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ABSTRACT
L. M. Contreras
Agricultural solid residues are a potential renewable energy source. Rice harvesting and production
C. R. Sebrango
in Sancti Spíritus province, Cuba, currently generates residues without an environmentally University of Sancti Spíritus ‘José Martí Pérez’,
Ave. de los Mártires 360,
sustainable disposal route. Rice residues (rice straw, rice husk and rice residues from the drying Sancti Spíritus,
Cuba
process) are potentially an important carbon source for anaerobic digestion. For this paper, rice
H. Schelle
residues were placed for 36 days retention time in anaerobic batch reactor environments at both Leibniz Institute for Agricultural Engineering
W W Potsdam-Bornim,
mesophilic (37 C) and thermophilic (55 C) conditions. Biogas and methane yield were determined as
Max-Eyth-Allee 100,
well as biogas composition. The results showed that rice straw as well as rice residues from the 14469 Potsdam,
Germany
drying process had the highest biogas and methane yield. Temperature played an important role in
I. Pereda (corresponding author)
determining both biogas yield and kinetics. In all cases, rice straw produced the highest yields; under Instituto Superior Politécnico ‘José Antonio
Echeverría’ (CUJAE),
mesophilic conditions the biogas yield was 0.43 m3 kgVS1, under thermophilic conditions biogas 11901, 114 Street,
yield reached 0.52 m3 kgVS1. In the case of the rice husk, the biodegradability was very low. Marianao, Havana,
Cuba
Methane content in all batches was kept above 55% vol. All digested material had a high carbon: E-mail: [email protected]
nitrogen (C:N) ratio, even though significant biodegradation was recorded with the exception of rice
husk. A first-order model can be used to describe the rice crop residues fermentation effectively.
Key words | anaerobic digestion, biodegradability, biogas yield, kinetic, methane potential, rice crop
residues
INTRODUCTION
Agricultural residues constitute a major biomass potential (Zhang & Zhang ). In the case of rice husk (RH) it is
that can be used as a renewable energy source. The biogas mainly converted into energy through thermo-chemical pro-
process, which is one of the most profitable processes to cesses considering its high content of inorganic components.
obtain energy from biodegradable residues, is carried out In the case of rice residues from the drying process (RD)
under anaerobic conditions where volatile solids are there are no reported values of energy production either
destroyed and converted to methane and carbon dioxide. As through biological or thermo-chemical conversion processes.
this gas contains a significant proportion of methane it may The anaerobic process is a well established technology
be utilized for energy production. Solid and liquid effluents and can be an alternative to convert not only the rice
constitute a high value by-product from anaerobic digestion. straw, but also the rice residues from the drying process
Rice crop residues are an important source of agricul- and the rice husk into energy. Two of the most important
tural wastes in rice-producing countries. In the case of factors to be considered when applying methane fermenta-
rice straw (RS), although there are methods available in tion to lignocellulosic material are the rate and extent
order to use it (animal feedstock, fuel, etc.) significant (biodegradability) of degradation. High biodegradability
amounts remain unused and are burned in the open fields. means not only more methane can be generated per unit
This practice provokes serious environmental damage and feed mass, but also that less residue results for the sub-
security problems both due to air pollution and fire disasters sequent disposal. A fast biodegradation rate reduces the
(Lei et al. ). Furthermore rice straw is also incorporated required size for a reactor, and thus makes the process
into the soil, reducing harvesting yields and increasing more attractive economically. Both factors are functions of
foliage diseases with a degradation of soil conditions the intrinsic properties of the lignocellulosic material itself
doi: 10.2166/wst.2012.951
1143 L. M. Contreras et al. | Methane potential and biodegradability of rice residues Water Science & Technology | 65.6 | 2012
and the microorganisms involved (Tong et al. ). It is were applied to characterize the residues. Characterization
therefore important to know the substrate characteristics is summarized in Table 1. Chemical characterization
when deciding the appropriate reactor configuration included pH, electrical conductivity (EC), total solids (TS),
(whether one- or two-stage operation) for different agro- volatile solids (VS), carbon (C), nitrogen (N), elemental sul-
industrial residues (Kang & Weiland ). phur (S), crude fibre (XF), and lignin (L). Method and
Biochemical methane potential (BMP) assay is used to references are mentioned in Table 1.
establish the anaerobic process performance, for determi- Rice residues were previously pre-treated (air-dried,
nation of biogas and/or methane potential and also for hammer-milled to about 1–10 mm) and then sieved to par-
determining the rate of biodegradation in general (Owen ticle sizes from 3–5 mm to facilitate biodegradability
et al. ; Angelidaki et al. ). Process kinetics play a during the anaerobic process.
fundamental role in the development and operation of
anaerobic treatment systems. Based on the biochemistry Lab-scale experiments
and microbiology of the anaerobic process, kinetics provide
a rational basis for process analysis, control and design. In The biochemical methane potential (BMP) test was used to
addition to the quantitative description of the rates of evaluate biogas/methane production rates. Batch exper-
waste utilization, process kinetics also deal with operational iments were carried out in lab-scale 2 L reactors
and environmental factors affecting theses rates. A sound according to the guideline VDI 4630 () under discon-
knowledge of the kinetics allows for the optimization of per- tinuous operation. Batches were conducted at 37 and
W
formance, a more stable operation and better process 55 C in triplicates. Total digestion time was 36 days. Meso-
control (Pavlostathis & Giraldo-Gómez ). philic and thermophilic fresh inoculums were used,
In Cuba, rice production and harvesting is one of the previously degassed in order to deplete the residual biode-
main agricultural activities since rice is a basic food for gradable organic material present in it. Principal inoculum
the Cuban population. During harvesting some residues characterization is shown in Table 2.
are generated without a proper final disposal. These
wastes i.e., rice straw, rice husk and rice residues from the Table 1 | Chemical parameters, methods, reference and residues characterization
drying process have no environmentally-sustainable dispo-
sal route at present and could be used as a carbon source Value
it necessary to determine the maximum biogas and methane VS (%TS) LUFA Bd. III 8.1a 77.8 79.6 77.5
yield, and the ultimate biodegradability from these residues C (%TS) Standard methods 37.7 37.9 36.9
when operating at both mesophilic and thermophilic con- N (%TS) Standard methods 0.38 0.88 1.12
ditions. The kinetic performance is also studied in the S (%TS) Standard methods 0.097 0.13 0.16
present paper. XF (%TS) LUFA Bd. III 6.1.2a 47.9 35.1 34.3
L (%TS) LUFA Bd. III 6.5.3a 18.9 8.6 10.4
C:N 99 43 33
MATERIALS AND METHODS a
Referred to in VDI 4630.
Substrate characterization
Table 2 | Inoculum characterization
Rice straw (RS), rice husk (RH) and rice residues from the Parameter Mesophilic inoculum Thermophilic inoculum
drying process (RD) are from the Cuban rice variety J-104. pH 7.6 8.3
Rice residues were harvested mid-summer 2008 at the
Total solids (%FM) 3.6 3.1
Cuban Rice Company ‘Sur del Jíbaro’, Sancti Spíritus,
Volatile solids (%TS) 62.3 57.3
Cuba. Standard methods from the Leibniz Institute for Agri-
Volatile solids (%FM) 2.2 1.8
cultural Engineering Potsdam-Bornim (ATB), Germany,
1144 L. M. Contreras et al. | Methane potential and biodegradability of rice residues Water Science & Technology | 65.6 | 2012
determined experimentally can be verified. Table 3 summarizes the total amount of biogas and
methane produced during the bioconversion test for each
b c 3d residual at both temperatures as well as the related biogas
Ca H b O c N d þ a þ H2 O exp
4 2 4 conversion efficiencies (YBiogas =YBiogas
theo
).
a b c 3d a b c 3d As expected, temperature plays an important role
! þ þ CO2 þ þ CH4 þ dNH3
2 8 4 8 2 8 4 4 in the anaerobic process and the possibility to approach
the theoretical biogas and/or methane yields. Under
thermophilic conditions higher values were obtained
The specific methane yield YCH4 in litres methane per in contrast to mesophilic conditions. The higher
gram of volatile solids (VS) can be calculated according to: biogas/methane production was obtained from RS fol-
lowed by RD for both temperatures (Table 3). 0.44 and
(4a þ b 2c 3d)22, 4 0.32 m3 kgVS1 were the corresponding values under
Ytheo CH4 ¼ (5)
(12a þ b þ 16c þ 14d)8
mesophilic conditions for RS and RD respectively
(biogas yield). Likewise 0.52 and 0.36 m3 kgVS1 were
In the case of rice straw (hydrogen content data was only the corresponding values of biogas yield for RS and RD
available for RS), the chemical structure on TS% basis is as under thermophilic conditions. The lowest values were
follows: C0.028H0.047O0.029N0.0005, thus the YtheoCH4 ¼ obtained from RH (0.044 m3 kgVS1). RS showed more
0.330 m3 kgVS1. In accordance with experimental potential to be treated by anaerobic digestion in order to
results (data not shown), RS reached 68 and 85% obtain energy. Conversely, RH showed a very poor
of the theoretical methane yield under mesophilic and biogas production (almost zero). The anaerobic degra-
thermophilic operation respectively. In this way a dation of rice residues from the drying process (RD) did
direct comparison can be made for both RS and RH. not vary noticeably from mesophilic to thermophilic
Consequently RD and RH achieved respectively 51 and 6% operation.
of theoretical maxima at mesophilic conditions and 59 and Average methane content was wide-ranging and did not
13% at thermophilic conditions. These results are in good follow a clear trend. Under mesophilic conditions average
accordance with expected behaviour. Theoretical biogas values of methane content were 45, 56 and 60% for RH,
yield was assumed to be 0.7 m3 kgVS1 for RD, RS and RH. RS and RD respectively. In addition, the average methane
Table 3 | Biogas, methane yield (m3 kgVS1) and conversion efficiency for rice residues
exp exp
Rice residue Biogas Methane Y Biogas =Y theo
Biogas Biogas Methane Y Biogas =Y theo
Biogas
content at thermophilic conditions was 51, 67 and 62% for A complete comparison of the results obtained in the
RH, RS and RD in that order. Additionally to reach more current study is not possible as thermophilic operation for
than 80% of the total biogas yield under mesophilic con- rice residues is not reported so far. It seems that chemical
ditions 19 days for RS, 21 days for RH and 13 days for RD pretreatment enhances biogas production. Similar results
were needed. When operating at thermophilic regimen RH are obtained in the present study with mechanically
needed the same period of time to overcome more than pretreated rice straw and increasing operation temperature
80% of the total biogas yield. (thermophilic data). In all cases, rice husk was shown to
Similar biogas and methane yield has been reported be an unsuitable residue to be treated with anaerobic diges-
mainly for rice straw (RS). Kalra & Panwar () studied tion. Values of biogas/methane yield from rice residues from
rice straw, rice husk and mixtures of both residues in the drying process (RD) are not reported by other authors.
equal proportions during anaerobic digestion resulting in a A graphical illustration of the ultimate biodegradability
cumulative biogas production of 0.220, 0.048 and (UB) of rice crop residues under mesophilic and thermophi-
0.131 LgMF1, respectively. These biogas yields were lic operation is presented in Figure 2. Table 4 summarizes
obtained at a very wide interval of temperature (13.8– UB values for mesophilic and thermophilic conditions, ηB
W
32.6 C). Other mixtures such as rice straw:manure were (biodegradability efficiency) as well as related lignin content
also tested obtaining 0.203 LgMF1 of methane yield at for rice residues.
W
25–36 C. Within this study it was proved that rice straw A biodegradability analysis was performed and ultimate
can provid a proper feedstock for biogas production. biodegradability (UB) values were in accordance with the
Zhang & Zhang () studied the digestion of rice anaerobic process evolution. UB is an important factor to
straw with supplemental nitrogen using a high-rate anaero- take into account because it establishes the bioconversion
W
bic system under mesophilic conditions (35 C). The biogas boundaries for the proper performance in the evaluation
yield could be improved with an increment of 17.5% by a of an anaerobic process. As can be observed from Figure 2,
proper combination of grinding (10 mm length), heating the refractory coefficient (R0) (the total volatile solids
W
(110 C) and ammonia treatment (2%). This combination remaining at infinity) was determined. The lowest values
resulted in the highest biogas yield, 0.47 LgSV1, in contrast
with untreated whole rice straw (0.38 m3 kgVS1). The
methane content was ∼50% for all test conditions. It was
proved that biogas yield can be increased by pre-processing
the rice straw using one or more different methods, such as
mechanical grinding or chopping, heating and ammonia
treatment. Physical pre-treatment (size reduction) had
more benefit when combined with thermal pre-treatment.
He et al. () studied rice straw digestibility and biogas
W
production in batch reactors at 35 C. The influence of
chemical pre-treatment with NaOH (6%) was also evalu-
ated. The highest biogas yield of 0.52 m3 kgVS1 occurred
when rice straw was pre-treated with NaOH, meanwhile
rice straw without pre-treatment had biogas yields equal to Figure 2 | Graphical illustration of the ultimate biodegradability of rice crop residues ___
0.36 m3 kgVS1. Zhao et al. () studied the influence of mesophilic operation ‐ ‐ ‐ thermophilic operation.
of R0 correspond to RS (0.248, 0.165 for both temperatures). are not adequate for modelling a particulate substrate
Lequerica et al. () reported values of R0 ¼ 0.365 under (Vavilin et al. ).
mesophilic conditions. To compare both studies will prob- First-order kinetics of the substrate degradation is the
ably lead to false conclusions, principally due to variations simplest model type and has been successfully used for a
in rice residues composition. description of the hydrolysis. The first-order hydrolysis func-
In the current study, the highest value of UB corre- tion is an empirical expression that reflects the cumulative
sponds to RS followed by RD with an important drop of effects of many processes. Large particles with a low sur-
UB values for RH (less than 10%VS of rice husk can be face-to-volume ratio are hydrolyzed more slowly than
degraded under anaerobic conditions) (Table 4). Moreover small particles. The model (Equation (2)) proposed by
lignin content of RH is the highest value observed in the resi- Roediger (Edeline ) and used by Fiestas et al. ();
dues studied. Although values of lignin and C:N ratios for Borja et al. (); Sánchez et al. (); Jiménez et al.
RS and RD are similar, ultimate biodegradability values () and Milán et al. () to determine k0 is one of the
demonstrate that the carbon source bioavailability varies analysed models within the current study. Since methane
extremely from one residue to another. is the main metabolite produced in this system, it can be
Biodegradability efficiency (ηB) was established to used as a parameter to evaluate the kinetics of the discon-
evaluate the anaerobic process taking into account tinuous process due to its direct relationship with substrate
the real biodegradable portion of each residue. ηB was esti- consumption and its relative ease of measurement. In
mated as: addition the Chapman model (Equation (3)) is analysed
and a modified Hill model (Equation (4)) was used for calcu-
exp 1 lating specific rates of methane production.
ηB ¼ YBiogas =YBiogas
theo
(6)
(1 R0 ) Table 5 summarizes the values of biogas yield (ymax) and
the kinetic constant (k) applying the models to the anaero-
According to ηB values it is possible to remark that bic process of rice residues.
the anaerobic process had efficiencies over 80% for all As can be observed, the first-order model and the Chap-
analysed residues within the biodegradability limits. man model have similar results for RS and RD in ymax
Temperature variations have no effect in RD bioconversion estimation. According to the first-order model, the highest
(ηB values were approximately 0.9 for both mesophilic and biogas yield was 0.503 m3 kgVS1 for RS and the highest
thermophilic conditions). Both RS and RD are adequate average biogas rate was 0.246 d1 for RD under thermophi-
rice residues for energy conversion through anaerobic lic conditions.
processes. Values are comparable with previous studies for rice
Several models and reactor configurations have been straw. Lei et al. () analysed the biodegradation of rice
developed in recent years which make it possible to predict straw particles at room temperature and with phosphate
real process response to specific operation conditions. For supplementation. Maximum biogas yields achieved were
example, a simple model has been developed to describe 0.33–0.35 m3 kgVS1 with methane yield of 0.27–0.29 m3
the relationship between the hydraulic retention time kgVS1, very similar to the ones obtained in the current
and the methane yield in the digestion of animal waste study. The average methane content was really high
(Chen & Hashimoto ). This model is based on the
maximum specific growth rate of microorganisms and Table 5 | Summary of ymax and k for first-order and Chapman models
(75.9–78.2%) if compared to the one obtained in the pre- carbohydrates (Kalra & Panwar ). Biodegradability is
sent study for RS (56–62%). The values of biogas and also affected by lignocellulosic biomass and is limited by
methane production rate constants in the referred investi- factors such as cellulose characteristics inside the biomass,
gation ranged from 0.027–0.031 d1 and from 0.028– available surface area and lignin content (Tong et al. ;
0.033 d1, and are lower than the ones obtained in the cur- Hendriks & Zeemann ). Bioavailability of the carbon
rent study under controlled temperature for mesophilic source in lignocellulosic materials is still a parameter
condition (0.078 d1). requiring careful investigation. This study found first-
Jash & Ghosh () also used a first-order model at order models satisfactorily describe the biodegradation of
W
mesophilic regime (37 C), the specific rate constants for rice crop residues.
rice straw and the corresponding correlation coefficients
were reported. It was shown that the rate constant (k)
reached 0.101 d1 with a particle size of 0.76 mm, agitation CONCLUSIONS
and urea addition. The biogas yield value was 0.280 m3
kgVS1. Rice straw and rice residues from the drying process are a
Temperature plays an important role in kinetics potential carbon source to obtain biogas by anaerobic
(Pavlostathis & Giraldo-Gómez ). Obtained kinetic digestion. Rice residues do not have an optimized C:N
values demonstrate that it is possible to reduce the hydraulic ratio even when the anaerobic digestion occurs properly,
retention time (HRT). The specific methane rate at both meso- with the exception of RH. The results showed that RS as
philic and thermophilic conditions was calculated (Equation well as RD had the highest values of biogas and methane
(4)). Figure 3 illustrates the effect of temperature on the yield. Increased temperature improved both biogas/
specific methane rate ranging from 0.023–0.029 m3 kgVS- methane yields and kinetics. In all cases rice straw
1d1
for RD and 0.014–0.033 m3 kgVS1d1 for RS. obtained the best results. Methane content in all batches
As can be observed in Figure 3, RS and RD substrates was kept above 55% vol. Biodegradability analyses demon-
can be anaerobically treated by 20 days of HRT approxi- strated that rice husk is not a proper substrate for anaerobic
mately, with little reduction in biogas production when digestion. In contrast, RS and RD showed ∼0.8 and 0.5 UB
applying thermophilic conditions. When deciding to adopt values. The anaerobic process had efficiencies over 80% for
this waste disposal solution an economic assessment is all analysed residues within the biodegradability limits.
essential. Temperature variations have no effect in RD bioconver-
Taking into account the obtained results it can be con- sion. The poor relationship between lignin content
cluded that RS, RD and RH had an expected behaviour and biogas rate indicates that factors other than lignin
with regards to chemical composition and operational par- content could play a role. According to a first-order
ameters during the anaerobic process. It is well known that model, the highest biogas yield was 0.503 m3 kgVS1 (RS)
biogas production is strongly affected by availability and and the highest average biogas rate was 0.246 d1 (RD)
biodegradability of the main components present in bio- under thermophilic conditions. First-order models describe
mass, as well as the association between lignin and the kinetics of rice crop residues’ biodegradation properly.
Figure 3 | Specific methane rate of rice crop residues under both mesophilic and thermophilic conditions.
1149 L. M. Contreras et al. | Methane potential and biodegradability of rice residues Water Science & Technology | 65.6 | 2012