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Catalytic Reduction of CO2 Into Hydrogen Using Micro Reactors
Catalytic Reduction of CO2 Into Hydrogen Using Micro Reactors
Catalytic Reduction of CO2 Into Hydrogen Using Micro Reactors
Catalytic
Reduction
of
CO2
Into
Hydrogen
Using
Microreactors
Malavarayan.S
Ravishankar.M
IInd
year
Chemical
Engineering,
Sri
Venkateswara
College
of
Engineering,
Sriperumbudur
Postal
Address:
No:
50,
NGO
Colony
2nd
street,
Vadapalani,
Chennai‐26.
Email:
malavarayan@gmail.com
Phone:
+91
9884314549
Abstract:
The
stoichiometric
reduction
of
carbon
dioxide
by
soluble
K[Ru[III]‐(EDTA‐
H)Cl].2H2O
complex
at
CO2
pressure
in
the
range
of
5‐70
atm
and
temperature
40‐80
°C
in
a
microreactor
gave
formic
acid
and
formaldehyde
as
the
reaction
products.
The
rates
of
formation
of
formation
of
formic
acid
and
formaldehyde
are
of
first
order
dependence
with
respect
to
the
catalyst
and
the
dissolved
carbon
dioxide
concentrations.
The
formic
acid
this
produced
is
converted
into
hydrogen
by
water‐gas
shift
method
using
10%
Cu‐Al2O3
as
a
catalyst
in
a
separate
microreactor
at
a
temperature
of
about
130
°C
to
give
hydrogen
gas
.
The
Energy
is
only
given
for
maintaining
the
overall
experimental
conditions.
The
hydrogen
thus
obtained
can
be
used
for
various
industrial
purposes
the
most
significant
being
the
conversion
of
hydrogen
into
Electrical
Energy
using
Fuel
Cells.
Introduction:
Carbon
dioxide
and
water
are
the
end
products
of
many
chemical
and
biological
processes.
The
Utilization
of
CO2
to
synthesize
value‐added
chemicals
is,
therefore,
of
much
importance
in
industry.
CO2
is
used
industrially
in
large
quantities
for
the
preparation
of
Urea
[1]
and
inorganic
compounds
such
as
carbonates
and
bicarbonates.
Activation
of
CO2
by
transition
metal
complexes
for
form
adducts
is
an
area
of
investigation
[2‐8].
The
synthesis
of
methyl
formate
by
the
reaction
of
CO2
,
H2
and
CH3OH
catalyzed
by
Ru(PPh3)Cl2
is
a
good
example
of
the
reductive
fixation
of
CO2
[9]
.
CO2
+
H2
have
been
used
in
the
place
of
CO
+
H2
in
the
synthesis
of
homologous
alkenes,
alcohols
and
amines
in
the
presence
of
NH3
[10‐12].
The
rhodium
complex
Rh(diphos)(BPh4)
catalyzes
the
co‐oligomerization
of
CO2
and
methyl
acetylene
to
give
cyclic
compounds
.
This
paper
reports
the
reduction
of
CO2
to
formic
acid
and
formaldehyde
by
the
water
soluble
K[RuIII(EDTA)Cl].2H2O
system
under
mild
experimental
conditions
(40
‐80
°C
,
5‐70
atm
).
The
system
suggests
the
possibility
for
a
catalytic
cycle
for
the
fixation
of
CO2
to
value
added
products.
The
reaction
is
carried
out
in
a
microreactor
that
can
provide
the
necessary
experimental
conditions
viz.
the
temperature
and
the
pressure.
A
stack
containing
‘n’
number
of
micro
reactors
can
be
employed
where
‘n’
would
depend
on
the
application
of
use.
Experimental:
The
carbon
dioxide
fixation
was
performed
in
a
300
ml
pressure
reactor
by
[3].
Carbon
dioxide
gas
with
a
purity
greater
than
99.5%
and
complex
K[RuIII(EDTA‐H)Cl).2H2O
were
used
in
the
300
ml
reactor
along
with
double
distilled
water.
The
complex
was
prepared
using
RuCl3.3H2O
and
disodium
salt
of
EDTA
[15].
In
a
sample
run,
a
known
amount
of
complex
1
was
dissolved
in
100
ml
of
distilled
water
and
placed
in
the
pressure
reactor.
The
bomb
was
pressurized
by
CO2
to
the
required
value
when
the
desired
temperature
was
attained.
The
progress
of
the
reaction
was
monitored
by
analyzing
liquid
samples
withdrawn
at
different
intervals
of
time
for
HCOOH
and
HCHO
contents.
The
concentration
of
HCHO
and
HCOOH
present
in
the
liquid
samples
were
estimated
spectrophotometrically
by
monitoring
the
peak
at
412
nm
using
Nash’s
reagent
[16,17].
From
the
graphs
of
time
vs.
amount
of
HCHO
or
HCOOH
formed,
the
rates
of
the
formation
of
both
the
products
evaluated.
Gaseous
samples
were
also
withdrawn
at
suitable
intervals
of
reaction
time
and
analyzed
for
CO2
and
CO
content
using
a
GLC.
The
column
used
for
the
analysis
of
gases
were
2.5
m
long,
100
mesh
with
a
TC
detector
(150
°C),
column
temperature
40
°C,
injector
temperature
50
°C
and
H2
carrier
gas
with
a
flow
rate
of
30
ml
min‐1.
The
required
solubility
data
of
CO2
in
water
at
different
temperatures
and
pressure
were
taken
from
the
reported
values
[18],
and
the
total
dissolved
CO2
concentration
needed
to
interpret
the
kinetic
data
was
calculated.
Results
and
Discussion:
In
order
to
fix
the
conditions
for
kinetic
study,
the
experiment
was
Conducted
with
1
mmol
of
complex
1,
a
CO2
partial
pressure
of
68.0
atm
And
at
80
°C.
The
yields
of
HCOOH
and
HCHO
formed
as
a
function
of
time
is
shown
in
Fig.
1.
It
is
clear
from
the
graph
that
the
concentrations
Of
both
HCHO
and
HCOOH
increase
with
time,
reaching
a
maximum
in
3
‐
4
h;
later
both
the
products
tend
to
dissociate,
resulting
in
a
decrease
in
their
concentrations.
The
reduction
in
the
concentration
of
HCHO
is
more
pronounced
than
that
of
HCOOH.
Therefore,
the
rates
of
formation
of
HCHO
and
HCOOH
were
evaluated
in
the
interval
between
1‐3
h,
which
ensured
a
linear
dependence.
The
decay
rate
of
HCHO
was
evaluated
in
the
declining
portion
of
the
curve
after
3.5h.
I 1
0 1 2 TIM:.(h) L 5 6
Fig. 1. The yields of HCOOH (0) and HCHO (A) in CO2 reduction by K[ Rum(ED
Fig
1.
The
yields
of
HCOOH
and
HCHO
in
CO2
reduction
by
K[RuIII(EDTA‐H)‐
C1]*2Hz0.
Cl].2H 2O
HCHO and HCOOH were evaluated in the interval between 1 - 3
Kinetics
ensured a linear dependence. The decay rate of HCHO’was evaluat
The
kinetic
experiments
on
CO2
reduction
were
conducted
by
declining portion of the curve after 3.5 h.
varying
the
concentrations
of
CO2
and
rates
of
formation
of
HCHO
and
HCOOH
were
evaluated.
Kinetics
Effect
of
complex
concentration
The kinetic experiments on CO* reduction were conducted by
the concentrations of COz, and rates of formation‐3
M
The
concentration
of
the
complex
1
was
varied
from
0.5
–
2
×10 of HCHO and
were evaluated.
with
a
constant
dissolved
CO 2
concentration
of
3.9
×
10
m
and
‐2
temperature
of
80
°C
for
all
the
runs.
The
dependence
of
rates
of
formation
of
HCHO
and
HCOOH
on
concentration
of
conplex1
are
Effect of complex concentration
shown
Fig.
2
and
3,
respectively.
Both
HCHO
and
HCOOH
rates
show
The concentration of complex 1 was varied from 0.5 - 2 X lop3
a
first
order
dependence
with
respect
to
complex
concentration.
a constant dissolved CO2 concentration of 3.9 X lo-* M and tempe
80 “CL! for all the 2
runs.
Effect
of
dissolved
CO The dependence of rates of formation of HC
concentration
HCOOH on the concentration of complex 1 are shown in Figs.
Figures
4
&
5
show
the
plot
of
rates
of
formation
of
HCHO
and
respectively. Both HCHO and HCOOH rates show a first order dep
HCOOH
vs.
dissolved
carbon
dioxide
concentration
the
experiments
with respect to complex 1 concentration.
were
performed
keeping
a
constant
complex
concentration
of
1
x
10‐
3
M
,
80
°C
and
varying
the
dissolved
CO
concentration
from
1.98
X
2
Effect of dissolved CO2 concentration
Figures 4 and 5 show the plot of rates of formation of HC
HCOOH vs. dissolved CO2 concentration. The experiments were pe
keeping a constant complex concentration of 1 X 10e3 M, 80 “C and
the dissolved CO2 concentration from 1.98 X lo-* M to 7.73 X
10‐2
M
to
7.73
X
10‐2
M.
The
rates
of
formation
of
both
HCHO
and
HCOOH
show
a
linear
dependence
of
CO2
concentration.
Temperature
The
temperature
of
the
experiments
for
reduction
of
CO2
by
complex
1
was
varied
between
40
‐
80
°C,
with
other
conditions
constant
such
as
Catalyst
concentration
of
1
X
10
‐3M
and
dissolved
CO2
concentration
of
3.9
X
10‐2
M.
Figure
6
shows
the
graph
of
‐‐In
rate
vs.
l/T.
From
the
slopes
of
both
the
straight
lines,
the
activation
energies
evaluated
for
HCOOH
and
HCHO
are
4.8
kcal
mol‐1
and
3.5
kcal
mol‐1
,
respectively
0 0.5 14 1.5
COMPLEX j_CONCENTRATiON,x103 M COMPLEX 1 CONCENTRATION, ~10~ M
Fig. 2. Effect of complex 1 con~entratj~n on the rate of HCHO formation.
3.9 X low2 M. Figure 6 shows the graph of --In rate us. l/T. From the slopes
of both the straight lines, the activation energies evaluated for HCOOH and
Fig. 4. Effect
HCHO are 4.8of kcal
dissolved CO2and
mol-* concentration on the, rate
3.5 kcd mol-' of HCHO formation.
respectively.
Mechanism
3.9 X low2 M. Figure 6 shows the graph of --In rate us. l/T. From the slopes
The the
of both reduction
straightoflines,
CO2 the
by activation
complex 1 energies
gave twoevaluated
products, for
namely HCHO
HCOOH and
and
HCHOHCOOH.
are 4.8The
kcalrates
mol-*of and
formation
3.5 kcd ofmol-'
both , the products have a first-order
respectively.
dependence with respect to catalyst and dissolved CO2 concentrations.
Mechanism
The reduction of CO2 by complex 1 gave two products, namely HCHO
Mechanism:
The
reduction
of
CO2
by
complex
1
gave
two
products,
namely
HCHO
and
HCOOH.
The
rates
of
formation
of
both
the
products
have
a
first‐
order
dependence
with
respect
to
catalyst
and
dissolved
CO2
concentrations.
Based
on
these
observations,
the
mechanism
proposed
for
the
reactions
is
shown
in
Scheme
1.
The
complex
1
undergoes
a
rapid
aquation
in
presence
of
water
to
give
Ru(III)
aquo
species
2
[19],
which
reacts
with
CO2
to
form
a
CO,
adduct
3.
The
formation
of
such
CO2
adducts
were
reported
in
the
literature
[3
–
5].
Species
3
activates
water
oxidatively
in
step
(2)
to
form
the
Ru(V)
species
4.
The
insertion
of
CO2
into
the
Ru‐H
bond
of
4
takes
place
in
step
(3)
to
form
an
η1‐formate
species
5.
The
metalloformate
complex
5
undergoes
a
rapid
intermolecular
proto‐
nation
resulting
in
the
formation
of
formic
acid
and
RuV‐oxo
species
6.
Reductive
elimination
of
metalloformate
complexes
to
formate
derivatives
such
as
methyl
formate
from
methanol,
CO2
and
H2
had
been
reported
[9].
The
electrons
needed
for
the
reduction
of
CO2
to
HCOO‐
in
our
case
are
obtained
by
the
hydride
insertion
step
(3).
The
formation
of
ruthenium
(V)
oxo
species
6
is
characterized
by
the
appearance
of
a
band
at
390
nm.
Species
6
also
gives
v(Ru=O)
at
810
cm‐‘.
In
step
(5),
the
formic
acid
formed
in
step
(3)
is
catalytically
decomposed
to
CO
and
Hz0
by
complex
2.
310
K
LRu**~(H~O) + co, s LRu”‘( COz) (1)
2 3
H
fast
LRu’“‘(C02) + Hz0 - L+v(Co,) (2)
OH
H
k 0
L&F&*) - LRuy_-+C” (3)
k--H ‘OR
!3H
5
fast
1
0
II
LRuV + HCOOH
6
/o kl H,
c -
c=O + Hz0 + LRuV (4)
LYv-cN
OH- H
OH H’
::
:
+I4 6
kz
HCOOH e CO + Hz0 (5)
LRur”(H20)
fast
1
0
II
LRuV + HCOOH
/o kl H,
c -
c=O + Hz0 + LRuV (4)
LYv-cN
OH- H
OH H’
::
:
+I4 6
kz
HCOOH e CO + Hz0 (5)
LRur”(H20)
k3
CO + H,O - COz + Hz (6)
111 I
2.8 2.9 3.0 3.1 3.2
' / T , 1O3 K