A Project Proposal

On

Hydrogenolysis of Glycerol Over supported Cu-Ni,

Cu-Ru Bimetallic Nanoparticle Catalysts

Submitted
To
The Department of Science & Technology, Government of India
Under the Fast Track Scheme for Young Scientists

By

Dr. Prakash Biswas, Assistant Professor

Department of Chemical Engineering
Indian Institute of Technology Roorkee, Roorkee-247667, Uttarakhand, India
Phone:+ 91-1332-285820 (O); +91-812-684-9030 (Mobile)
Fax: 01332-276535, 273560
Email: [email protected]; [email protected]

1
 Application Format
Fast Track Proposal for Young Scientists

1. Broad subject area (Life Sciences, Physical Sciences, Chemical Sciences, Earth &
Atmospheric Sciences, Mathematical Sciences, Engineering Sciences):

Engineering Science (Chemical Engineering)

2. Specialization : Catalysis, Chemical Reaction Engineering, Kinetic Modeling

3. Title of the proposed project:

Hydrogenolysis of Glycerol over Supported Cu-Ni, Cu-Ru Bimetallic Nanoparticle Catalysts

4. Name and address of the Investigator: (including Tel.No., Fax, Email, etc.)

Dr. Prakash Biswas

Assistant Professor
Department of Chemical Engineering
Indian Institute of Technology Roorkee
Roorkee-247667, Uttarakhand, India
Phone: + 91-1332-285820 (O); +91-812-684-9030 (Moile)
Fax : 01332-276535, 273560
Email: [email protected]; [email protected]

5. Details of the proposed project to be undertaken

5.1.Origin of proposal
Biodiesel derived from vegetable oils and animal fats has received considerable attention in
recent years. Worldwide biofuels demand is predicted to increase up to 98 million tonnes in 2011
with an annual growth rate of 20% [1]. Biodiesel consists of fatty acid methyl esters produced via
the transesterification of triglycerides with methanol in the presence of basic or acidic catalysts.
For every 9 kg of biodiesel produced, about 1 kg of crude glycerol by-product is also formed [2].
Superfluous glycerol from biodiesel production could not only flood the current market for
glycerol but also negatively impact the economic viability of biodiesel. Finding new outlets for
glycerol consisting of high value-added products can contribute to biodiesel promotion. This crude

2
glycerol could be use as a renewable feedstock for the production of value added chemicals and
fuels as an alternative to the fossil-derived products. Finding new uses of glycerol would make
biodiesel production a cost effective process. Glycerol has been identified by the U.S. Department
of Energy as one of the top-12 building block chemicals that can be derived from sugars and
converted to high-value bio-based chemicals or materials [3]. Until now, a great deal of effort has
been put toward the utilization of glycerol [4-6].

Glycols such as propanediols and ethylene glycol are important chemicals usually produced
from petroleum derivatives. The hydrogenolysis of glycerol to 1,2- and 1,3-propanediol is an
attractive innovative green process for the production of renewable value-added chemicals. 1,2-
propanediol (1,2-PDO) is a major commodity chemical with a 4% annual market growth. Typical
uses of 1,2-propanediol are in unsaturated polyester resins, functional fluids,
pharmaceuticals/cosmetics, paints, etc. 1,3-Propanediol is mainly used for the production of
polyesters via co-polymerization with terephthalic acid. These two products are currently produced
from petroleum derivatives such as propylene oxide (1,2- propanediol) and ethylene oxide or
acrolein (1,3-propanediol) by chemical catalytic routes [3,7,8]. Their production from renewable
glycerol could potentially offer great environmental benefits.

Hydrogenolysis of glycerol is generally carried out in liquid phase under high H2 pressures.
The main products obtained by the glycerol hydrogenolysis are 1,2-propanediol, 1,3-propanediol
and ethylene glycol. Reaction pathways for the conversion of glycerol into lower polyols and
alcohols through hydrogenolysis are shown in Figure 1. Hydrogenolysis reaction is known as a
bifunctional reaction. It requires catalysts both for dehydration and for hydrogenation
functionality. Besides the hydrogenolysis reaction, degradation reactions involving C–C breaking
also occur. The products from C–C cracking are mainly ethylene glycol, methanol, ethanol and
methane. Therefore, the selective conversion of glycerol into propanediols requires a suitable
catalyst with bifunctional acid sites/metal surface, favoring the cleavage of the glycerol C–O bonds
(dehydration/hydrogenation) by hydrogen and eliminating C–C bond scission. Development of
selective catalysts is necessary for successful development of industrial process employing
hydrogenolysis of glycerol into glycol formation.

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Figure 1. Reaction pathways for the conversion of glycerol into lower polyols and alcohols through
hydrogenolysis [9]

5.2.Research work engaged in at present

None

5.3. Objectives of the proposed project

 Preparation and characterization of Cu-Ni and Cu-Ru bimetallic catalyst supported on
carbon, γ-Al2O3 or SBA-15 .
 Elucidating the role of nanoscale structure and composition of Cu-Ni and Cu-Ru alloys
on their activity and selectivity in vapor phase hydrogenolysis of glycerol.
 Investigating the effect of process parameters on the glycerol conversion and glycol
selectivity.
 Developing a kinetic model for the vapor phase hydrogenolysis of glycerol over supported
bimetallic catalysts.

5.4. Review of R&D in the proposed area (National & International Status, Importance, patents
etc.)

5.4.1. National Status

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 Balaraju et al. [10] investigated liquid phase glycerol hydrogenolysis over Ru/C catalysts.
Solid acid such as niobia, 12-tungstophosphoric acid (TPA) supported on zirconia, cesiumsalt of
TPA and cesiumsalt of TPA supported on zirconia were used as co-catalyst. The influence of
acidity of the catalysts on glycerol conversion and selectivity was studied. Initial results on
glycerol hydrogenolysis suggested that 5%Ru/C catalyst was more active as compared to Pd, Pt or
Rh supported on carbon. The conversion of glycerol over the solid acid catalysts was in the order
of Nb2O5 > TPA/ ZrO2 > CsTPA > CsTPA/ZrO2. Effect of hydrogen pressure, temperature and
glycerol concentration was studied. Glycerol conversion was found to increase with temperature
(120 -210 0C) and pressure (20 to 80 bar) whereas conversion was decreased with glycerol
concentration (20-80%). Over Ru/C (3%) + Nb2O5 (6%) mixed catalyst, 44.6% conversion of
glycerol (20wt.% aqueous solution as feed) with 60.9% selectivity to 1,2-propanediol was obtained
at 180 0C after 8 h of reaction at 60 bar hydrogen pressure. These results suggest that the total
acidity of the catalyst played a major role in the overall glycerol conversion. They also suggested
that moderate acid sites are sufficient to get reasonable glycerol conversion.

5.4.2. International Status

5.4.2.1. Liquid phase hydrogenolysis of glycerol
Hydrogenolysis of glycerol takes place under high hydrogen pressure and mild temperature
in presence of suitable catalytic materials. Mostly, liquid phase hydrogenolysis of glycerol has
been investigated over noble metal as well as non-noble metal catalysts so far. Some of the recent
achievements in liquid phase hydrogenolysis of glycerol are shown on Table 1.

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Table 1
Some recent achievements in liquid-phase hydrogenolysis of glycerol: catalysts and performance

Catalyst tested Glycerol Reaction Best Catalyst Catalytic Reference

condition performance
Carbon supported Ru, Pt, Rh, Pd and Amberlyst 20 mass% H2 pressure = 8
15, H2SO4 (aq.), HCL (aq.) as acid catalyst, NaCl glycerol solution MPa; T = 390K; t Ru/C + X = 12.9%; S1,2PDO Miyazawa et
(aq.), Na2SO4(aq.) as reference. = 10h Amberlyst 15 = 55.4% al. [11-13]
1wt.% glycerol H2 pressure = 40 Ru/C + 0.8 (M) X = 100 % (after 5
Carbon supported Ru, Pt and NaOH, CaO as solution bar; T = 473 K; t NaOH and h reaction); Maris and
base = 5h Pt-Ru + 0.8 (M) S PG (Carbon Devis [14]
PtRu/C, AuRu/C NaOH selectivity) = 0.37 Maris et al.
[15]
80 wt.% H2 pressure = 9.0
CuO/SiO2 with residual amount of sodium aqueous solution MPa; T = 453 K; CuO/SiO2 with X = 28.6%; Huang et al.
t = 12h 1.9 wt.% Na S1,2-PD = 99.0% [16]
Pure glycerol H2 pressure = 8.0 (a) Ru / γ-Al2O3 (a) X = 69%;
Ru based γ-Al2O3, SiO2, ZrO2 MPa; T = 240 0C; (prepared with S1,2-PDO = 37.9% Vasiliadou et
t = 10h chloride al. [17]
precursor)
(b) Ru/SiO2 (b) X = 21.7%;
prepared with S1,2-PDO = 60.5%
nitrate precursor

6
 H2 pressure = 8 X = 51.7%;
Ru-Re/SiO2; Ru/SiO2 40 wt.% MPa; T = 160 0C; Ru-Re/SiO2 S1,2-PDO = 44.8% Ma and He
glycerol t = 8h [18]
aqueous solution
(a)Ni/Al2O3 (a) X = 32.3%;
SiO2 supported Co, Cu, Ni, Pd, Ru; H2 pressure = 5 S1,2-PDO = 55.1%
Cu/ZnO/Al2O3, Cu/Cr2O3, Ni/Al2O3, Pd/C 60 mass% MPa; T = 200 0C; (b) X = 20.4%; Huang et al.
glycerol t = 10h (b)Cu/ZnO/Al2O S1,2-PDO = 80.1% [19]
3

(c) Pd/C, Low active but

Pd/SiO2 highly selective to
1,2-PDO
Highly dispersed Silica supported Copper 80 wt.% H2 pressure = Cu/SiO2 X = 73.4%;
nanoparticles glycerol 9MPa; T = 453 S1,2-PDO = 94.3% Huang et al.
aqueous solution K, t = 12h [20]
Cu-ZnO (0.6); Cu-ZnO (1.0) 20wt.% glycerol H2 pressure = 4.2 Cu-ZnO (0.6) X = 22.5%;
Cu-ZnO (2.0); CuO aqueous solution MPa; T = 473 K, S Propylene glycol = Wang and Liu
ZnO t = 12 h 20.4% [21]
Series of Copper-Chromites Catalyst 40wt.% glycerol H2 pressure = X = 51%;
CuO, Cr2O3, aqueous solution 4.15 MPa; T = Cu : Cr = 1:2 S 1,2-PDO= 96% Liang et al.
210oC, t = 10 h [22]
Mg/Al, Zn/Al, Ni/Mg/Al, Co/Zn/Al, Cu/Zn/Al 5wt.% glycerol H2 pressure = 200 Cu/Zn/Al X = 67.2%;
aqueous solution psig; T = 200oC, t S 1,2-PDO= 63.0% Meher et al.
= 24 h [23]

7
5.4.2.2. Vapor phase hydrogenolysis of glycerol

Very few studies have been found on vapor phase hydrogenolysis of glycerol. Huang et al.
[24] carried out the direct conversion of Glycerol into 1,3-Propanediol (1,3-PDO) over Cu-
H4SiW12O40/SiO2 catalyst in vapor Phase, under the hydrogen pressure below 0.54 MPa. The
effect of temperature, weight hourly space velocity, pressure, and initial water content was
investigated to obtain the optimum hydrogenolysis conditions of glycerol. The selectivity to 1,3-
Propanediol and 1,2-Propanediol (1,2-PDO) were improved with increasing hydrogen pressure.
The best results were obtained at 210 0C, 0.54 MPa over the Cu-H4SiW12O40/SiO2 catalyst. The
glycerol conversion was 83.4% with the selectivity to 1,3-PD and 1,2-PDO was 32.1% and 22.2%,
respectively. Akiyama et al. [25] investigated the activity of commercial Cu/Al2O3 (N- 242),
Cu/Cr2O3 (N-201), Cu/ZnO (N-211) and Ni/SiO2 (N-111) catalyst. They found that alumina-
supported copper was the most active catalyst and the selectivity to hydroxyacetone was greater
than 90 mol.% at an ambient hydrogen pressure and 250 0C. They reported that that copper catalyst
have the hydrogenation activity in both the double bond of C=O and C=C and recommended that
copper-based catalyst would be suitable for the reaction of glycerol because copper catalyzes the
dehydration of glycerol as well as the hydrogenation of ketones. Ni/SiO2 catalyzed C–C cleavage
of glycerol and the decomposition of glycerol into gaseous products. Over Cu/Al2O3 and Cu/ Cr2O3
catalysts the selectivity to 1,2-propanediol was higher than 70% at 200 0C. Over Cu/ Al2O3 (N-
242) catalyst, the conversion of glycerol was varied from 68% to 100% with the temperature range
of 170 -190 0C, while the selectivity to 1,2-PDO varied from 60% to 80%. The complete
conversion of glycerol was obtained at high temperature (>200 0C).

However, they also reported that, at higher temperature, glycerol decomposes into ethylene
glycol, methanol, ethanol, 1-propanol, and 2-propanol. The highest yield of 1,2-PDO (80%) was
reported at 190 0C. Over Cu/Al2O3 catalyst, glycerol was converted into 1,2-PDO with the yield
of more than 96% at 200–120 0C. The catalytic performance of Cu/ Al2O3 catalyst was almost
unaffected on water content in feed. Sato et al. [26] reported that the glycerol converted into 1,2-
PDO through dehydration-hydrogenation via hydroxyacetone (HA) over copper alumina catalyst.
Chiu et al. [27, 28] optimized the parameter such as concentration, water content, pressure,
temperature and residence time to achieve selectivity to propylene glycol higher than 90%.

8
Copper-chromite catalysts were tested in a packed bed reactor. They reported that low
concentration of glycerol is an important factor to reduce the byproduct formation in vapor phase
hydrogenolysis. Water content is an important parameter to reduce the dehydration reaction and
indirectly helps to maintain more isothermal operation. An optimal hydrogen partial pressure
between 5 and 15 bars has been recommended to minimize the cumulative amount of by-product
formation which are obtaine by the hydrocracking versus dehydration side-reactions.

5.4.3. Importance
5.4.3.1. Importance of Gydrogenolysis of glycerol

Glycerol, a by-product in biodiesel production has been identified as one of the top building
blocks in the biorefinery feed stocks in this decade [29, 30]. Large amounts of glycerol will be
produced in biodiesel industry as by-products during transesterification of oils [31–33]. Biodiesel
production will soon look into new applications to convert its by-product glycerol to value-added
products to make the biodiesel industry economically more attractive. Hydrogenolysis of glycerol
has received recent attention [34-38] because the cost of glycerol as a by-product is projected to
decrease significantly as biodiesel production increases [39]. Hydrogenolysis of glycerol leads to
the formation of 1,2-PD and 1,3-PDO and ethylene glycol (EG) as main products. These glycols
are used widely in the syntheses of pharmaceuticals, polymers, agricultural adjuvant, plastics and
transportation fuel [40-43]. The commercial route to produce propylene glycol or ethylene glycol
is by the hydration of propylene oxide or ethylene oxide derived from propylene or ethylene [44].
The production of glycols by the catalytic hydrogenolysis of glycerol is a green process, as the
existing methods use petroleum-derived products (fossil resources) [44, 45].

5.4.3.2. Importance of vapor phase drogenolysis of glycerol

In the liquid phase hydrogenolysis of glycerol, the maximum conversion of 100% has been
reported over Ru/C with 0.8 (M) NaOH catalysts at very high (40 bar) hydrogen pressure [13, 14].
At this condition the main product was propyleneglycol with a selectivity of 37%. Huang et al.
[20] reported 73.4% conversion at 9 MPa hydrogen pressure with a selectivity to 1,2-propanediol
of 94.3% over highly dispersed copper nanoparticle supported on SiO2 catalyst.

9
The information of vapor phase hydrogenolysis is very limited in literature. Over Cu based
catalysts showed much better results in terms of activity (68-100%) as well as selectivity to glycols
(60-96%) at much lower hydrogen pressure (close to 1 atm.)[24-28]. Therefore, study of vapor
phase hydrogenolysis of glycerol over novel catalysts system at atmospheric pressure is very
promising.

5.4.3.2.1. Limitation of liquid phase hydrogenolysis

Liquid phase hydrogenolysis of glycerol has been studied so far. The major disadvantages of
liquid phase reaction are:
1. Reaction takes place at very high hydrogen pressure (1-80 bar)
2. Difficult to analyze the gaseous product
3. Difficult to separate the catalysts from the reaction mixture
4. Some studies also showed that during the reaction catalyst dissolution takes place in the
reaction mixture [14, 15].
5. Further improvements of the catalytic activity and propanediol selectivity are necessary for the
successful development of industrial process employing glycerol hydrogenolysis reaction.
6. It is highly important to design highly active and selective catalyst to perform the reaction at
low hydrogen pressure and temperature.

5.4.3.2.2. Limitation of catalysts tested

Supported noble metals [11-17, 70] and non noble metal [16, 19, 20-23] catalysts have
been tested for liquid phase hydrogenolysis of glycerol. It has been reported that, the noble metals
are active for hydrogenolysis of glycerol. The noble metal promotes excessive C-C cleavage which
is known as over hydrogenolysis which reduces the selectivity to glycols and facilitates the
formation of undesirable hydrocarbons mainly methane and other linear alcohol. The studies over
transition metal catalysts are rather very limited. The hydrogenolysis mechanism proposed by
Sohounloue et al. [46] is a good foundation to begin a study on glycerol hydrogenolysis over
transition metal catalyst. As a less expensive alternative, copper-based catalysts have been reported
to have a superior performance in this reaction due to their poor activity for C-C bond cleavage

10
and high efficiency for C-O bond hydro-hehydrogenation. Recently, Huang et al. [20] reported
that highly dispersed silica supported copper nanoparticles are very efficient catalysts for glycerol
hydrogenolysis. As reported in the literature that the hydrogenolysis of glycerol are extremely
sensitive to the catalysts particle size [20]. The hydrogenolysis reaction is known as bifunctional
reaction [10]. It is requires catalysts both for dehydration and for hydrogenation functionality.
Therefore, development of catalysts having dual active site may be a good choice.

5.4.3.3. Importance of supported bimetallic nanoparticle catalysts

The use of well-defined metal nanoparticles (1–10 nm) for catalytic processes is a rapidly
growing area [47-50]. Metal nanoparticles have been proved to be efficient and selective catalysts
for hydrogenation of olefins or C–C couplings. Supported bimetallic nanoparticle catalysts have
received much attention from both industrial and academic sectors because these systems often
exhibit higher activity, selectivity, and stability making them superior to monometallic catalysts
in a given reaction. Through the combination of different metals, their surface geometries and
electronic structures can be varied over wide ranges, and, as a consequence, the reactivity of these
surfaces can also be tuned. Application of several bimetallic or ternary catalysts in some important
chemical reactions are reported in the literature, such as Ni-Cu/ZrO2 [51], Ni-Cu/Al2O3 [52], Ni-
Cu/CNT [53], Ni-Cu-Nb2O5 [54], and Ni-Cu/SDC [55] for steam reforming reaction, Cu-Ni/KL
[56] for hydrogenation of citral, Cu(100) modified by Ni for methanol synthesis, Cu-Pd/CeO2 [57,
58], Pt-Re/CeO2-ZrO2 [59], Au-Pt/CeO2 [60], and Mn-Cu/Al2O3 [61] for WGS reaction. In the
past decade, the development of alloy catalysts has almost been accomplished by trial and error.
However, recent advances in both experimental and theoretical methods have facilitated the
development of new and improved alloy catalysts based on fundamental surface science and first
principle studies [62-65]. Advanced nanosynthesis techniques, including dendrimer-based
approaches [66] and atomic layer deposition techniques [67] hold a high promise of a large scale
preparation of nano-size alloy catalysts with superior performance as compared to monometallic
or bulk alloy catalysts.

Previous studies of hydrogenolysis of glycerol shows that the noble metal based catalysts
are usually more active than Cu based catalyst, but the selectivity to propanediols is lower [68].

11
Cu [16, 19-22, 69] and Ru [11-15, 17, 70] based catalysts with and without acidic solid oxide
additives were found to be very active for hydrogenolysis of glycerol. According to Dasari et al.
[69] the activity of supported metal catalysts for hydrogenolysis of a 80% glycerol solution at 470
K and 15 bar decreased in the order Ru ≈ Cu ≈ Ni > Pt > Pd. Huang et al. [16, 19, 20] reported
that copper based catalysts show poor activity for C–C bond cleavage and high efficiency for C–
O bond hydro-dehydrogenation. Guo et al. [68] found that Cu/γ-Al2O3 catalyst was highly
selectivity to propanediols under mild reaction condition. It has been reported that, CuO/SiO2
catalyst was much active and stable in glycerol hydrogenolysis reaction due to smaller particle size
and higher dispersion of copper species with a strong metal-support interaction, and more
resistance to sintering [20].

Kusunoki et al. [70] and Miyazawa et al. [11-13] reported that Ru/C in presence of solid
acid catalyst (Amberlyst 15) is very active and selective for hydrogenolysis. They proposed that
the glycerol dehydration to acetol is favorable over solid acid catalyst whereas Ru/C catalyst is
highly active for hydrogenation of acetol to 1,2-PDO. The degradation of glycerol proceeds as a
side reaction in glycerol hydrogenolysis, and Ru/C can analyze the degradation reaction. Ru/C
catalyst play an important role in the dehydration of glycerol to 3-hydroxypropionaldehyde, which
can be converted to 1,3-PDO through subsequent hydrogenation and other degradation products.
In particular, the contribution of Ru-OH species is suggested in the dehydration of glycerol.
Vasiliadou et al. [17] reported Ru supported on silica with the use of nitrate precursor showed the
highest selectivity to 1,2-PDO (65%).

The activity of bimetallic catalysts in hydrogenolysis of glycerol is very limited [15, 18].
Hydrogenolysis reactions are well known to be structure sensitive; that is, the activity and
selectivity depend on catalyst surface structure or particle size. Bimetallic catalysts have been used
to alter the activity and selectivity of various reactions, including hydrogenolysis reactions [71-
75]. Bimetallic catalysts can exhibit catalytic activities that surpass those of their monometallic
analogues [74]. Ma and He [18] showed the higher activity of bimetallic Ru-Re/SiO2 catalyst than
monometallic Ru/SiO2 catalyst in the hydrogenolysis of glycerol.

12
 In this study, Cu-Ni and Cu-Ru bimetallic nanoparticle catalysts supported on various
supports such as γ-Al2O3, SiO2 (SBA-15), Vulcan XC-72 carbon black, have been chosen for vapor
phase hydrogenolysis of glycerol. These catalysts may be the promising catalysts for the gas phase
hydrogenolysis of glycerol into 1,2-PDO and 1,3-PDO.

5.4.3.4. Importance of synthesis of SBA15

One of the goals of catalysis research is to design and fabricate a catalyst system that
produces only one desired product out of many other possible products (100% selectivity) at high
turnover rates. Such a “green chemistry” process eliminates the production of undesirable waste.
To design a catalyst for the “green chemistry” era, an understanding of the molecular ingredients
that influence selectivity must be incorporated into catalyst synthesis. To use a model catalysts 2-
D transition metal/metal oxide array catalysts, many of the molecular features that usually control
the activity and selectivity need to be considered. These include the surface structure, metal particle
size, site blocking (i.e., selective poisoning of the catalyst surface), bifunctional catalytic systems,
and certain metal-oxide interfaces capable of performing unique chemistry. One of the most
mature areas of selectivity control in heterogeneous catalysis is shape selective catalysis.
Therefore, designs of catalytic support are very important to get the maximum desired product
selectively.
It is important to control the properties of support materials systematically which will help
to control various parameters on reaction activity and selectivity. Departing from the traditional
catalytic synthetic techniques (i.e., incipient wetness, ion exchange), development of synthetic
method is required which will allow the precise control of the metal particle size and tuning of the
support (e,g, mesoporous SBA-15 silica support) pore diameter. Control of the metal nanoparticle
size can be achieved with solution based alcohol reduction methods. Metal nanoparticles (<20 nm)
will be synthesized and incorporated into a mesoporous silicate support using low-power
sonication that facilitates bimetallic nanoparticles particle entry into the SBA-15 channels by
capillary inclusion.

5.4.4. Patents

13
 Drent et al. [76] have shown Pt based catalysts are active in liquid phase homogeneous
hydrogenolysis of glycerol. Metal nitrates and strong acids were used as metal and anion sources,
respectively. Suppes et al. [77] reported that (CuO)x(Cr2O3)y catalysts are the preferred catalysts at
180-2200C and 1-25 bar pressure.

5.5. Work plan (including detailed methodology and time schedule)

5.5.1. Catalysts synthesis

5.5.1.1. Preparation of mesoporous SBA 15

Silica SBA-15 will be prepared according to the method reported in the literature [78]. Pluronic
P123 (BASF, EO20PO70EO20, EO = ethylene oxide, PO = propylene oxide) and tetraethoxysilane
(TEOS, 99+ %) will be used as precursors. Pluronic P123 (6 g) will be dissolved in 45 g of water
and 180 g of 2 M HCl solution with stirring at 308 K for 30 min. TEOS (12.75 g) will be added to
the solution with stirring at 308 K for 20 h. The mixture will be aged at 373 K for 24 h. The white
powder obtained will be recovered through filtration, washed with water and ethanol thoroughly,
and will be dried in air. The product will be calcined at 823 K for 12 h to produce SBA-15 with a
pore diameter of 9 nm. The surface area of the finally calcined material will be around 765 m2 g-1
with a pore volume of 1.16 cm3 g-1.

5.5.1.2. Synthesis of bimetallic nanoparticles

The information regarding the synthesis of Cu-Ni and Cu-Ru bimetallic nanoparticles is
very limited. Therefore, synthesis of bimetallic nanoparticles is a challenging task. Recent
advances in nanoparticle preparation techniques [79-81] offer new opportunities for the
preparation of supported bimetallic catalysts. In this process, which is analogous to the cluster
route, surface protected mono- or bimetallic nanoparticles are prepared in solution, deposited onto
a support, and the colloid stabilizers are removed yielding supported particles with known,
characterizable, and reproducible synthetic histories. Because nanoparticle compositions may be
within bulk miscibility gaps, the colloid method also offers opportunities to prepare and investigate
new bimetallic nanoparticle catalysts in a rational, controlled fashion. Further, heterogeneous
catalysis and some catalyst characterization techniques directly probe the surface chemistry of

14
supported nanoparticles and thus can be considered additional tools in the investigation of
nanoparticle chemistry and the discovery of new nanoparticle properties.

The nanoparticle will be synthesized using dendrimer. The catalyst preparation method
using PAMAM dendrimers as nanoparticle templates/ stabilizers has been discussed elsewhere
[82]. Dendrimer stabilize the metal nanoparticles in aqueous solution. The nanoparticle obtained
in the aqueous solution will be deposited onto a high surface area support. Supported nanoparticles
will be obtained by the thermal treatment. PAMAM dendrimers can be removed completely at 300
°C, although the time require to remove organic residues may vary with the metal to dendrimer
ratio [83]. Dendrimer-encapsulated metal nanoparticles (DENs), can be prepared in solution with
reproducible and variable synthetic schemes. Utilizing DENs as catalyst precursors offers the
opportunity to exert a degree of control over metal particle size and composition, while varying
the carrier or substrate (see Scheme 1).

Scheme 1. Schematic route to dendriemr-derived supported nanoparticle catalysts [84]

The potential to ultimately control nanoparticle size and composition [85-87] makes DENs
extremely attractive as potential precursors for studying supported-metal catalysts. Because the
particles are prepared ex-situ and can be deposited onto a substrate or support, DENs offer the
opportunity to bridge the gap between surface science studies of model systems and real world
catalysts on high surface area supports. The possibility of varying particle size and composition

15
through nanoparticle preparation schemes makes DENs uniquely suited to exploring and
understanding the relative importance of these effects on catalytic reactions using materials
comparable to those employed as industrial catalysts.

5.5.2. Vapor phase hydrogenolysis of glycerol

The catalysts will be tested for the vapor phase hydrogenolysis of glycerol to glycols at
atmospheric pressure. The experimental set-up will be fabricated in the laboratory. The schematic
diagram of the experimental set up is shown in the Figure-1.

Heating Liquid T
tape feed C

MF pump
C
Furnace

Hydrog
en MF Recircu
C lating
cooling
bath
Nitrog
1
G
en MFC= Mass flow C
controller
GC = Gas
Chromatography
TC = Thermocouple

Figure-1 Schematic diagram of vapor hydrogenolysis of glycerol

The experimental set up essentially consists of a flow system, a reaction unit and analysis system.
The reaction will be carried out in a tubular packed bed reactor place inside a programmable
tubular furnace. The feed gas flow will be controlled by using mass flow controllers. The liquid
mixture will be introduced to the reactor by a liquid feed pump with proper control of flow. The

16
reaction product will be passed through a recirculating cooling bath to cool down the unreacted
glycerol and some other condensable. The liquid and gaseous products will be analyzed by online
and offline gas chromatography, respectively.

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5.5.3. Time Schedule

Time in Months

20
 Work to be done 0-6 7-12 13-18 19-24 25-30 31-36

Literature review, procurement of chemicals,

procurement of glass wares.
Design and fabrication of experimental setup,
Synthesis of catalysts.
Synthesis of catalysts, Characterization of
catalysts.
Study of glycerol hydrogenolysis, Preliminary
data analysis, Optimization of reaction
parameter.
Study of hydrogenolysis of glycerol over all
catalysts, Catalysts characterixation.

Kinetic analysis, report writing.

5.6. Future plans

Conversion of biomass derived carbohydrate into lower alcohols over supported nanoparticle
catalysts.

5.7. Details of the research funding received in the past and/ongoing projects (mention Ref. no.,
title, duration, cost, funding agency, and brief achievements).

Not Applicable

6. Name and address of the institution where the proposal will be/likely to be executed

Department of Chemical Engineering

Indian Institute of Technology Roorkee
Roorkee-247667, Uttarakhand, India.

21
7. Facilities provided/to be made available at the host institute

Micromeritics 2705 for BET, TPR, TPD, TPO and H2-chemisorption measurement, Particle
size analyzer, CHNS analyzer, UV-VIS-NIR Spectroscopy, AAS, FTIR.
XRD, SEM, TEM (Central Facility)

8. Name(s) and address(es) of Indian expert(s) in the proposed area

Dr. Deepak Kunzru

Professor, Department of Chemical Engineering
Indian Institute of Technology Kanpur
Kanpur-208016, U.P, India.
Phone No: +91-512-2597193, Fax: 91-0512-2590104
Email: [email protected]

Dr. Goutam Deo

Professor and HOD
Department of Chemical Engineering
Indian Institute of Technology Kanpur
Kanpur-208016, U.P, India.
Phone No. +91-512-2597881, 2597363, Fax: 91-0512-2590104
Email: [email protected]

Dr. K. K. Pant
Associate Professor
Department of Chemical Engineering
Indian Institute of Technology Delhi
Hauzkhas, New Delhi-110016
E-mail: [email protected]; [email protected]
Phone No: 91-11-26596172/77; Fax No: 91-11-26581120
Dr. P. Ray
Professor, Department of Chemical Engineering
University College of Science and Technology

22
University of Calcutta
92 A.P.C Road, Kolkata-9, West Bengal, India.
Email: [email protected]
Phone No. +91-33-23601612 (D)/23501397 (O)/25565037 (R)

9. Details of financial requirements for three years (with justifications) and phasing for each
year

S.No. Head 1st Year 2nd Year 3rd Year Total

1. Fellowship @ Rs. NA NA NA NIL
20,000/- p.m.*
2. Manpower** Rs. 14,000 x Rs. 14,000x12 Rs. Rs. 5, 16 ,000
12 =1,68,000 =1,68,000 15,000x12
=1,80,000
3. Consumables Rs. 1,00,000 Rs. 1, 00, 000 Rs. 50,000 Rs. 2,50,000
4. Travel (within India) Rs. 10,000 Rs. 15,000 Rs. 15,000 Rs. 40,000
5. Contingency Rs. 25,000 Rs. 25,000 Rs. 25,000 Rs. 75,000
7. Equipment (Generic Name with minimum required accessories, make
& model & cost in Indian Rupees)
Cataly Ultrasonic bath Rs. 30,000 Rs. 30,000
st
Centrifuge Rs. 50,000 Rs. 50,000
synthe
sis

Experi Mass flow controller Rs. 2,00,000 Rs. 2,00,000

mental (2)
Setup Liquid feed pump Rs. 1,00,000 Rs. 1,00,000
Swagelok fittings Rs. 50,000 Rs. 50,000
and accessories
Tubular Furnace Rs. 50,000 Rs. 50,000

23
 Thermocouples & Rs. 20,000 Rs. 20,000
Heating Tape
Gas Cylinder with Rs. 60,000 Rs. 60,000
regulator (H2, N2)
Gas Chromatography Rs. 5,00,000 Rs. 5,00,000
with data station and
accessories
Grand total of estimated project cost Rs. 19, 41,000
8. Overhead costs @ 20% of project cost Rs. 3,88,200
Total cost including over head costs Rs. 23,29,200

* Applicable to scientist having no regular employment and are not drawing any fellowship during
the project tenure
** Applicable for researcher holding regular position.

Justification of financial requirements

 Manpower
I am working as an Assistant Professor in the department of Chemical Engineering at IIR
Roorkee, Roorkee-247667, Uttarakhand, India. I joined in this department on 31st December, 2009.
At present, I do not have any PhD scholar to carry out this proposed work. To successful
completion of this work, I need a full time research scholar (JRF).
 Consumables
To carry out the catalysts synthesis and hydrogenolysis of glycerol, lot of chemicals and
glassware are required. Therefore, the financial assistance requested is bare minimum.
 Travel within India
Travel within in India is necessary to carry out the materials characterization to IIT Kanpur or
IIT Delhi.
 Contingency
The materials developed and the reaction product sample need to analyze in other department
will be required some charges. To purchase/repair some essential small accessories such as gas

24
regulator, GC-syringe, printer cartridge and maintenance of laboratory some financial assistance
will be required.
 Equipment
*Ultrasonic bath and centrifuge is necessary to synthesis of nanoparticles.
*Mass flow controller required to control the feed gas flow rate.
*Liquid feed pump is required to feed aqueous solution of glycerol in controlled rate.
*Swagelok fittings and accessories are required to fabricate the gas phase reaction set up.
*Tubular Furnace, thermocouples and heating tape are required to control the reaction temperature.
*Gas cylinder with regulator (H2, N2) is the feed gas tank.
*Gas Chromatography with data station and accessories (column, syringe and others) are required
to analysis the product concentration.

10. Have you ever applied before under Scheme or Women Scientist Scheme? ) If yes, give details
(Name and Scheme, Title, Subject area, Reference number, if any, year and the decision).
No
11. Any other information in support of the proposed project:

Please see Annexure-II

12. Statement of the present Employer as per Annexure-I (In respect of person holding regular
position)
Attached

Annexure-I

25
 (Statement from Employer, if employed)

This is to certify that:

I. Dr. Prakash Biswas, the principle Investigator in the project entitled, “Hydrogenolysis of
Glycerol over Supported Cu-Ni, Cu-Ru Bimetallic Nanoparticle Catalysts”, will assume
full responsibility for implementing the project.
II. The date of appointment starts from the date on which the University/Institute receives the
bank draft/cheque from the Department of Science & Technology.
III. The Investigator will be governed by the rules and regulations of the University/Institute
and will be under administrative control of the University/Institute for the duration of the
project.
IV. The grant-in-aid by the Department of Science & Technology will be used to meet the
expenditure on the project and for the period for which the project has been sanctioned as
indicated in the sanction letter/order.
V. No administrative or other liability will be attached to the Department of Science &
Technology at the end of the project.
VI. The University/Institute will provide basic infrastructure and other required facilities to the
investigator for undertaking the research project.
VII. The University/ Institute will take into ints books all assets received under this sanction
and its disposal would be at the discretion of Department of Science & Technology.
VIII. Institute assumes to undertake the financial and other management responsibilities of the
project.

Signature
Seal of University/Institute Registrar of University/Head of Institute

26