, M/Fe  1/5).
LOU AND CHANG
CO, N2, and air, to yield the required chemical compo-
sition. The reactor is made in stainless steel with a dou-
ble pipe structure, which has an outer pipe with an in-
ternal diameter of 21 mm and an inner pipe with an
external diameter of 6.4 mm. The reaction gas enters
from the inlet of outer pipe and flows down, passing the
preheating stage and thus increasing the temperature.
The reaction is performed on the catalyst bed, which is
at the bottom of the annular space between the outer
and inner pipes. The catalyst bed has, in order from bot-
tom to top, a 0.5 cm layer of quartz wool at the bottom,
a 1-cm layer of quartz sand, a 10-cm3 volume of cata-
lyst, and a 1-cm layer of quartz sand. The reaction gas
passed through the catalyst bed and transferred into the
inner pipe, turning upward and then flowing. Finally,
the gas left the reactor and passed to vent. A K-type
thermocouple is placed from the top of the inner pipe.
It is extended to the bottom of the inner pipe to mea-
sure the reaction temperature. The reactor is placed in
the furnace to maintain the reaction temperature. The
furnace can accurately set and control the wall temper-
ature to within 0.1°C. Under fixed conditions (inlet
gas composition, space velocity, and furnace tempera-
ture), the reaction system reaches a steady state. The re-
action temperature reaches a specified value by suitably
adjusting the furnace temperature. The concentrations
of CO and O2 are measured using a gas analyzer
Cu-ferrite
Mn-ferrite
Cr-ferrite
Zn-ferrite
Ni-ferrite
Pure-ferrite
Blank
160 200 240 280 320 360 400
CATALYTIC OXIDATION OF CO
(IMR2000, Germany). Gas chromatography (GC-14B,
Shimadzu, Japan) with FID, TCD, Pork-R following a
Pork-Q series column and CO conversion installation
was used to identify the category and concentration of
production.
EXPERIMENTS
Selection of active metal
Five ferrite catalysts (MxFe(3-x)O4 , M:Cu, Zn, Mn,
Ni or Cr), each with a metal/iron molar ratio
(M/Fe˜x/(3-x)) of 1/5, formed from the FP, were tested.
The catalyst was screened by comparing its ability to
promote the oxidation of CO.
Effect of M/Fe on catalytic performance
Using the optimum active metal identified in the fore-
going section, several metal/iron ratios (M/Fe  1/2.5,
1/5, 1/10, 1/20) were tested to plot the influence of the
proportion of active metal on the catalytic performance.
Effect of concentration of O2 on
catalytic performance
The concentrations of O2 were set to 20, 6, 3, and 1%
to determine the effect of this concentration on CO con-
version. Besides ferrite catalysts, two kinds of metallic
100
80
CO Conversion, %
60
40
20
0
40 80 120
Reaction Temperature, °C
Figure 3. Effect of M/Fe on CO conversion over Cu-ferrite (Reaction conditions: O2  6%, inlet concentration of CO  4,000
ppm, space velocity  6,000 h1).
1027
oxide catalysts (Co supported on Al2O3, Co/Al2O3, and
Cu supported on Al2O3, Cu/Al2O3) were tested under the
same reaction conditions to compare catalytic perfor-
mance.
Effect of concentration of CO2 and humidity on
catalytic performance
To clarify the restraining effect of CO2, the reaction
was conducted under the conditions: O2 concentration
6%, and CO2 concentrations 0, 5, 10, and 15%. Addi-
tionally, an extreme condition with O2 concentration of
1% and CO2 concentration of 15% was also performed.
A humidifier was used to control the humidity and thus
determine its effect. The reaction was performed at ab-
solute humidity (partial pressure) of 30, 100, and 350
mmHg.
Physical properties of catalyst generated from
the FP
The surface areas of the fresh and used ferrite cat-
alysts were analyzed using a BET specific surface an-
alyzer (Model ASAP 2000, Micromeritics, USA).
SEM (JEOL, JSM-6400) were used to observe the sur-
face and particle size of catalysts. To determine the
particle size distribution of ferrite, a little catalyst was
put in a glass bottle containing deionized water mixed
with dispersing agent. The glass bottle was oscillated
Cu/Fe=1/2.5
Cu/Fe=1/5
Cu/Fe=1/10
Cu/Fe=1/20
Pure Ferrite
160 200 240 280 320 360 400
ENVIRON ENG SCI, VOL. 23, NO. 6, 2006
1028 LOU AND CHANG

100

80

CO Conversion, %
60

40
O2= 20%
O2= 6%
O2= 3%
20
O2= 1%

40 80 120 160 200 240

Reaction Temperature, °C
Figure 4. Effect of O2 concentration on CO conversion over Cu-ferrite (Reaction conditions: inlet concentration of CO  4,000
ppm, space velocity  6,000 h1, M/Fe  1/2.5).

using ultrasonic waves for 1 min., then upper strata size analyzer based on the principle of laser scattering
liquid was sampled and diluted by deionized water (NANO-ZS, MALVERN). The data can be adopted if
mixed with dispersing agent. The particle size distri- the result remains unchanged with increasing dilution
bution of the sample was analyzed using the particle times.

100

80
CO Conversion, %

60

40
O2= 20%
O2= 6%
20
O2= 3%
O2= 1%

40 80 120 160 200 240

Reaction Temperature, °C
Figure 5. Effect of O2 concentration on CO conversion over Cu-ferrite (Reaction conditions: inlet concentration of CO  4,000
ppm, space velocity  6,000 h1, M/Fe  1/2.5).
CATALYTIC OXIDATION OF CO 1029

100

O2 =20%
80 O2 =6%
CO Conversion, % O2 =3%
O2 =1%
60

40

20

40 80 120 160 200 240

Reaction Temperature, °C
Figure 6. Effect of O2 concentration on CO conversion over Cu/Al2O3 (Reaction conditions: inlet concentration of CO  4,000
ppm, space velocity  6,000 h1).

RESULTS AND DISCUSSION an O2 concentration of 6%, and an inlet concentration of

Selection of active metal
Figure 2 shows that the Cu–ferrite catalyst has the
greatest catalytic ability at a space velocity of 6,000 h1,
CO  4,000 ppm. An Mn–ferrite catalyst is the second
option for converting CO to CO2. Ni, Cr, and Zn ferrite
catalysts are much worse than Cu–ferrite and Mn–ferrite
catalysts. No catalyst is present in the reactor, even when
the reactor is heated to 400°C, so converting CO to CO2

100

80
CO Conversion, %

60

40
CO2= 0%, O2=6%
CO2= 5%, O2=6%
20 CO2=10%, O2=6%
CO2=15%, O2=6%
CO2=15%, O2=1%
0

40 80 120 160 200 240

Reaction Temperature,°C
Figure 7. Effect of CO2 concentration on CO conversion over Cu-ferrite (Reaction conditions: inlet concentration of CO 
4,000 ppm, space velocity  6,000 h1, M/Fe  1/2.5).

ENVIRON ENG SCI, VOL. 23, NO. 6, 2006

1030 LOU AND CHANG

to better catalytic performance. Figure 3 shows that a con-

version of 50% can be achieved at a lower reaction tem-
perature: the temperature is 225°C for pure ferrite, but
only 130°C for a Cu/Fe ratio of 1/20. The Cu–ferrite cat-
alyst with a Cu/Fe ratio of 1/2.5 yielded 50% conversion
at a temperature of merely 102°C, and 100% conversion
at a temperature of only 140°C.

Figure 8. SEM photograph of Cu-ferrite catalyst.
is difficult. Pure ferrite (Fe3O4) is also catalytic. The cat-
alytic effect is greatly improved when appropriate met-
als are captured in the spinel structure of the ferrite. Cu
greatly promotes its catalytic effect, while Ni, Cr, and Zn
do not.
Effect of M/Fe on catalytic performance
Four Cu–ferrite catalysts with Cu/Fe molar ratios of
1/2.5, 1/5, 1/10, and 1/20 are tested to determine the ef-
fect of M/Fe on catalytic ability. The experimental re-
sults reveal that a greater proportion of Cu corresponds
Effect of concentration of O2 on
catalytic performance
Experimental results indicate that the effectiveness of
ferrite catalysts is nearly independent of the concentra-
tion of O2. Figure 4 reveals catalytic performances of the
Cu–ferrite at O2 concentrations of 20, 6, 3, and 1% are
almost the same, respectively. Even though the concen-
tration of O2 is very low, the ferrite catalyst can effi-
ciently adsorb O2 onto its surface, increasing the reaction
rate. This is a very important advantage, and explains
why the ferrite catalyst can be used in the catalytic reac-
tion, and especially oxidation. CO is generated from in-
complete combustion, and therefore, gas containing CO
generally has a low concentration of O2.
Co/Al2O3 and Cu/Al2O3, both catalysts frequently
used in oxidation reactions, are compared with the fer-
rite catalyst under the identical reaction conditions. These
two catalysts have proportions of active metal of 22%
(w/w), approximating the proportion of Cu in the Cu–fer-
rite of M/Fe  1/2.5. Figure 5 displays the influence of
the concentration of O2 on the catalytic performance of
Co/Al2O3. Contrasting Figs. 4 and 5 reveals that the abil-

Mean with Max-Min error bar

50

40
Volume, %

30

20

10

0
1 10 100 1000 10000
Particle Size, nm
Figure 9. Particle size distribution of Cu-ferrite catalyst.
CATALYTIC OXIDATION OF CO
ity of Co/Al2O3 and Cu–ferrite are similar when the con-
centration of O2 exceeds 6%. When the concentration of
O2 is below 3%, the CO conversion performance of
Co/Al2O3 reduces sharply, while that of Cu–ferrite re-
mains little changed. Figure 6 shows that the concentra-
tion of O2 strongly influences the performance of
Cu/Al2O3. Contrasting Figs. 4 and 6 reveals that the CO
conversion ability of Cu/Al2O3 is inferior to that of
Cu–ferrite. Although both have the same active metal,
the ability of Cu–ferrite is better. Ferrite containing Cu,
Zn, Mn, Ni, or Cr and even pure ferrite, can all tolerate
low concentrations of O2, meaning that the spinel struc-
ture of ferrite has excellent O2 supply. Summarizing the
measurement results of GC/TCD and GC/FID revealed
no other byproducts in all conditions in this study. That
is, CO2 is the exclusive compound turned from CO.
Effect of concentration of CO2 and humidity on
catalytic performance
Figure 7 showed the CO2 effect for CO conversion
over the Cu–ferrite catalyst. The experiment results dem-
onstrate a clear inhibiting of CO2 at low temperature. At
100°C, the CO conversion changed from 52.4 to 8.5%
when concentration of CO2 changed from 0 to 5%. The
CO conversion was just 4.3% when the CO2 concentra-
tion increased to 15%. However, the inhibiting effect of
CO2 is not obvious, given increasing temperature. A CO2
concentration of below 15% does not obstruct the 100%
CO conversion when the reaction temperature exceeds
200°C. Bond (1990) summarized the adsorption phe-
nomenon on the metals and indicated that Fe, Cu, Ni,
Mn, and Cr could adsorb CO and O2 efficiently. For CO2,
Fe, Ni, and Cr exhibit strong chemisorption, while Cu
and Mn do not. Therefore, Cu and Mn have better cat-
alytic performance because they have better CO2 de-
sorption ability than others. This study observed that the
higher Cu/Fe displayed less CO2 inhibiting. This phe-
nomenon was consistent with the above theory.
The influence of humidity on the CO conversion is un-
clear. Under 140°C, the CO conversion remained at 100%
even when the absolute humidity was increased to 350
mmHg.
Physical properties of catalyst generated from
the FP
The surface area of the Cu–ferrite catalyst (M/Fe 
1/2.5) is determined using a BET specific surface ana-
lyzer. The specific surface area of fresh catalyst was 49
m2/g, while that of the used catalyst was 47.5 m2/g. Fig-
ure 8 shows the SEM photograph of the Cu–ferrite cat-
alyst. Clearly, a catalyst powder is formed with numer-
ous tiny primary ferrite particles and irregular holes.
1031
Figure 9 shows the primary particle size distribution of
Cu–ferrite is between 68–106 nm.
Potential of the FP to produce ferrite catalyst
This study demonstrates that FP is both an effective
wastewater treatment method and an effective means of
producing a catalyst. If the wastewater is stable, the re-
quired metal proportion of catalysts can be generated by
changing the amount of FeSO4. One phenomenon is par-
ticularly interesting. In general, the production cost of the
catalyst increases with the amount of active metal (such
as Cu). However, in the production of ferrite catalysts in
the FP, FeSO4 is the main cost. Restated, the active metal
is free, and so becomes cheaper as the proportion of ac-
tive metal increases. The proportion of active metal can-
not increase without limit. Theoretically, the M/F ratio
cannot exceed 1/2 for divalent metal cation, since the
spinel structure of the ferrite catalyst must be obtained.
During actual operation, the M/F ratio must exceed 1/2.5
to ensure that the FP leaves a low concentration of haz-
ardous metal in liquid.
CONCLUSIONS
Ferrite is a strong catalyst. In this study, the Cu–fer-
rite catalyst can completely convert CO to CO2 at an
inlet CO concentration of 4,000 ppm and a space ve-
locity of 6,000 h1 were held at 140°C. The catalytic
performance of Cu–ferrite did not reduce even when
the concentration of O2 was just 1%. The influence of
humidity is not obvious. The inhibiting effect of CO2
on catalytic performance can be solved by increasing
reaction temperature. Recycling the sludge formed in
the FP as a catalyst can not only promote the com-
mercial value of the FP, but can also solve the prob-
lems associated with heavy metal sludge. The prices of
catalysts are high, so this method has great potential
for development.
ACKNOWLEDGMENTS
The authors thank the National Science Council of the
Republic of China, Taiwan, for financially supporting
this research under Contract Number NSC 92-2211-E-
110-006.
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