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Hydrogen Evolution
Hydrogen Evolution
Chapter 4A
4A.1 BACKGROUND
carries the energy originally stored in the primary source. In this context water
future. The main obstacle in the commercial exploitation of water electrolysis for
large scale hydrogen production is the high electricity consumption which makes
(HER) is of industrial interest and, therefore has attracted much research effort.
The development of novel materials with low overpotential towards HER has been
the subject area of many studies. A number of contributions have also touched
upon the kinetics and reaction mechanism for HER. The principal focus has been
*
Parts of this Chapter have been published in International Journal of Hydrogen Energy
33
where n is the stoichiometric number of electrons consumed in the electrode
the electrode-electrolyte interface. Due to this reason, their reaction rates are
M + e– ↔ M ¯ {4A.1}
At equilibrium, the rate of the forward reaction is just equal to the rate of the
current. In order to have an appreciable cathodic reaction the rate of the forward
reaction must be made appreciably higher than that of the reverse reaction. In
practical parlance this would be measured by the current density at the cathode.
For this to happen the actual applied potential at the cathode must be of a higher
magnitude (more negative) than that implied by the equilibrium potential. In fact,
34
The departure of the electrode potential from the equilibrium value upon
where,
electrode charge transfer, and other surface phenomena like adsorption, desorption
etc.
As mentioned above, at equilibrium, the net current is zero. But even when
the net current is zero at the equilibrium, we still envision balanced faradaic
density,
j0 = i0 / A (4A.6)
35
The exchange current can be viewed as a kind of idle current for charge exchange
only a small fraction of this bidirectional idle current, then only a small
overpotential will be required to extract it. The role of the slight overpotential is to
unbalance the rates in the two directions so that one of them predominates. Higher
the net current we require higher the additional activation energy we must supply.
Hence, higher the overpotential required. From this perspective, we see that the
exchange current is the measure of any system’s ability to deliver a net current
residues, produced in small pulp and paper mills, poses a disposal problem. Hence,
these mills consider this resource rich material as a liability. Being aqueous
2 H2O → 2 H2 + O2 {4A.2}
The exact reaction mechanism at the electrodes and the elementary reaction steps
36
feature of black liquor electrolysis was that negligible gaseous products are
produced at the anode. This could be verified through repeated experimental runs
setup schematically presented in Figure 3.1 to understand the basic facets of black
were used in these preliminary experiments. Laboratory pulping conditions and the
initial characteristics of the black liquor are reported in Table 4A.1 and Table
potassium hydroxide in distilled water replacing black liquor with all other
conducted with wheat straw black liquor 1. In Run 1 a new set of electrodes were
used. Solids deposited at anode were removed and the electrodes were then reused
in Run 2. Similarly, Run 3 and Run 4 were conducted with bagasse black liquor
and Run 5 and Run 6 were conducted on eucalyptus black liquor. Control
experiments Contl 1 and Contl 2 were carried out with 4 % w/w KOH and Contl 3
are shown in Table 4A.3. It can be seen that the energy stored as hydrogen from
black liquor electrolysis (at HHV) is in the range of 84% - 96% of the electrical
alkaline water electrolysis, Contl 2 and Contl 4 resulted in 49% and 66%,
37
Table 4A.1
Laboratory pulping conditions
Table 4A.2
Initial characteristics of black liquor
It may be mentioned here that modern water electrolyzers with advanced designs
and zero gap arrangement of electrodes are capable of storing 85% - 90% of
electrical energy as hydrogen (Kreuter and Hofmann, 1998; Gonzalez et al., 2004).
From this perspective these early results indicated that black liquor electrolysis
38
Table 4A.3
Results of preliminary electrolysis runs
39
is competitive with, and in some cases better than, water electrolysis in terms of
electrode potential required for electrolysis. As evident from Table 4A.3, hydrogen
density rapidly dropped and electrolysis ceased within a very short span of time
Table 4A.3) was then carried out with increased inter electrode potential. Control
experiments 3 and 4 were carried out with increased electrolyte concentration. But,
here also, no hydrogen production was observed at lower inter electrode potential
electrolysis vis a vis water electrolysis, it certainly provided the basis for future
research keeping in mind that inter electrode potential is directly linked with
was that negligible gaseous products are produced at the anode. This can give the
methods. First, since only one gaseous product, i.e. hydrogen, is produced during
40
the cathode and the anode to prevent the gases from mixing with each other, which
is the case in water electrolysis. This not only can simplify the electrolyzer design
but can also reduce the ohmic resistance which would otherwise have been there
Second, and more importantly, the alkali lignin separated at the anode is a
valuable product in itself. As shown in Table 4A.3, it has good calorific value to
be used as a fuel. Thus, when taken in conjunction with the hydrogen produced the
process can give more useful energy than the electrical energy spent in the process,
separated lignin can also be used in several important industrial applications thus
evolution reaction in black liquor electrolysis. Alkaline water electrolysis was also
studied as a reference system with control experiments carried with 0.1 M aqueous
the reaction steps (Rosalbino et al., 2003; Wu et al., 2004; Rosalbino et al., 2005;
41
M + H2O + e– ↔ MHads + OH¯ (Volmer reaction step) {4A.3}
with an equilibrium potential (Eeq) , of – 1.07 V vs. SCE (Kreysa and Hakansson,
1986; Rosalbino et al., 2005; Bard and Faulkner, 2006). When black liquor is
illustrated, the behaviour very closely fits the Tafel equation (Rosalbino et al.,
where,
j = current density
b = Tafel constant
η = overpotential
42
-500
Alkaline water
Eucalyptus
-450
Wheat straw
Bagasse
-400
-350
Overpotential (mV)
-300
-250
-200
-150
-100
-50
0.01 0.1 1 10 100
0
0.01 0.1 1 10 100
Log j (mA/cm2)
Figure 4A.1. Steady state polarization curves for hydrogen evolution reaction
in alkaline water electrolysis and black liquor electrolysis
It is evident from Figure 4A.1 that the electrode processes are similar in
alkaline water electrolysis and black liquor electrolysis. In the high overpotential
range (η between –150 to – 400 mV), the polarization plots are linear. The
cathodic Tafel slopes are –112.8 mV dec-1, –116.9 mV dec-1, 137.9 mV dec-1, and
–135.3 mV dec-1 for alkaline water, wheat straw black liquor, bagasse black liquor
and eucalyptus black liquor, respectively. These values are in agreement with
those obtained for the hydrogen evolution reaction in alkaline water by other
investigators (Rosalbino et al., 2005; Jafarian et al., 2007; Kaninski et al., 2007)
and indicate the Volmer reaction step to be the rate determining step (Wu et al.,
2004; Metikos et al., 2006; Azizi et al., 2007; Kaninski et al., 2007). The
43
corresponding values for the exchange current densities are 1.075 mA/cm2, 2.194
mA/cm2, 1.585 mA/cm2 and 9.856 mA/cm2, respectively. Since the exchange
current density is a measure of the kinetic facility of the electrode process (Bard
AJ, Faulkner, 2006), the results suggest facile electrode kinetics for hydrogen
electrolysis.
deviation from linearity with decreasing Tafel slopes. This indicates that the
2.5
Eucalyptus
Current density (mA/cm2)
1.5
1
Wheat straw
Bagasse
0.5
Alkaline water
44
At low overpotential, the bevaiour is better represented by linear j ― η plots
(Figure 4A.2). Significantly, this Figure reveals that alkaline water electrolysis
comparison, for black liquor electrolysis, these overpotentials are much lower,
being 17.9 mV for wheat straw black liquor, 13.9 mV for bagasse black liquor and
preliminary findings.
45
*
Chapter 4B
4B.1 BACKGROUND
and an anode. The complete cell reaction, thus, has two components, the cathodic
alkaline media, water is reduced to hydrogen and hydroxyl ions at the cathode as
represented in reaction {4A.6}. Actual half reaction taking place at the anode,
however, would depend on the composition of the electrolyte and the potential
employed. Thus in water electrolysis hydroxyl ions are oxidized to oxygen and
2 O → ׃O2 {4B.1b}
Overall,
cell would be
where,
*
Parts of this chapter have been published in International Journal of Hydrogen Energy
46
Eeq(cathode) = Equilibrium potential for cathodic half reaction
the forward and the backward reactions would be proceeding at the same rate with
applied for a given overall rate of electrolysis, therefore, would include other
where,
Eohmic = Potential drop due to resistance offered by various components of the cell
In equation (4B.2), the term, Eeq(anode), would depend on the anodic counter
reaction. It is clear that the half reaction at the anode and the equilibrium potential
associated with it, has a role to play in determining the required cell voltage. It
would, therefore, influence the energy dynamics of the process and mandates
investigation.
through a series of steps to different potentials with the recording of the current
time curves, to yield a three dimensional i-t-E surface. However, potential steps
that are very closely spaced are needed for well resolved i-E curves. Alternatively,
47
more information can be gained in a single experiment of Linear Sweep
Voltammetry, wherein the electrode potential is linearly varied with time and the i-
three dimensional i-t-E realms. For a single electrode reaction the observation is a
electrode reactions. Crucial insights about the electrode charge transfer process is
revealed by the analysis of the shape of the current-potential response, the peak
measurement cycles. Over many cycles, the waveform is a bipolar square wave
per cycle, at the end of each pulse. Consequently, the result of single square wave
voltammetry has several advantages. Among these are its excellent sensitivity and
48
4B.2 EARLY FINDINGS
electrolysis was that negligible gaseous products are produced at the anode.
Instead, alkali lignin was separated, and deposited as particulate solids, at the
reaction or other secondary reactions. If reaction {4B.1} is the half reaction taking
place at anode then the oxygen produced should be obtained as gaseous product
irrespective of the presence of black liquor solids. But this is not the case. One of
involving the organic constituents of black liquor. The atomic oxygen produced in
the reaction step {4B.1a} then has a competing reaction pathway in addition to the
Molecular oxygen produced as result of the reaction step {4B.1b} may also react
with black liquor organics albeit at a much slower rate as compared to reaction
{4B.3}. Atomic oxygen is well known for its very high reactivity owing to its two
unpaired electrons. At any point of time the amount of molecular oxygen produced
will depend on the relative rates of the reactions {4B.1b} and {4B.3}; higher the
rate of reaction {4B.3} compared to reaction {4B.1b} lower will be the amount of
There is another possibility which can account for the negligible gaseous
49
reaction pathway (Clayton et al., 1983) resulting in organic anions (Rojas and
Salager, 1994). Anions present in the black liquor are mainly lignin degradation
products resulting from the reaction of native lignin with alkali during alkaline
pulping (Clayton et al., 1983; Sjostrom, 1993; Vu et al., 2003). Therefore, in black
liquor, organic anions are also present besides OH¯ ions and the possibility of
From the results of Table 4A.3, it may be argued that the amount of alkali
lignin separated in different experimental runs, are not in the same mass ratio with
the amount of hydrogen produced. This can be due to two reasons. One, the alkali
different species of raw material as well as within the same raw material
the reaction conditions prevailing during pulping (Clayton et al., 1983). Thus, in
different samples of black liquor, the ionic fragments of alkali lignin will have
different charge to mass ratio. Since, from the Faraday’s law of electrolysis the
amount of any chemical species deposited for a given amount of electrical charge
passed during electrolysis is dependent on the charge to mass ratio of the ionic
species, the amount of alkali lignin separated for a given amount of hydrogen
The second reason might be the presence of OH¯ ions, though in small
total charge carried by the anions will be actually carried by OH¯ ions. Different
50
hydroxyl ion concentration in different black liquor samples, therefore, will carry
different proportions of the total charge carried by the anions. This will also alter
the amount of alkali lignin separated for a given amount of hydrogen produced for
liquor electrolysis were studied with standard electrochemical techniques and the
ELECTROLYSIS
reaction {4B.1}. This reaction has an equilibrium potential of 0.16 V vs. SCE
(Bard and Faulkner, 2006). The significance of this reaction is that for hydrogen
minimum value by the sum of cathodic and anodic overpotentials required to drive
(LSV) obtained for the anodic activity in alkaline water electrolysis as compared
to black liquor electrolysis. For all the electrolytes, noticeable OER could be
51
12
10 Eucalyptus
Current density (mA/cm2)
Wheat straw
Alkaline water
8 Bagasse
0
-1.5 -1 -0.5 0 0.5 1 1.5 2
E (V)
absence of any electroactive anion other than OH¯, OER is the only anodic
liquor electrolysis, wheat straw, bagasse, and eucalyptus, however, strong anodic
from the OER region. In soda black liquor extracted from laboratory pulping
experiments, the only inorganic anion present will be OH¯. The additional anodic
52
electroactivity in black liquor electrolysis, thus, arises from some of the organic
anions present in black liquor. Black liquors from the alkaline pulping of
consistent with the preliminary findings that organics are electrodeposited on the
examined using cyclic voltammetry (CV) and the results are shown in Figures
4B.2, 4B.3, and 4B.4 for wheat straw black liquor, bagasse black liquor, and
eucalyptus black liquor, respectively, using scan rates of 20 mV/s and 40 mV/s.
2.5
20 mV/s
Current density (mA/cm2)
40 mV/s
2
1.5
0.5
-0.5
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4
E (V)
53
3
2.5
20 mV/s
Current density (mA/cm2)
40 mV/s
2
1.5
0.5
-0.5
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4
E (V)
5
20 mV/s
Current density (mA/cm2)
40 mV/s
4
-1
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4
E (V)
of the potential scan, suggesting sluggish electron transfer kinetics (Bard and
Faulkner, 2006). For the wheat straw black liquor, the anodic peak shifted to –
15.1 mV from – 36.8 mV upon increase in the scan rate from 20 mV/s to 40 mV/s.
Similar shifts from – 56.7 mV to – 32.9 mV, for bagasse black liquor, and from –
77.7 mV to – 66.3 mV, for eucalyptus black liquor, was observed with the increase
in scan rate. This shift in the anodic peak towards more positive potentials upon
increase in the potential scan rate also supports totally irreversible charge transfer
(Nicholson and Shain, 1964; Bard and Faulkner, 2006). Using the relationship
Where,
Ep/2 = potential at which the current is half the peak value (mV)
the value of αn is found to be 0.528, 0.507, and 0.564 for wheat straw black liquor,
bagasse black liquor, and eucalyptus black liquor, respectively. For most of the
charge transfer processes, including organic moieties, the value of α is close to 0.5
(O’Dea et al., 1993; Codognoto et al., 2002). Since the value of n can only be a
positive integer, these results suggest a one electron oxidative charge transfer.
Figures 4B.5, 4B.6, and 4B.7 are the square wave voltammetry (SWV)
responses of black liquor electrolysis for wheat straw black liquor, bagasse black
55
250
200
Difference
Current density (μA/cm2)
Forward
Reverse
150
100
50
-50
-600 -400 -200 0 200 400 600
E (mV)
Figure 4B.5. Square wave voltammograms of anodic electroactivity in
electrolysis of wheat straw black liquor
250
200
difference
Current density (uA/cm2)
forward
reverse
150
100
50
-50
-600 -400 -200 0 200 400 600
E (mV)
25
Difference
Current density (μA/cm2)
Forward
20 Reverse
15
10
-5
-600 -400 -200 0 200 400 600
E (mV)
liquor, and eucalyptus black liquor, scanning a potential window from – 0.5 V to
0.5 V. The irreversibility of the oxidative electron transfer was again obvious from
the absence of cathodic peak in the reverse current voltammograms. From the
theory of square wave voltammetry (Nuwer, 1991; Fatouros and Krulic, 1998;
Miles and Compton, 2000) for such systems, involving one electron oxidative
charge transfer:
α = 1.66 RT/WF
where, W is the half width on the negative side of the difference current
voltammogram at mid height with respect to the peak potential. Accordingly, the
value of α was found to be 0.568, 0.519, and 0.508 for wheat straw black liquor,
57
bagasse black liquor, and eucalyptus black liquor, respectively. These values are in
close agreement with those obtained from cyclic voltammetry. Also, in the case of
bagasse, and eucalyptus black liquors, it is important to note that the square wave
voltammetry response consists of several minor current peaks, which suggest that
steps. Such splitting of the voltammetric response in square wave voltammetry for
organic moieties is not unusual, going by the inherently high sensitivity of the
technique (O'Dea et al., 1993; Mirceski et al., 1997; Diaz et al., 2000; Mirceski et
al., 2000).
irreversible electrode kinetics, the position of the current peak in square wave
voltammetry is shifted from the formal potential, E1/2. For oxidative charge
transfer, the peak potential, Ep, should be at a more positive potential than E1/2
(O'Dea et al., 1981). The magnitude of this shift, Ep – E1/2, varies almost linearly
with log (κτ1/2) (O'Dea et al., 1981). Here, κ is the kinetic parameter given by
κ = k0/DOα/2DR(1-α)/2
and τ is the period of the square wave voltammetry signal, for the general scheme
of reaction
R → O + e–
k0 is the standard rate constant and DO and DR are the diffusivities. In the absence
of the value of κ for the system under study, a precise determination of Ep – E1/2 is
not possible from the SWV peak positions. However, these values are expected to
58
be in the range of 100 – 300 mV (O'Dea et al., 1981). Thus, from Figures 4B.5,
4B.6, and 4B.7, it follows that E1/2 is between – 0.24 V to – 0.44 for the anodic
between – 0.31 V to – 0.51 V for bagasse black liquor, and – 0.27 V to – 0.47 V
0.6 V compared to 1.23 V for alkaline water electrolysis. This agrees with the
inter-electrode potential would exclude the OER. This is consistent with the
previous observation that no gaseous products are formed at the anode in black
physical barrier between the cathode and the anode to prevent the two gaseous
products from mixing with each other. Therefore, in black liquor electrolysis it
thereby lowering the ohmic losses. This in turn should result in further increase in
the energy efficiency of the process. One could argue that with the exclusion of
OER the process would only have a small anodic current density as apparent from
59
Figures 4B.1 to 4B.4. This would require larger electrode surface area for the same
production rate, thus additional fixed cost. This can be partly offset by improved
benefits of reduced energy consumption should far outweigh the added fixed costs
60
*
Chapter 4C
Lignin characterization
4C.1 BACKGROUND
as a fuel to meet the in-house energy demand. However, there is increasing trend
saving measures. Consequently, a part of the lignin may not be needed in-house
and could be sold. In small mills, without a chemical recovery system in place, any
lignin separated from black liquor should be a product in hand. The most apparent
feedstocks.
characteristics depend, not only on its biological origin, but also profoundly on its
and totally unaltered native lignin. Lignins are heterogeneous in relation to the
presence of functional groups and type of bonds between functional units. Once
separated from black liquor, with its characteristics known, lignin can possibly be
*
Part of this paper has been published in Industrial Crops and products. Another part is accepted
for publication in Thermochimica Acta.
61
put to industrial applications besides its traditional use as a biofuel. Presently, Acid
precipitation is the most common method to recover lignin from black liquor.
provide the analysis of the whole lignin structure and direct detection of lignin
moieties. In particular, the advent of NMR techniques has extended the prospect of
lignin structural analysis considerably. 13C NMR spectroscopy has been shown to
temperature in an inert atmosphere. Owing to its high carbon content, lignin can be
a good precursor material for preparing carbon products, like fibers and films.
Here also, different lignins would behave differently and thermochemical analysis
degradation.
black liquor samples as outlined in chapter 3. For these studies, soda black liquor
of wheat straw and bagasse were obtained from different mills while eucalyptus
62
chips were pulped in the laboratory. Initial characteristics of the black liquors are
Table 4C.1
Initial characteristics of black liquor
Figures 4C.1, 4C.2, and 4C.3 show the IR spectra of black liquor organics
separated by acidification of wheat straw black liquor, bagasse black liquor, and
eucalyptus black liquor. These contain most of the characteristic absorption bands
of such organics and assigned accordingly (Thring et al. 1991; Sun et al. 2000; Sun
and Tomkinson 2002; Angles et al. 2003). Prominent among these are 3437 cm-1
(wheat straw), 3397 cm-1 (bagasse), and 3393 cm-1 (eucalyptus), assigned to O–H
stretching of hydroxyl, 2928 cm-1 (wheat straw), 2931 cm-1 (bagasse), and 2934
1637 cm-1, 1604 cm-1, 1516 cm-1 (wheat straw), 1600 cm-1, 1509 cm-1 (bagasse),
1598 cm-1, 1509 cm-1 (eucalyptus), assigned to aromatic skeletal vibrations, 1454
cm-1 (wheat straw), 1458 cm-1 (bagasse), 1459 cm-1 (eucalyptus), assigned to C –
H deformations and aromatic ring vibrations, 1440 cm-1 (wheat straw), 1417 cm-1
63
Figure 4C.1. FTIR spectrum of acid precipitated lignin from wheat straw black liquor
64
Figure 4C.2. FTIR spectrum of acid precipitated lignin from bagasse black liquor
65
Figure 4C.3. FTIR spectrum of acid precipitated lignin from eucalyptus black liquor
66
cm-1 (wheat straw), 1339 cm-1 (eucalyptus), assigned to syringyl ring breathing with CO stretching,
1284 cm-1 (wheat straw), 1278 cm-1 (bagasse), 1266 cm-1 (eucalyptus), assigned to guaiacyl ring
breathing with C–O stretching, and 1039 cm-1 (wheat straw, and eucalyptus), 1022 cm-1 (bagasse),
assigned to aromatic C–H guaiacyl type and C–H deformation of primary alcohol. Acid precipitated
lignin from bagasse had a unique band at 1703 cm-1 (assigned to unconjugated carboxyl–carbonyl
stretching) which is absent in other lignin formulations. Besides these there are few other bands
which could be assigned as under. 1201 cm-1 (wheat straw), 1216 cm-1 (bagasse) and 1221 cm-1
(eucalyptus) assigned to C–C, C–O, and C=O stretching (Scholze and Meier, 2001; Zhao and Liu,
2010). 1070 cm-1 (wheat straw) from C3̶ OH valence vibration (Fackler et.al., 2010; Yang et.al.,
2010). 1119 cm-1 (bagasse and eucalyptus) assigned to C−O stretching and symmetric stretching of
C–O–C (Zhao and Liu, 2010). 949 cm-1 (bagasse) arising from C–H deformation in degraded
carbohydrates (Yang et.al., 2010). 829 cm-1 (bagasse) and 833 cm-1 (eucalyptus) from C–H out of
plane deformation in position 2,5,6 of guaiacol (Scholze and Meier, 2001; Fackler et.al., 2010).
Bands between 586-726 in different samples could be generally assigned to lateral C–C bond and the
648 cm-1 band in eucalyptus probably arises from carboxylic groups (Liu et.al., 2008).
In contrast, if we look at the IR spectra of solids deposited on the anode during electrolysis
(Figure 4C.4 for wheat straw, 4C.5 for bagasse, and 4C.6 for eucalyptus), it is obvious that these
spectra are similar to that of Figures 4C.1 to 4C.3 in the high frequency region (4000 – 2200 cm-1)
showing characteristic absorption of O–H stretching of hydroxyl (3450 cm-1 for wheat straw, 3406
cm-1 for bagasse, 3393 cm-1 for eucalyptus), and C–H stretching of methyl and methylene groups
(2924 cm-1 for wheat straw, 2933 cm-1 for bagasse, 2930 cm-1 for eucalyptus). However, the
In wheat straw the frequencies 1637 cm-1, 1510 cm-1 (assigned to aromatic skeletal
67
Figure 4C.4. FTIR spectrum of electrodeposited lignin from wheat straw black liquor
68
Figure 4C.5. FTIR spectrum of electrodeposited lignin from bagasse black liquor
69
Figure 4C.6. FTIR spectrum of electrodeposited lignin from eucalyptus black liquor
70
vibrations) are also similar. However, the similarity ends here and the spectrum of
Figure 4C.4 is markedly different from that of Figure 4C.1 in the intermediate and
low frequency regions. Notable differences are as follows: The frequencies 1612
cm-1 and 1604 cm-1 (aromatic skeletal vibrations) are absent. In Figure 4C.4 the
frequencies 1423 cm-1, and 1222 cm-1 can be assigned to aromatic skeletal
Figure 4C.5 (bagasse) the important frequencies similar to Figure 4C.2 are 1604
cm-1, 1512 cm-1 (assigned to aromatic skeletal vibrations), 1458 cm-1 (assigned to
ring breathing with C–O stretching), and the presence of frequency 1325 cm-1
important similarities with Figure 4C.3 are the absorption bands 1602 cm-1, 1511
cm-1 (aromatic skeletal vibrations), 1458 cm-1 (CH deformations and aromatic ring
stretching), and 1266 cm-1 (guaiacyl ring breathing with C–O stretching). Rather
the band assigned to syringyl ring breathing with CO stretching is shifted to 1322
71
In all the FTIR spectra, detailed interpretation of the bands between 1400
and 1000 cm-1 is difficult since the variations in different modes couple and
therefore make the contribution to the different absorption bands more complex.
electrodeposited solids are chemically different from the acid precipitated solids,
especially in their aromatic part. Also, for wheat straw and bagasse the inter and/or
peaks, has long been applied to estimate the different structural features in lignin
formulations (Goncalves et al. 2000; Guerra et al., 2004). The 1H-NMR spectra of
wheat straw lignin, bagasse lignin, and eucalyptus lignin are shown in Figures
4C.7, 4C.8, and 4C.9 (acid precipitated lignin) and Figures 4C.10, 4C.11, and
1999; Goncalves et al. 2000; Guerra et al., 2004; Hiltunen et al. 2006). This
1
enables us to compare the H NMR spectrum of organics separated by
of the samples (Table 4C.3), these are assigned empirical formulae as presented in
Table 4C.4.
72
Table 4C.2
1
H NMR signal integrations and assignments
Table 4C.3
Elemental analysis of lignin samples
73
Figure 4C.7. 1H NMR spectrum of acid precipitated lignin from wheat straw black liquor
74
Figure 4C.8. 1H NMR spectrum of acid precipitated lignin from bagasse black liquor
75
Figure 4C.9. 1H NMR spectrum of acid precipitated lignin from eucalyptus black liquor
76
Figure 4C.10. 1H NMR spectrum of electrodeposited lignin from wheat straw black liquor
77
Figure 4C.11. 1H NMR spectrum of electrodeposited lignin from bagasse black liquor
78
Figure 4C.12. 1H NMR spectrum of electrodeposited lignin from eucalyptus black liquor
79
Table 4C.4 (A)
Formula for Electrodeposited Lignin samples
80
Subsequently, the customary C9 lignin formulae are worked out (Table 4C.4)
taking into account the total signal integrations for all protons, and those
4C.2, an area of 81.03 arbitrary units corresponds to 6.73 hydrogen atoms in the
empirical formula. The area representing methoxyl group is 2.42 units which
would be equivalent to 0.2 hydrogen atoms in the empirical formula. Since, in the
methoxyl group, every carbon atom is associated with three hydrogen atoms, 0.2
From Table 4C.4, it can be seen that electrodeposited lignin has lesser
the acid precipitated lignin has 38 methoxyl groups per 100 phenylpropane units
whereas this number is only 12 for electrodeposited lignin. In bagasse, the acid
eucalyptus.
also reveals that EDL has larger proportion of aromatic protons compared to APL.
This indicates lesser extent of substituent groups and linkages through the aromatic
ring for EDL. Signal integrations between δ 4.5 – 5.2 ppm and δ 0.0 – 1.6 ppm
81
represent the βH (hydrogen attached to the β carbon), and hydrogen in non-
electrodeposited lignin, from all black liquors, has higher carbon to hydrogen ratio
the solids shown in Figures 4C.13, 4C.14, and 4C.15 (for acid precipitated solids)
13
and Figures 4C.16, 4C.17, and 4C.18 (electrodeposited lignin). In C NMR
spectra of lignins the signals in the region from 100 to 155 ppm originate from
aromatic carbons (Kuo et al., 1991; Landucci et al., 1998; Goncalves et al., 2000;
Sun and Tomkinson, 2002; Jaaskelainen et al., 2003; Wu and Argyropoulos, 2003;
Capanema et al., 2004; Pu and Ragauskas, 2005; Hiltunen et al., 2006). Of these,
the region 129 – 155 ppm represents quaternary carbons (Landucci et al., 1998;
152.14, δ 147.49, δ 115.50, δ 115.22, δ 115.04 and δ 101.84 ppm (wheat straw), δ
aromatic signals in acid precipitated solids (Signals at δ 152 and δ 147 ppm) could
82
Figure 4C.13. 13C NMR spectrum of acid precipitated lignin from wheat straw black liquor
83
Figure 4C.14. 13C NMR spectrum of acid precipitated lignin from bagasse black liquor
84
Figure 4C.15. 13C NMR spectrum of acid precipitated lignin from eucalyptus black liquor
85
Figure 4C.16. 13C NMR spectrum of electrodeposited lignin from wheat straw black liquor
86
Figure 4C.17. 13C NMR spectrum of electrodeposited lignin from bagasse black liquor
87
Figure 4C.18. 13C NMR spectrum of electrodeposited lignin from eucalyptus black liquor
88
be assigned to condensed and etherified substructures of syringyl and guaiacyl moieties
(Landucci et al., 1998; Capanema et al., 2004; Pu and Ragauskas, 2005). Signals at 115
and 101 ppm arise from various protonated aromatic carbons (Capanema et al., 2004; Pu
and 4C.18) do not show the presence of any quaternary aromatic carbon by total absence
of signals between δ 129 to δ 155 ppm. This is rather interesting and totally
with the well known C6C3 backbone of lignins and could not be explained.
In the aliphatic part of the spectra the signals at δ 75 – 72 ppm are similar in acid
precipitated lignins and electrodeposited lignins and so are the signals at δ 56 ppm. δ 75
the side chain (Landucci et al., 1998; Capanema et al., 2004; Pu and Ragauskas, 2005). δ
56 ppm signal arises from methoxyl group carbon, a common feature of lignin
ppm, assigned to Cγ̶ OH (Gil and Pascoal, 1999) in acid precipitated lignin.
The thermal transformations of wheat straw lignin, bagasse lignin, and eucalyptus
lignin are shown in Figures 4C.19, 4C.20, and 4C.21, respectively. For all the black
89
10
Wheat straw EDL
0 Wheat straw APL
139 mJ/mg -128 mJ/mg
-10
70 Cel
-20 390 Cel
DTA (uV)
69 Cel
145 mJ/mg
-30
-40
-50
-60
-70
0 100 200 300 400 500 600 700 800
Temperature (oC)
Figure 4C.19. DTA results of lignins from wheat straw black liquor
10
Bagasse EDL
392 Cel
0 Bagasse APL
210 mJ/mg
-10 75 Cel
-20 75 Cel
DTA (uV)
-50
-60
-70
0 100 200 300 400 500 600 700 800
Temperature (oC)
90
10
390 Cel
Eucalyptus EDL
0 Eucalyptus APL
156 mJ/mg -140 mJ/mg
-10
166 mJ/mg
-20 70 Cel
DTA (uV)
70 Cel
-30
-40
-50
-60
-70
0 100 200 300 400 500 600 700 800
Temp. (oC)
respectively, for wheat straw, bagasse, and eucalyptus. This is due to the presence of
adsorbed water and confirms to the results previously reported in literature (Pucciariello
et.al., 2004). The associated enthalpy changes were 139 mJ/mg, 210 mJ/mg, and 156
mJ/mg, respectively. For wheat straw solids the transformation occurred between 29 0C
and 145 0C, for bagasse solids this spanned from 33 0C to 158 0C, and for eucalyptus it
ranged from 32 0C to 152 0C. In addition, the EDL from bagasse black liquor exhibited
two more endothermic transformations involving modest enthalpy changes of 12.8 and
12.1 mJ/mg. The first transformation was centered at 249 0C spanning from 215 0C to 282
0
C. The second one occurred between 320 0C and 367 0C with the peak at 344 0C.
91
In comparison, the acid precipitated lignins, from all the black liquors, had similar
initial endothermic transformations. For wheat straw (Fig. 4C.19) it occurred between 32
0
C and 149 0C, peaking at 69 0C, with an enthalpy change of 145 mJ/mg. For bagasse
(Fig. 4C.20), the transformation was observed between 36 0C and 160 0C with the peak at
75 0C and enthalpy change of 169 mJ/mg. In eucalyptus, this transformation was noticed
mJ/mg. However, upon further heating all the acid precipitated lignin samples exhibited a
electrodeposited lignin. For wheat straw this exothermic transformation, evolving 128
mJ/mg of energy, took place in the temperature range of 319 0C to 443 0C with the
maximum at 390 0C. The similar transformation for bagasse evolved 196 mJ/mg of
energy in the temperature range of 321 0C to 447 0C with the maximum at 392 0C. And
for eucalyptus the exothermic transformation occurred between 315 0C and 452 0C with
0
an expulsion of 140 mJ/mg heat; the peak being at 390 C. Such exothermic
available kraft lignin (Khezami et al., 2005) and lignin precipitated from black liquor
Figures 4C.22, 4C.23, and 4C.24 present the TGA thermograms of wheat straw
92
120
Wheat straw EDL
Wheat straw APL
100
80
TGA (%)
60
40
20
0
0 100 200 300 400 500 600 700 800
Temperature (oC)
Figure 4C.22. TGA results of lignins from wheat straw black liquor
120
Bagasse EDL
Bagasse APL
100
80
TGA (%)
60
40
20
0
0 100 200 300 400 500 600 700 800
Temperature (oC)
93
120
Eucalyptus EDL
100 Eucalyotus APL
80
TGA (%)
60
40
20
0
0 100 200 300 400 500 600 700 800
Temp. (oC)
300
Wheat straw EDL
357 Cel
271.7 ug/min Wheat straw APL
250
357 Cel
200 227.2 ug/min
DTG (ug/min)
63 Cel
133.3 ug/min
150
67 Cel
125.2
100
50
0
0 100 200 300 400 500 600 700 800
Temperature (oC)
Figure 4C.25. DTG results of lignins from wheat straw black liquor
94
350
320 Cel Bagasse EDL
329.2 ug/min
300
Bagasse APL
361 Cel
286.1 ug/min
250
DTG (ug/min)
200 70 Cel
152.4 ug/min
70 Cel
150
147.9 ug/min
100
50
0
0 100 200 300 400 500 600 700 800
Temperature (oC)
300
377 Cel Eucalyptus EDL
281.9 ug/min
Eucalyptus APL
250
357 Cel
72 Cel 238.8 ug/min
200 164 ug/min
DTG (ug/min)
150 73 Cel
126.2 ug/min
100
50
0
0 100 200 300 400 500 600 700 800
Temp. (oC)
95
The rates of thermal degradation are presented in Figures 4C.25, 4C.26, and 4C.27. TGA
results for the electrodeposited lignin samples show two distinct phases of weight loss.
Initially, upon heating, the electrodeposited lignin from wheat straw black liquor
underwent a weight loss of 8.65% with a maximum rate of 125.2 μg/min. at 67 0C. As can
be seen, this initial loss in weight coincided with the endothermic peak of the DTA
results, and was due to the expulsion of residual amount of moisture. Such moisture loss
upon heating is normal in the case of lignins obtained from black liquor (Fierro et al.,
2005) as also for other types of lignins (Pucciariello et.al., 2004). Similar results were
observed for bagasse where the initial heating resulted in 9.02% weight loss with a
maximum rate of 152.4 μg/min. at 70 0C. And for eucalyptus, this initial weight loss was
7.57%; maximum rate of 164 μg/min weight loss occurring at 72 0C .Upon further
heating, the wheat straw electrodeposited lignin had a profound thermal degradation
between 250 0C to 450 0C accounting for 27.7% weight loss. The rate of this degradation
peaked at 357 0C with the maximum rate being 227.2 μg/min. Beyond 450 0C the material
continued to degrade at a much slower rate leaving a char residue of 47% at 800 0C.
Similar behavior was observed for bagasse where the prominent thermal degradation
between 250 0C to 450 0C accounted for 30.7% weight loss. The peak thermal
degradation rate of 329.2 μg/min. occurred at 320 0C. Gradual thermal degradation
continued above 450 0C and a char residue of 46.5% was obtained at 800 0C. In the case
of eucalyptus, again a profound degradative weight loss of 25.6% was noticed between
245 0C and 450 0C. Here, the maximum rate of thermal degradation was 281.9 μg/min.,
which was observed at 377 0C. Beyond this temperature the material continued to thermo-
degrade at a slower rate and a final char residue of 49% was left. For all the
96
electrodeposited lignins, the notable feature of the high temperature degradation was its
Two distinct phases of weight loss upon heating is also evident for the acid
precipitated lignin. For wheat straw the initial expulsion of residual moisture, coinciding
with the DTA endothermic peak, accounted for 7.21% weight loss with a maximum rate
7.59% weight loss and a maximum dehydration rate of 147.9 μg/min. at 70 0C. In
eucalyptus the initial weight loss was 7.49%. The maximum dehydration rate was 126.2
μg/min. at 73 0C. Upon further heating all the acid precipitated lignin samples underwent
thermal decomposition. For wheat straw, appreciable weight loss of 26.53% was noticed
between 300 0C and 450 0C with a maximum decomposition rate of 271.7 μg/min. at 357
0
C. For bagasse, similar fast decomposition, accounting for 25.75% weight loss, took
place in the temperature span of 300 0C to 450 0C. Decomposition rate peaked to 286.1
μg/min. at 361 0C. In eucalyptus there was a steep weight loss of 23.85% in the
temperature range of 310 0C to 440 0C. A maximum rate of weight loss of 238.8 μg/min.
was observed at 357 0C. However, in comparison to electrodeposited lignins, the high
exothermic phenomenon as indicated in the DTA thermograms. For these solids gradual
thermal degradation continued as they were heated past 440 – 450 0C leaving a char
residue of 43%, 44%, and 45%, respectively, for wheat straw, bagasse, and eucalyptus.
Acid precipitated lignins from black liquor are reported to yield 40 – 50 % char upon
similar thermal degradation (Tejado et al., 2007). Higher char residues obtained for
electrodeposited lignins are consistent with their higher carbon content (Table 4C.3). This
97
could also arise from the structural differences between electrodeposited lignins and acid
condensed aromatic structures leading to char residues (El-Saied and Nada, 1993; Tejado
et al., 2007).
98
*
Chapter 4D
4D.1 BACKGROUND
It has been spelled out in Chapters 1 and 2 that disposal of the black liquor
generated poses an existential dilemma for the small pulp and paper mills on account of
environmental concern. This is mainly due to the enormous pollution load carried by the
untreated black liquor. Organics present in the black liquor exert a very high oxygen
demand on the receiving water bodies. Most of these organics are of bio-recalcitrant and
bio-inhibitory nature manifested by a high COD. Also, they are a potential source of
carbon neutral energy. Besides these the black liquor contains inorganic constituents
which are of economic value to the mill. To be viable, any potential black liquor
Lignin is the main constituent of black liquor organics and the main contributor
towards its high oxygen demand. Chapters 4A, 4B, and 4C, have established that lignin is
separated from black liquor during its electrolysis. Its removal from black liquor,
therefore, should reduce the pollution load and make it more amenable to disposal.
examined, however, if the treated liquor left after electrolysis is suitable for disposal.
Further, a detailed estimation of the material and energy balances involved in the process
*
Part of this chapter is published in Tappi Journal.
99
4D.2 LOW POTENTIAL ELECTROLYSIS
shown in Figure 3.2 and as per the procedure detailed in Chapter 3. The initial
Table 4D.1
Initial characteristics of black liquors
al., 2003)
proceeds with an equilibrium potential (Eeq) of – 1.07 V vs. Saturated Calomel Electrode.
et al., 2007)
takes place at an Eeq of 0.16 V vs. Saturated Calomel Electrode. In practice, however,
of 200 mV. In comparison organic anions in black liquor could be electrolyzed at the
100
anode at much lower potential as discussed in Chapter 4B. As a result, in low potential
black liquor electrolysis organics are electrodeposited at the anode with negligible
oxygen evolution.
interelectrode potential was applied. The characteristics of electrolyzed black liquor are
shown in Table 4D.2. The electrolyzed black liquor had a reduced proportion of organic
solids and less COD compared to untreated black liquor. After prolonged electrolysis for
72 hours the COD of a 25 ml sample could be reduced by 13.8%, 13.4%, and 9.3%, for
wheat straw, bagasse and eucalyptus black liquors, respectively. Though, this COD
reduction is not sufficient to make it suitable for discharge into receiving water bodies,
the partial removal of organics could be helpful in situations where the combustion
capacity of the recovery boiler is the limiting factor. Further, for the three black liquors,
every gram of COD reduced was accompanied by the production of 178, 196, and 251 ml
of hydrogen and 0.55, 0.56, and 0.61 grams of lignin with the electrical energy
consumption of 1983, 2185, and 2809 joules, respectively. The hydrogen produced was
free from carbon dioxide as no change in the concentration of bubbling KOH solution
was observed.
101
Table 4D.2
Results of low potential electrolysis
102
respectively, were achieved for the three black liquors. Thus, besides the initial
COD of the black liquor, the percentage COD reduction depended on the
parameter, COD loading per unit electrode surface. Modern industrial electrolyzers
with their compact designs and closely spaced electrodes (Kreuter and Hofmann,
1998; Ulleberg, 2003) are likely to achieve a very low value for this parameter and
black liquor the parameter COD reduced per unit electrode area remained almost
The process is energetically attractive. For the wheat straw black liquor the
energy equivalent of hydrogen produced at the Lower Heating Value (LHV) is 401
J which is 96.2 % of the electrical energy consumed in the process. These values
are 95.8%, and 95.5%, respectively, for bagasse black liquor and eucalyptus black
liquor. These results are consistent with the earlier findings for low potential black
(Kasseris et al., 2007; van Ruijven et al., 2007). This amounts to an overall energy
thermal energy (USDOE, 2002). For small mills, selling the hydrogen as an eco-
103
runs were performed. The results are shown in Figure 4D.1. Here, it is important to
note that the rate of COD reduction decreases with time and reaches a plateau
region after nearly 28 hours. As discussed in Chapters 4A and 4B, in low potential
black liquor electrolysis, electroactive organic anions are responsible for the
electroactive organic anions goes on reducing which reflects in the falling rate of
COD reduction.
40
25 Bagasse (low
COD loading)
20
Bagasse (high
COD loading)
15
Eucalyptus (low
10 COD loading)
Eucalyptus (high
5 COD loading)
0
0 20 40 60 80
Time (h)
Figure 4D.1. COD reduction with varying extent of low potential electrolysis
104
4D.3 ELECTROLYSIS AT HIGHER POTENTIAL
reactive nascent oxygen. Following were the distinct observations in high potential
oxidation of the organics present in the black liquor; thus giving complete
COD removal.
At the end an aqueous solution with some precipitated solids was obtained.
up into arrays of any capacity (Ulleberg, 2003; Dale et. Al., 2008; Deshmukh and
Boehm, 2008). This opens up the possibility for small scale operation.
105
Table 4D.3
Results of high potential electrolysis
Black liquor Electrical Sodium Hydrogen Carbon Lignin Silica separated Time of
type energy spent (J) carbonate produced (ml) dioxide separated (mg) electrolysis
recovered (mg) produced (mg) (h)
(mg)
Interelectrode Wheat straw 26914 (10790)a 780 (314) 2082 (838) 1505 (603) 28 70 114 (45)
potential 1.5 Bagasse 27848 856 2144 1560 26 29 122
V Eucalyptus 34768 1100 2666 2045 23 negligible 127
Interelectrode Wheat straw 56246 (22597) 782 (314) 2090 (842) 1509 (605) 25 71 62 (25)
potential 3 V Bagasse 58884 858 2140 1557 27 30 66
Eucalyptus 72890 1098 2660 2041 25 negligible 68
Interelectrode Wheat straw 112118 778 (315) 2087 (840) 1509 (606) 26 69 34 (14)
potential 6 V (39915)
Bagasse 117445 855 2138 1558 27 29 37
Eucalyptus 146293 1100 2664 2040 25 negligible 40
Interelectrode Wheat straw 225051 784 (318) 2085 (840) 1503 (600) 29 72 19 (8)
potential 12 (89739)
V Bagasse 234245 856 2132 1552 30 29 20
Eucalyptus 292297 1096 2672 2048 22 negligible 22
a
All values in brackets indicate electrolysis results for 10 ml black liquor samples diluted to 25 ml.
106
The quantitative results of high potential black liquor electrolysis are shown in
Table 4D.3. Here, 1363, 1366, and 1380 ml of hydrogen was produced,
respectively, for the three black liquors, for every gram of COD reduced. Whereas,
the lignin separated per gram of COD reduced was only 18, 17, and 12 mg,
mainly responsible for the COD reduction in this case. The generation of nascent
oxygen could provide oxidizing conditions strong enough for the complete
oxidation of the organics present in the black liquor with the main chemical
reactions being:
This explains the recovery of inorganics, present in the black liquor, as aqueous
KOH. This amounted to 0.98, 0.99, and 1.06 gram, respectively, of carbon dioxide
produced for every gram of COD reduced in this case. In addition, 68 % of the
silica present in the wheat straw black liquor precipitated out from the solution,
and was obtained as solids. For the bagasse black liquor 50 % of the silica initially
electrical energy required for the process and time required for the completion of
the process. For the wheat straw black liquor it took 17614 J of electrical energy
107
for the removal of one gram of COD at interelectrode potential of 1.5 V. It
interelectrode potential. At the same time, the time required for complete COD
removal decreased from 114 hours to 19 hours. Similar changes were observed for
the other two black liquors. The other way of reducing the time requirement
consumption, was to decrease the ratio, COD loading per unit electrode surface.
Thus, for the selected electrolysis experiments using 10 ml black liquor diluted to
25 ml, the time requirement reduced for the similar electrical energy consumption
Table 4D.4. Electrical energy is spent in the process. Of this energy, the energy
stored as hydrogen, and the energy in the form of separated lignin is directly
interelectrode potential could remove COD at a faster rate only at the expense of
useful electrical energy through fuel cells (Kasseris et al., 2007; van Ruijven et al.,
108
As the organics present in the black liquor are oxidized, the exothermic
reactions involved would release energy in the form of heat. In the bench scale
Table 4D.4
Energy balance in high potential electrolysis
recoverable. One gram of COD removed would release about 14.5 kJ of thermal
energy. The extent to which this energy can be put to productive use would depend
upon the process and equipment design. This can have significant bearing on the
Table 4D.5 presents simulated results for a model agricultural residue pulp
mill for possible black liquor treatment through electrolysis. It envisages two
109
scenarios; one wherein the hydrogen produced is utilized for captive CHP
generation. A pulp mill with 50 t/day pulp production is likely to produce 56.5
tonnes sodium carbonate and 2 tonnes lignin every day for electricity consumption
of 273081 kWh. In addition, process heat to the tune of 538.5 – 834.5 GJ should
be available daily. In the second scenario, the hydrogen produced is sold as a value
added product. Here, in addition to the daily production of sodium carbonate and
lignin, 13.5 tonnes of hydrogen should be available for sale at the expense of
542500 kWh of electricity. Process heat available should be 296 – 592 GJ.
Table 4D.5
Simulated results for a model agro residue pulp mill for one day operation
Parameters Values
Unbleached pulp production 50 tonnes
Black liquor generated 1750 m3
Total COD load 108.5 tonnes (at 62 g/l)
Total electrical energy required 542500 kWh (@ 18000 J/g COD
removed)
Energy equivalent of hydrogen 1616.5 GJ
generated
Electricity that could be produced from 269419 kWh (@ 60 % efficiency)
hydrogen
Process heat that could be available 242.5 GJ (@ 15 % efficiency)
from CHP generation
Net electrical energy required 273081 kWh
Hydrogen produced (mills can opt for 13.5 tonnes
selling the produced hydrogen instead
of captive power generation)
Sodium carbonate produced 56.5 tonnes
Lignin produced 2 tonnes
Process heat that could be available 296 GJ (at 20 % heat recovery)
from oxidation of organics 444 GJ (at 30 % heat recovery)
592 GJ (at 40 % heat recovery)
110
4D.4 IMPACT ON AIR ENVIRONMENT
emission of greenhouse gases (GHG) and other air pollutants owing to the use of
fossil fuels in internal combustion engines (Gonzalez et al., 2004; Rosa et al.,
policymakers (Salgado and Martinez, 2004). When used in fuel cell vehicles the
2007)
Where
LHVhyd = lower heating value of hydrogen, 120 MJ/kg (Greiner et al., 2007)
LHVgas = lower heating value of gasoline, 32.7 MJ/l (Hetland and Mulder, 2007)
Today’s internal combustion engine driven gasoline fuelled vehicles have about
by the year 2010 (GM, 2002; Hetland and Mulder, 2007). Compared to this,
current hydrogen powered fuel cell driven vehicles are reported to have 36%
efficiency which is likely to improve to 44% by 2010 (Hetland and Mulder, 2007).
Some estimates even put the efficiency of fuel cell vehicles at as high as 50 – 60%
111
(Suppes et al., 2004; van Ruijven et al., 2007). With 36% efficiency of fuel cell
replace between 6.95 to 7.14 liters of gasoline. This figure is expected to be 8.28
liters in year 2010. With an emission factor of 72 kg CO2 per GJ for gasoline
(Damen et al., 2007), a kg of hydrogen replacing gasoline will save the emission of
nearly 16.5 to 17 kg of CO2. This can increase to 19.5 kg CO2 emission saved if
harmful air pollutants like NOx and SOx will be curbed with hydrogen powered
liquor electrolysis will co-produce 110 to 146 tonnes of hydrogen in a year with
transport. If the electricity required for the electrolysis could be sourced from a
carbon neutral source (e.g. wind, solar, etc.), this amounts to 1807 to 2847 tonnes
of additional CO2 emission saved annually besides curbed emission of SOx and
NOx. This will significantly improve the environmental acceptability of the mill
annually (Table 4D.5, assuming 330 working days in a year). If the mill opts for
the sale of hydrogen to the transport sector, this could amount to potential
112
emission curbed annually, when the electricity required for the electrolysis could
113
*
Chapter 4E
Economic evaluation
4E.1 BACKGROUND
black liquor electrolysis and established its technical viability as a treatment option
for non sulfur black liquor. Its environmental benefits have also been brought into
focus. Businesses, however, are run for earning profits. For this reason, for a
et al., 2005) is used. To determine the present worth of any sum X from the n th
Where
Xp = present worth of X
i = rate of inflation
r = discount rate
At payback period, N,
Present worth of total earning = AE [1 – {(1 + i)/(1 + r)}N] / [1 – {(1 + i)/(1 + r)}]
+ Sp (4E.3)
*
Part of this chapter is published in Tappi Journal.
114
Present worth of total cost = I + AC [1 – {(1 + i)/(1 + r)}N] / [1 – {(1 + i)/(1 + r)}]
(4E.4)
Where
AE = Annual earning
I = Capital investment
AC = Annual cost
For low potential black liquor electrolysis annual earning will include
proceeds from selling hydrogen and lignin. For high potential black liquor
electrolysis annual earning will include proceeds from selling hydrogen and lignin,
and the economic value of sodium hydroxide that would be available to the mill by
causticizing the sodium carbonate produced during electrolysis. In both the cases,
black liquor electrolysis will require capital investment on the electrolyzer and
hydrogen storage. Electrolyzer will also need annual cost of operation and
maintenance. Annual cost would include the cost of electricity, in both the cases.
also involve annual cost. The key economic parameters and their range of values
discount rate of 6% is taken for the economic evaluation. Currency exchange rate
115
Table 4E.1
Key economic parameters
Using equations, (4E.2), (4E.3), and (4E.4), the payback period for low
116
Where
For low potential black liquor electrolysis the best economic scenario
pertains to an electrolyzer capital cost of Rs. 28000 per kW (€ 400 per kW). As
vehicular transport. Higher the prevailing gasoline price higher should be the
hydrogen selling price and the revenue earned on account of it. Lower the
electricity price, better it would be economically for the electrolysis process. With
these considerations, in the best case scenario, low potential black liquor
electrolysis should have a payback period of 0.6 years. This value is 4.2 years in
Keeping all other parameters constant, except the capital cost of the
117
Economics of low potential black liquor electrolysis will depend upon the capital
3.5
The payback period increases almost linearly with increase in the capital costs; the
Rs./kW (400 €/kW) to 91000 Rs./kW (1300 €/kW). There is, however, a fair bit of
production has not yet reached wide commercialization level. There is currently a
electrolyzers have been reported to be 63000 Rs./kW (900 €/kW) (Khan and Iqbal,
118
2005), 91000 Rs./kW (1300 €/kW) (Greiner et al., 2007), 17500 – 94500 Rs./kW
(250 – 1350 €/kW) (van Ruijven et al., 2007), 28000 – 105000 Rs./kW (400 –
1500 €/kW) (Kasseris et al., 2007), and 10500 – 49000 Rs./kW (150 – 700 €/kW)
Rs./kW (170 €/kW or 250 US$/kW) by the year 2015 compared to the 2005 cost
of 35000 Rs./kW (500 €/kW or 730 US$/kW) (USDOE, 2006). The sensitivity
analysis, therefore, covers a range of 28000 – 91000 Rs./kW (400 – 1300 €/kW) as
electrolyzer capital cost. With all these diverse possibilities, Figure 4E.1 shows the
payback period for low potential black liquor electrolysis to vary from a low of 0.7
investment. This analysis includes a compressed hydrogen storage facility for one
day production for a capital investment of 62300 Rs./kg (890 €/kg) (Khan and
Iqbal, 2005). Again, there is a lot of uncertainty for these cost values as also the
various storage options for hydrogen. Realistic estimates put the capital investment
for compressed hydrogen storage at 48300 Rs./kg (690 €/kg) in present scenario
with projected values of 26600 Rs./kg (380 €/kg) by 2015 (Kasseris et al., 2007).
If the 2015 projections were actually realized, low potential black liquor
electrolysis could have a payback period of as low as 0.4 years in the best
economic scenario.
119
4E.2.1.2 Effect of gasoline price
Figure 4E.1 also reveals the economic sensitivity of low potential black
liquor electrolysis on gasoline price and electricity price. Keeping all other
C gas is the gasoline price. To see the effect of gasoline prices on the economic
price. Payback period is all the more sensitive in the low gasoline price regimes.
This is certainly expected as sale proceeds from hydrogen would constitute the
major earning. With low investment costs, payback period less than 1 year should
be possible even with a gasoline price of 50 Rs./l (0.7 €/l). Even with high
investment costs the expected payback period is less than 1.5 years if the gasoline
Gasoline prices are associated with lot of uncertainty and speculation, not
marketing cost for expected crude price of around 4100 Rs./barrel (59 €/barrel or
120
3.5
3
Payback period (year)
2.5
Electrolyzer cost Rs.
2 28000/kW
Electrolyzer cost Rs.
1.5 49000/kW
Electrolyzer cost Rs.
1
70000/kW
0.5 Electrolyzer cost Rs.
91000/kW
0
0 20 40 60 80
Gasoline price (Rs./l)
price has already touched 150 USD/barrel and can again reach such levels in
future. This is due to an ever increasing energy demand combined with dwindling
Australia ranges from 55 – 63 Rs./l (0.8 to 0.9 €/l) (NRMA, Australian energy
Germany, Italy, and Spain) is 96 Rs./l (1.38 €/l) (IEA, 2007). In United Kingdom
gasoline sells in the price range of 100 – 105 Rs./l (1.4 – 1.5 €/l) (British market
sources). Current price in Canada is 50 Rs./l (0.7 €/l) (IEA, 2007). In India, with
121
an administered price regime for petroleum derived fuels, the prevailing price of
gasoline is about 50 Rs./l (0.7 €/l), down from the high of about 58 Rs./l (0.85 €/l)
electricity. Keeping all other parameters constant, except the electricity price,
Payback period has a slight non linear dependence on the electricity price.
Compared to gasoline price, payback period is less sensitive to electricity price and
varies within a much narrower window. With a low capital cost, and gasoline price
of 55 Rs./l (0.8 €/l) (which is reasonable from the previous discussion), economic
breakeven should be achieved within 1 year for the entire range of electricity
prices. Even with high capital cost, the payback period is within 1.5 years for
geographical regions of the globe. These may be due to choice and availability of
electricity prices of 2800 – 4900 Rs./MWh (40 – 70 €/MWh) (Damen et al., 2007).
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It is reported to be 3100 Rs./MWh (44 €/MWh) in a Chinese study (Chang et al.,
2007). Price of electricity in India is around 3850 Rs./MWh (55 €/MWh) (Kothari
2
1.8
1.6
Payback period (year)
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organic pollutants with all inorganic chemicals recovered for reuse in the mill.
electricity consumption. Using equations, (4E.2), (4E.3), and (4E.4), the payback
period for high potential black liquor electrolysis can be calculated as:
Where, AENaOH is the annual earning from NaOH produced and AC caust is the
annual cost of causticizing. Similar to low potential electrolysis, here also a low
investment cost, low electricity price and a high gasoline price would be
would carry significant economic value. On the other hand causticizing would
involve expenditure. With all these considerations, in the best case scenario, high
potential black liquor electrolysis should have a payback period of 0.7 years. This
value is 14.5 years in the worst case scenario. It is apparent that high potential
potential electrolysis.
Keeping all other parameters constant, except the capital cost of the
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Where, K6 and K7 are constants dependent on economic conditions chosen.
9
Gasoline price Rs.
8 35/l, electricity price Rs.
3500/MWh, NaOH price
7 Rs. 14000/Mt
Payback period (year)
cost of the electrolyzer. Payback period would be upwardly revised by more than
100% if the electrolyzer capital cost increases from a low of 28000 Rs./kW (400
€/kW) to a high value of 91000 Rs./kW (1300 €/kW). In most of the economic
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scenarios, however, a payback period of around 2.5 years should be possible which
makes reasonable economic sense. As for low potential electrolysis, here again,
the hydrogen storage cost would contribute to the total capital cost. If the best
projections on this front are realized and all other economic conditions are
From the analysis for low potential electrolysis it was borne out that the
gasoline price has a profound influence on the economic performance. Keeping all
other parameters constant, except the gasoline price, equation (4E.9) reduces to
Analysis for high potential black liquor electrolysis is depicted in Figure 4E.5. The
there is a steep increase in payback period if the gasoline price falls below 50 Rs/l
(0.7 €/l). For a gasoline price of 63 Rs./l (0.9 €/l) and above a payback period of 2
years or less should be achievable for all capital cost regimes. Running high
potential electrolysis would not be a sound investment if the gasoline price is less
than about 50 Rs./l (0.7 €/l) with the electrolyzer cost also high.
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9
8
7 Electrolyzer cost Rs.
Payback period (year)
28000/kW
6
Electrolyzer cost Rs.
5 49000/kW
1
0
0 20 40 60 80
Gasoline price (Rs./l)
Keeping all other parameters constant, except the electricity price, equation
(4E.9) reduces to
price 55 Rs./l (0.8 €/l), the payback period for high potential black liquor
electrolysis should be 3 years or less for any electricity price or capital cost. The
simulations are shown in Figure 4E.6. The non linearity in the variation of payback
period with electricity price is much less than that observed for gasoline price.
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Even with moderately high electrolyzer cost, the payback on investment is
expected to be achieved within nearly 2 years if electricity price does not exceed
3500 Rs./MWh (50 €/MWh). As discussed above such electricity prices are quite
reasonable. Payback periods of about 3 years should also be acceptable for running
3.5
3
Payback period (year)
2.5
Electrolyzer cost Rs
2 28000/kW
Electrolyzer cost Rs
1.5 49000/kW
1 Electrolyzer cost Rs
70000/kW
0.5 Electrolyzer cost Rs
91000/kW
0
0 1000 2000 3000 4000 5000
Electricity price (Rs./MWh)
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It was argued in Chapter 4D that if the electricity required for the
electrolysis could be sourced from a carbon neutral source (e.g. wind, solar, etc.)
the hydrogen replacing gasoline could curb significant amounts of CO2 emission
earning valuable carbon credits for the mill. With the advancements in technology
al., 2007; Griener et al., 2007). In the last couple of decades wind energy
technology has matured as one of the most encouraging renewable energy sources
(Hoogwijk et al., 2004; Kose et al. 2004). For developing countries it opens a
instruments. In the European Climate Exchange, future contracts price for trading
of carbon credits have varied between 1400 – 1750 Rs./t (20 – 25 €/t) in the first
three months of 2008 (ECE, 2008). The current prices are in the range of 900 –
1050 Rs./t (13 – 15 €/t) owing to a decrease in demand arising out of the economic
downturn.
One of the important value added products from high potential black liquor
reuse in pulping. Economic value associated with this should, therefore have a
important ones being the demand push or pull, not only for sodium hydroxide
itself, but more so for chlorine, the accompanying product in brine electrolysis. As
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a result, large variation in the sodium hydroxide price can be noticed. Keeping all
other parameters constant, except the sodium hydroxide price, equation (4E.9)
reduces to
the NaOH price. The simulated effect of the price of sodium hydroxide on the
payback period for high potential black liquor electrolysis is shown in Figure 4E.7.
2.5
Payback period
2 Electrolyzer cost Rs
28000/kW
1.5 Electrolyzer cost Rs
49000/kW
1 Electrolyzer cost Rs
70000/kW
0.5
Electrolyzer cost Rs
91000/kW
0
10000 15000 20000 25000
NaOH price (Rs./t)
130
Compared to other economic parameters sodium hydroxide price has a less
pronounced effect and the payback period decreases almost in proportion to the
increase in price. With the more likely prices of electricity and gasoline as
discussed above payback period for high potential black liquor electrolysis should
be within 2.5 years if the sodium hydroxide prices are at least 17500 Rs./t (250
€/t).
heat would be available in high potential black liquor electrolysis for mill use. The
exact economic value for this could not be ascertained as it would depend on the
manner of its recovery and how a particular mill makes use of it. However, this
available process heat should certainly have a positive economic contribution and
On the basis of equivalent biofuels a reasonable upper limit for lignin price
could be between 1050 Rs./MWh (15 €/MWh) (Axelsson et al., 2006) and 850
Rs./MWh (12 €/MWh) (Wising et al., 2006). In the present analysis lignin price of
1050 Rs./MWh (15 €/MWh) has been used. Lignin price would probably be higher
than 1750 Rs./MWh (25 €/MWh) if lignin were used e.g. as raw material for
specialty chemicals or as a replacement for fossil fuels (Olsson et al., 2006). The
(Axelsson et al., 2006). Sulfur free lignin from small facilities, which typically use
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