SUPERCRITICAL WATER GASIFICATION

OF MODEL EFFLUENTS FROM FRUIT

PROCESSING (FRUCTOSE) AND DAIRY
INDUSTRIES (LACTOSE) TO HYDROGEN
FUEL

Sonil Nandaa, Ajay K. Dalaib, Ian S. Butlerc, Janusz A. Kozinskia

a
Lassonde School of Engineering, York University, Toronto, Ontario, Canada
b
Department of Chemical and Biological Engineering, University of
Saskatchewan, Saskatoon, Saskatchewan, Canada
c
Department of Chemistry, McGill University, Montreal, Quebec, Canada

ABSTRACT: The adverse effects of climate change resulting from increasing greenhouse
gas emissions and intense consumption of fossil fuels are well-known. The pollution of
natural resources, such as water, air and soil, by industrial wastes has also become a
global environmental concern. The effluents from fruit processing and dairy industries are
two of such wastes that require proper attention prior to disposal. The fruit processing
effluents are rich in fructose, whereas dairy industry effluents including whey waste and
milk-based residues are enriched in lactose that could potentially be converted to biofuels
and biochemicals. Fructose and lactose were examined as respective model compounds
of fruit processing and dairy industry effluents for gasification in supercritical water using a
continuous flow tubular reactor. Four parameters impacting supercritical water gasification
were studied, namely temperature (550-700°C), residence time (30-75 s), feed
concentration (4-10 wt%) and catalyst loading. The best total gas yields, carbon
gasification efficiency, H2 yields and other major gases (CO2 and CH4) were obtained at
700°C using a feed concentration of 4 wt%, a residence time of 60 s and pressure of 25
MPa both for fructose and lactose. Maximum H2 yield (10.7 mol/mol) was obtained from
fructose using 0.8 wt% KOH than 0.8 wt% NaOH (9.9 mol/mol) and non-catalytic
gasification (3.4 mol/mol). Furthermore, catalytic lactose gasification involving 0.8 wt%
Na2CO3 resulted in maximum H2 yield (22.4 mol/mol) compared to those obtained by 0.8
wt% K2CO3 (21.5 mol/mol) and non-catalytic gasification (16 mol/mol). The results indicate
that waste effluents from fruit processing and dairy industries could potentially serve as
attractive raw materials for hydrogen production through gasification.

KEYWORDS: Fruit waste, dairy waste, fructose, lactose, supercritical water, gasification, hydrogen, syngas

Proceedings Venice2016, Sixth International Symposium on Energy from Biomass and Waste,
14 - 17 November 2016
Great School of St. John the Evangelist, Venice, Italy
© 2016 by CISA Publisher, Italy
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Sixth International Symposium on Energy from Biomass and Waste

1. INTRODUCTION

The adverse effects of climate change resulting from increasing greenhouse gas emissions
and intense consumption of fossil fuels are well-known. The pollution of natural resources such
as water, air and soil by industrial wastes and effluents has also become a global
environmental concern. Substantial amounts of waste food are obtained globally that, via
landfill, contribute majorly to the production of greenhouse gases such as CO2 and CH4. The
effluents from dairy industries are a similar kind to industrial wastes that require proper
attention prior to disposal.
Fructose is a model sugar compound that is enriched in the waste effluents from fruit
processing and beverage industries. On the other hand, dairy effluents are comprised chiefly
of spoiled milk, yogurt, cream, cheese whey, fat and other milk-based products. The dairy
industry effluents, including whey waste and milk-based residues, are enriched in lactose and
minor amounts of glucose. Owing to the significant levels of lactose and fructose, the aerobic
microbial digestion of dairy and fruit processing effluents is usually malodorous, and attracts
insects and pests. The main product of anaerobic digestion of these wastes is CH4 that is
nearly 25 times more potent greenhouse gas than CO2 (Li et al., 2011).
Fructose (C6H12O6) is a ketonic monosaccharide predominantly found in fruits, berries and
vegetables. On the other hand, lactose (C12H22O11) is a disaccharide sugar found in milk and
derived from galactose and glucose. As fructose and lactose are significantly enriched in the
waste effluents from fruit processing and dairy industries, they have tremendous potential to
be converted to biofuels. Supercritical water gasification (SCWG) has found several
applications in lignocellulosic biomass conversion for syngas production (Nanda et al., 2014).
Supercritical water (SCW) is a homogeneous fluid that exists when the critical temperature and
critical pressure of water rise above 374°C and 22.1 MPa, respectively (Reddy et al., 2014).
SCW has both liquid-like viscosity and gas-like diffusivity that dissolves most organic matter to
gases such as H2, CO, CO2 and CH4. With the objective of valorizing fruit processing and dairy
industrial effluents, their respective model compounds, i.e. fructose and lactose, were
subjected to SCWG for producing H2-rich syngas. Both fructose and lactose were gasified in
SCW using a continuous flow tubular reactor and the effects of different parameters such as
temperature, feed concentration, residence time and catalysts loading were investigated.

2. MATERIALS AND METHODS

2.1 Feedstock and catalysts

D-Fructose and D-Lactose monohydrate were used as model sugar compounds for fruit
processing and dairy industry effluents. Homogeneous alkali catalysts such as KOH, NaOH,
K2CO3 and Na2CO3 were used to examine their impacts on total gas yields and composition in
SCWG. All the chemicals were purchased from Sigma-Aldrich Canada Co., ON, Canada.

2.2 Supercritical water gasification

SCWG experiments were performed in a stainless steel continuous flow tubular reactor (outer
diameter: 0.5 inch, inner diameter: 0.37 inch, length: 18 inches). The gasification set-up
consisted of a feed tank, a high-pressure pump, a pressure gauge, a relief valve, a check
valve, a preheater, a tubular flow reactor, a thermocouple, a water-cooled tube cooler, a 2 µm
filter, a back pressure regulator, a gas-liquid separator, a mass flow meter and other
necessary valves and tube connectors. All the tubing, fittings, filters, hoses, valves and tube
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accessories used in the assembly were made up of stainless steel (SS316) and purchased
from Swagelok® (Swagelok Central Ontario, ON, Canada).
The feed (fructose and lactose) solutions were separately introduced into the reactor using
a high-pressure LabAlliance Prep pump (Scientific Systems Inc., PA, USA). The feed solution
passed through the preheater (outer diameter: 0.25 inch, inner diameter: 0.12 inch, length: 12
inch) which was located prior to the SCWG reactor for preheating to 80-100°C. The tubular
SCWG reactor was placed inside an ATS furnace (Applied Test Systems, PA, USA). The
preheater and furnace temperatures were regulated by a ATS Type K, T/C temperature control
system. The gasification products exiting the SCWG reactor were cooled down by passing
through a tube cooler. The condensed gasification products (liquid and gases) were collected
and separated using a gas-liquid separator. The gases passed through a moisture trap and a
mass flow meter to measure the gas flow rates before being collected in gas sampling bags for
compositional analysis via gas chromatography.
SCWG of fructose and lactose was performed at 25 MPa to study the impact of temperature
(550-700°C), feed concentration (4-10 wt%) and residence time (30-75 s). Homogeneous
alkali catalysts such as KOH, NaOH, K2CO3 and Na2CO3 at 0.8 wt% loading were used to
examine their influence on enhancing syngas yield and composition from fructose and lactose.
The gases were analyzed in an Agilent 7820A gas chromatograph (Agilent Technologies, CA,
USA) with thermal conductivity detector including three packed columns and one capillary
column. The individual gas yield, total gas yield and lower heating value (LHV) were
determined using the quantitative data obtained from the gas chromatography, as well as
volumetric flow rate of gas products.

3. RESULTS AND DISCUSSION

The effect of temperature was studied from 550 to 700°C for SCWG of fructose and lactose at
a fixed feed concentration of 4 wt%, pressure of 25 MPa and residence time of 60 s (Fig. 1).
As the temperature increased from 550 to 700°C, the total gas yields also increased from 0.2
to 1.04 L/g from SCWG of 4 wt% fructose. The H2 yield increased significantly from 0.27 to
3.37 mol/mol with the rise in temperature from 550 to 700°C (Fig. 1a). The yields of CO2 and
CH4 also increased in the ranges of 0.47-3.25 mol/mol and 0.14-1.2 mol/mol, respectively. The
rise in the yields of H2, CO2 and CH4 at higher temperatures is due to water-gas shift reaction
and methanation reaction (Nanda et al., 2016). The LHV of gas products from fructose
gasification steadily increased from 1281 kJ/Nm3 at 550°C to 2482 kJ/Nm3 at 700°C. The LHV
is dependent on the concentration of combustible gases i.e. H2, CO and CH4, hence greater
yields of H2 and CH4 at higher temperatures led to a greater LHV of the gas products.
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Figure 1. Effect of temperature on supercritical water gasification of (a) fructose and (b) lactose at 4
wt% feed concentration and 25 MPa pressure with 60 s of residence time.

Similar to fructose, an increase in temperature also led to a rise in gas yields from lactose
gasigication. The SCWG of 4 wt% lactose showed an increase in total gas yields from 0.43 L/g
at 550°C to 1.07 L/g at 700°C. The LHV of gases, which is also dependent on the
concentrations of H2, CO and CH4, increased from 1855 kJ/Nm3 at 550°C to 3513 kJ/Nm3 at
700°C. The H2 yield improved from 1.8 to 16 mol/mol with an increase in temperature from 550
to 700°C (Fig. 1a). The respective yields of CO2 and CH4 also increased from 1.5 to 6 mol/mol
and from 0.6 to 2 mol/mol. Compared to fructose gasification, the yields of individual gases
and total gases were higher in the case of lactose.

Figure 2. Effect of feed concentration on supercritical water gasification of (a) fructose and (b) lactose at
700°C and 25 MPa pressure with 60 s of residence time.

The feed concentrations of fructose and lactose were varied between 4 and 10 wt% to
determine their impact on SCWG and gas yields at a constant residence time of 60 s and
temperature of 700°C. The total gas yields decreased from 1.04 L/g to 0.83 L/g with the rise in
fructose concentration from 4 wt% to 10 wt%. Total gas yield is found to decrease as feed
concentration increases (Lu et al., 2006). The H2 yields decreased from 3.37 to 2.52 mol/mol
during SCWG of fructose at 700°C with increase in feed concentration from 4 to 10 wt% (Fig.
2a). The CO2 yields were also reduced from 3.25 to 1.95 mol/mol with an increase in fructose
concentration from 4 to 10 wt%. On the other hand, CH4 yield increased from 1.20 at 4 wt%
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fructose to 1.43 mol/mol at 10 wt% fructose. This was because of more efficient methanation
reaction at higher feed concentration where CO2 and H2 react to produce CH4 and H2O (Reddy
et al., 2014). C2H6 yields also increased from 0.33 to 0.43 mol/mol with increasing fructose
concentration. The LHV of gas product was higher with 10 wt% fructose (2515 kJ/Nm3) when
compared to that of 4 wt% fructose (2482 kJ/Nm3).
The total gas yields from SCWG lactose decreased from 1.69 (at 4 wt% feed concentration)
to 1.26 L/g (at 10 wt% feed concentration). Although a similar trend as fructose, yet lactose at
the same feed concentrations gave greater gas yields than fructose. The H2 yields decreased
from 16 to 8.7 mol/mol with a rise in lactose concentration from 4 to 10 wt% (Fig. 2b). The CO2
yields also dropped from 6 to 4.9 mol/mol at 10 wt% lactose concentration. The CO yields
increased from 1.5 mol/mol (at 4 wt% lactose concentration) to 3 mol/mol (at 10 wt% lactose
concentration). The LHV of gases was relatively higher at 4 wt% lactose (3513 kJ/Nm3) than at
10 wt% lactose (2719 kJ/Nm3).

Figure 3. Effect of residence time on supercritical water gasification of (a) fructose and (b) lactose with 4
wt% feed concentration at 700°C and 25 MPa pressure.

The effects of residence time (30-75 s) were tested for fructose and lactose gasification
in SCW with 4 wt% feed concentration at 700°C and 25 MPa. The total gas yields from
SCWG of fructose increased from 0.38 L/g at 30 s to 1.05 L/g at 75 s. The H2 yield also
increased from 0.8 mol/mol at 30 s to 3.37 mol/mol at 60 s, after which it reduced to 3.26
mol/mol at 70 s (Fig. 3a). The highest H2 yield at 60 s resulted in the LHV being highest i.e.
2482 kJ/Nm3 compared to that at 30 s (1626 kJ/Nm3) and at 75 s (2463 kJ/Nm3). The
yields of CO2 (3.25 mol/mol) and CO (0.19 mol/mol) were also higher in the gas products
collected at 60 s. However, the yields of CH4 and C2H6 gradually increased with prolonged
residence times.
The total gas yields increased from 1.19 L/g at 30 s to 1.69 g/L at 60 s and 1.68 L/g at
75 s from SCWG of 4 wt% lactose at 700°C. The LHV of the gas products was greatest at
60 s (3513 kJ/Nm3) than at 75 s (3444 kJ/Nm3) and at 30 s (3263 kJ/Nm3). The total gas
yields, H2 yields and LHV of the gas products were higher from lactose gasification than
that of fructose. The H2 yield from 4 wt% lactose increased from 10.2 mol/mol (30 s) to 16
mol/mol (60 s), and reduced to 15.4 mol/mol (70 s) (see Fig. 3b). The yields of CO2 was
also highest at 60 s (6.03 mol/mol) compared to that at 30 s (4.6 mol/mol).
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Figure 4. Effect of 0.8 wt% catalysts on supercritical water gasification of (a) fructose and (b) lactose
with 4 wt% feed concentration at 700°C, 25 MPa pressure and 60 s of residence time.

In order to enhance the H2 and total gas yields, four different alkali catalysts (i.e. KOH,
NaOH, K2CO3 and Na2CO3) were examined specific to fructose and lactose at a constant
loading of 0.8 wt% with 4 wt% feed concentration at 700°C and 25 MPa. Compared to non-
catalytic SCWG of 4 wt% fructose, 0.8 wt% KOH and NaOH resulted in higher total gas yields
of 2.01 and 1.89 L/g, respectively. In contrast to 0.8 wt% NaOH (9.86 mol/mol), higher H2 yield
(10.67 mol/mol) was obtained with the addition of 0.8 wt% KOH in fructose gasification (Fig.
4a). A 0.8 wt% KOH (3630 kJ/Nm3) resulted in a higher LHV of the gas products than that of
0.8 wt% NaOH (3576 kJ/Nm3) due to higher yields of H2.
In the case of lactose gasification in SCW, addition of 0.8 wt% K2CO3 increased the yields
of H2 and CO2 to 21.5 and 8.01 mol/mol, respectively (Fig. 4b). The total gas yields escalated
from 1.69 (no catalyst) to 2.2 and 2.13 L/g in the presence of 0.8 wt% Na2CO3 and K2CO3. The
comparatively higher activity of water-gas shift reaction with 0.8 wt% Na2CO3 resulted in the
highest H2 and CO2 yields of 22.4 and 8.15 mol/mol, respectively. The LHV of gas product
from 0.8 wt% Na2CO3 was highest (3741 kJ/Nm3) compared to 0.8 wt% K2CO3 (3715 kJ/Nm3)
and non-catalytic gasification (3513 kJ/Nm3) of 4 wt% lactose at 700°C and 60 s.

5. CONCLUSIONS

Based on the total gas yields, carbon gasification efficiency and maximum H2 yields from
lactose and fructose, the optimal temperature, feed concentration and residence time were
determined to be 700°C, 4 wt% and 60 s, respectively. The total gas yield from fructose
gasification was higher at 700°C (1.04 L/g) compared to that at 550°C (0.2 g/L). Similarly,
lactose gasification resulted in a higher total gas yield at 700°C (1.7 L/g), which was greater
than that at 550°C (0.4 g/L). The H2 yield from fructose at 700°C (3.4 mol/mol) was higher than
that at 550°C (0.3 mol/mol). The H2 yield from lactose at 700°C was higher (16 mol/mol) as
compared to fructose (3.4 mol/mol). Among all the residence times examined, 60 s was found
to be optimal for its higher H2 yields compared to 15 s. For instance, at 700°C, H2 yield from
lactose was higher at 60 s (15.4 mol/mol) than at 30 s (10.2 mol/mol). Similarly for fructose, H2
yield at 60 s (1.04 mol/mol) was more when compared to 30 s (0.4 mol/mol). Lower feed
concentration of 4 wt% resulted in greater total gas yields (1.04 L/g) from fructose compared to
higher feed concentration of 10 wt% (0.8 L/g). A lower feed concentration of 4 wt% also
resulted in greater total gas yields from lactose (1.7 g/L) compared to higher feed
concentrations of 10 wt% (1.3 g/L). The addition of alkali catalysts such as KOH and NaOH
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enriched the total gas yields from fructose to 2.01 L/g and 1.9 L/g, respectively. Maximum H2
yields of 10.7 and 9.9 mol/mol from fructose were obtained with the addition of 0.8 wt% of
KOH and NaOH, respectively. Furthermore, catalytic lactose gasification involving 0.8 wt%
Na2CO3 resulted in maximum H2 yield (22.4 mol/mol) compared to that of 0.8 wt% K2CO3 (21.5
mol/mol) and non-catalytic gasification (16 mol/mol). The results indicate that waste effluents
from fruit processing facilities and dairy industries could be potential feedstocks for H2
production through supercritical water gasification.

AKNOWLEDGEMENTS

We thank Natural Sciences and Engineering Research Council of Canada (NSERC) for
funding this research via Discovery, Strategic, and Collaborative R&D grants.

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