International Journal of Hydrogen Energy 29 (2004) 1607 – 1616

www.elsevier.com/locate/ijhydene

Feasibility of biohydrogen production by anaerobic

co-digestion of food waste and sewage sludge
Sang-Hyoun Kim, Sun-Kee Han, Hang-Sik Shin∗
Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology,
373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701, Republic of Korea

Accepted 24 February 2004

Abstract
Anaerobic co-digestion of food waste and sewage sludge for hydrogen production was performed in serum bottles under
various volatile solids (VS) concentrations (0.5–5.0%) and mixing ratios of two substrates (0:100–100:0, VS basis). Through
response surface methodology, empirical equations for hydrogen evolution were obtained. The speci5c hydrogen production
potential of food waste was higher than that of sewage sludge. However, hydrogen production potential increased as sewage
sludge composition increased up to 13–19% at all the VS concentrations. The maximum speci5c hydrogen production potential
of 122:9 ml=g carbohydrate-COD was found at the waste composition of 87:13 (food waste:sewage sludge) and the VS
concentration of 3.0%. The relationship between carbohydrate concentration, protein concentration, and hydrogen production
potential indicated that enriched protein by adding sewage sludge might enhance hydrogen production potential. The maximum
speci5c hydrogen production rate was 111:2 ml H2 =g VSS=h. Food waste and sewage sludge were, therefore, considered as a
suitable main substrate and a useful auxiliary substrate, respectively, for hydrogen production. The metabolic results indicated
that the fermentation of organic matters was successfully achieved and the characteristics of the heat-treated seed sludge were
similar to those of anaerobic spore-forming bacteria, Clostridium sp.
? 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Anaerobic co-digestion; Food waste; Hydrogen; Protein; Sewage sludge; VS concentration

1. Introduction biological processes, fermentative processes that use wide

range of organic substances are technically simpler than pho-
Due to the limited resources and pollutants emission
tosynthetic processes [4]. Carbohydrates are the preferred
(CO2 , CO, Cn Hm , SOx , NOx , ashes, etc.), fossil fuels should
substrate for fermentative hydrogen-producing bacteria such
be substituted with renewable and non-polluting energy
as Clostridium species (sp.). Stoichiometrically, Clostrid-
sources [1]. As a sustainable energy source with minimal or
ium sp. can produce 2 moles of hydrogen with 1 mole of
zero use of hydrocarbons and high-energy yield (122 kJ=g),
n-butyrate or 4 moles of hydrogen with 2 moles of acetate
hydrogen is a promising alternative to fossil fuels. In addi-
from 1 mole of hexose [5]. In most cases, using soluble
tion, hydrogen can be directly used to produce electricity
de5ned substrates, hydrogen production yield and a ma-
through fuel cells [2]. Since conventional physico-chemical
jor byproduct were 0.7–2:1 mole=hexoseconsumed and a ma-
hydrogen production methods (e.g. water electrolysis or
jor by-product was n-butyrate, respectively [6,7]. Hydrogen
chemical cracking of hydrocarbons) require electricity de-
was hardly produced from protein and lipid [8–10]. How-
rived from fossil fuel combustion, interest in biohydrogen
ever, protein was indispensable, sometimes, as a nitrogen
production has increased signi5cantly [3]. Between two
source for the hydrogen production in both pure and mixed
cultures [11–13].
∗ Corresponding author. Tel.: +82-42869-3613; fax: +82- Organic wastes may become a plentiful source of
42869-3610. inexpensive organic substrate for fermentative hydrogen
E-mail address: hangshin@kaist.ac.kr (H.-S. Shin). production [4]; by which reduction and stabilization of

0360-3199/$ 30.00 ? 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2004.02.018
1608 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616

organic wastes also can be accomplished. In recent years, Table 1

some experimental results using municipal solid waste Characteristics of substrates
[8–10,14], food manufacturing waste [8,13,15,16], waste Parameter Unit Food Sewage
activated sludge [17,18] were reported. The maximum hy- waste sludge
drogen production potential and hydrogen production rate
were in the range of 49–298 ml H2 =g carbohydrate-COD Total solids % 15.9 5.0
Volatile solids % 15.2 2.5
and 17–142 ml H2 =g VSS=h, respectively. However, gen-
Total COD g/l 158.4 31.9
eral guideline on optimum conditions such as water content,
Soluble COD g/l 50.3 0.14
carbohydrate concentration, carbohydrate/protein balance Total carbohydrate g COD/l 84.9 5.0
was not suFciently provided yet. Besides, there was no Total protein g COD/l 37.7 18.4
systematic attempt at co-digestion of diGerent substrates, Total Kjeldahl nitrogen g N/l 4.4 2.3
which might enhance hydrogen production. Total VFA
Food waste and sewage sludge are the most abundant and pH 4.6 7.5
problematic organic solid wastes in Korea. The generation Alkalinity g CaCO3 =l 0.4 4.7
of food waste reaches about 11; 000 tons per day, accounting
for 23% of municipal solid wastes [19]. It is the major source
of odor emanation, vermin attraction, toxic gas emission
and groundwater contamination in collection, transportation 2.2. Substrate
and land5ll of solid wastes due to the high organic con-
centration (volatile solids/total solids: 0.8–0.9) and mois- The substrate was a mixture of food waste and sewage
ture content (75–85%). However, food waste might be suit- sludge. Food waste, sampled from a dining hall, was crushed
able for fermentative hydrogen production, because it is the by an electrical blender under anaerobic condition. Sewage
carbohydrate-rich and easily hydrolysable waste [20]. On sludge was taken from a gravity sludge thickener into which
the other hand, approximately 5700 tons of sewage sludge primary and secondary sludges were added at the same
cakes are generated daily [19], of which 72% is disposed by amount of VS. All the substrates were 5ltered through a
ocean dumping. However, it would be prohibited according stainless steel sieve (US Mesh No. 10 with corresponding
to London Convention in recent future [21]. The enhance- sieve opening of 2:00 mm), of which the characteristics are
ment of anaerobic digester is, therefore, urgent to reduce summarized in Table 1.
the amount of the sludge cakes and to improve the quality
for reuse. Co-digestion of sludge with carbon-rich wastes is 2.3. Operating procedure
known as an economic and feasible approach to retro5t con-
ventional digesters [22,23]. If hydrogen can be produced by The experiments were conducted using 415 ml Wheaton
anaerobic fermentation of food waste with sewage sludge, media lab bottles. A total of 32 bottles with diGerent volatile
they would be the important source for hydrogen production solids (VS) concentrations and mixing ratios of food waste
due to the amount. and sewage sludge were simultaneously operated. Total VS
In this work, the feasibility of anaerobic co-digestion of concentrations were controlled to be 0.5%, 1.0%, 1.5%,
food waste and sewage sludge for hydrogen production was, 2.0%, 3.0%, and 5.0%. The mixing ratios of food waste
therefore, carried out under various VS concentrations and to sewage sludge were designed to be 100:0, 80:20, 60:40,
mixing ratios. Response surface methodology employing a 40:60, 20:80, and 0:100 on VS basis; however, the experi-
full quadratic model was then conducted to 5nd out the re- ments at 20:80, and 0:100 for VS 3.0%, and 40:60, 20:80,
lationship between VS concentration, mixing ratio and hy- and 0:100 for VS 5.0% could not be conducted due to low
drogen production. VS concentration of sewage sludge. Total carbohydrate and
protein concentrations, therefore, ranged 1.0–28:0 g COD=l
and 1.3–22:1 g COD=l, respectively. Seed sludge of 40 ml,
appropriate amounts of food waste, and sewage sludge were
2. Materials and methods added to individual bottles, while seed sludge and distilled
water were added to the blank reactor. Each bottle was sup-
2.1. Seed sludge plemented with 200 mg of KH2 PO4 , 14 mg of MgCl2 ·4H2 O,
2 mg of Na2 MoO4 ·4H2 O, 2 mg of CaCl2 · 2H2 O, 2:5 mg of
The seed sludge was taken from an anaerobic digester MnCl2 · 6H2 O, and 10 mg of FeCl2 · 4H2 O, which was mod-
in a local wastewater treatment plant. The pH, alkalinity, i5ed from Lay et al. [14]. NaHCO3 was also added to adjust
and volatile suspended solids (VSS) concentration of the total carbohydrate/alkalinity ratio to 1:0 ± 0:1. Each bottle
sludge were 7.6, 2:83 g CaCO3 =l, and 5:5 g=l, respectively. was then 5lled to 200 ml with distilled water and pH was
It was heat-treated at 90◦ C for 10 min to inactivate hy- adjusted to 6.0 using either 1 M HCl or 1 M KOH. Sub-
drogen consumers and to harvest spore-forming anaerobic sequently, the headspaces of the bottles were Lushed with
bacteria [3]. N2 gas for 1 min and the bottles were tightly sealed using
 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616
open-top screw caps with rubber septa. The bottles were
then placed in a reciprocating shaker at 35◦ C and 100 rpm.
The biogas production was determined using a glass syringe
of 20–200 ml [24]. At the same time, gas composition was
measured and the sample from the supernatant was taken to
analyze pH and organic concentrations. During cultivation,
if the pH value was out of 5.0–6.0, it was adjusted using
0 +
1 x1 +
2 x2 +
11 x12 +
22 x22 +
12 x1 x2 ; (2)
injection of either 1 M HCl or 1 M KOH by syringes.
2.4. Analytical methods
0 was the oGset term,
1 and
2 were linear
11 and
22 were squared coeFcients, and
12
Hydrogen content in biogas was measured by a gas chro-
matography (GC, Gow Mac series 580) using a thermal
conductivity detector and a 1:8 m × 3:2 mm stainless-steel
column packed with molecular sieve 5A with N2 as a car-
rier gas. The contents of CH4 , N2 , and CO2 were measured
using a GC of the same model noted previously with a
1:8 m × 3:2 mm stainless-steel column packed with pora-
pak Q (80/100 mesh) using helium as a carrier gas. The
temperatures of injector, detector, and column were kept
at 80◦ C, 90◦ C, and 50◦ C, respectively, in both GCs. VFA
(C2–C6), and lactate were analyzed by a high performance
liquid chromatograph (Spectrasystem P2000) with an
ultraviolet (210 nm) detector and an 300 mm × 7:8 mm
Aminex HPX-97H column using H2 SO4 of 0:005 M as
mobile phase. Aliphatic alcohol was determined using an-
other high performance liquid chromatograph (DX-600,
Dionex) with an electrochemical detector (ED50A) and an
250 mm × 4 mm Dionex CarboPac PA10 column using
NaOH of 0:01 M as mobile phase. The liquid samples were
pretreated with 0:45 m membrane 5lter before injection
to both HPLCs. Chemical oxygen demands (COD), Sus-
pended solids (SS), VSS, TKN, ammonia, and pH were
determined according to Standard Methods [25]. Carbohy-
drate was determined by the colorimetric method of Dubois
et al. [26] with wavelength at 480, 484 and 490 nm us-
ing glucose as standard. Total protein was calculated from
organic nitrogen (9:375 g COD=g organic nitrogen) [27].
2.5. Assay methods
The hydrogen production curve was 5tted to a modi-
5ed Gompertz equation (1), which was used as a suitable
model for describing the hydrogen production in batch tests
[28–30].

 
Rm
H = P × exp − exp (
− t)e + 1 ; (1) = − 39:793 + 2:069x1 + 48:431x2
P
where H was cumulative hydrogen production (ml), P was
ultimate hydrogen production (ml), Rm was hydrogen pro-
duction rate (ml/day),
was lag-phase time (days), and e
was exponential 1.
In many biological 5elds, the basic knowledge of phe-
nomena is insuFcient to build a mechanistic model. In this
case, response surface methodology, a collection of empir-
ical models and statistical analyses, can play an extremely
1609
important role in elucidating basic mechanisms in complex
situations and thus providing better process design and con-
trol [31]. In this study, the eGects of VS concentrations and
mixing ratios of food waste and sewage sludge on biohy-
drogen production were analyzed using the full quadratic
model as shown below [32].
Y =
where Y was the predicted response, x1 and x2 were indepen-
dent variables,
coeFcients,
was the interaction coeFcient.
All the parameters in Eqs. (1) and (2) were evaluated
using the ‘Fit curve’ function with a Newtonian algorithm in
Sigmaplot 2001. In order to minimize the sum of the square
errors (SSE) between the experiment and the estimation 100
iterations were made. The parameters were diagnosed by
SSE, correlation coeFcient (R2 ), standard errors (SE), 95%
con5dence limits, t-values of the parameters, and F-test. The
response surface contour plots were also constructed using
Sigmaplot 2001.
3. Results and discussion
3.1. E6ects of VS concentrations and mixing ratios
on fermentative hydrogen production
Hydrogen was not produced in seven reactors includ-
ing the blank in which no food waste was added or
carbohydrate concentration was lower than 2:0 g COD=l.
The cumulative hydrogen production curves from the 25
hydrogen-producing reactors were well described by Eq.
(1). All the correlation coeFcients, R2 , were larger than
0.984 as shown in Table 2. Additionally, all the t-values
for parameters were larger than t0:025; 5 = 2:571 (table value)
(data not shown).
The speci5c hydrogen production potential (ml/g
carbohydrate-COD) was obtained from P and the carbohy-
drate added. The obtained values were, then, subjected to
the response surface analysis to evaluate the relationship
between food waste composition (x1 ), VS concentration
(x2 ), and the speci5c hydrogen production potential, and
they generated the following:
(Speci5c H2 production potential)
−0:011x12 − 8:103x22 − 0:015x1 x2
(R2 = 0:898; F = 31:52): (3)
The calculated values of F were greater than F0:05; 5; 25 =
2:60 (table value), which meant that statistically signi5-
cant regression models were obtained [32]. Fig. 1 illus-
trates that the speci5c hydrogen production potential was
found to be higher than 75:2 ml=g carbohydrate-COD at
1610 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616

Table 2
Kinetic parameters on hydrogen production calculated from Eq. (1)

VS Food waste Carbohydrate Protein P Rm

R2
(%) (%, VS basis) (g COD/l) (g COD/l) (ml H2 ) (ml/day) (days)

5.0 100 28.0 12.5 339.7 596.6 0.23 0.993

5.0 80 24.4 17.3 308.0 367.0 0.23 0.993
5.0 60 20.8 22.1 146.3 139.9 0.09 0.994
3.0 100 16.8 7.5 355.1 504.2 0.28 0.999
3.0 80 14.6 10.4 347.2 419.8 0.26 0.993
3.0 60 12.5 13.3 212.5 290.4 0.15 0.999
3.0 40 10.3 16.1 48.6 78.9 0.12 0.999
2.0 100 11.2 5.0 208.9 359.0 0.78 0.992
2.0 80 9.8 6.9 186.5 369.6 0.49 0.993
2.0 60 8.3 8.8 120.0 248.2 0.34 0.999
2.0 40 6.9 10.8 38.4 71.3 0.12 0.999
2.0 20 5.4 12.7 8.8 29.0 0.16 0.999
2.0 0 4.0 14.6 — — — —
1.5 100 8.4 3.8 119.5 79.2 0.24 0.988
1.5 80 7.3 5.2 105.7 150.5 0.35 0.999
1.5 60 6.2 6.6 55.2 110.9 0.25 0.994
1.5 40 5.2 8.1 28.8 29.0 0.23 0.990
1.5 20 4.1 9.5 4.7 7.9 0.24 0.992
1.5 0 3.0 11.0 — — — —
1.0 100 5.6 2.5 74.4 81.8 0.44 0.998
1.0 80 4.9 3.5 69.4 84.5 0.36 0.999
1.0 60 4.2 4.4 47.4 71.3 0.37 0.994
1.0 40 3.4 5.4 17.6 44.9 0.14 0.992
1.0 20 2.7 6.3 1.9 2.6 0.27 0.986
1.0 0 2.0 7.3 — — — —
0.5 100 2.8 1.3 35.9 73.9 0.28 0.999
0.5 80 2.4 1.7 18.2 21.1 0.00 0.984
0.5 60 2.1 2.2 3.4 7.9 0.05 0.993
0.5 40 1.7 2.7 — — — —
0.5 20 1.3 3.2 — — — —
0.5 0 1.0 3.7 — — — —
Blank — — — —

all VS concentrations and waste composition of 100:0
(food waste:sewage sludge). The potential increased up
to 121:6 ml=g carbohydrate-COD as VS concentration
increased up to 3.0%. It decreased as VS concentration
increased further, which might be due to product inhibition
by H2 and VFAs [28,33]. Sewage sludge showed lower hy-
drogen production potential than food waste; the maximum
value was 32:6 ml=g carbohydrate-COD. Less hydrogen
production from sewage sludge might be caused by hardly
hydrolysable organics contained in the sludge [17].
However, the hydrogen production potential was en-
hanced when the sewage sludge was added by 20% except
at the VS 0.5% (Table 2). Eq. (3) also estimated that addi-
tion of sewage sludge up to 13–19% (VS basis) increased
the hydrogen production potential at all the VS concentra-
tions. The maximum speci5c hydrogen production potential
(122:9 ml=g carbohydrate-COD) was, therefore, found at
the waste composition of 87:13 and the VS concentration
of 3.0%. At the condition, hydrogen production based on
VS was 60:1 ml=g VS, which was in the range of reported
maximum values (21–91 ml=g VS) for organic wastes
such as bean curd manufacturing waste, cabbage, rice, rice
bran, and wheat bran [8,9,15]. Hawkes et al. [3] suggested
that hydrogen production using concentrated substrates
higher than 1% TS would be feasible for suitable energy
production system. These results, therefore, showed that
food waste supplemented with sewage sludge could be an
appropriate source for hydrogen production.
It was reported that adequate control of inorganic nu-
trients could enhance biohydrogen production yield [3].
However, in this study, the concentrations of nutrients such
as phosphorus and iron were suFciently supplemented
in all cases [7,29]. The ratio of carbohydrate to nitrogen
ranged from 2.2 to 19:2 g carbohydrate-COD/g TKN-N
without an external dose of nitrogen, indicating that nitro-
gen content was also suFcient [6,33,34]. Enriched protein
would be an explanation for the enhanced hydrogen pro-
duction by adding sewage sludge. It was well known that
protein such as peptone or yeast extract was a better nitro-
gen source than ammonium salts or urea for activation and
 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616 1611

5.0
10 90
30 40 50 60 70 80
20
4.5 100

50 60 110
40 70
4.0 30 80 90 100
110
3.5 120
VS concentration (%)

80
3.0 40 50 60
70 100 110

2.5
120
90

2.0

110
1.5
30 80 100
20 40 50 60
1.0 70 90
10
0
-10 80
0.5
0 20 40 60 80 100
Foodwaste composition (%)

100 80 60 40 20 0
Sewage sludge composition (%)

Fig. 1. Contour lines of speci5c hydrogen production potential (ml H2 =g carbohydrate-COD) versus waste composition and VS concentration;
dotted line indicates the optimum condition.

growth of Clostridium sp. [35]. Yokoi et al. [13] reported The calculated values of F and R2 showed that the re-
that 0.1% polypeptone was added as an indispensable nu- gression was an available representation of the experimental
trient to the fed-batch cultures from a de5ned microbial data. Fig. 2 con5rms that addition of protein increased hy-
consortium on sweet potato starch residues. Ueno et al. drogen production potential at all VS concentrations. The
[12] also showed that when 0.5% peptone replaced NH4 Cl, optimum carbohydrate concentration, protein concentration,
H2 production increased twice with a culture selected from and C/N ratio were 16:3 g COD=l, 9:8 g COD=l, and 1:66 g
aerobic compost. As shown in Table 1, food waste was carbohydrate-COD/g protein-COD, respectively. Sewage
carbohydrate-rich waste (0:56 g carbohydrate-COD/g VS sludge, therefore, would be an appropriate auxiliary feed
and 0:25 g protein-COD/g VS), while sewage sludge was for H2 production as a protein source.
protein-rich waste (0:20 g carbohydrate-COD/g VS and The speci5c hydrogen production rate (ml/g VSS/h) was
0:73 g protein-COD/g VS). Increase of sewage sludge obtained from Rm and the inoculum weight. Modeling of the
composition from 0% to 19% decreased the ratio of carbo- speci5c hydrogen production rate was done by a response
hydrate to protein from 2.24 to 1:44 g carbohydrate-COD/g surface analysis evaluating the relationship between food
protein-COD. EGects of carbohydrate concentration (x1 ) waste composition (x1 ), VS concentration (x2 ), and the spe-
and protein concentration (x2 ) on speci5c hydrogen pro- ci5c hydrogen production rate, as shown below.
duction potential were evaluated as follows:
(Speci5c H2 production rate)
(Speci5c H2 production potential)
= − 14:950 + 0:089x1 + 16:060x2
= − 24:619 + 12:806x1 + 6:444x2
−0:505x12 − 0:717x22 + 0:434x1 x2 +0:001x12 − 4:980x22 + 0:354x1 x2

(R2 = 0:968; F = 43:00): (4) (R2 = 0:890; F = 38:85): (5)

1612 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616

010 50 60 70 60
50
shape of a ridge system for both variables [36]. Hydrogen
20
20
30
40 70 80 40
30 production rate increased as VS concentration increased
25 90 80
100 70 up to 5.0%. It was known that the inhibition of high car-
50 60 80
90 90 bohydrate concentration on hydrogen production rate was
70 100 110
60 less severe than that on hydrogen production potential
Carbohydrate (g COD/L)

20 50
40
[28,33]. The maximum speci5c hydrogen production rate
110
80
90 100 120 110
100 80 30 was 111:2 ml H2 =g VSS=h at waste composition of 100:0.
Most of reported values in serum bottle test using organic
20
70
10
15 100 120 90 wastes were less than 43 ml H2 =g VSS=h [14,18,28]. Only
Mizuno et al. [15] reported the maximum speci5c hydrogen
90 110 60
50
production rate of about 142 ml H2 =g VSS=h from bean
110 100 40 0
80 30

10 100 90
70 20
10
curd manufacturing waste by hydrogen-producing anaer-
90 60 obic microLora enriched in a separate continuous culture.
80
80
70
50
40
30 0 The high speci5c hydrogen production rate using unac-
70
5
60
60 20 climated biomass in this experiment con5rmed that food
10
50
40
50
40 waste could be suitable for fermentative hydrogen produc-
30
30 20 0 tion. Unlike the speci5c hydrogen production potential,
20 10
the speci5c hydrogen production rate was not enhanced by
5 10 15 20
addition of sewage sludge. However, the speci5c hydrogen
Protein (g COD/L) production rate higher than 56 ml H2 =g VSS=h could be
obtained at the waste composition from 81:19 to 100:0 and
Fig. 2. Contour lines of speci5c hydrogen production potential (ml
the VS concentration from 2.2% to 5.0%.
H2 =g carbohydrate-COD) versus carbohydrate concentration and
protein concentration; dotted line indicates the optimum condition.
3.2. Characteristics of hydrogen fermentation

Fig. 4 shows that the typical production of biogas (hy-

5.0
10 20 40 50 60 70 80
90 110 drogen and methane), carbohydrate, VFA and alcohol in
4.5
0
90
this study. In all the tests, cumulative hydrogen production
20 30 40
60 100 reached the maximum values within 3 days. Lag-phase
4.0 10 50
80
times (
) for hydrogen production were less than 0.78
0 70
day, which was shorter than reported values (2–4 days)
in batch tests with heat-treated inocula [14,28]. It seemed
VS concentration (%)

3.5 30

10
20 90 that environmental conditions such as substrate, protein,
3.0
40 60 80 inorganic nutrients, and pH were appropriate for spore ger-
0
50 70 mination and enzyme activation in this study [3]. Methane
2.5
was observed in all bottles where sewage sludge was
30
0 20
60 added, mainly due to methanogenic bacteria in sewage
40
sludge [17]. However, the amount of methane was less than
2.0 10
50

30
8:1 ml=g VS, which was much lower than reported values
1.5 40
20 (17:5 l=g VS) in which the methanogenic bacteria was ex-
1.0 0
10
20
30
ternally dosed [37]. Carbohydrate degradation and organic
10 acid production almost ceased as hydrogen production
0 10
0.5 0 ended up. Organic acid included mainly n-butyrate, acetate
0 20 40 60 80 100
and propionate, plus negligible quantities of formate, lac-
Food waste composition (%)
tate, iso-butyrate, n-valerate, iso-valerate and n-caproate.
100 80 60 40 20 0 Among them, n-butyrate was produced almost simulta-
Sewagesludge composition (%) neously with hydrogen production. Concurrent n-butyrate
production implied that Clostridium sp. would be related
Fig. 3. Contour lines of constant speci5c hydrogen production rate with hydrogen production [5,38]. The ultimate amount
(ml H2 =g VSS/h) versus waste composition and VS concentration; of hydrogen produced was also in proportion to that of
dotted line indicates the optimum condition. n-butyrate as shown in Fig. 5. The hydrogen yield based on
butyrateproduced (1:54 mole H2 =mole n-butyrate) was compa-
rable to the theoretical value (2 mole H2 =mole n-butyrate).
The regression model was considered to be suitable H2 and VFA production were followed by alcohol produc-
based on the calculated values of F and R2 . Fig. 3 shows tion, which represented hydrogen not liberated as a gas
that the speci5c hydrogen production rate curves had the [3]. In normal batch cultures, clostridia produced H2 =VFAs
 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616 1613

400 18
Cumulative H2 production

16
300

H2 produced (mmole)
14
(mL, STP)

200
12
FW:SS 100:0 10
FW:SS 80:20 Slope = 1.54
100 FW:SS 60:40 8 r2=0.960
FW:SS 40:60
6
0
20 4
Cumulative CH4 production

2
15
0
(mL, STP)

0 1 2 3 4 5 6 7 8 9 10
10 n-Butyrate produced (mmole)
Fig. 5. Relationship between n-butyrate production and hydrogen
5 production.

0
20000
Carbohydrate (mg COD/L)

during the exponential growth phase, and alcohols in the

15000
late growth phase [12,14]. Ethanol was the most abundant
alcohol, and small amounts of 2-propanol, 1-butanol and
10000
2-pentanol were also detected. Table 3 summarized COD
balances of metabolic products at day 3.
In anaerobic digestion of organic solid wastes, the produc-
5000
tion of liquid by-products (i.e., organic acid and alcohol) as
well as biogas is important to assess the process propriety.
0
16000 High proportion of organic acid and alcohol in the digestion
Organic acid (mg COD/L)

products enhance volume reduction of waste and methane

12000 production in the following methanogenic stage [39]. Fur-
thermore, they have great potential to be used as substrate
8000 for photosynthetic biohydrogen production process or bio-
logical nutrient removal process for wastewater treatment
4000
[13,29]. Table 3 shows that the fermentation eFciencies (the
total amounts of fermented products) ranged from 17.8% to
0
73.8%. The eFciencies were similar to, even higher than,
8000 the reported values (37–57% in food waste and 6–18% in
n-Butyrate (mg COD/L)

sewage sludge) employing acclimated acidogenic microor-

6000 ganisms [20,27,40]. It implied that hydrogen fermentation
could substitute the conventional acidogenic process for or-
4000 ganic solid wastes. The high eFciency of fermentation might
be originated from the ability of clostridia in the heat-treated
2000 sludge to use wide range of biopolymers with various ex-
tracellular enzymes or enzyme complexes [35]. As shown
0 in Fig. 6, the fermentation eFciencies ranged from 52.6%
5000 to 73.8% at the waste composition of 80:20 and 100:0. The
maximum fermentation eFciency was found at the waste
Alcohol (mg COD/L)

4000
composition of 80:20 and the VS concentration of 2.0%.
3000
DiGerence in optimum conditions for the maximum
hydrogen production, the speci5c production rate, and the
2000 fermentation eFciency was also reported in previous re-
searches [25,33,36]. Nevertheless, it was found that the ad-
1000
dition of sewage sludge up to 13–19% enhanced hydrogen
0 ←−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Fig. 4. Development of H2 , CH4 , carbohydrate, organic acid,
Time (days) n-butyrate and alcohol at 3.0% of VS concentration.
1614 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616

Table 3
COD balances of products at day 3

VS Food waste Initial Products (%, COD basis)

(%) (%, VS basis) COD (g)
H2 CH4 Organic acid Alcohol Total

HAca HPr b n-HBuc Totald

5.0 100 10.4 2.3 0.0 5.8 1.5 16.4 50.8 0.4 53.5
5.0 80 10.9 2.0 0.1 10.2 8.1 17.3 45.4 3.3 50.8
5.0 60 11.3 0.9 0.5 10.9 11.5 8.1 34.8 5.4 41.6
3.0 100 6.3 4.0 0.0 19.4 7.1 23.0 50.4 6.2 60.6
3.0 80 6.5 3.8 0.2 15.7 11.0 21.0 48.5 4.7 57.2
3.0 60 6.8 2.2 0.6 9.5 10.5 11.4 37.4 4.0 44.2
3.0 40 7.0 0.2 0.7 7.0 6.8 2.6 18.7 11.8 31.4
2.0 100 4.2 4.1 0.0 5.5 11.0 22.5 39.8 22.2 66.1
2.0 80 4.4 3.5 0.2 13.5 14.6 19.7 58.2 11.9 73.8
2.0 60 4.5 2.9 0.3 12.0 14.7 15.1 42.5 4.5 50.2
2.0 40 4.7 0.6 1.1 1.8 4.0 4.0 14.2 16.5 32.4
2.0 20 4.9 0.1 1.5 3.7 6.1 1.3 11.5 9.8 22.9
2.0 0 5.0 0.0 0.4 3.1 6.2 0.9 10.4 7.0 17.8
1.5 100 3.1 2.6 0.0 18.6 20.1 17.5 56.3 8.4 67.3
1.5 80 3.3 2.4 0.3 8.4 18.4 17.3 46.3 11.2 60.2
1.5 60 3.4 1.2 0.4 5.5 13.7 10.0 31.7 10.0 53.3
1.5 40 3.5 0.6 0.8 2.7 11.2 4.2 18.2 13.9 33.6
1.5 20 3.7 0.1 0.4 3.8 5.8 2.1 12.1 13.8 26.4
1.5 0 3.8 0.0 0.2 2.4 0.6 0.0 3.1 15.4 18.7
1.0 100 2.1 2.6 0.0 13.7 18.8 14.9 49.3 13.4 65.3
1.0 80 2.2 2.3 0.5 8.4 16.9 12.3 41.6 16.4 60.8
1.0 60 2.3 1.5 0.5 2.3 16.2 8.1 32.0 18.0 52.0
1.0 40 2.3 0.6 1.3 0.0 8.4 5.4 15.0 20.8 37.7
1.0 20 2.4 0.1 1.9 0.3 6.9 0.0 8.1 21.5 31.6
1.0 0 2.5 0.0 0.4 3.3 3.3 0.7 9.0 15.5 24.9
0.5 100 1.0 2.5 0.0 18.6 20.1 12.9 37.1 13.0 52.6
0.5 80 1.1 1.3 0.4 7.2 6.5 6.0 19.7 33.0 54.4
0.5 60 1.1 0.2 0.7 12.0 11.5 1.8 25.6 16.9 43.4
0.5 40 1.2 0.0 0.5 12.9 13.1 1.6 27.6 19.6 47.7
0.5 20 1.2 0.0 0.4 6.7 6.4 1.0 15.0 15.5 30.9
0.5 0 1.3 0.0 0.2 3.9 3.1 0.4 10.5 13.7 24.4
a HAc=acetic acid.
b HPr=propionic acid.
c n-HBu=n-butyric acid.
d Total=sum of acetic acid, propionic, n-butyric, formic, lactic, iso-butyric, n-valeric, iso-valeric, and n-caproic acids.

production as the hydrogen production was the highest at 4. Conclusions

the moderate reaction rate and fermentation eFciency. Also
the addition of sewage sludge to food waste would be ben-
e5cial in 5eld-scale operation by reducing dilution water
and alkaline dosage. The control of pH was a crucial factor
to hydrogen production and it was reported that pH below
5.0 inhibited hydrogen production [7,9,30]. As organic acids
were produced along with hydrogen, alkaline addition was
needed to prevent pH drop during fermentation [3]. Food
waste should require high alkaline dose due to its low al-
kalinity of 0:4 g CaCO3 =l. When food waste is mixed with
sewage sludge at the waste composition of 87:13, alkalinity
increases to 2:5 g CaCO3 =l. The enriched alkalinity could
reduce the amount of required alkali.
Thirty-two batch tests were performed to evaluate the
feasibility of biohydrogen production by anaerobic co-
digestion of food waste and sewage sludge under various VS
concentrations (0.5–5.0%, w/v), mixing ratios (0:100–
100:0, as VS basis). Response surface methodology success-
fully found the inLuences and interactions of variables on the
speci5c hydrogen production potential and the speci5c
hydrogen production rate. Food waste and sewage sludge
were considered as a suitable main substrate and a useful
auxiliary substrate, respectively, for hydrogen production.
The metabolic results showed that Clostridium sp. dom-
inated in the heat-treated anaerobic sludge. The principle
 S.-H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 1607 – 1616
80
70
Fermentation efficiency (%)
60
50
40
30
20
10
0 1 2 3
VS concentration (%)
Fig. 6. Fermentation eFciency at day 3.
conclusions are as follows.
(1) Food waste showed higher speci5c hydrogen pro-
duction potential than sewage sludge. The maximum
speci5c hydrogen production potentials of food waste
and sewage sludge were 121.6 and 32:6 ml H2 =g
carbohydrate-COD, respectively.
(2) The addition of sewage sludge on food waste up to 13–
19% could enhance hydrogen production potential due
to balanced carbohydrate/protein ratio. The maximum
speci5c hydrogen production potential of 122:9 ml=g
carbohydrate-COD was found at the waste composition
of 87:13 (food waste:sewage sludge) and the VS con-
centration of 3.0%.
(3) The speci5c hydrogen production rate increased up to
111:2 ml H2 =g VSS=h as both food waste composition
and VS concentration increased.
(4) The metabolic results revealed that hydrogen produc-
tion was accompanied by n-butyrate production. Fer-
mentation eFciencies at day 3 ranged from 17.8% to
73.8%, which implied that heat-treated sludge would be
suitable for the acidi5cation of real organic solid wastes
as well as hydrogen production.
Acknowledgements
This work was supported by grant No. M1-0203-00-0063
from the National Research Laboratory Program of the
Korean Ministry of Science and Technology.
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