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international journal of hydrogen energy 34 (2009) 88548858

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Bio hydrogen generation from kitchen waste in an inclined


plug flow reactor
S. Jayalakshmi a,*, Kurian Joseph b, V. Sukumaran c
a

Institute of Remote Sensing, Anna University Chennai, Chennai 600 025, India
Centre for Environmental Studies, Anna University Chennai, Chennai 600 025, India
c
Department of Biotechnology, Periyar Maniammai University, Vallam 613 403, Thanjavur, India
b

article info

abstract

Article history:

The performance of inclined plug-flow reactor of 0.15 m3 for hydrogen generation from

Received 19 June 2009

kitchen waste using 100  C heat treated biogas plant slurry as inoculum under solid phase

Received in revised form

anaerobic digestion was studied. The reactor pH stabilized at 5.6 after 21 days of its

17 August 2009

operation. 40% VS degradation was obtained and it generated 72 mL H2/gVS added. The

Accepted 23 August 2009

soluble metabolites in the reactor were predominantly butyric acid (4550%), acetic acid

Available online 20 September 2009

(2030%) and propionic acid (1020%).


2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Keywords:
Biohydrogen
Anaerobic digestion
Kitchen waste
Inclined plug-flow reactor

1.

Introduction

Waste materials such as food wastes, industrial wastes,


wastewater treatment plant wastes and municipal solid
wastes having higher fraction of biodegradable as well as
carbonaceous materials are used for anaerobic digestion to
generate methane [14]. The use of methane as a fuel could be
debatable, due to its global warming potential. This calls for
study of alternate eco friendly, high efficiency future energy
options such as biohydrogen. Hydrogen is a clean fuel since its
combustion does not generate polluting emissions. According
to energy experts, hydrogen is safe, versatile and has highenergy content as well as high utilization efficiency [1].
Much recent interest has been expressed in the biological
generation of hydrogen from waste materials by dark
fermentation, due to its potential importance in economy
[25]. Though the conventional low solid anaerobic digestion

is a proven technology for methane generation from Municipal Solid Waste (MSW) the technology for solid phase
anaerobic digestion system has not yet been developed. This
paper presents the feasibility of solid phase anaerobic digestion for generating hydrogen from kitchen waste using an
inclined plug flow reactor.

2.

Materials and methods

2.1.

Characterisation of kitchen waste

The kitchen waste used as the feedstock was collected from


kitchen of a hostel with around 1000 inhabitants. The
composition of the kitchen waste was studied by manual
segregation. The kitchen waste was analysed for moisture

* Corresponding author. Tel.: 91 44 22203135; fax: 91 44 22352166.


E-mail address: j_lak2001@yahoo.co.in (S. Jayalakshmi).
0360-3199/$ see front matter 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.08.048

8855

international journal of hydrogen energy 34 (2009) 88548858

content, pH, carbon, nitrogen, total solids and volatile solids


as per standard methods [6].

2.2.

Inclined plug flow reactor

A pilot scale Inclined plug flow reactor was used for the
hydrogen generation study. The principal objective of developing such a design was to achieve a low initial investment,
high efficiency and relatively simple operational and maintenance operation [25]. The cylindrical shaped reactor was
200 cm long and 30 cm in diameter with an internal volume of
0.15 m3. The reactor was fabricated using mild steel plates
painted with anti corrosives. The reactor was kept at 20 angle
with horizontal to facilitate easy movement of the wastes
within the reactor.
The crosssection of the plug-flow reactor is presented in
Fig. 1. The hopper shaped feed arrangement for material
supply was provided at the down end of the reactor along with
an arrangement made for collecting the digested material
from the reactor at the top end. A screw arrangement was
provided inside the reactor to achieve mixing and to push the
material from the inlet end to the outlet end. The screw was
designed with 14 leads to maintain 7 days retention time
when operated manually by rotating two turns of the screw
per day. In one rotation the waste materials get pushed by one
lead.
The reactor was initially filled with 3 kg of heat-treated
inoculum (HTI) and kept undisturbed for 15 days under
anaerobic condition. The inoculum was heat treated at 100  C
for 30 min [10] for inactivating the non-spore forming
methanogens. The harvested spore forming acidogens such as
Clostridium sp. and Enterobacter sp. were used for producing
hydrogen from KW. Continuous feeding of the reactor was
done at the rate of 7 kg of kitchen waste per day after 15 days
of the startup. The reactor was fed twice in a day at the rate of

3.5 kg at 12 h interval. At the time of each feeding the screw


was fully rotated once.
The digested slurry moved up the reactor was collected at
the top end after 7 days. The slurry was characterized for pH,
Total Solids (TS), Volatile Solids (VS), Total Organic Carbon
(TOC) and Total Kjeladal Nitrogen (TKN) as per standard
methods [6]. The Total Volatile Fatty Acid (TVFA) concentration was analysed once in three days. The quantity of biogas
generated was measured using a gas flow meter and the
composition of the biogas was analysed for hydrogen and CO2
daily using Chemito 1000 model gas chromatograph fitted
with a thermal conductivity detector and a 1.83 m  3.18 mm
ID stainless-steel column packed with molecular sieve 5A. The
operational temperatures of injector, detector and column
were kept at 80  C, 90  C and 50  C respectively. Nitrogen was
used as a carrier gas at a flow rate of 50 mL/min. Volatile fatty
acid (VFA) was quantified using gas chromatograph Chemito
1000 model fitted with Flame Ionization detector and a 1 m
stainless steel column packed with GDX 103 (60/80 mesh).
The temperature at injector, detector and column were 175  C,
190  C and 145  C respectively. Nitrogen was used as a carrier
gas at a flow rate of 45 mL/min.

3.

Results and discussion

3.1.

Characteristics of kitchen waste

The average composition and characteristics of kitchen waste


used for this study is depicted in Tables 1 and 2 respectively.
The waste consisted of about 96% of biodegradable organics,
which were suitable for anaerobic digestion system [7]. The
food waste was around 66% of the total waste. Vegetable
waste was around 27% of the total waste. The egg shell,

Gas Outlet

70

372

300

68

50
70

Inlet

33.3x3.35

90
43 50

Screw Handle

Digested Material
Outlet
Screw Shaft

33.4x3.3

70

68

Screw Arrangement

11

0
50

50

All Dimensions are in mm

33.3x3.35

Leachate Outlet

2000

Fig. 1 Crosssection of inclined plug-flow reactor.

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international journal of hydrogen energy 34 (2009) 88548858

Table 1 Composition of the kitchen waste used for the


Biohydrogen Studies.
Component

Weight
(kg/day)

Weight
(%)

Standard
Deviation

1
2
3
4
5
6
Total

Food Waste
Vegetable Waste
Tea Waste
Egg Shell
Packing Materials
Ash

51.40
20.10
0.75
0.85
1.10
2.80
77.90

66.02
26.96
0.96
1.09
1.36
3.61
100.00

1.86
2.80
0.20
0.24
0.32
0.33
3.37

Biogas (L/kgwaste)

Sl.No

Biogas

Hydrogen

7
6
5
4
3
2
1
0
0

10

20

30

40

50

60

70

80

90

100

110

Time (Days)
packing material and ash content were around 1.1%, 1.4% and
3.6% of the total waste respectively.
The optimal pH reported in literature for anaerobic
hydrogen generation was essentially within the range of 5.5
6.7 [8,9]. pH of the waste was 5.51  0.021; moisture content
was 83.81  0.2% wet wt. Total solids and Volatile solid were
16.20  0.2% wet wt. and 86.13  0.44% dry wt. respectively.
TOC and TK was 47.58  1.04% dry wt. and 2.26  0.12% dry wt.
respectively. The C/N ratio was around 20:1 to 23:1, which
showed the suitability of the kitchen waste for anaerobic
digestion.

3.2.

Hydrogen generation

The biogas generation in the pilot scale reactor is depicted in


Fig. 2. The biogas and hydrogen generation rate was only
about 0.1 L/kgwaste in the initial days. Then it gradually
increased to around 6.5 L/kg waste after 31 days of the reactor
operation there after it maintains the same. When butyric acid
is the end product, a theoretical maximum of 7 L H2/Kg Waste is
possible, but it only generates 3.84 L H2/kg waste [14]. More
hydrogen generation is possible if more butyrate is found in
the system.
The yield of hydrogen was observed around 72 mL H2/g VS
added. This is 20% reduced yield than the yield obtained in
laboratory scale reactors [10]. The increased iron concentration in the pilot scale reactor due to rusting by generated acids
is the possible reason for the reduction of yield [11]. The
variation of shape and configuration of the laboratory scale

Fig. 2 Daily variation of biogas and hydrogen generation


in pilot scale reactor.

reactor and pilot scale reactor may also be the possible


reasons for the reduced yield.
Biogas typically refers to a gas produced by the biological
breakdown of organic matter in the absence of oxygen. The
biogas contained only hydrogen and CO2 as depicted in Fig. 3.
Methane was not reported in this study. The hydrogen
concentration in the initial days of the reactor operation was
only around 10%. Then the hydrogen concentration increased
gradually upto around 50% in the later days. After 15th day of
the reactor operation the hydrogen concentration remained
the same as 50% till the end of the reactor operation.

3.3.

Variation of pH in hydrogen generation

The initial pH of the pilot scale reactor was 5.5 as presented in


Fig. 4. The pH reduced to 4.5 in 3 days and at this stage the
hydrogen generation was very low (Fig. 2). The higher
concentration of TVFA was the reason for the drop of pH in the
reactors [12]. Then the reactor pH increased from 4.55.6 in 21
days and thereafter maintained at pH 5.6. This is due to the
efficient conversion of VFA into hydrogen [13]. The hydrogen
generation also increased with increased pH. This result also
falls with the earlier researchers results that the optimum pH
for hydrogen generation is 5.56.0 [1416].

100

Sl.No.
1
2
3
4
5
6
7

Parameter

Average

Standard Deviation

pH
Moisture Content
(% wet wt.)
Total Solids
(% wet wt.)
Volatile Solids
(% dry wt.)
Total Kjeladal
Nitrogen (% dry wt.)
Organic Carbon
(% dry wt.)
C/N

5.51
83.81

0.002
0.200

16.20

0.200

86.13

0.440

2.26

0.115

47.58

1.038

21:1

Biogas Composition (%)

90

Table 2 Characteristics of kitchen waste.

H2
CO2

80
70
60
50
40
30
20
10
0
0

10

20

30

40

50

60

70

80

Time (Days)
Fig. 3 Composition of biogas.

90

100

110

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international journal of hydrogen energy 34 (2009) 88548858

Hpr
16%

6
5

pH

n-Hbu
49%

3
2
1

Hac
35%

0
0

10

20

30

40

50

60

70

80

90

100 110

Time (Days)
Fig. 6 Profile of TVFA in biohydrogen generation.

Fig. 4 pH variation on hydrogen generation.

3.4.

Effect of VFA on hydrogen generation

The variation of TVFA and soluble metabolites is depicted in


Fig. 5. The TVFA concentration in the initial days was low then
it began to increase. It reaches a maximum of around
5142 mg/kg. After 21 days TVFA generation in the reactor was
constant. In this experimental method the soluble metabolites principally consisted of butyric acid, acetic acid and
propionic acid. The butyric acid concentration was around 45
50%, acetic acid concentration was 2030% and butyric acid
concentration was around 1020% of the TVFA (Fig. 6). This
shows that the hydrogen generation follows the butyrate
biochemical pathway of equation (1) [15]. This result falls with
the earlier study carried out in the mesophilic temperature
condition [17]. The butyric acid and acetic acid concentration
in the initial days were almost same but after 14 days the
concentration of butyric acid increased.
C6H12O6 / CH3CH2CH2COOH (Butyrate) 2H2 2CO2

useful indicators for monitoring hydrogen generation. H2


generation is normally accompanied with the acid generation
due to the acidogenic metabolism where generation of acidic
intermediates reflects changes in the metabolic pathway of
the microorganisms [18,19]. The metabolic pathway also
provides a better knowledge of such changes and conditions
favorable for H2 generation. The pH drop is generally considered as the index of VFA generation and the existing buffering
capacity in the system.

3.5.
Characteristics of slurry digested in pilot scale
reactor
The variation of TS, VS, TOC and TKN of the digested slurry in
the reactor is presented in Table 3 respectively. In the early
days of the reactor operation the digestion of TS and VS was
slow. Then it gradually began to increase. After the third week
of the reactor operation the reactor TS and VS got stabilized
with TS around 8.5% wet wt. and VS around 40% dry wt.

(1)

The formation of hydrogen is accompanied with VFA


generation during an anaerobic digestion process. Therefore,
the VFA concentration distributions and their fractions are

Table 3 Characteristics variation of digested slurry in


biohydrogen generation.
Sl.No Days

5500

Total
Volatile
solids
solids
(% wet wt.) (% dry wt.)

5000
TVFA
n-Hbu
Hac
Hpr

4500

VFA (mg/kg)

4000
3500
3000
2500
2000
1500
1000
500
0
0

16 24 32 40 48 56 64 72 80 88 96 104 112

Time (Days)
Fig. 5 Variation of VFA in biohydrogen generation.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

0
7
14
21
28
35
42
49
56
63
70
77
84
91
98
105

16.2
10.34
9.85
8.76
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5
8.5

86.13
68
59
52
43
44
44
44
44
44
44
44
44
44
44
44

Total
Total
organic
Kjeladal
carbon
nitrogen
(% dry wt.) (% dry wt.)
47.58
39.86
39.1
38.98
38.65
38.31
38.31
38.31
38.31
38.31
38.31
38.31
38.31
38.31
38.31
38.31

2.26
2.5
2.7
3.1
3.3
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5
3.5

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international journal of hydrogen energy 34 (2009) 88548858

In the initial days of the reactor operation the rate of TOC


reduction was low. This may be because of the lower quantity
of microbial concentration in the initial days. After the 14th
day of the reactor operation the TOC reduction rate increased
appreciably. This may due to the utilization of organic
compounds for microbial metabolism by the bacteria [20]. The
TKN in the reactor showed continual increase due to accumulation of ammonical nitrogen [2124].

4.

Conclusion

The yield of hydrogen was observed around 72 mL H2/gVSadded


in the pilot scale inclined plug-flow reactor. Hydrogen
concentration of around 46  7% was found in the biogas and
the rest was CO2. The maximum hydrogen generation from
kitchen waste was observed in the pH of 5.56.0. TVFA
generated contains only butyric acid, acetic acid and propionic
acid. The hydrogen generation was followed the butyric acid
pathway. From the findings it is evidenced that the inclined
plug-flow reactor is suitable for hydrogen generation from
kitchen waste under solid phase anaerobic digestion.

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