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Energy & Fuels 2009, 23, 22252228

2225

Anaerobic Codigestion of Kitchen Waste with Cattle Manure for


Biogas Production
Rongping Li,, Shulin Chen, Xiujin Li,,* Jam Saifullah Lar, Yanfeng He, and
Baoning Zhu
Department of EnVironmental Science and Engineering, Beijing UniVersity of Chemical Technology,
Beijing 100029, China, Department of Biological Systems Engineering, Washington State UniVersity,
Pullman 99164, WA, USA
ReceiVed October 11, 2008. ReVised Manuscript ReceiVed January 31, 2009

Kitchen waste (KW), cattle manure (CM), and the mixture of KW and CM were anaerobically digested.
The performances of single digestion with KW or CM and of codigestion with KW and CM were investigated
and compared. Two loading rates of 10 and 20 g volatile solid (VS) L-1 were used for KW, CM, and their
mixture digestion, respectively. NaOH was used as supplementary for KW, and sulfuric acid pretreatment was
used for CM to explore the effects of alkalinity and acidification on methane production to verify the roles of
codigestion. Scanning electron microscopy (SEM) was used to analyze the structural changes of CM fibers.
The results showed that the codigestion of KW and CM increased methane yield by 44% as compared to the
single digestion of KW, and the increase could be attributed to the synergistic effect in the codigestion process.
A 32% more methane yield was achieved for the KW with NaOH addition than raw KW, which was due to
increased alkalinity and buffering capacity. The methane yield and VS reduction for acid-pretreated CM were
116 and 74% higher than raw CM. SEM analysis showed that the structural changes of CM fibers were helpful
for methane production. The results showed that codigestion could obtain better and stable performances and
might be one of many options for efficient biogas production.

1. Introduction
In China, disposal of municipal solid waste (MSW) is a major
concern in large cities. Kitchen waste (KW), which is defined
as the food residuals generated from restaurants, cafeterias,
hotels, and households etc., is a main organic fraction of MSW,
accounting for 37-55% of the total MSW. Anaerobic digestion
of organic waste to produce biogas has been regarded as an
attractive technology of treating waste biomass, for example,
agriculture waste, organic fraction of MSW, as well as organic
waste from food industry.1,2 In terms of high biodegradability
of KW, it is a typical organic waste suitable for anaerobic
digestion.3 Anaerobic digestion can decrease the amount of KW
to be handled while producing bioenergy in methane form.
Anaerobic codigestion of various organic wastes for energy
production has attracted more interests recently. Codigestion
treats two or more substrates with complementary characteristics
in the same digester, for example, codigestion of fruit/vegetable
waste and animal manure4,5 or organic solid waste with sewage
sludge. 6-8 The benefits of codigestion included improved biogas
* To whom correspondence should be addressed. Telephone and fax:
+86-10-6443-2281; e-mail: xjli@mail.buct.edu.cn.
Beijing University of Chemical Technology.
Washington State University.
(1) De Baere, L. Water Sci. Technol. 2000, 41 (3), 283290.
(2) Pang, Y. Z.; Liu, Y. P.; Li, X. J.; Wang, K. S.; Yuan, H. R. Energy
Fuels 2008, 22, 27612766.
(3) Zhang, R.; El-Mashad, H. M.; Hartman, K.; Wang, F.; Liu, G.;
Choate, C.; Gamble, P. Bioresourc. Technol. 2007, 98, 929935.
(4) Callaghan, F. J.; Wase, D. A. J.; Thayanithy, K.; Forster, C. F.
Bioresourc. Technol. 1999, 67, 117122.
(5) Viotti, P.; Genova, P. D.; Falcioli, F. Waste Manage. Res. 2004, 22,
115128.
(6) Romano, R. T.; Zhang, R. Bioresourc. Technol. 2008, 99, 631637.

yield, economic advantages derived from the sharing of equipment, and easier handling of mixed wastes, etc.9
The better performance of codigestion was attributed to the
improvement of nutrients balance,10 the enhancement of buffer
capacity,11 or the positive synergisms, namely, the combined
effects established in the digestion medium.12 The synergistic
effect obtained in codigestion has been reported. Mshandete et
al.13 reported that codigestion of sisal pulp and fish wastes at a
volatile solids (VS) ratio of 2:1 gave an increase of 59-94%
in methane yield as compared to that obtained from the digestion
of pure fractions. Llabres-Luengo and Mata-Alvarez14 found that
the ultimate methane yield in the codigestion of straw and pig
manure obtained a maximum value of 0.42 L g-1 VS at 43%
VS (straw VS/total VS).
KW contains more readily biodegradable compositions and
is easily converted to biogas, but it has a low buffer capacity
and is easy to acidify. Usually, buffer materials needs to be
added for achieving stable digestion and better efficiency, when
a highly biodegradable substrate such as KW is digested alone.
(7) Sosnowski, P.; Wieczorek, A.; Ledakowicz, S. AdV. EnViron. Res.
2003, 7, 609616.
(8) Davidsson, .; Lovstedt, C.; la Cour Jansen, J.; Gruvberger, C.;
Aspegren, H. Waste Manage. 2008, 28 (6), 986992.
(9) Mata-Alvarez, J.; Mace, S.; Llabres, P. Bioresour. Technol. 2000,
74, 316.
(10) Yen, H. W.; Brune, D. E. Bioresourc. Technol. 2007, 98, 130
134.
(11) Murto, M.; Bjornsson, L.; Mattiasson, B. J. EnViron. Manage. 2004,
70, 101107.
(12) Gelegenis, J.; Georgakakis, D.; Angelidaki, I.; Mavris, V. Renewable
Energy 2007, 32 (13)), 21472160.
(13) Mshandete, A.; Kivaisi, A.; Rubindamayugi, M.; Mattiasson, B.
Bioresourc. Technol. 2004, 95, 1924.
(14) Llabres-Luengo, P.; Mata-Alvarez, J. Resources, ConserVation and
Recycling 1988, 1, 2737.

10.1021/ef8008772 CCC: $40.75 2009 American Chemical Society


Published on Web 03/03/2009

2226 Energy & Fuels, Vol. 23, 2009

Li et al.

Table 1. Characteristics of Kitchen Waste (KW), Cattle Manure


(CM), and Seeding Sludgea

Table 2. Experimental Designs for Anaerobic Batch Digestion


initial loading
(g VS L-1)

parameter

KW

CM

seeding sludge

reactors

feedstock

TS (%, wb)
VS (%, wb)
tCOD (g O2 L-1)
pH
alkalinity (g CaCO3 L-1)
carbohydrate (%, db)
protein (%, db)
lipids (%, db)
cellulose (%, db)
hemicellulose (%, db)
lignin (%, db)

246.6 (0.8)
232 (0.2)
255.7 (11.1)
5.1 (0.2)
NA
55.2 (2.1)
15.0 (1.3)
23.9 (0.8)
NA
NA
NA

196.3 (1.2)
166.4 (0.7)
274.2 (14.0)
7.8 (0.1)
3.4 (0.2)
60.4 (4.5)
21.8 (4.4)
2.6 (0.1)
21.2 (0.1)
30.4 (0.2)
11.6 (0.0)

85.1 (0.3)
49.6 (0.8)
60.1 (1.8)
7.6 (0.1)
44.1 (1.0)
NA
NA
NA
NA
NA
NA

R1
R2
R3
R4
R5
R6
R7
R8

KW
CM
KW and CM at a VS Ratio of 1:1
KW
CM
KW and CM at a VS Ratio of 1:1
KW + 0.82 g of NaOH
CM pretreated by diluted sulfuric
acid (pH of 6, 3 days)

Note: NA (no analysis), units were based on wet base (wb) or dry
base (db). Data are the means of three measurements, and numbers in
parentheses are the standard deviations.

For instance, Llabres-Luengo and Mata-Alvarez14 found that


the methane yield was significantly improved after adding
powered CaCO3 in batch digestion of wheat straw and pig
manure. Cattle manure (CM) contains more fibers and is
relatively hard to be digested, but it has good buffer capacity.
CM might need to be pretreated by acids when high digestion
performance is desired.15 Codigestion of KW and CM would
combine together the positive characteristics of both feedstocks
and could potentially bring better digestion performances.
The objectives of this study were: (1) to compare the
anaerobic digestion performances of KW, CM, and their
mixture; and (2) to investigate the roles of alkalinity and
acidification in codigestion.
2. Experimental Section
2.1. Feedstock Characteristics. The KW used in this study was
collected from the restaurants at Beijing University of Chemical
Technology. The KW consisted of fried vegetables, starches, rice,
and meat, etc. It was shredded into slurry state by a food grinder
after the bones, chopsticks, plastic bags, and other inorganic
residuals were removed. The CM was collected from Fuhua Beef
Center located in Dachang County in the southeast of Beijing. A
scraping system was used for manure collection, and the manure
was then stacked in open field. The prepared KW and CM were
stored in a freezer at -20 C for later uses. The characteristics of
KW and CM are shown in Table 1.
2.2. Inoculums. The sludge from a swine waste treatment plant
(Shunyi, Beijing) was used as the inoculums. It had a pH of 7.6,
total solids (TS) of 85.1 g L-1, VS of 49.6 g L-1, and mixed liquid
suspended solids (MLSS) of 69.7 g L-1. Each digester was seeded
with 215 mL of sludge to maintain the mixed liquid suspended
solids (MLSS) at the level of 15 g L-1 in the digester.2
2.3. Batch Laboratory Tests. The methane yields of feedstock
were determined by laboratory-scale anaerobic batch tests described
in Pang et al.2 The tests were performed in 1 L reactors containing
substrate of 10 or 20 g of VS (Table 2). R1, R2, and R3 were
operated with KW, CM, and the mixtures of KW and CM at a VS
mixing ratio of 1:1, 10,12 respectively. The same loading rate of
10 g VS L-1 was applied for R1, R2, and R3. Loading rate of 20 g
VS L-1 was applied for R4, R5, and R6. A 0.82 g portion of NaOH,
which was the equivalent alkalinity contained in CM, was added
into R7 to investigate the effect of alkalinity. The CM was pretreated
by 1% sulfuric acid at a pH of 6.0 for 3 days. After acid
pretreatment, the whole liquid was fed into R8 for the batch
digestion.
After inoculation, all batch reactors were sparged thoroughly with
nitrogen gas to create an anaerobic condition. The prepared digesters
were then placed in shakers (Taicang DHZ-DA, China) for
(15) Liao, W.; Liu, Y.; Liu, C.; Chen, S. Bioresourc. Technol. 2004,
94, 3341.

10
10
10
20
20
20
10
10

Table 3. Results Obtained from Batch Digestion


cumulative
methane
VS reduction
initial final methane yield
yield
(%)
digester pH
pH
(mL, STP) (mL g-1 VS, STP)
R1
R2
R3
R4
R5
R6
R7
R8

7.3
7.7
7.6
7.2
7.7
7.5
8.6
7.7

7.3
7.3
7.2
6.2
7.7
7.4
7.4
7.4

3134
357
2986

313.4
35.7
298.6

67.7 ( 0.4
44.6 ( 0.2
52.5 ( 0.3

750
6216
4584
770

37.5
310.8
458.4
77.0

44.0 ( 0.3
65.8 ( 0.2
74.9 ( 0.2
77.5 ( 0.2

anaerobic digestion tests at mesophilic temperature (35 ( 1 C)


and 120 rpm shaking speed. Two replicates for each sample were
tested: only one for biogas production and another is for pH
measurement and other analytic measurements.
2.4. Scanning Electron Microscopy (SEM). Structural changes
of different types of CM fiber were studied using a SEM (Hitachi
S-4700, Japan). The dry samples were mounted on double-sided
tape placed on aluminum stubs. A thin layer of gold (15 nm for 10
min sputtering) was sputtered onto the mounted sample to reduce
electron-altering effects using a Hummer V sputtering device
(Technics, CA). Finally, the gold-coated samples were observed
in a SEM with an accelerating voltage of 20 kV.
2.5. Other Analytical Methods. The daily biogas production
was recorded by water displacement method,2 and the cumulative
biogas volume and methane yield were calculated after correction
at standard temperature and pressure (STP). Methane and carbon
dioxide in the biogas were measured by gas chromatography (Beifen
SP-2100, China) equipped with a 2 m 3 mm stainless steel
column packed with TDX-01 and a thermal conductivity detector.
Temperatures of the detector, injector, and oven were 150, 150,
and 120 C, respectively. TS, VS, alkalinity, and pH were
determined according to the standard methods.16 The lipids was
determined by a Soxhlet system at 65 C with more than 60 times
of circulation using the petroleum ether as extractive reagent. The
sample weights before and after extraction were used to calculate
the lipids content. Total nitrogen (TN) was analyzed with the total
Kjeldahl nitrogen analyzer (Foss 2003, Sweden). The samples for
TN were digested at 460 C for 40 min and then titrated using
H2SO4 after the samples cooling down. Protein was calculated by
multiplying TN by 6.25. Carbohydrate was calculated as the fraction
of VS remaining after the subtraction of protein and lipids. The
content of cellulose, hemicellulose, and lignin were analyzed
according to the procedure of Van Soest.17 Total chemical oxygen
demand (tCOD) and soluble COD (sCOD, the COD of filtrate
passing through a 0.45 m filter) were measured by using the COD
analyzer (HACH, DR/2500, USA). The degree of COD solubilization was calculated by the following equation: 18
(16) APHA. Standard Methods for the Examination of Water and
Wastewater, 20th ed.; American Public Health Association: Washington,
DC 1998.
(17) Van Soest, P. J.; Robertson, J. B.; Lewis, B. A. J. Dairy Sci. 1991,
74, 35833597.
(18) Kim, J; Park, C.; Kim, T.; Lee, M.; Kim, S.; Kim, S.; Lee., J.
J. Bioscience Bioengineering 2003, 95 (3), 271275.

Energy & Fuels, Vol. 23, 2009 2227

COD solubilization (%) )


Soluble COD after pretreatment
100 (%)
Total COD after pretreatment
3. Results and Discussion
3.1. Methane Production. Table 3 shows the cumulative
methane production (CMP), methane yields, and VS reduction
in batch experiments. Among R1-R6, it was found that R1
with KW as single substrate at a loading of 10 g VS L-1
achieved the highest methane yield of 313.4 mL g-1 VS. The
digestion process in R4 with KW failed. Acidification phenomenon occurred in R4, as indicated by the lower pH values below
5.4 from the third day to the 15th day. The reason was thought
to be the high loading of 20 g VS L-1 employed, leading to
acidification and high food to microorganism (F/M, on VS basis)
ratio of 1.9 g VS/g VS. For batch digestion, the F/M ratio is an
important parameter.19 According to the result obtained from
Chynoweth et al.,20 F/M ratio of 0.5 g VS/g VS gave maximum
conversion rate. The higher the F/M ratio is, the lower the
methanogenic activity would be. The F/M ratio in R4 was too
high and caused the failure of digestion.
However, the acidification of KW at the loading of 20 g VS
L-1 could be overcome through adding other supplements. This
was verified by the successful operation of codigestion of KW
and CM in R6. R6 obtained high methane yield of 310.8 mL
g-1 VS at the loading of 20 g VS L-1. No irreversible
acidification phenomenon was found. The reason was believed
to be the addition of CM, which not only provided more
balanced nutrients for anaerobic bacteria, but also enhanced the
buffering capacity of the digester. The alkalinity of KW and
CM was 0 and 3.4 g CaCO3 L-1, respectively. Adding CM to
KW increased the buffering capacity and avoided the occurrence
of acidification phenomenon in R6. Llabres-Luengo and MataAlvarez14 investigated the effect of alkalinity in batch digestion
and found that the methane yield was significantly improved
after adding powered CaCO3.
R2 and R5 used CM as single substrate but used different
loading. Both obtained similar results. Their methane yields were
35.7 and 37.5 mL g-1VS, respectively, which are lower than
other results.21,22 This might be due to that the fibers were not
separated from the CM. As shown in Table 1, lignin, cellulose,
and hemicellulose (LCH) accounted for 63.2% of the total dry
matter. The fiber content was higher than that of the manure
used by other reserachers.15 Fibers are hard to break down due
to the ester bonds of lignin-carbohydrate complexes; thus,
pretreatment is usually required prior to anaerobic digestion.23
Liao et al.24 reported that separating fibers from the raw manure
could enhance methane production and methane content of
biogas.
3.2. Synergistic Effect. R1 and R2 were loaded with 10 g
VS of KW and 10 g VS of CM and obtained the CMPs of 3134
and 357 mL (Table 3), respectively. For the same amount of
substrate of 20 g VS loaded, the CMP in R6 with mixture of
KW and CM reached 6216 mL, which was 44% higher than
the total CMP of R1 with KW and R2 with CM. This increase
was attributed to the synergistic effect from the codigestion of
(19) Nallathambi, G. V. Biomass Bioenergy. 1997, 13 (1/2), 83114.
(20) Chynoweth, D. P.; Turick, C. E.; Owens, J. M.; Jerger, D. E.; Peck,
M. W. Biomass Bioenergy 1993, 5 (1), 95111.
(21) Demirbas, A. Energy Sources, Part A, 2006, 28 (1), 7178.
(22) Mller, H. B.; Sommer, S.G. ; Ahring, B. K. Biomass Bioenergy,
2004, 26, 485495.
(23) He, Y.; Pang, Y.; Liu, Y.; Li, X.; Wang, K. Energy Fuels 2008,
22, 27752781.
(24) Liao, P. H.; Lo, K. V.; Chieng, S. T. Energy Agric. 1984, 3, 61
69.

Figure 1. Comparison on daily methane production of raw CM and


pretreated CM.

KW and CM. The synergistic effect was mainly due to the


complementary characteristics of KW and CM when codigested,
including increased alkalinity, more balanced nutrients, and
improved biodegradability. Gelegenis et al.13 found that biogas
production rate in the codigestion of whey with diluted poultry
manure was increased by 40% in a continuously stirred tank
reactor. Yen and Brune10 reported that codigestion of waste
paper and algal sludge at a VS ratio of 1:1 increased the methane
production rate to 1170 ( 75 mL/day, as compared to 573 (
28 mL/day of algal sludge digestion alone, and both operated
at 4 g VS/day, 35 C, and 10 days HRT.
3.3. Effect of Alkalinity on KW Digestion. The alkalinity
of the KW used was 0, indicating that the KW had almost
no buffering capacity by itself. This could lead to rapid
acidification and low methane yield, as found in R4. The
inhibition from rapid acidification could be overcome by
either codigestion of KW with CM or supplementation of
other materials with high alkalinity.25 To verify the effect of
alkalinity on anaerobic digestion of KW, NaOH was used as
buffer supplementary and was added to enhance buffering
capacity of KW. R7 was compared with R1 for CMP and
methane yield (Table 3). R7 obtained 4584 mL of CMP and
458.4 mL g-1 VS of methane yield, which were 32% higher
than R1. The result indicated that NaOH addition was
beneficial to enhance the methane production of KW digestion and also verified the important role of alkalinity in batch
digestion. It has been reported that the methane yield was
significantly enhanced after increasing the alkalinity by
addition of CaCO3 in batch digestion of wheat straw and pig
manure.14 Although the better outcome in methane yield was
obtained in R7 with NaOH addition, the chemical addition
in industrial application could be a costly process when
treating large amounts of waste. The codigestion of KW and
CM seems to be more attractive in terms of operation cost
and from a viewpoint of integrated solid waste treatment.
3.4. Effect of Acidification on CM Digestion. As mentioned
above, low methane yield was obtained for R2 and R5, which
used CM as the single substrate. This might be due to the high
proportional recalcitrant fibers contained in the CM (Table 1).
Sulfuric acid was used to pretreat CM in order to decompose
the fibers before anaerobic digestion. It was found that considerable lignocelluloses were degraded after acid pretreatment. The
total LCH, cellulose, and hemicellulose contents were reduced
by 13.1, 9.4, and 28% (dry basis), respectively, and the
(25) Neves, L.; Ribeiro, R.; Oliveira, R.; Alves, M. M. Biomass
Bioenergy, 2006, 30, 599603.

2228 Energy & Fuels, Vol. 23, 2009

Li et al.

Figure 2. SEM of fibers collected from different types of cattle manure (CM): (A) raw CM fiber; (B) diluted sulfuric acid pretreated fiber (pH of
6.0, 3 days); and (C) fiber in the CM codigested with KW in the 4th day of digestion.

corresponding contents of the LCH, cellulose, and hemicellulose


were decreased from 63.2, 21.2, and 30.4% to 54.9, 19.2, and
21.9%, respectively.
The pretreated CM was anaerobically digested. The daily
methane production of raw CM (R2) and pretreated CM (R8)
is shown in Figure 1. There were obvious differences in daily
methane production and digestion time between R2 and R8.
The methane production of R2 started in the fifth day and
reached a peak of 63 mL on the ninth day, whereas R8 started
after seeding and reached its biggest peak value of 128 mL on
the third day. The methane started generating later but lasted
longer for R2 as compared to R8. The methane yield and VS
reduction of R8 were 77 mL g-1 VS and 77.5%, which was
116 and 74% higher than R2, respectively. These results implied
that pretreated CM became more biodegradable and was more
easily used by microorganisms after acid pretreatment, thus
producing more methane in less time. It could be further verified
by the degree of COD solubilization of CM before and after
acid pretreatment. The tCOD of raw CM was 274.1 g L-1. The
sCOD of CM samples before and after acid pretreatment were
23.8 and 67.1 g L-1, respectively. The COD solubilization after
acid pretreatment was improved from 8.7 to 24.5%. The increase
of COD solubilization indicated the improvement of biodegradability.
To further explore the effect of acidification on fibers
decomposition, the structure of fibers were observed using SEM.
The pictures of raw CM, acid-pretreated CM, and CM codigested with KW in the fourth day of digestion are shown in
Figure 2, panels A-C, respectively. It can be seen that the
texture of the raw CM was regular and smooth, whereas the
structure of acid-pretreated CM and CM codigested with KW
were rough and partially destroyed. A number of small holes
were observed in the fiber samples of acid-pretreated CM and
codigested CM. The diameters of the holes were in the range
of 3-8 m. Liao et al.15 reported that the small holes in the
manure fibers meant that part of hemicellulose was degraded
from the backbone of fibers. The structural changes of fibers in
acid-pretreated CM and codigested CM implied, from another
angle, that acid pretreatment or codigestion with KW would

help hydrolysis of CM and contribute to the methanogensis


improvement.
4. Conclusions
KW and CM can be used as feedstock to produce biogas
through an anaerobic digestion process. They can be either
single-digested or codigested. The synergistic effect was found
in the codigestion process, which contributed 44% more methane
production. The addition of NaOH increased alkalinity and
buffering capacity and helped produce 32% more methane yield.
The acid-pretreated CM achieved 116 and 74% more methane
yield and VS reduction than raw CM, respectively. SEM analysis
showed that the structural changes of fibers in CM were helpful
to methane production. These findings verified the roles of
codigestion in helping enhance KW buffering capacity and
improve CM solubilization indirectly. The results showed that
codigestion of KW with CM might be one of options for
efficient biogas production and waste treatment.
Acknowledgment. This work was supported by the fund from
the Hi-Tech Research and Development Program of China (Grant
number: 2008AA062401). The authors gratefully acknowledge Dr.
Liu Guangqing for his valuable suggestions.

Nomenclature
CM ) Cattle manure
KW ) Kitchen waste
MLSS ) Mixed liquid suspended solids
MSW ) Municipal solid waste
SEM ) Scanning electron microscopy
sCOD ) Soluble chemical oxygen demand
TAN ) Total ammonia nitrogen
tCOD ) Total COD
TN ) Total nitrogen
TS ) Total solids
VFA ) Volatile fatty acids
VS ) Volatile solids
EF8008772