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Generation of biogas using crude glycerin from biodiesel production as a supplement to cattle slurry
S. Robra a,*, R. Serpa da Cruz b, A.M. de Oliveira b, J. A. Almeida Neto a, J.V. Santos b
rias e Ambientais, Universidade Estadual de Santa Cruz, Rod. Ilhe us/Itabuna km 16 s/n, CEP 45662-000 Departamento de Cie ncias Agra us, Bahia, Brazil Ilhe b gicas, Universidade Estadual de Santa Cruz, Rod. Ilhe us/Itabuna km 16 s/n, CEP 45662-000 Departamento de Cie ncias Exatas e Tecnolo us, Bahia, Brazil Ilhe
a

article info
Article history: Received 25 July 2008 Received in revised form 26 March 2010 Accepted 13 April 2010 Available online 26 May 2010 Keywords: Co-digestion Biodigestion Methane Biofuel

abstract
The inuence of crude glycerin on biogas production and methane content of the produced biogas was studied, when added to cattle slurry. The experimental design consisted of 5% wt (Gli 5), 10% wt (Gli 10), and 15% wt (Gli 15) of crude glycerin added to cattle slurry, and one control digester without addition of crude glycerin. Anaerobic digestion was carried out in 4 laboratory size CSTR-type biogas digesters with a working volume of 3 L, in semicontinuous regime at mesophilic conditions, over a period of 10 weeks. The highest biogas yields (825.3 mL g1 and 825.7 mL g1, respectively) relative to mass of volatile compounds added, were produced by the treatments Gli 5 and Gli 10. The control treatment produced 268.6 mL g1, whereas the treatment Gli 15 produced 387.9 mL g1. This low value was due to the breakdown of the process. Compared to the control, methane contents was increased by 9.5%, 14.3%, and 14.6%, respectively, for the treatments Gli 5, Gli 10, and Gli 15. 2010 Elsevier Ltd. All rights reserved.

1.

Introduction

Biodiesel is usually produced by transesterication of vegetable oil with an alcohol, p. ex, methanol, and a catalyst, such as, KOH, potassium methylate, sodium methylate, and others. The main by-product is crude glycerin, with about 10% wt. As biodiesel production is rapidly growing all over the world, a surplus of crude glycerin in global scale is to be expected [1,2]. In Brazil, the mandatory addition of biodiesel to petrol diesel over the past ve years has led to an increasing production of biodiesel in the past years. In January 2010, the addition of 5% of biodiesel became mandatory [3e5]. Based on the projection of [6], this would, in near future, cause a demand of 3.7 hm3 of biodiesel throughout the country and lead to a production of about 370 dam3 of crude glycerin.

Glycerin is an important platform chemical with a wide range of applications. The expected surplus of crude glycerin on the other hand, together with variations and differences in quality, and, in Brazils case, the logistics cost of moving the glycerin to market makes it sale to users uneconomic [7]. Crude glycerin obtained from the alkaline or acid transesterication process consists basically of glycerin (C3H5OH), a sugar alcohol also known as propane-1,2,3-triol, and varying proportions of impurities including esters, water, soap stock, alcohol, and catalyst, depending on the vegetable oil quality and chemical process used. In order to obtain a merchantable good, the crude glycerin has to undergo a costly rening process to comply with the technical standards required by the consumer industry. Rening unit on-site is said to require only 20% of the total plant capital investment in Brazil [7], but

* Corresponding author. Tel.: 55 73 3680 5274; fax: 55 73 3680 5254. E-mail address: srobra@web.de (S. Robra). 0961-9534/$ e see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biombioe.2010.04.021

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according to other information, the net gain is reported to be in the range of 10e15% of the biodiesel turnover and the investment and operating costs of a glycerin purication unit are such that only the larger biodiesel plants producing 60e80 dam3 y1 are viable [8]. Therefore, practical alternative uses for this material have to be found that are economically and ecologically feasible and at the same time can be adapted to Brazilian reality [9]. Crude glycerin appears to be a suitable carbon source for anaerobic microbiological processes. One possible solution for the recovery of crude glycerin from biodiesel production in Brazil therefore is the anaerobic treatment of crude glycerin in biodigesters and the production of biogas, a renewable and versatile energy source which is planned to take an important part in Brazils agroenergy policy [10]. There is empirical evidence for the codigestion of glycerin in the EU [11,12] and the US [13]. Whereas biodigestion of crude glycerin as a monosubstrate is not viable as no nitrogen would be available for formation of bacterial mass, the addition of crude glycerin as a carbon source to substrates with sufcient nitrogen content, but lack in energy content, seems a promising approach. When supplementing 6% wt of glycerin to pig manure and maize silage, Amon et al. observed biogas production of 1.114 and 0.679 m3 kg1 of volatile solids (VS, normal basis), respectively, as well as an increase in methane proportions of 5.6% and 9.8%, respectively, causing higher than the summarized CH4 yields of both substrates if digested separately, and contributed their ndings to a synergistic cofermentation effect which showed best results with glycerin added in the range of 3e6% wt [12]. A continuous experiment conducted by Chen et al., using a mixture of cow manure and 45% glycerin on volatile solids basis, resulted in a biogas yield of 0.470 m3 kg VS and methane content was 63e70%, at a VS loading rate of 0.5 g L1 d1 to 1.0 g L1 d1 [13]. On the other hand, methanol residues in the crude glycerin can have inhibitory effects on the biocenosis [12], especially on the methanogenic microorganisms. An adverse effect was also observed for elevated contents of potassium hydroxide (KOH) of 2.5e5.0 g L1 [14] or 8.301 g L1 [15]. In order to maintain a stable anaerobic process there are limitations on the organic loading rate which depend both on the substrate and the type of digester. According to Gruber, the organic loading rate in common mesophilic CSTRs should not exceed 4 g L1 of volatile compounds in order to guarantee process stability [16]. The above mentioned loading rate is based on the digestibilities of the substrates normally used in this type of biogas digester, like cattle slurry and energy crops,

especially cultivated for use as substrates in biodigestion for biogas production, and do not consider substrates with higher digestibility of the organic matter. Therefore, a source of highly digestible carbon, like crude glycerin, could negatively affect process stability even if the upper limit of 4 kg m3 d1 were not exceeded [17]. Nevertheless, biodigesters with long-term process stability under higher organic loading rates than 4 m3 L1 d1 of volatile compounds are reported. However, higher organic loading rates were observed to result in immature efuents with higher residual methane potential, higher contents of odorcausing volatile acids and higher C:N ratio [18]. The objective of this work was to study the effect of different proportions of crude glycerin, when added to cattle slurry, on biodigestion process stability and on biogas yield, in mesophilic conditions.

2.
2.1.

Materials and methods


Laboratory biodigester

Four lab scale digester systems were constructed, consisting of a reactor vessel, a reservoir for biogas storage and a tank for the sealing liquid, all of which connected by PVC-tubes. Transparent vessels, made of PET, with a volume of 5 L were used as biogas reactors, and closed with rubber stoppers with three holes. Three PVC-tubes were inserted into the holes. One of the tubes was used for feeding the biogas reactor, the other was used for the removal of the digested efuent and the third was the gas line. A water bath maintained at a temperature range from 35  C to 37  C was used to keep the reactors at the necessary process temperature. The substrate was introduced to the bottom of the reactor vessel and the digested substrate was removed close to the surface. No stirring device was used, as the upward movement of the emerging gas bubbles, the turbulences caused by addition of new feed, and gentle shaking of the reactor vessels after adding the feeding substrate were considered sufcient for the mixing of the substrate. The biogas was led through the PVC gas line and collected in a 20-L-plastic tank, where the increasing pressure of the produced biogas displaced the sealing uid to the sealing uid reservoir. Gas production was measured daily by the difference of level of the displaced acidied brine prepared according to [19].

Table 1 e Proportions of cattle slurry and crude glycerin. Treatment % wt


Cattle slurry Crude glycerin Total 100 0 100

Gli 0 Estimated VS g L1 d1
1.9 e 1.9

Gli 5 % wt
95 5 100

Gli 10 % wt
90 10 100

Gli 15 % wt
85 15 100

Estimated VS g L1 d1
1,5 1.1 2.6

Estimated VS g L1 d1
1,0 1.3 2.3

Estimated VS g L1 d1
1.0 1.6 2.6

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Table 2 e Physicalechemical composition of the inoculum used. Analyzed characteristics pH (%) DM (%) VS (%) Ca Mg (%) K2O (%) N (%) P2O5 (%)
7.9 0.6 0.29 0.05 0.02 0.12 0.02 0.02

2.5.

Crude glycerin

Analyses realized by the Laboratory of Soil and Fertilizer Science of the CEPLAC in December 2005.

The crude glycerin used in this experiment was obtained from the optimized methylic alkaline transesterication process of castor oil, using sodium-methoxide as catalyst [21]. As the analysis of crude glycerin was not possible, values obtained from literature were used. The typical composition of crude glycerin is shown in Table 4.

2.6.
The sealing liquid has to be chemically inert and must not allow the growth of algae and microorganisms. In the experiment, this liquid was composed of acidied brine prepared according to [19].

Determination of feed quantities

2.2.

Experimental setup

Four treatments were tested in the experiment: one control treatment (Gli 0) without any addition of crude glycerin, and the treatments Gli 5, Gli 10, and Gli 15, where proportions of 5%, 10%, and 15% wt, respectively, of the cattle slurry were substituted by crude glycerin (Table 1). The experiment was conducted as a semi-continuous process, fed once a day, and maintained at mesophilic conditions.

The proportions of the components of the feed mixture were determined according to the physicalechemical parameters of the cattle slurry and, in case of the glycerin, on literature values, and the quantities of the mixtures of cattle slurry and crude glycerin used in the experiment were determined according to an upper limit of the overall organic loading rate of 3 g L1 when substituting the cattle slurry with 5% wt, 10% wt, and 15% wt of crude glycerin. The quantities of FM, DM, and VS added daily to the control and to the three treatments with glycerin addition are depicted in Table 5.

2.7.

Estimated biogas yields

2.3.

Inoculum

The inoculum used for the start-up of this experiment was obtained from the efuent of a rural biodigester being operated on cattle slurry. The experiment was started when the inoculum stopped biological activity, visible by the cessation of biogas production. Inoculum was analyzed for dry matter and volatile solids. Table 2 shows the composition of the inoculum.

Values from literature were used to calculate the theoretical values for biogas yields from cattle slurry (280 mL g1) and crude glycerin (850 mL g1), on a VS base [22]. The expected biogas yields are shown in Table 6.

2.8.

Start-up of the biodigesters

2.4.

Cattle slurry

Cattle slurry was collected from the inlet of the rural biodigester mentioned above and was stored frozen at 15  C in 1 L vessels. Before feeding, the thawed slurry was homogenized by a liqueer. The cattle slurry was also analyzed according to methodology of the A.O.A.C. [20] for the parameters mentioned above. The physicalechemical compositions of the cattle slurry used in the experiment are listed in Table 3.

In the start-up phase, each of the biodigesters was lled with 3 L of inoculum. After the biological activity of the inoculum had ceased, which became visible by interruption of biogas production, the substrate was added starting with 33% of the predetermined feeding quantity, and was increased stepwise according to the adaptation of the biocenosis until nally the dened quantities were reached. The feeding of the biodigesters was realized once a day, by manually injecting the dened feeding quantity through the feeding tube into the base part of the digester vessel. At the same time, a corresponding quantity of efuent was removed close to the surface of the substrate liquid.

Table 3 e Physicalechemical composition of the cattle slurry used. pH DM


6 9.4

Table 4 e Typical composition of crude glycerin from biodiesel production (adapted from [23] and [24]). Component
Glycerin Soapstock Methyl ester Methanol Water and other components

% VS
7.87

Range
56e60% 14e34% 18e20% 3e12% 2e5%

Ca
0.25

Mg
0.07

K2O
0.41

N
0.11

P2O5
0.1

Analyses realized by the Laboratory of Soil and Fertilizer Science of the CEPLAC in December 2005.

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Table 5 e Quantities of FM, DM and VS added daily. Treatment % wt


Cattle slurry Crude glycerin Total 100 0 100

Gli 0 Estimated biogas, ML g1 VS


532 e 532

Gli 5 % wt
95 5 100

Gli 10 % wt
90 10 100

Gli 15 % wt
85 15 100

Estimated biogas, ML g1 VS
420 935 1355

Estimated biogas, ML g1 VS
280 1105 1385

Estimated biogas, ML g1 VS
280 1360 1640

Table 6 e Calculated biogas yields based on values from [22]. Treatment % wt


Cattle slurry Crude glycerin Total 100 0 100

Gli 0 Estimated biogas ML g1 VS


532 e 532

Gli 5 % wt
95 5 100

Gli 10 % wt
90 10 100

Gli 15 % wt
85 15 100

Estimated biogas, ML g1 VS
420 935 1355

Estimated biogas, ML g1 VS
280 1105 1385

Estimated biogas, ML g1 VS
280 1360 1640

2.9.

Analytical methods

The biogas yield was recorded daily according to the displaced sealing liquid and calculated to a normal basis. The pH of the efuent was measured right after its removal from the biodigester. Process temperature was recorded daily. Methane proportions of the biogas were measured by gas chromatography twice a week, using a Varian CP-3800 with ame ionization detector and a CP-SIL 8 CB 30 m capillary column with 0.25 mm interior diameter and 0.25 m phase diameter, under the following conditions: injector temperaow: 1.5 mL min1, oven program: ture: 250  C, 1   90 C / 15 C min / 140  C / 10  C min1 / 250  C (3 min), detector temperature: 280  C, splitless and injection volume 50 mL with a gastight syringe [25]. Gas production and methane proportions were compared using ANOVA and the Tukey-test, where mean values were considered to be signicantly different for a < 0.05.

3.

Results and discussion

The control treatment showed an average biogas yield of 268.6 mL g1 VS. The highest biogas yields (825.3 mL g1 and 825.7 mL g1, respectively), on a normal basis, and relative to mass of volatile compounds added, were produced by the treatments Gli 5 and Gli 10, whereas the addition of 15% crude glycerin to cattle slurry led to process failure and the treatment Gli 15 only produced 387.9 mL g1 (Fig. 1). The difference in the quantities of biogas produced among the treatments was highly signicant between the control treatment and the treatment Gli 5, and between the treatments Gli 10 and Gli 15. No statistically relevant differences could be found between the quantities of biogas produced by the treatments Gli 5 and Gli 10 (Fig. 1). Note: the bars indicate the minimum and maximum values. Values with the same letter did not show signicant differences (Tukey-test for a < 0.05). When comparing the observed biogas yields from Gli 5 and Gli 10 with the calculated theoretical biogas yields from Table 5,

it appears that there is a synergistic co-fermentation effect of glycerin, corresponding to the ndings of Amon et al. [12]. Compared to the control treatment, methane content was increased by 9.5%, 14.3%, and 14.6%, respectively, for the treatments Gli 5, Gli 10, and Gli 15 (Fig. 2). The increase in methane proportion of the treatments with glycerin addition was signicant, compared to the control. Between the treatments Gli 5 and Gli 10 no signicant difference in methane proportions was observed. The quantities of biogas produced by treatment Gli 10 were not signicantly higher than the quantities produced by treatment Gli 5, although a higher proportion of crude glycerin had been fed. This was attributed to an inhibition of the process due to higher concentrations of methanol and KOH in the substrate. Due to the high concentration of the glycerin, an easily degradable carbon source, as well as the presence of methanol and higher concentrations of KOH in the substrate, the biocenosis of treatment Gli 15 was, in terms of process stability, the most fragile. Therefore, the failure of the heating system in the sixth week of the experiment was probably the principal cause for the collapse of the biocenosis of this treatment, as the acetogenic and methanogenic bacteria consortia suffered

Fig. 1 e Comparison of biogas yields from the four treatments.

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Estado da Bahia. The authors would also like to thank EVONIK Degussa Brazil Ltda for the generous donation of the catalyst sodium-methoxide.

references

Fig. 2 e Comparison of the increase in methane contents.

depression from the thermic shock and, consequently, were no longer able to digest all of the metabolic products from the less thermo-sensible hydrolytic and acidogenic bacteria, which led to accumulation of these metabolic products and, consequently, to acidication of the substrate.

4.

Conclusion

Due to its physicalechemical properties, crude glycerin from biodiesel production proved to be a suitable carbon source in biogas production in mesophilic conditions, when added to cattle manure, a substrate decient in easily degradable carbon, as it led to increased gas production as well as to higher methane contents, compared to biogas production from cattle slurry alone. The results of this study led to the conclusion that the optimal proportion of crude glycerin added as supplement to cattle slurry in anaerobic biodigestion is between 5% and 10% wt, and that for the use of crude glycerin as a supplement an adequate time for the adoption of the biocenosis has to be considered, as well as close monitoring of the process. This study showed that the addition of small proportions of crude glycerin from the biodiesel production process to cattle slurry enhanced the production of biogas and its quality as a fuel, by elevating the methane content Thus these ndings could be useful for the recovery of crude glycerin from Brazilian biodiesel production in rural biodigesters that are treating cattle manure produced by beef production or on dairy farms. This could turn the anaerobic treatment and the generation of biogas a more attractive option for these branches of rural industry in Brazil, thus contributing to savings in greenhouse gas emissions, and to a more efcient production of renewable energy.

Acknowledgements
This work was supported by a fellowship granted by the National Counsel of Technological and Scientic Development CNPq e Conselho Nacional de Desenvolvimento Cient co e gico, and was nanced by the FINEP Financiadora de Tecnolo ` Pesquisa do Estudos e Projetos e FAPESB e Fundac a o de Amparo a

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