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Biomethane production from maize and liquid cow manure Effect of share
of maize, post-methanation potential and digestate characteristics
Mari Seppl a,, Ville Pyykknen a,1, Ari Visnen b, Jukka Rintala a,2
a
b
University of Jyvskyl, Department of Biological and Environmental Science, P.O. Box 35, FI-40014 University of Jyvskyl, Finland
University of Jyvskyl, Department of Chemistry, P.O. Box 35, FI-40014 University of Jyvskyl, Finland
h i g h l i g h t s
" Co-digestion of cow manure and maize was studied in different share of maize.
" The highest methane yield was achieved, when share of maize was 40% VS of feed.
" Post-methanation potential was low, when methane yield from reactor was high.
" Trace elements content decreased in digestate when the share of maize increased.
a r t i c l e
i n f o
Article history:
Received 23 April 2012
Received in revised form 14 December 2012
Accepted 18 December 2012
Available online 8 January 2013
Keywords:
Anaerobic digestion
Trace elements
Manure
Methane production
Maize
a b s t r a c t
This study investigates the co-digestion of liquid cow manure and maize with different share of maize in
continuously stirred tank reactors (CSTRs). The objective was to determine the methane yield of reactor
and the post-methanation potential of the digestate from different reactor trials. The highest specic
methane yield (259 Nl CH4/kg volatile solids (VSs)) was obtained when the share of maize in the feedstock was 40% (VS) and the second highest specic methane yield was when the proportion of maize
was 60% (VS) (234 Nl CH4/kg VS). The post-methanation potential of the digestate was determined in
batch assays. The minimum value (maize 40%, 75 1 Nl CH4/kg VSfeed) occurred when the methane yield
in the reactor was at a maximum and when the methane yield was at a minimum (maize 67%,
153 46 Nl CH4/kg VS) the potential at a maximum (140 Nl CH4/kg VSfeed). Plant nutrients and trace elements were determined in the feedstock and the digestate. As maize contained fewer nutrients than
manure the concentration of the nutrients and trace elements in the digestate decreased when the share
of maize in the feedstock increased. Thus it seems that even though the CSTR co-digesting maize and
manure can be operated with high organic loading rate (OLR) and short hydraulic retention time (HRT)
a signicant part of the methane yields of the feedstock may be lost, if the post-methane potential is
not considered. Based on the yield results of the reactor trials a biogas plant (270 kW) could produce
energy (methane) almost 2400 MW h, when the reactor operates at OLR 2.5kg VS/m3/d and feedstock
consists of 60% VS of maize and 40% VS of liquid cow manure.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Biogas production is one of the most promising ways to produce
renewable energy from energy crops and other organic materials.
The benets of anaerobic digestion include the production of two
usable products: biogas and digestate. The biogas can be used in
heat and power production or upgraded to biomethane and used
a vehicle fuel or injected into the gas grid. Agricultural wastes like
Corresponding author. Tel.: +358 40 8053904; fax: +358 14 617 239.
E-mail address: mari.p.seppala@jyu. (M. Seppl).
Present address: MTT Agrifood Research Finland, Animal Production Research, FI71750 Maaninka, Finland.
2
Present address: Tampere University of Technology, Department of Chemistry
and Bioengineering, P.O. Box 541, FI-33101 Tampere, Finland.
1
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.12.069
cow and pig manures are commonly available and are used feedstock in the biogas production. Manures have a low biogas yield
potential and that is why co-digestion with crop material or organic wastes is useful. Manures provide good buffering capacity and a
wide range of nutrients, while the addition of energy crops increases the energy yield of the process. The anaerobic digestion
is also recycling the nutrients as it captures nutrients from agricultural wastes and energy crops and recycles them to the land in the
form of organic fertilizer, which is a valuable fertilizer for crops.
Maize (Zea mays) is considered a chill-sensitive species with a
relative high temperature required for germination, development,
and dry matter accumulation. Improvements in temperature tolerance would assist maize cultivation in northern Europe. Maize cultivation for biogas production has recently gained interest also in
210
Table 1
The characteristics of inoculum, liquid cow manure, and maize, variety valdes, standard deviation.
Inoculum
Maizea
Cow manure Ia
Cow manure II
TS (%ww)
VS (%ww)
Ntot (g/l)
NH4N (g/l)
SCOD (g/l)
5.0
16.4
5.7
5.0
3.9
15.2
4.7
4.3
2.5
15b
2.3
1.5
0.15b
0.76
0.45
12.0
134b
13.1
8.6
Nl CH4/kg TS
Nl CH4/kg ww
81
360 8
212 18
104
334 7
172 16
4
55 1
10 2
Cow manure I was used in feedstock during days 166, and cow manure II during days 67136.
a
Methane production of inoculum subtracted.
b
mg/g TS.
Table 2
Operational conditions, feedstock and digestate characteristic, and methane production in CSTRs standard deviation.
Substrate
Cow manure
R1
I
R2
I
II
III
R3
I
II
III
(% VS)
(% ww)
0
0
20
8
30
11
40
17
50
18
60
26
67
35
(% ww)
(kg VS/m3 /d)
(d)
2
23
2
27
2
28
2
30
29
2
25
15
2.5
25
6
3
25
(d)
d/HRT
042
1.8
042
1.6
4391
1.5
98140
1.4
042
1.7
4383
1.6
8491, 98126
1.4
TS (%)
VS (%)
SCOD (g/l)
NH4N (g/l)
Ntot (g/l)
5.7
4.7
13.6
0.72
2.3
6.4
5.4
14.5
0.67
2.4
6.2
5.4
11.7
0.45
1.6
6.7
5.9
11.7
0.33
1.7
5.7
5
14.8
0.63
2.2
6.9
6.3
13.9
0.41
1.8
8.3
7.5
14.9
0.32
1.9
TS (%)
VS (%)
SCOD (g/l)
NH4N (g/l)
Ntot (g/l)
NO3N (g/l)
pH
VFAtot (mg/l)
Soluble P (g/l)
Ptot (g/l)
Ktot (g/l)
4.8 0.2
3.7 0.3
10.0 1.0
0.87 0.04
2.5 0.1
0
7.5 0.1
60 104
0.11
0.51
3.38
5.0 0.4
3.9 0.4
10.4 0.4
0.81 0.05
2.5 0.1
0
7.5 0.1
69 119
0.16
0.51
3.47
4.5 0.1
3.4 0.1
12.2 1.0
0.84 0.03
2.3 0.1
0
7.4 0.1
1918 568
0.15
0.46
3.22
4.0 0.1
3.1 0.1
10.3 1.0
0.66 0.03
1.9 0.1
0
7.4 0.1
55 22
0.18
0.37
3.05
4.7 0.0
3.7 0.1
10.5 0.8
0.79 0.04
2.4 0.0
0
7.47 0.1
112 165
0.13
0.44
3.42
4.7 0.2
3.7 0.2
9.1 0.7
0.65 0.05
2.2 0.1
0
7.4 0.1
1079 129
0.15
0.38
3.55
4.9 0.1
4.0 0.1
12.7 1.0
0.53 0.05
1.9 0.1
0
6.9 0.3
4854 798
0.21
0.35
3.4
TS removal (%)
VS removal (%)
CH4 content (%)
16
21
57 2
22
27
52 1
28
36
44 6
41
48
52 2
18
26
51 3
32
41
48 2
41
47
41 9
(Nl/kg VS)
212
241
256
271
286
301
311
(Nl/kg VS)
(Nl/kg ww)
193 2
9.0 0.1
91
198 7
10.7 0.4
82
194 84
10.5 4.5
76
259 6
15.3 0.3
95
221 14
11.0 0.7
77
234 16
14.6 1.0
78
153 46
11.5 3.5
49
Reactor
Feeding regime (FR)
Share of maize
Feedstock
Digestate
211
212
and they were sealed with butyl rubber stoppers and aluminium
crimps. The contents of the vials were ushed with nitrogen gas
for 3 min to remove residual oxygen. The post-methanation potentials of the digestates were measured from R2 and R3, when the
share of maize in the feedstock was 30%, 40%, 60%, and 67%. The
post-methanation assays were incubated for a total of 125136 d.
213
300
R2
250
200
150
100
R3
50
R1
R2
R3
0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
days (d)
Fig. 1. Specic methane yields as weekly averages in digestion of manure alone (R1) and co-digestion of cow manure with maize 20%, 30% and 40% of feedstock VS (R2) and
50%, 60% and 67% of feedstock VS (R3). The vertical dashed line indicates the change of the share of maize in the feedstock.
Table 3
The co-digestion of the animal manure and plant material in CSTRs operated within the mesophilic temperature range as reported in literature.
Feedstock (ratio on VS basis)
HRT (d)
VS removal (%)
CH4 (%)
Reference
5
5
5
5
5
5
30
5
5
5
5
5
5
5
5
2
2
2
2
2.5
3
3.84
2
3
4
5
3
4
5
6
27
28
30
25
25
25
16
33
30
28
26
29
22
18
15
27
36
48
26
41
47
46
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
198
194
259
221
234
153
210
171
263
304
300
240
220
210
210
52
44
52
51
48
41
67
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
n.r.
This
This
This
This
This
This
[28]
[9]
[9]
[9]
[9]
[10]
[10]
[10]
[10]
study
study
study
study
study
study
Table 4
The post-methanation potential of the digestate at 35 C calculated per feedstock (TS or VS) of CSTR.
Share of maize (OLR)
30%
40%
60%
67%
(2 kg VS/m3/d)
(2 kg VS/m3/d)
(2.5 kg VS/m3/d)
(3 kg VS/m3/d)
TS (%)
6.2
6.7
6.9
8.3
VS (%)
5.4
5.9
6.3
7.5
full scale digester the OLR was doubled from 2.11 to 4.25 kg VS/m3/
d and stable operation was still achieved at OLR 5.5 kg VS/m3/d
with maize and pig manure [25]. In this study the overloading of
reactor (R3) occurred when the share of maize in the feedstock
was increased to 67% and OLR was 3 kg VS/m3 d. In co-digestion
of crop silage and cow manure the overloading occurred the OLR
7.78 g VS/l/d and the share of crop silage in the feedstock was
81% VS [6], while the process performed well at OLR of 5.15 g VS/
l/d and the cow manure VS:crop silage VS was 29:71 [6]. In the
present study the HRT was 25 d while in the study by Comino it
was ca 42 d [6]. In this study the HRT was too short for efcient
degradation, as the amount of non-degraded matter in the digestate increased leading to an increase in the post-methanation potential (Table 4).
The post-methanation potential of the digestate was determined for digestates when the share of maize was 30%, 40%, 60%
Post-methanation potential
Nl CH4/kg/VSfeed
Nl CH4/kg/TSfeed
Nl CH4/kg/ww
99
75
101
140
86
66
92
127
5
4
6
11
SCOD (g/l)
214
15
14
13
12
11
10
9
8
7
R1
R2
R3
R2
R3
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
110
120
130
140
150
110
120
130
140
150
110
120
130
140
150
6000
VFAtot (mg/l)
5000
R3
4000
3000
2000
R2
1000
0
0
10
20
30
40
50
60
70
80
90
100
NH4 -N (g /l)
1.2
1.0
R2
0.8
0.6
R3
0.4
0
10
20
30
40
50
60
70
80
90
100
6.0
TS (%)
5.5
R3
5.0
4.5
4.0
R2
3.5
0
10
20
30
40
50
60
70
80
90
100
Time (d)
Fig. 2. The characteristics (SCOD, VFA, NH4-N, TS% of digestate) of the digestates in digestion of the manure alone (R1) and the co-digestion of the cow manure with maize
20%, 30% and 40% of the feedstock VS (R2) and 50%, 60% and 67% of the feedstock VS (R3). The vertical dashed line indicates the change of the share of maize in the feedstock.
215
Table 5
The trace element (plant nutrient and heavy metal) content of the maize, liquid cow manure, inoculum and digestate from CSTR in this study and biogas plant in Austria (maize
silage and digestate 100% maize) [30].
Plant nutrients
S
(mg/kg TS)
Mg
(mg/kg TS)
K
(mg/kg TS)
Na
(mg/kg TS)
Maize
Maize silagea
Inoculum
Cow manure I
Cow manure II
534
990
3728
3706
2855
1428
1250
6164
5595
4181
19327
8000
47360
40753
33207
90
50
2751
1616
2496
2089
3590
8322
7346
6046
3659
3840
3597
3195
3336
3169
2915
3610
7200
7488
6704
5875
6254
5427
4375
4120
50673
57327
50600
49273
62617
49370
43377
28020
2413
2680
2599
2705
2764
2009
1722
680
9663
9809
9347
8621
7994
7562
7041
14170
Reactor
Share of
maize
1
2
2
2
3
3
3
Digestate 100%
maizeb
0
20
30
40
50
60
67
P
(mg/kg TS)
Heavy metals
Cd
0.82.7c
(mg/kg TS)
Cu
1.24.3c
(mg/kg TS)
Cr
1.13.7c
(mg/kg TS)
Maize
Maize silagea
Inoculum
Cow manure I
Cow manure II
0.0
n.a.
0.0
0.0
0.0
4.3
4.9
20.8
18.1
14.7
0.0
<0.05
2.7
2.5
1.3
0.0
0.0
0.0
0.0
0.0
0.0
0.0
n.a.
17.5
18.1
20.0
22.3
17.2
16.8
14.2
23.9
4.1
3.6
1.3
1.7
2.8
1.7
1.7
1.9
Reactor
Share of
maize
1
2
2
2
3
3
3
Digestate
100% maizeb
0
20
30
40
50
60
67
Si
(mg/
kg TS)
Ca
(mg/kg TS)
C
(g/
kg TS)
N
(g/
kg TS)
C:N rate
108
80
526
345
430
515
n.a.
3071
1925
960
2991
1800
10597
9675
7225
442
n.a.
413
441
438
16
n.a.
22
20
16
28
n.a.
19
22
27
555
562
618
773
463
536
554
1640
4840
5719
2007
2083
6687
2274
1778
n.a.
12543
12867
11723
10670
11600
9779
8987
9140
416
412
407
403
409
410
430
n.a.
23
24
23
24
25
23
23
n.a.
18
17
18
17
16
18
19
n.a.
Fe
(mg/kg TS)
Ni
26.6c
(mg/kg TS)
Zn
310c
(mg/kg TS)
Pb
1.86c
(mg/kg TS)
As
1.75.5c
(mg/kg TS)
0.0
0.7
2.8
2.6
2.1
21.5
22.4
92.5
85.2
65.1
0.0
n.a.
0.0
0.0
0.0
0.0
n.a.
0.0
0.0
0.0
3.0
3.0
4.7
16.6
2.3
2.0
0.0
3.1
109.1
93.4
90.2
90.7
85.4
80.8
72.5
150.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
n.a.
0.0
0.0
0.0
0.0
0.0
0.0
0.0
n.a.
with syringe during operating the reactor (Fig. 2). Also during the
overloading the VFAtot concentration was high, 4854 798 mg/l,
when 67% feedstock VS was maize (Fig. 2, Table 2), consisting
mainly of acetate (3950 mg/l) and propionate (980 mg/l). The
VFAtot concentrations were about 1% of SCOD concentrations in
reactors, except when the share of maize was 30%, 60% and 67%.
In that case the VFA contributed for 16%, 12% and 38% of the SCOD,
respectively. During the trials in the three reactors, the ammonium
concentration of the digestate varied from 0.53 to 0.87 g/l (Fig. 2),
Ntot from 1.9 to 2.5 g/l indicating decreasing trends during the trials due to the lower nitrogen content of maize as compared to
manure and inoculum (Table 1, Fig. 2). TS and VS removal were calculated for all operational conditions in the reactors. TS removal
was 16% and VS removal 21% of liquid cow manure reactor (R1).
When the share of maize was increased (share of maize 30% in
the feedstock) the TS and VS removals increased being 28% and
36%, respectively and 41% (TS) and 48% (VS), when the share of
maize was 40% in the feedstock (Table 2). The TS and VS removals
were at low level, which is due to short HRT. This can be noticed
also in the relatively high post-methanation potentials (Table 4).
Based on the results of these reactor experiments a biogas plant
(270 kW) could produce about 240,000 Nm3 of methane annually if
the reactor (liquid volume 1000 m3) operates with OLR 2.5 kg VS/
216
Acknowledgements
This study was supported by grants from the University of
Jyvskyl and the Fortum Foundation. The authors wish to thank
the Kalmari biogas farm for providing the liquid cow manure and
inoculum, and Agrifood Research Finland (MTT) in Piikki for providing the maize material. Furthermore, Mervi Koistinen is kindly
acknowledged for her help in the laboratory.
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