Accepted Manuscript

Title: Innovative porous SiC-based materials: from nanoscopic

understandings to tunable carriers serving catalytic needs

Authors: Patrick Nguyen, Charlotte Pham

PII: S0926-860X(10)00549-1
DOI: doi:10.1016/j.apcata.2010.07.054
Reference: APCATA 12742

To appear in: Applied Catalysis A: General

Received date: 12-3-2010

Revised date: 22-7-2010
Accepted date: 27-7-2010

Please cite this article as: P. Nguyen, C. Pham, Innovative porous SiC-based materials:
from nanoscopic understandings to tunable carriers serving catalytic needs, Applied
Catalysis A, General (2010), doi:10.1016/j.apcata.2010.07.054

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*Graphical Abstract

Graphical Abstract

“Innovative porous SiC based materials: from nanoscopic understandings to tunable carriers serving
catalytic needs”

Patrick Nguyen and Charlotte Pham

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SICAT Technical Centre, 1 rue du Brotsch 67700 Otterswiller

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New porous self bonded beta Silicon carbide (SiC) materials have been prepared using metallic silicon
powder and carbon black. Pore size distribution has been tailored by varying the raw materials and
by adding pore formers. The surface chemistry can be tuned by adding promoters in the process.

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Page 1 of 38
 Innovative porous SiC-based materials: from nanoscopic understandings to
tunable carriers serving catalytic needs

Patrick Nguyen* and Charlotte Pham

5 SICAT Technical Centre, 1 rue du Brostch 67700 – Otterswiller, France
* To whom all correspondence should be addressed

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10 Abstract

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Progress in developing a new class of catalyst carrier materials based on porous self bonded
silicon carbide (SiC) is reviewed. Since the demonstration of scalable economically viable β-
SiC production process, innovative β-SiC based materials with tunable physical and chemical
15
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properties were successfully synthesized. Silicon carbide has superior mechanical and
thermal properties which, coupled to chemical inertness, avoids several of the problems
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inherent in the use of commercial oxide and carbon based supports and catalysts. High
surface area SiC (35 m²/g) can now be easily synthesized, with unmatched mechanical
properties, tailored pore size distribution (meso and macroporous network and total pore
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20 volume up to 1 cm3/g) and at reasonable cost. It can be shaped directly into extrudates, (µ-)
spheres, monoliths, open cell foams, 3D forms depending to the downstream applications.
Furthermore, it can also be chemically modified for specific catalytic applications through the
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addition of promoters (oxides like Al2O3, TiO2, ZrO2, carbides and metals) rendering the
fabrication simple and cost effective. In many respects, it combines the best properties of
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25 oxide and carbon based supports without suffering many of their disadvantages. New
structured TiO2/SiC composites have been prepared and are expected to be the next
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photocatalytic media. The ability of the SiC material to be used as catalyst support will be
illustrated in the present work by two exothermic reactions, namely the selective oxidation of
trace amount of H2S and the Fischer-Tropsch synthesis. For this later, a direct comparison
30 was also made with a traditional support, i.e. alumina.

Keywords: catalyst carrier, tailored porosity, mechanical strength, tailored surface chemistry,
porous self bonded beta (β) silicon carbide (SiC), Al2O3, TiO2, ZrO2, thermal conductive,
photocatalyst, structured material, H2S oxidation, Fischer-Tropsch synthesis.
35

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 1. Introduction

A typical heterogeneous catalyst is generally constituted of three components: an

40 active phase, a promoter which increases activity and/or stability, and a carrier (support)
which serves to facilitate the dispersion and the stability of the active catalytic phase [1].
Most commercial common catalysts carriers are alumina, silica, carbons and titania. New

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catalyst support material are not often reported in literature with almost no new materials

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being incorporated into commercial use since World War II. These supports have been
45 continuously improved but today, major catalyst carriers of commercial catalysts are still

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supported on the four materials listed above. The main breakthrough and change in catalytic
material science was the introduction of zeolites in commercial catalytic process first by

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Union Carbide (1959) followed several years later by Mobil (1962) [2].
Thanks to its high thermal conductivity, mechanical strength, chemical inertness and
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oxidation resistance, SiC with high surface area was expected to be an ideal catalyst carrier
candidate. Since the late 90’s several research groups focused their investigations on the
synthesis and use of porous beta silicon carbide as catalyst support. Moene has synthesized
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porous SiC with surface areas ranging from 30 to 80m²/g by a gas solid reaction [3-8]:

55 C(s) + H2(g) → CH4(g) (1)

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SiCl4(g) + CH4(g) → SiC(s) + 4HCl (2)

Ledoux et al. have developed another synthesis method called the shape memory synthesis
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and based on the transformation of a carbon skeleton into SiC [9,10]. In a first step an
60 equimolar mix of silicon and silica react to form SiO vapours which then react in a second
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step with the solid carbon to produce porous β-SiC according to the following equations:
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Si(s) + SiO2(s) → 2SiO(g) (3)

SiO(g) + 2 C(s) → SiC(s) + CO(g) (4)
65
This synthesis method allows converting a porous shaped carbon body into porous
shaped beta SiC with surface areas ranging form 10 to 100m²/g. Since the late 90’s French
aluminium producer Pechiney, in collaboration with Ledoux’s group , have developed and
patented processes to manufacture β-SiC products with high surface area, which could be
70 used as catalyst supports. From these research raised in 2001 an innovative company
named SICAT. The aim of this so called start up was to demonstrate the economic viability of
the manufacturing process and superior behaviour of porous beta SiC based materials for

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Page 3 of 38
 use as catalyst carrier. The original concept of the “Shape memory process” was still applied
but modified in order to scale up the process from a technical and economical point of view.
75 The trick was to use conventional techniques of powder and ceramic technology, thermal
management and also non expensive raw materials for cost competitive. Porous beta SiC
based materials are now prepared by siliconization of a preshaped body containing carbon
and metallic silicon, the binder is generally made by a high carbon yield resin (which is also
converted into porous beta SiC during synthesis). The SiC precursor is converted into porous

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80 self bonded SiC by a thermal treatment under the melting point of silicon and under argon

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atmosphere. This very flexible process allows producing a large panel of porous SiC with
various size and shape, i.e. extrudates, rings/tubes, spheres, monoliths, plates as well as

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open cell foams and other structured materials. Recent developments allow the tailoring at
will of the pore size distribution by selecting right properties of the starting materials and by

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85 adding pore former during the synthesis process. Finally, by adding textural promoters and
/or metals, a new class of hybrid materials can be prepared to reach the specifications of the
target reactions and processes.
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The aim of the present short review is to report on the synthesis and characterizations
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of self bonded porous silicon carbide based catalyst carrier and to demonstrate the benefit
90 brought by the unique conjunction of thermal, structural and chemical properties. Selective
oxidation of H2S reaction was used as test reaction to show how silicon carbide properties
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can be optimized as a function of reaction demand. Preliminary results obtained on the highly
demanded Fischer-Tropsch synthesis (FTS) will be also presented and compared with
conventional alumina-based catalyst. Next steps towards a fully adaptable catalyst carrier
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95 are also described for higher specific surface areas and tuneable chemical surface properties
as well.
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2. Experimental
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2.1 Self bonded SiC based material synthesis

100
Silicon carbide materials were all prepared by using stoechiometric mixture of micronized
(< 20µm) metallic silicon and carbon (carbon black, Cabot and high carbon yield binder as
carbon precursor). Temporary binder, i.e. methyl cellulose, polyvinyl alcohol, polyethylene
glycol, sodium silicate, SiO2 sol, can be also added. After mechanical mixing of the raw
105 materials, the SiC precursor is shaped into green bodies using standard technologies, like
extrusion, spheronisation, granulation, pelletizing and so on. To produce open cell foams or
3D structures, the replica method is used [11,12]: a slurry is prepared using the same raw

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 materials but the amount of temporary binder is increased and rheological additives are used
to meet the required viscosity/thixotropy for the slurry. The preparation is then coated onto
110 polyurethane foam or onto 3D fiber fabric. The green body is then dried overnight at room
temperature following a thermal treatment at atmospheric pressure under argon in an
electrical furnace up to 1360°C. The thermal treatment was lasted for 1h in order to
synthesize self bonded porous silicon carbide materials. The reaction temperature is kept
under the silicon melting point (< 1400°C). During the thermal treatment, the high carbon

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115 yield resin is pyrolized into amorphous carbon binding the carbon black and the silicon

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particles together. Above 1000°C, the metallic silicon will then react with residual traces of
oxygen to form SiO(g) which siliconize the carbon structure into SiC according to equation

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(5), whereas CO is allowed to carburize the metallic silicon, the crossed reactions being

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120 SiO + 2C → SiC + CO (5)
CO + 2Si → SiO + SiC (6)

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After synthesis the SiC material was submitted to an oxidative treatment in air at
800°C for 2 h in order to remove the residual unreacted carbon species in its matrix. The as
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125 synthesized silicon carbide is “self bonded” and highly porous which allows it to be fully used
as catalyst support.
This general experimental procedure enable us to produce a large panel of well
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controlled SiC materials with controlled size and shape with medium to high specific surface
area and adaptable morphology regarding the down stream catalytic applications. Some
130 examples of these SiC-based materials are presented in Figure 1.
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2.2 Materials characterization

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Powder XRD was performed on a Siemens Model D-5000 diffractometer using Cu Kα

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135 non-monochromatic radiation. The sample was crushed in an agate mortar and the powder
was packed in 0.5 mm depressions of 40 x 44mm polymer slide. The XRD pattern was
recorded from 10° to 90° of 2θ angle with a step scan mode. The nature of crystalline phases
in the sample was checked using the data base of the Join Committee Powder Diffraction
Standards (JCPDS).
140 The pore size and the surface area measurements have been performed on a
Micromeretics Tristar 3000 porosimeter using N2 as adsorbent at liquid nitrogen temperature.
SBET is the surface area of the sample calculated from the nitrogen isotherm using the BET
method [13,14].

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Page 5 of 38
 Pore size distribution was also measured by mercury intrusion using a Micromeretics
145 Autopore III, assuming an Hg contact angle of 130° and a surface tension of 0.485N/mm.
Previous to analysis, the sample was out-gased for 2 minutes under 6.67Pa.
Scaning electron microscopy (SEM) observation was performed using a JEOL JMS-
840 microscope operating at 20 kV. Samples were supported on a copper holder.
Transmission electron microscopy (TEM) was carried out on a TOPCON 002B UHR
150 or a JEOL 2100F microscopes operating at 200 kV. The sample was sonicated in an ethanol

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solution for 5 minutes and then, a drop was deposited onto a copper grid covered with a

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holey carbon membrane for observation.
The XPS measurements were performed on a Multilab 2000 (Thermo Electron)

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spectrometer equipped with Al K anode (h = 1486.6 eV). The C1s peak fixed at 284.4 ±
155 0.2 eV was used to correct the different XPS peaks from charging effects. All the spectra

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were decomposed assuming several contributions, each of them having a Doniach-Sunjic
shape and a Shirley background subtraction.

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Mechanical resistance was measured by the grain crushing strength ASTM method,
known as the GCS test, consisting in subjecting a grain to an increasing load up to breaking
160 point. The force applied at the moment of failure is determined in Newton (N). The result is a
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mean value of 10 to 20 individual measurements.
Tests of chemical resistance were carried out by immersing SiC extrudates for two
weeks into various aqueous solutions at room temperature. At the end of the treatment, the
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sample was washed with deionised water and dried.

165
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2.3 Selective oxidation of H2S

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The silicon carbide supported iron catalyst was prepared by incipient wetness impregnation
of the support (m=10g; 2mm extrudates) with 1.08g of iron (III) nitrate nonahydrate
170 (Fe(NO3)3, 9H2O, Merck) dissolved in 6mL of distilled water mixed with 1.2 g of glycerol
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(C3H8O3, Fluka).The amount of iron nitrate was fixed to have 1.5 wt % of Fe on the final
catalyst. After impregnation, the material was dried at room temperature and the iron nitrate
was decomposed into iron oxide at 350°C during 2h under static air. Selective oxidation of
H2S was carried out in an all glass apparatus working at atmospheric pressure and in an
175 isothermal mode. An amount of 1.5 g (2.25 mL) of catalyst was placed on silica wool housed
in a tubular Pyrex reactor (18 mm inner diameter and 600mm height). The catalyst
preparation and set up have been described previously [15,16]. The composition of the
reactants feed was H2S (1.0 vol.%), O2 (2.5 vol.%), H2O (30.0 vol.%) and balanced He,
corresponding to a oxygen to hydrogen sulfide ratio of 5 according to the Eq. (7), and a gas
180 hourly space velocity (GHSV) varying from 3000 to 4000h-1 .

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 H2S + 1/2O2 → H2O +1/n Sn (7)

The inlet and outlet gases were analyzed online using a Varian CP-3800 gas chromatograph
185 equipped with a Chromapack CP-SilicaPLOT capillary column allowing the separation of O2,
H2S, H2O and SO2, a thermal conductivity detector (TCD) and a calibrated six sample
injection with a six port valve

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2.4 Fischer-Tropsch synthesis

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190
The Fischer-Tropsch synthesis (FTS) which consists by the transformation of a

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synthesis gas mixture (CO + nH2) into liquid hydrocarbons has received an over-increasing
interest since the last decades [17-19]. The final market for the liquid fuels produced by the

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FTS process is the transportation, and chemical intermediates markets where sulfur-free
195 fuels are demanded.

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The FTS process is one of the most complexe one regarding the various reactions
that take place during the gas-to-liquids transformation. The most relevance reactions are
presented below:
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nCO + (2n + 1)H2  CnH2n+2 + nH2O ∆H = -167 kJ. mol-1

200 nCO + 2nH2  CnH2n + nH2O

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CO + 3H2  CH4 + H2O ∆H = -206 kJ. mol-1

CO + H2O  CO2 + H2 ∆H = -41 kJ. mol-1

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Nowadays, the most employed FTS metal are iron and cobalt, either pure or doped
with trace amount of noble metal [20-22]. Due to it relatively high price the cobalt active is
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205 exclusively employed in a supported form. The support should have a high specific surface in
order to achieve the high dispersion of the active phase, good mechanical and hydrothermal
resistance and additionally, high chemical inertness in order to reduce the fraction of hardly
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reducible phase during the thermal treatment steps. Among the different supports, alumina is
the most appropriate one to fulfil the requirements cited above. However, the low thermal
210 conductivity of the alumina support render it more sensitive to the problem of temperature
runaway and hot spot formation which compromise the plant security and decrease the
selectivity towards the liquid hydrocarbons.
The metal-support interactions between the deposited phase and the alumina support
also reduce the available fraction of metal for the reaction and also render difficult the
215 recovery of the metal and support after the end-life of the catalyst. It is consequently of
interest to discover and develop new support materials that can efficiently replace those cited

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 above, mainly in terms of physical properties, which could provide an improvement of the
catalytic performance. The new support should also be cheap and be readily available in the
same shape as those usually employed in order to reduce the cost incentive linked with extra
220 additional modifications of the plant itself.
To our knowledge SiC as catalyst support for fixed-bed FTS reaction has not been
reported so far in the literature. It is though that the intrinsic thermal conductivity of the SiC
could help in the heat dissipation throughout the catalyst body and thus, avoid the formation

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of local hot spots which could modify the overall selectivity of the reaction. In addition, the

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225 chemical inertness of the support also allow the easy recovery of both the active phase and
the support by a simple acid or basic washing unlikely to the traditional catalysts based on

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alumina or silica where recovery need a complex chemical treatments to be efficiently
achieved.

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The Fischer-Tropsch synthesis reaction was carried out in a tubular fixed-bed
230 stainless steel reactor (i.d. = 24.5 mm) with circulating silicon oil as heating source. The

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reduced catalyst (10 g of catalyst, the support is either in a foam or beads forms, containing
2.7 g of cobalt) was deposited between quartz wool plugs in the midle of the reactor. The
reactor pressure was slowly increased from 0.1 to 4 MPa (ramping rate of 1 MPa. h-1) under
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argon. At 4 MPa the reactor temperature was raised from room temperature to the desired
235 reaction temperature, 210°C (heating rate of 2°C. min-1). Then, the argon flow was replaced
by a 50:50 v:v mixture of syngas and argon (CO:H2 = 1:2). The catalyst was activated under
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a syngas-argon mixture with different syngas concentrations during three days before
evaluated under pure syngas condition. The catalyst bed temperature was monitored with a
thermocouple (Ø 0.3 mm) inserted inside a stainless steel finger (Ø 1 mm) passing through
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240 the catalyst bed. The products were condensed in two high pressure traps maintained at
85°C and 15°C respectively. The exit gas was analyzed on-line, both by Thermal
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Conductivity Detector (TCD) and Flame Ionization Detector (FID), with a gas
chromatography (GC Varian 3800 equipped with a Carbobond capillary column).
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245
2.4 Composites SiC based materials

Composites based materials are synthesized by a simple process. ZrO2/SiC composites

are obtained by adding a zirconium oxide precursor into a mixture during the mixing step of
250 the raw materials (Si, carbon black and binder). The mixture is extrudated in cylindrical
shapes and the synthesis was carried out in the same conditions as described previously (<
1400°C, Ar). The amount of ZrO2 precursor, either zirconium (IV) oxynitrate hydrate
(ZrO(NO3)2, XH2O, Sigma-Aldrich) or zirconium (IV) oxide (ZrO2, Sigma-Aldrich), has been

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 adjusted to reach 10 wt.% of ZrO2 in the final composite. A more detailed description of the
255 preparation was previously reported [23]. TiO2/SiC materials are obtained by synthesizing
TiC/SiC composites which is further oxidized to transform the TiC into its corresponding TiO 2
phase. The high oxidative resistance of the SiC allows it to be unaffected during the oxidative
treatment. The titanium carbide-silicon carbide composite was obtained by mixing a titanium
dioxide (P25 Aeroxyde, Evonik) to the SiC precursor mixture. The amount of P25 was
260 calculated to have 16 wt.% of TiC in the final material. After shaping the green body was

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submitted to the same reaction conditions as that use for SiC synthesis to form TiC/SiC.

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TiO2/SiC was obtained by oxidizing the TiC/SiC material in an electric furnace under static
air, at temperatures ranging from 350 to 800°C.

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Ultimately, structured TiO2/SiC and TiC/SiC materials have been successfully prepared

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265 for the first time and are expected to be a new class of structured photocatalysts or
photocatalyst carriers. Indeed, structured TiC/SiC materials like open cell foams or 3D
structures can be prepared using the well known replica method. Choosing the right
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oxidation temperature allows to convert selectively the TiC into TiO2 (anatase or rutile). This
multifunctional material solves several critical issues for the photocatalysis application. First,
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270 TiO2 particles are strongly anchored at the surface of the material avoiding a loss of TiO2
nanoparticles under flow. Secondly, structured materials such as open cell foams or 3D
materials exhibit high geometric surface areas which provide a high contact surface between
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the TiO2 active phase and the reactant mixture while the tortuosity of the material acting also
as a static mixer to allow a high degree of mixing of the reactant. Finally such large void
275 structure allows the UV radiation to access deeply through the media offering the maximum
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of irradiation to the supported TiO2. High specific surface area (compared to bare beta SiC)
i.e. 116m²/g are achieved with such composite material. All these new developments bridge
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the gap between chemical process and material science engineering.

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280 3. Results

3.1 Pure self bonded porous SiC characterization

Figure 2A shows the XRD pattern of pure self bonded beta silicon carbide [24]. The XRD
pattern of the SiC exhibits the presence of two polytypes: hexagonal (α-SiC) and face-
285 centered-cubic (β-SiC). The diffraction line originated from the α-SiC is attributed to the
presence of stacking faults along the (111) easy growth direction of the material. The
stacking faults can be clearly visualized in the high-resolution TEM micrograph of the SiC
taken along the (111) direction in Figure 2B. No residual metallic silicon is observed

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 confirming the complete conversion of the raw materials into silicon carbide. The HR-TEM
290 micrograph (Fig. 2B) also indicates the presence of a thin amorphous layer on the topmost
surface of the SiC material. Such amorphous phase was originated to the passivation of the
SiC surface when it comes into contact with oxygen atmosphere and is mostly consisted by a
mixture of SiO2 and SiOxCy according to the XPS spectrum of the Si2p presented in Fig. 2C.
Figure 3A and B show the SEM micrographs of carbon black used as carbon source
295 and of the corresponding final SiC product, respectively. The SEM observation clearly

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indicates that the morphology of the carbon is maintained during the C-to-SiC transformation.

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This observation is in accordance with the solid gas mechanism proposed in the literature
where gaseous silicon oxide reacts with the carbon to form well crystallized beta silicon

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carbide particles.
300

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The specific surface area of the SiC materials varies from 10 to 35 m²/g depended to
the physical properties of the starting materials. For example, when using a carbon black,

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exhibiting a mean particle diameter of 20nm and a BET surface area of 100 m²/g, the final
porous β-SiC exhibits a specific surface area of 35 m²/g. For non porous spheres having a
305 density of 3.2, an external surface area of 35 m²/g corresponds to surface arranged by
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spheres with a diameter of 27 nm, as compared to 20nm for the initial carbon, which is in
good agreement with what is observed on Fig.3B. This confirms the general concept of
generating a SiC structure by a simple conversion of its carbonaceous homologue as far as
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the carbon structure is thermally stable at the reaction temperature (starting at 1200°C).
310 From this observation it should be understood that if carbon structure is submitted to
sintering with subsequent decrease of exposed surface area, part of the initial carbon surface
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will not be duplicated in the final SiC material. As an illustration of this limitation, an activated
carbon (Fluka 5110) having a BET surface area of 735 m²/g, with a large proportion of
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microporous surface, has been submitted to a thermal treatment at 1400°C for 2 h. The
315 thermal treatment significantly decrease the activated charcoal specific surface area from
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735 to 312 m2/g, indicating that a large part of the micropores was collapsed during the
thermal treatment leading to a strong modification of the carbon microstructure. Such
structure collapse induces a negative influence on the final properties of the SiC. Indeed,
under the same synthesis conditions, carbon black with a lower specific surface area, i.e.
320 100 m2/g, yields SiC with a final surface of 35 m2/g, whereas using activated charcoal with
much higher specific surface area, i.e. 735 m2/g, SiC with only 17 m2/g was obtained due to
the collapse of the carbon precursor microstructure during the course of the synthesis (Table
1).
Besides the simple sintering effect, there may be a second limitation due to the very
325 small pore diameter of the high surface area materials as compared to effective diameter of

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Page 10 of 38
 the gaseous SiO molecule at high temperature. Thus SiO diffusion inside micropores might
be too slow to convert surface carbon inside the pore before the aperture plugging by SiC
formation.

330
TABLE 1: Specific surface areas of the starting carbon source and the corresponding final β-SiC
products.

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BET surface area (m²/g)

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Carbon source After 2h at
Fresh carbon Final SiC
1400°C, Ar

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Carbon black, Cabot 100 ± 5 104 ± 5 35 ± 5
Activated carbon, Fluka 5110 735 ± 5 312 ± 5 17 ± 5

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During the synthesis and according to the equation (5), gaseous CO is formed and
diffuses out of the material. One thus understands the important role of the CO partial
335 pressure that governs the rate of CO diffusion in the solid, and the temperature that fixes the
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final degree of crystallinity. These two parameters are determinant for the final porous
structure of the SiC product. CO formation plays a role in the porosity development of the
final ceramic material as observed by Lednor and co-workers [25] for the pyrolysis of organo-
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silicon materials.
340
Figure 4 shows the pore size distribution obtained for different self bonded silicon
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carbide extrudates. One should observe that a wide panel of pore size distribution can be
obtained by simply varying the precursor properties. By changing the raw material
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specifications (carbon source, binder, additives...) the porous properties of the final SiC
345 material are dramatically affected for both, total pore volume and mean pore diameter. Of
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course, the grain size of the staring materials is important but the specifications of the carbon
source, silicon powder and of the binder (aqueous or organic) will affect significantly the final
properties of the ceramic (porous properties, specific surface area, mechanical properties).
This can be understood by knowledge of the microstructure of the carbon source or silicon
350 and also by the wetting properties of the binder. Pore size distributions, especially in the
macroporous range, can be tailored thanks to the addition of pore formers (scattered lines on
figure 4). Usually, pore formers are thermally degradable polymeric granules (polyethylene,
acrylic...), or coming from plants like starch, walnut flour and so. Figure 4 points the effect of
these products (scattered lines) in a standard formulation. For example the pink (scattered)
355 line illustrates the pore size distribution of extrudates obtained by adding polyethylene

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Page 11 of 38
 granules and the light green (scattered) curve by adding potato starch to the raw materials.
The total pore volume can be tuned by the load of pore former in the mix and the medium
pore radius of the final ceramic will be determined by the grain size distribution of the pore
former. In other words, a high loading of pore former will increase the total pore volume and
360 large grains (of the pore former) will give large pores in the SiC material. A right balance
must be found to keep an acceptable mechanical strength in order to accept the material in
industrial processes. The total pore volume and the pore radius will dramatically affect the

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mechanical strength in common sintered ceramics, but in the described process even with

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high pore volumes and larges pores, the porous SiC materials remains mechanically
365 resistant. Most appreciable pore formers are made of starch or walnut flour which are

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inexpensive materials and will not affect the process and the final product during the thermal
cycle. One of the important benefits of using porous beta SiC is its outstanding mechanical

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strength which is appreciable for highly porous articles. For example, macroporous
extrudates (3mm in diameter with a length of 5mm) with a total pore volume of 1cm 3/g and
370 an
macropores in the micron range present a bulk crushing strength of 70N which is quite high
for highly porous products. Thus complex or fragile shapes can be prepared in this material
assuring a good mechanical strength.
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Crushing strength resistance of porous SiC is summarized in Table 2 for both
375 extrudates and spheres for standard materials. Compared to a current silico-aluminate with
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similar pore volume (0.55 cm3/g) and surface area (30 m²/g), SiC appears to be much
stronger.
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Table 2: Bulk crushing strength (BCS) of porous beta SiC extrudates and spheres and BCS of a
commercial silica-alumina carrier in the same range of pore volume. For extrudates, values are given
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for a length of 5 mm.

Self bonded porous β-SiC

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Ø (mm) Competitor silica/alumina

(0.6 cm3/g) (0.55 cm3/g)
2mm extrudate* 100N -
3mm extrudate* 150N 30N
5.5 spheres 260N -
* for a length of 5 mm
380
3.2 Chemical resistance tests
Silicon carbide is well known for its high resistance toward chemically and thermally
aggressive environments, and is often used specifically for this reason [20, 21].

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Page 12 of 38
 A standard porous SiC sample has been subjected to chemical attack to estimate its long
385 term behaviour in very aggressive environments. The results presented in Table 3 confirm
the extremely high chemical resistance of the material. As a consequence, porous SiC
carrier with medium to high specific surface area should be a very good candidate for
catalytic applications not only in aggressive environments, but also when frequent
regenerations are needed, or for an easy active phase recovery and subsequent recycling of
390 SiC carrier. Previous work carried out has shown that cobalt active phase can be completely

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recovered from the SiC support via a HNO3 (35 vol. %) treatment at room temperature. The

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acid treated SiC can be further impregnated with the same active phase and re-used without
any loss in term of activity and selectivity (Ref).

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Table 3: Chemical resistance evaluation of the porous beta SiC extrudates in various corrosives

us
media; neither the crushing strength nor the specific surface area are not altered.
Fresh HF 40% HCl 37% HNO3 68% NaOH 5M 500°C- 30%H2O/70%Air
2mm Extrudates
β-SiC 3 weeks 2 weeks 2 weeks 2 weeks 4 weeks
Δ weight (%)
Cr. strength (N/mm)
BET SA (m2/g)
-
20
30
-1,8
18
29
-0,4
21
30
an 0
21
29
-0,5
21
30
-1,5
24
28
M
395

3.3 Selective oxidation of H2S

ed

Two Fe2O3/SiC catalysts have been prepared; the first one (1.5% Fe2O3/SiC-MP) on a
support with a total pore volume of 0.31 cm3/g and a mean pore diameter of 42 nm, and the
400 second one (1.5% Fe2O3/SiC-HP) on a material with a total pore volume of 0.55 cm3/g and a
pt

mean pore diameter of 70 nm. The pore size distributions of the two supports are presented
in Figure 5.
ce

The TEM micrographs with different magnifications of the Fe2O3/SiC-MP are

Ac

405 presented in Figure 6. Low magnification TEM micrograph (Fig. 6A) indicates that the Fe 2O3
phase is well dispersed on the SiC support with an average particle size centered at around
5 nm. It is worth noting that no aggregates were observed among the catalyst. High-
resolution TEM micrograph showing the flat interface between the Fe2O3 particle and the SiC
support which confirms the high wetting behavior of the deposited on the ceramic surface.
410 The high dispersion observed was attributed to the presence of a thin layer of SiO 2-SiOxCy
on the topmost surface of the SiC (see XPS results above) which plays a role of natural
washcoat. TEM analysis on the Fe2O3/SiC-HP shows the similar results indicating that the
dispersion of the active phase was not altered.

12
Page 13 of 38
415 The desulfurization activities of the two catalysts are presented in Figure 7. It is worth
noting that both supports present the same surface area i.e. 25 m²/g and same surface
chemistry, only the pore size distribution differs. On the medium pore size catalyst (MP) the
sulfur activity, expressed in term of conversion, slowly decrease as a function of time on
stream. The sulfur selectivity remains stable at around 91 % after about 30 h of test. It is well
420 known that the catalyst carrier for this reaction requires special specifications. Berben has
pointed in his previous work that the selective oxidation of H2S is most favorable on an -

t
alumina based catalyst contained mainly macropores 28-30, sulphur yield ranging from 80

ip
to 92% at 230°C have been claimed but without any catalyst life time indications. The
macroporous network of the support favors molecular diffusion and also contributes to the

cr
425 increase of the sulfur selectivity. The rate of the sulfur escaping is high inside the
macropores network and thus, reducing the secondary reaction leading to the formation of

us
SO2. If the active iron oxide particles are located in small pores, the residence time of the Sn
molecules is higher than if active particles are localized in larger pores. Thus, in smaller

430
an
pores the probability to further oxidize Sn into SO2 is higher consequently decreasing the
selectivity. However, as alumina exhibits Claus activity (reverse Claus reaction: 3/nSn + 2
H2O↔ 2H2S + SO2), the author suggested to coat the carrier with a continuous film of iron
M
oxide to cover the basic sites of the alumina [30] in order to inhibit the Claus activity. The two
side reactions damaging the selectivity of the process are the continued oxidation of sulphur
(1/nSn+O2→SO2) and the retro Claus reaction.
ed

435 Van den Brink has developed later an iron oxide supported on silica catalyst which was used
as the commercial Super-Claus catalyst [31]. Higher selectivity has been achieved due to
pt

lower Claus activity of silica compared to alumina [32]. Superior catalytic activity was
obtained thanks to pores larger than 40nm. In the present work one can observed the similar
ce

drawback as developed by Berben above when using SiC support with small pore size. This
440 is expressed by the low selectivity represented by the circles on Figure 7A. The sulphur
formed inside small pores is oxidized into SO2 reducing the overall sulphur yield. The
Ac

conversion represented by squares drops significantly indicating also that active phase is
less accessible than if located in larger pores.
Figure 7B shows the desulfurization activity of the 1.5% Fe2O3/SiC-HP catalyst tested
445 under the same reaction conditions. One should observe that by changing only the pore size
distribution and by increasing the total pore volume, the catalytic behavior is drastically
improved. The activity remains extremely stable at about 99.5 % of conversion whereas 95
% of sulfur selectivity is reached thanks to the larger pores promoting the high evacuation of
the formed sulfur. Active phase is located in large pores much more accessible for the
450 reactants as for the catalyst prepared with a less porous carrier. This can be seen on figure
7B. by a stable conversion (squares) under process stream and the selectivity is also higher

13
Page 14 of 38
 compared to the previous catalyst leading to the same conclusions. The test was performed
during more than 1000 hours (not shown) on stream with a stable sulphur yield (ranging from
90 to 94%). In this work no optimization has been performed on the support (textural
455 promoter) as well as the active phase which can be promoted to increase the activity or
stability. Compared to a silica-based catalyst, the SiC-based catalyst has a similar activity but
with superior mechanical strength. The high mechanical strength allows one to avoid the fine
formation inside the catalyst bed during the reactor loading which could give rise to a

t
pressure drop within the catalyst bed. Furthermore, thanks to its chemical inertness, silicon

ip
460 carbide based catalyst can be easily recycled by chemical treatment in order to recover both
the active phase and the SiC carrier. Silicon carbide also exhibits a medium thermal

cr
conductivity compared to alumina or silica which prevents hot spot formation inside the
catalyst bed, during non steady-state working conditions and/or in the presence of a higher

us
H2S concentration, which decrease the overall sulfur selectivity [33].
465
3.4 Fischer-Tropsch synthesis reaction
an
The cobalt phase was deposited onto the supports via an incipient wetness
impregnation method using an aqueous solution containing cobalt nitrate. The cobalt loading
M
was set at 30 wt. %. After impregnation the solid was allowed to dry at room temperature for
470 2 h and then oven-dried at 110°C for 2 h. The solid was calcinated in air flowing (300 ml. min-
1
) at 350°C for 2 h in order to decompose the nitrate into its corresponding oxide. The oxidic
ed

form was further reduced in flowing hydrogen (300 ml. min-1) at 300°C for 6 h. In order to
prevent excessive air oxidation during the exposure of the catalyst a passivation process was
performed before discharging of the catalyst (surface passivation was carried out with a
pt

475 mixture of O2-1 vol.% diluted in helium at room temperature).

The XRD patterns (not shown) recorded on the SiC-based catalyst indicates that the
ce

cobalt phase was completely reduced after the reduction treatment whereas on the alumina-
based catalyst the reduction was not complete and some cobalt oxide phase was still
Ac

present.
480 The FTS activity, expressed in terms of CO conversion, and C5+ selectivity obtained
on the different Co-based catalysts as a function of time on stream is presented in Figure 6.
On the Al2O3 catalyst the CO conversion at 220 °C is relatively high and level-off at about
77% after 25 h on stream. It is worth noting that on the Al2O3-based catalyst, the C5+
selectivity is extremely low at around 54% and the methane contributes to the main light
485 product.
Under a similar reaction conditions, the SiC-based catalyst exhibits a slightly lower
CO conversion compared to the Al2O3 catalyst, i.e. 71% instead of 77%, along with a more
pronounced period of activation during which the conversion was slowly decreased before

14
Page 15 of 38
 reaching the steady-state. On the SiC-based catalyst, the C5+ selectivity is extremely high
490 compared to that was observed on the Al2O3 catalyst, i.e. 85% instead of 54%. It is also
worth mentioning that on the SiC catalyst the CO2 was extremely low which indicates that the
Water Gas-Shift contribution is negligible.
The low CO2 formation on the SiC-based catalyst compared to that observed on the
Al2O3-based catalyst could be attributed to the difference in terms of the porosity between the
495 two supports. The relatively large pore size of the SiC allows the rapid evacuation of the

t
steam formed during the reaction to the gas phase. On the Al2O3 the small pore size could

ip
favorize the steam condensation or retention which underwent reacted with CO according to
the water gas shift reaction leading to the formation of CO2: H2O + CO  CO2 + H2. Steam

cr
condensation is also favoured by the condensed liquid hydrocarbons which partly filled up
500 the pore.

us
The low C5+ selectivity observed on the Al2O3 catalyst could be partly attributed to
the higher temperature excursion compared to that measured in the SiC catalyst bed, i.e. 18

an
°C instead of 8 °C. It is expected that the catalyst bed temperature measured is far lower
compared to the real temperature inside the catalyst bed due to the poor contact between
505 the thermocouple finger and the catalyst and thus, a higher internal temperature should be
M
present on the catalyst surface. Such temperature excursion could favorize the secondary
hydrolysis reaction leading to the low C5+ selectivity. The difference in terms of C5+
selectivity on the Al2O3 catalyst could be also due to the difference in terms of the support
ed

surface chemistry and/or intrinsic thermal conductivity between the two supports.
510
pt

In summary, Fischer-Tropsch synthesis with high activity and C5+ selectivity can be
achieved on the Co-based catalyst supported on SiC carrier. On the insulator support, Al2O3,
ce

the FTS activity was similar to those obtained on the SiC support with higher thermal
conductivity. However, a large difference in terms of the C5+ selectivity was observed
515 between the tested catalysts, i.e. 80% for the SiC-based catalyst and only 60% for the Al2O3-
Ac

based catalyst. Such low C5+ selectivity on the Al2O3-based catalyst was attributed to the
presence of local hot spot on the catalyst surface which favorize the secondary cracking
reactions.

520 3.4 Chemically modified SiC composites

It is expected that pure β-SiC material with specific surface areas ranging from 10 to 35
m²/g cannot be a universal catalyst support, new SiC composite materials have been
designed to enlarge the field of their application in catalysis. Textural promoters and active

15
Page 16 of 38
525 phases can be added during the first stage of the synthesis process, i.e. raw material mixing.
It presents a unique advantage to be an economic way of tuning properties of the final
product by using conventional powder technologies. Thus Lewis acidity can be obtained by
adding Al2O3 precursors (leading to a high mechanical strength silica-alumina/SiC composite,
active for the DME synthesis); TiO2 nanoparticles dispersed on SiC carrier matrix is obtained
530 by oxidizing a TiC/SiC composite, and ZrO2/SiC composite is obtained by adding ZrO2 (or
zirconium precursors) to raw materials before the synthese.

t
ip
3.4.1. ZrO2/SiC
Figure 9 shows the XRD patterns of two samples of beta SiC extrudates promoted

cr
535 with zirconium oxide. Depending on the zirconium oxide precursor used as starting material,
different ZrO2 phases are observed in the final product. Thereby, using ZrO(NO3)2 as

us
zirconium oxide precursor leads mainly to tetragonal ZrO2 phase whereas the ZrO2
monoclinic phase was mainly observed when using directly zirconium oxide (< 5µm

540
an
powders). In addition, the specific surface areas of both samples are slightly different
depending on the nature of the zirconium oxide precursors. When using a nitrate precursor, a
higher specific surface area is observed (38 m²/g) whereas using directly zirconium oxide as
M
ZrO2 source leads to a composite with lower surface area (27 m²/g). This observation can be
correlated with SEM observation of both samples as illustrated in Figure 10. The ZrO2
particles in the sample prepared from ZrO2 are bigger (100-200 nm) than those observed
ed

545 when using zirconium oxynitrate (20-60 nm). This is tentatively attributed to the fact that
zirconium oxynitrate generates small ZrO2 clusters during the thermal treatment like a
conventional catalyst impregnation by incipient wetness. One possible explanation could be
pt

the difference of the nucleation and formation mechanism using a molecular precursor
instead of already prepared material with a certain particle size distribution.
ce

550
According to the observed results one can be able to prepare ZrO2/β-SiC composite
Ac

materials with various ZrO2 particles size which are strongly anchored on and in the beta SiC
matrix. Thus, this method is an easy and strong way to prepare porous self bonded beta SiC
materials promoted with ZrO2, especially when unmatched mechanical strength are needed.
555 Such materials can find various applications as Fischer-Tropsch catalyst carrier where ZrO2
promotes the catalytic activity and selectivity in C5+ as suggested by many authors [34-37].

3.4.2. TiO2/SiC
TiO2/SiC composites have been prepared in various shapes especially as structured
560 media for photocatalytic applications. Our target was to synthesize a photocatalytic substrate
offering a large geometric and accessible surface area in order to increase the contact

16
Page 17 of 38
 surface of the photocatalyst to the reactant mixture and to maximize the light (U.V.) diffusion
through the catalytic bed. Another parameter which needs to be controlled is the strong
anchorage of the nanosized photocatalyst onto the surface of the SiC media for health and
565 security concerns. Our approach was to create a composite of TiC/SiC and to selectively
oxidize the titanium carbide into anatase TiO2. Previously TiS/SiC powders haven prepared
successfully and presented increased photocatalytic behaviour compared to commercial
anatase [38]. The material, in powder form is not attractive for photocatalysis applications

t
and for the first time is here reported the synthesis of a structured shaped media. As

ip
570 structured TiC exhibits weak mechanical strength, the combination of titanium carbide and
porous silicon carbide seemed to be an optimal in term of surface chemistry and mechanical

cr
strength and macroporsity. Fig. 11 shows the shapes designed of the TiO2/SiC composite for
photocatalytic applications.

us
575 The TiC is formed during SiC synthesis by reaction between the TiO 2 and the carbon.

an
The diffraction lines of the titanium carbide (cubic structure) are at the same angles as for the
beta SiC (cubic structure). The XRD pattern of the TiC/SiC composite is shown in Figure 12.
M
The amount of TiC present in the SiC composite was 16 wt%. The surface area of the
580 final TiC/SiC material was about 55m²/g with pores centred around 2 and 25 nm and in the
macroporous range whereas beta SiC material exhibit only pores greater than 30 nm. By
ed

oxidizing the composite at different temperatures the TiO2 structure can be tuned at will, i.e.
anatase, rutile or both[39]. Several thermal treatments have been performed ranging from
350°C to 800°C. At low temperatures (i.e. 350°C 8 hours) the TiC was oxidized into
pt

585 amorphous TiO2 and only diffuse diffraction lines were observed (XRD not presented). On
the other hand, the BET surface area was drastically increased from 55 m2/g, for the starting
ce

composite before oxidation, to about 116 m²/g. The porosity of the material changed and
pores of 4 and 10 nm are observed couple with a macroporous network. The TiC crystals are
Ac

smaller than beta SiC crystals. Oxidizing the TiC crystals at low temperature will generate
590 smaller TiO2 crystals. By increasing the oxidation temperature the TiO2 becomes much more
crystallized. These observations have been also made by Shen et al. [40] who found an
optimized thermal treatment at 350°C during 8 hours to convert TiC into well crystallized
anatase. The increase of surface area after mild oxidation can be explained by the
transformation of bigger TiC particle into smaller TiO2 nanoparticles with higher exposed
595 surface area. Fig. 13 shows the XRD patterns of the TiC/SiC composites after an oxidative
treatment at different temperatures. In this work, we found that at 400°C during 6 hours the
TiC was converted into anatase and no rutile phase was observed amongst the composite.
Increasing the oxidation duration has no benefit on the crystallization of the titanium dioxide.

17
Page 18 of 38
 Increasing the oxidation temperature promotes the formation of the TiO2 rutile phase which is
600 less active for photocatalysis.
Fig. 14 shows the SEM observation of a TiO2/SiC composite (16 wt % of TiC vs SiC).
The starting TiC in the composite was well distributed leading to a very high TiO 2 dispersion
at the surface of the material after oxidation (350°C 8 hours). The TiO2 (anatase) particle size
anchored on the surface of the SiC matrix was around 100 nm as suggested by the SEM
605 observation in Fig. 14A. From the drastic increase of surface area through the oxidative

t
treatment, this material should be a good adsorbent and if the TiO2 nanoparticles are

ip
photocatalyticly actives, this new class of structured composite could be the next generation
of photocatalytic catalyst. The high specific surface area of this low-temperature oxidation

cr
composite could also render it useful for use as catalyst support in other reactions where a
610 high and thermally stable surface area could represent a great advantage with a carrier

us
exhibiting a high mechanical strength. Finally such composites can also be shaped into
classical catalyst carrier shapes i.e. extrudates, rings, spheres, bringing the benefit of the
shape memory synthesis of SiC.
an
615 4. Conclusions
M
Porous self bonded beta SiC materials with controlled size and shape, tailored pore
size distribution and tuning surface chemistry have successfully been prepared at industrial
scale and economic viability. The specific surface area can be adjusted from 10 to 35 m²/g
ed

for standard undoped β-SiC material and up to 110 m²/g for TiO2/SiC composite. The
620 microstructure of the silicon carbide is the replica of the carbon source used for the synthesis
while the macroscopic shape can be easily controlled by controlling the performing of the
pt

material precursor. The SiC material mostly contains meso- and macroporous network
whereas no micropores are observed which render it extremely useful for use as catalyst
ce

support where mass transfer should be minimized. SiC, unlikely alumina and silica, is also a
625 conductive material which could prevent hot spot formation in the exothermic reactions
Ac

reducing by this way, the problem of selectivity loss by secondary reactions.

Another major advantage of using beta SiC carriers in the heterogeneous catalysis field
is its unmatched mechanical strength, even for a highly porous (especially macroporous)
grade. Beta SiC macrospheres exhibit a compressive strength of 260 N. Different chemical
630 resistance tests have been performed on the material and no chemical attacks have been
observed even in very concentrated corrosive media, i.e. HF, HCl and HNO3. Such chemical
resistance properties could be extremely helpful regarding the active phase and support
recovery at the end-life of the catalyst, especially when the active phase is constituted by
expensive (Pt, Pd, Rh, etc.) or toxic metals. The possibility of recovery the support allows

18
Page 19 of 38
635 one to phase-out the problem linked with the solid waste disposal which is in line with a more
and more strict environmental legislations.
Beta SiC supports with different pore size distribution and pore volume have been
tested for the selective oxidation of H2S into elemental sulfur. Fe2O3 nanoparticles have been
successfully deposited on the SiC surface owing to the presence of a thin passivated layer of
640 SiO2-SiOxCy playing a role of natural washcoat. According to the results, support with high
pore size and pore volume exhibits a higher desulfurization activity and sulfur selectivity due

t
to the easy access of the reactant to the active phase and to the high escaping rate of the

ip
intermediate product.
The flexibility of the synthesis process allows one to prepare doped β-SiC materials

cr
645 with either carbides or oxides. The ZrO2/SiC composites are successfully prepared by adding
zirconium oxynitrate or zirconium oxide to the SiC precursors. Such hybrid composites could

us
find use as catalyst support in the most demanded reaction, namely the Fischer-Tropsch
synthesis.

650
an
Structured TiO2/SiC composites have been prepared by mild oxidative treatment of the
TiC/SiC material. During the oxidative treatment the titanium carbide has been selectively
oxidized into TiO2 crystallized in a anatase phase. The composite exhibits a higher specific
M
surface area (110 m²/g) compared to conventional porous β-SiC (35 m2/g). Such structured
material are expected to be the next generation of structured photocatalysts.
Finally, it has been demonstrated through the present work that a unique production
ed

655 process can lead to a whole family of SiC based porous materials. More specifically it has
been shown that customized pore size distribution, surface areas, shapes and surface
chemistry can be achieved while keeping the well known mechanical and thermal benefits of
pt

SiC material.
ce

660
Acknowledgements
Ac

The authors would like to acknowledge Dr. C. Pham-Huu for helpful discussions during the
preparation of this review. Shabnam Hajesmaili (LMSPC) is also acknowledged for
665 performing the characterization of the different TiC/SiC composites.

19
Page 20 of 38
 Fig.1. Self bonded porous β-SiC catalyst carriers with various shapes, i.e. extrudates, rings,
spheres, open cell foams, microspheres and structured 3D material.
670
Fig. 2. (A) XRD pattern of the self bonded porous SiC material with the presence of two
polytypes: hexagonal α-SiC (2Θ = 33.5°) and face-centered-cubic β-SiC. . (B) HR-TEM
micrograph of the SiC along the (111) direction evidencing the presence of stacking faults.
The SiC material is also covered by a thin amorphous layer consisted by a mixture of SiO2

t
675 and SiOxCy. (C) XPS Si2p spectrum of the as-synthesized SiC showing the presence of

ip
several Si-based phases on the material surface: SiC, SiO2 and SiOxCy.

cr
Fig.3. SEM micrographs of (A) carbon black, Cabot and (B) corresponding beta SiC material
showing the complete morphological conservation of the material during the C-to-SiC

us
680 transformation.

Fig. 4. Typical pore size distribution for different self-bonded β-SiC materials obtained by
an
mercury intrusion. Scattered lines: pores obtained with pore formers; lines: pore obtained by
changing raw materials properties.
M
685
Fig. 5. Pore size distribution of the two SiC supports used in the selective oxidation of H2S:
MP: 0.31 cm3/g and HP: 0.55 cm3/g with larger pores.
ed

Fig.6. TEM analysis of the Fe2O3/SiC-MP. The mean particle size is about 5nm.
690
pt

Fig.7. Catalytic activity of A: 1.5%Fe2O3/SiC-MP and B: 1.5%Fe2O3/SiC-HP.

ce

Fig. 8. FTS activity and C5+ selectivity on the Co/SiC and Co/ Al2O3 catalysts. Reaction
conditions: H2:CO molar ratio = 2, total pressure = 40 atm., reaction temperature = 220°C.
Ac

695
Fig.9. XRD pattern of a) pure β-SiC, b) 10%ZrO2/SiC prepared from ZrO(NO3)2 precursor
and c) 10%ZrO2/SiC prepared from ZrO2 precursor.

Figure 10. SEM picture using atomic contrast mode; (A, B) 10% ZrO2/SiC extrudates
700 prepared from ZrO2 and (C) prepared from ZrO(NO3)2.

Fig. 11. TiO2/SiC structured composites (ex. TiC/SiC) in tube like shape and open cell foam
plate.

20
Page 21 of 38
705 Fig. 12. XRD pattern of typical TiC/SiC composite.

Fig.13. XRD patterns of the TiC/SiC composites after an oxidative treatment at different
temperatures.

Fig. 14. SEM observations of TiO2 (anatase)/SiC structured composite.

710 matrix (high crushing strength, tailored porosities, high thermal conductivity) coupled to the

t
TiO2 surface chemistry.

ip
cr
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M
ed
pt
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21
Page 22 of 38
 Figure 1

t
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715
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22
Page 23 of 38
 Figure 2

t
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an
M
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Si - Ox
Si - C Si - O2
Counts (a.u.)

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SiC
Ac

98 99 100 101 102 103 104 105 106 107 108

Binding energy (eV)

23
Page 24 of 38
720 Figure 3.

t
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cr
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ed
pt
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Ac

24
Page 25 of 38
 Figure 4
725

t
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25
Page 26 of 38
 Figure 5.
730

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26
Page 27 of 38
 Figure 6.
735

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27
Page 28 of 38
 Figure 7.

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740

28
Page 29 of 38
 Figure 8

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745

29
Page 30 of 38
 Figure 9.

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30
Page 31 of 38
Figure 10.

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31
Page 32 of 38
755 Figure 11.

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32
Page 33 of 38
 Figure 12.
760

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33
Page 34 of 38
 Figure 13
765

A Anatase TiC-SiC
R Rutile 400/6h
* TiC 500/6h
600/6h

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AR

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AR

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A

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* * *
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20 40 60 80
2theta angle (°)
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34
Page 35 of 38
 Figure 14
770

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Page 36 of 38
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ip
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cr
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