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Improved Anaerobic Digestion by the Addition of Paper Tube Residuals: Pretreatment, Stabilizing, and Synergetic Eects
Anna Teghammar,*,, Maria del Pilar Castillo, Johnny Ascue, Claes Niklasson, and Ilona Sar var i Horvat h

School of Engineering, University of Boras atan 1, 50190 Boras , Alleg , Sweden Department of Chemical and Biological Engineering, Chalmers University of Technology, 41296 Goteborg, Sweden Swedish Institute of Agricultural and Environmental Engineering (JTI), 750 07 Uppsala, Sweden ABSTRACT: This study deals with the addition of paper tube residuals to a nitrogen-rich mixture of organic waste obtained from industrial and municipal activities. This nitrogen-rich mixture, called buer tank substrate (BTS) in the following text, is used in a large-scale biogas plant. The eects were investigated in semi-continuous co-digestion processes, and variations in operational conditions were studied. The addition of paper tubes had stabilizing eects, prevented the failure of the process, and made it possible to decrease the hydraulic retention time from 25 to 20 days. Furthermore, synergetic eects were found, with 1534% higher methane yields, when paper tubes were co-digested with BTS. Moreover, steam explosion pretreatment of the paper tube waste with the addition of 02% NaOH was evaluated by batch digestion experiments. Increasing the NaOH concentrations used in the pretreatment resulted in increasing methane yields, with the highest of 403 N mL of CH4 g1 of volatile solids (VS) corresponding to an increase by 50% compared to that when untreated paper was digested (268 N mL of CH4 g1 of VS). The long-term eects of this best pretreatment were further investigated by continuous co-digestion experiments, leading to a higher methane yield when pretreated paper tubes were used in the co-digestion process compared to untreated.

1. INTRODUCTION The European Commission has set the goal that, by 2020, 20% of the energy consumed should come from renewable energy sources, as well as 10% of the energy consumed within the transport sector.1 To be able to reach this goal, especially in the transport sector, the production and use of biogas provides a good alternative. New substrates, however, are needed to be able to produce larger amounts of biogas than what is possible today. Lignocellulosic-rich waste materials have a high potential for biogas production. They are produced in abundant amounts worldwide, in the form of agricultural waste streams, such as straws, stalks, and manure, as well as wood and paper. These materials oer the additional advantage of not competing with land usage for food and feed cultivation compared to energy crops. A signicant drawback with lignocellulosic materials, however, is that they are hard for the microorganisms in the anaerobic digester to digest.2 The three main biopolymers in lignocellulosic-rich materials are cellulose, hemicellulose, and lignin, which are present in a complex and cross-linked structure.2,3 To make these materials degradable by the bacteria, dierent pretreatments are often needed. Pretreatments can be carried out by mechanical, physical, chemical, and/or biological methods,35 which are able to open up the structure of the lignocellulose, improve the accessibility of the enzymes to the material, and sometimes combine with a degradation of the indigestive lignin.3 One of the most promising pretreatment methods is steam explosion. This method uses a combination of high-pressure steam (1520 bar) and high temperature (up to 250 C) followed by a
2012 American Chemical Society

pressure-drop explosion. Steam explosion pretreatment has previously been studied on lignocelluloses prior to anaerobic digestion on paper tube residuals,6 wheat straw,7 biobers from digested manure,8 salix,9,10 oat straw,11 and bulrush.12 Studies on semi-continuous co-digestion assays have previously been performed on manure, sewage sludge, and/or industrial food waste.1321 However, only a few studies have been found on the use of lignocelluloses in co-digestion processes. One study was found on dry continuous anaerobic co-digestion, where paper waste was added to food and livestock waste.22 In another study, wheat straw hydrolysate from an ethanol pilot plant with hydrothermal pretreatment was co-digested with cow and pig manure in continuous stirredtank reactors (CSTRs).23 Powdered rice and wheat straw added to cattle dung in semi-continuous reactors resulted in increased methane production in a study by ref 24. However, no studies have been found on continuous co-digestion on a lignocellulosic-rich material, which has been pretreated to improve the biogas production, according to the authors knowledge. The addition of lignocellulosic-rich materials to anaerobic codigestion processes can have additional positive eects, leading to better nutritional balance. Feedstocks that are rich in proteins can lead to ammonia inhibition when degraded, if care is not taken.25 In Sweden, slaugtherhouse waste or other protein-rich substrates are often added together with municipal solid waste into the anaerobic digester, which can lead to high protein levels.26 Ammonia inhibition can lead to the
Received: October 4, 2012 Revised: December 11, 2012 Published: December 11, 2012
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dx.doi.org/10.1021/ef301633x | Energy Fuels 2013, 27, 277284

Energy & Fuels accumulation of volatile fatty acids (VFA), with a possible failure of the digestion process as a consequence.25 The carbon/nitrogen (C/N) ratio should ideally be something between 10:1 and 30:1 for the digester to work at its full potential. 27 The addition of carbon-rich materials, as lignocelluloses, to the anaerobic digestion process with nitrogen-rich feedstocks will result in an increased C/N ratio, which would stabilize the process.13,25 The specic objectives of this study were to investigate the eect of using paper tube residuals as a co-substrate in the continuous digestion of a nitrogen-rich substrate. Pretreated and untreated paper tubes were used, and the biochemical methane potential of both pretreated and untreated paper was also determined. The addition of untreated paper tubes was studied at two dierent operational sets, while the treated paper was studied at one operational set. Table 1. Feedstock Streams in BTS1 and BTS2
substrate OFMSWa industrial biosludgeb industrial wastewater sludge slaughterhouse waste industrial food waste citrus wastes sh sludge total
a

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BTS1 (%) 35.2 28.7 2.9 13.0 4.0 16.2 100

BTS2 (%) 47.6 30.0 4.8 6.1 6.4 5.1 100

OFMSW = organic fraction of municipal solid waste. bSludge from a slaughterhouse wastewater treatment plant.

2. EXPERIMENTAL SECTION
2.1. Materials. The paper tube residuals used as a substrate in this study were the discarded material obtained from Nordens Pappersindustri AB (Boras , Sweden). These residuals consisted of a mixture of 10% raw paper tubes without glue, 35% tubes with the glue sodium silicate, and 55% tubes with the glue polyvinyl alcohol. This mixture was used for all pretreatments and digestions. The paper tubes were milled to 12 mm particle size with a knife-milling Warring commercial blender. The composition of the mixture in dried form was 53% cellulose, 10% hemicellulose, 23% lignin, and 10% glue (mixture of sodium silicate and polyvinyl alcohol). The total solids (TS) content was 95%, and the volatile solids (VS) content was 85%. All compositional analyses were performed as reported previously in ref 6, except the analysis of total C (43%) and total N (0.13%), which was performed by SP Technical Research Institute of Sweden. The elementary analysis resulted in a C/N ratio of 330:1. 2.2. Pretreatment Conditions. The paper tubes were subjected to thermochemical steam explosive pretreatments in an explosive pilotscale reactor (Process och Industriteknik AB, Sweden), with a reaction chamber of 10 L and an expansion tank for the explosive ushing. The pretreatments were performed at 1520 bar and 190 C for 10 min and with the addition of 02% sodium hydroxide. The reactor was heated with 60 bar steam provided by a power plant (Boras Energi och Miljo AB, Boras , Sweden). The substrate was mixed with water to achieve a concentration of 10% TS and an appropriate amount of added sodium hydroxide prior to the pretreatment. During the pretreatment, the paper tube solution was diluted by the condensed steam to a concentration of about 5% TS. 2.3. Inoculum and Buer Tank Substrate. The inoculums and the buer tank substrate (BTS) used were obtained from the largescale biogas plant at Boras Energi och Miljo AB (BEMAB), Boras , Sweden. The inoculums and BTS were collected on two dierent occasions, 5 months apart (inoculums 1 and 2 and BTS1 and BTS2). The composition of dierent feedstock streams in BTS1 and BTS2 is presented in Table 1, and the characteristics of the inoculums 1 and 2 and BTS1 and BTS2 can be found in Table 2. The BTS2 substrate was selected at a time when the process was unstable and, thus, faced operating problems because of the characteristics of the feedstock streams. 2.4. Batch Anaerobic Digestion Assay. Batch anaerobic digestion assays were performed to evaluate the eect of the sodium hydroxide concentration in steam explosion pretreatment on the methane yield of paper tube samples. The assays were performed at thermophilic conditions (55 C), and the experiment was run for 50 days. The cultures were prepared in serum glass bottles with a working volume of 2.1 L and closed with butyl rubber seals and aluminum caps. Before digestion, the pretreated and untreated samples were neutralized to pH 7 with either NH4OH or H3PO4. Each ask contained a VS ratio of 2:1 inoculum/substrate, with a total of 3 g of VS from each substrate. The volume of the added inoculum was 260 mL; the ammonium phosphate buer was 200 mL (50 mM); and the
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amount of substrate corresponded to the VS content mentioned above. Finally, water was added to each ask to reach a nal total volume of 600 mL. The headspace of each ask was ushed with a mixture of 80% nitrogen and 20% carbon dioxide. The cultures were run in triplicate for each substrate, with three control asks detecting the gas production of only inoculum running in parallel. Gas analysis of methane and carbon dioxide was performed according to a previous method by ref 28. Gas samples of 0.25 mL were withdrawn regularly from the headspace, using a pressure-tight syringe (VICI, Precision Sampling, Inc., Stockton, CA) to analyze the composition of the gas. The composition of the gas was then analyzed by a gas chromatograph (Auto System Perkin-Elmer, Waltham, MA) equipped with a packed column (6 ft 1.8 in. outer diameter, 80100 mesh, Perkin-Elmer, Waltham, MA). The injection temperature was 150 C, and the carrier gas was nitrogen, operated with a ow rate of 20 mL/min at 60 C. To avoid overpressure in the glass asks, excess gas was released through a needle after the gas analysis, and gas analysis was performed again. All methane volumes are presented at normal conditions (1 atm and 0 C). One-way analysis of variation (ANOVA) was used to quantify the treatment impact of NaOH on methane production. The ANOVA calculation was performed with the software package Minitab. 2.5. Continuous Co-digestion Assay. The continuous experiments were performed in 10 L CSTRs, with a culture volume of 5 L. The assays were performed in three dierent operational sets. In the rst set, three reactors were run in parallel. The rst reactor was used as a control using BTS1 as the only substrate. Untreated paper tubes (UP) were added together with BTS1 in the second reactor, while pretreated paper tubes (PP) were added together with BTS1 in reactor 3. The pretreatment of the paper tubes was selected as the treatment with the highest methane potential according to the batch experiment. Inoculum 1 was used in this rst set of experiments. All three reactors were run with an organic loading rate (ORL) of 1.3 g of VS L1 day1 from BTS1, with the addition of 0.4 g of VS L1 day1 from paper tubes in reactors 2 and 3, corresponding to a VSBTS/VSpaper (g/g) ratio of 3:1, and all three reactors were run at a hydraulic retention time (HRT) of 25 days (Table 3). The reactors were run for a period of three HRTs after a stable process was reached. In the second and third operation sets of continuous experiments, two reactors were run in parallel, with the rst reactor with BTS2 only and the second reactor with BTS2 + UP. In the second operational set, the reactors were run with an OLR of 1.5 g of VS L1 day1 from BTS2, with the addition of 0.5 g of VS L1 day1 from untreated paper tubes in reactor 2, corresponding to the VSBTS/VSpaper (g/g) ratio of 3:1, and both reactors were run at a HRT of 25 days. After a stable process was reached, and the reactors acted stationary, the reactors were run for an additional period of three HRTs. This was followed by a third operational set on the same reactors but with a change of the HRT to 20 days and an OLR of 1.3 g of VS L1 day1 from BTS2 with the addition of 0.7 g of VS L1 day1 from untreated paper tubes in reactor 2, corresponding to the VSBTS/VSpaper (g/g) ratio of 2:1 (Table 3). The reactors were operated under these conditions again for a period of three HRTs. All reactors were fed daily, and the incubation temperature was 55 C. The gas composition was analyzed by gas chromatography (PerkinElmer ARNEL, Clarus 500) equipped with a
dx.doi.org/10.1021/ef301633x | Energy Fuels 2013, 27, 277284

Energy & Fuels Table 2. Characteristics of the Two Dierent Inoculums and Buer Tank Substrates Used
substrate inoculum 1 inoculum 2 BTS1 BTS2
a

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TS (%) 2.16 2.05 20.5a 26.0a


a

VS (%) 1.43 1.37 18.1a 23.4a


a

pH 7.83 7.77a 5.42c 4.41c


a

VFA (g/L) 3.55 3.72a 15.4c 8.0c


a

NH4+ (g/L) 2.54a 2.52a 2.62a 1.76a

Ntot (g/L) nab nab 12.5a 15.7a

fats (g/L) nab nab 76.3a 78.4a

proteins (g/L) nab nab 67.3a 78.2a

carbohydrates (g/L) nab nab 59.8a 92.9a

C/N nab nab 6.20a 5.98a

COD (g/L) nab nab 225a 288a

Data from Boras Energi och Miljo AB. bna = not available. cData from SP Technical Research Institute of Sweden.

packed column (7 ft HayeSep N 60/80, 1/8 in. SF), a ame ionization detector (FID) at 250 C, helium as a carrier gas (31 mL/min), and the injection temperature at 60 C. All of the injections were performed with a headspace sampler TurboMatrix 110. Gas samples were taken every 24 h. All methane volumes are presented at normal conditions (1 atm and 0 C). 2.6. Analytical Methods. The TS and VS were measured according to the standard method SS 028113.29 The ammonia concentration was measured according to ISO 1173230 and SIS 028134.31 The organic nitrogen and total nitrogen were measured according to SS-ISO 13878.32 Total carbon was analyzed according to SS-ISO 10694,33 and the pH was analyzed according to SS 028122.34 The concentrations of VFA were analyzed by high-performance liquid chromatography (HPLC, Agilent 1100 system, Agilent, Sweden) equipped with a refractive index detector. An ion-exchange column (Rezex ROA organic acid H+) was used for the separation operating at 60 C, and 5 mM H2SO4 with a ow rate of 0.6 mL/min was used as an eluent.

3. RESULTS Pretreatments with steam explosion were performed on the paper tubes and evaluated by batch assays measuring the biomethane potential. Pretreated samples showing the best performance in batch experiments were used in the continuous co-digestion experiments and were co-digested with a nitrogenrich feedstock (BTS1). Furthermore, the untreated paper tube residuals were also co-digested with an unstable nitrogen-rich substrate (BTS2) to study possible stabilizing eects. 3.1. Biomethane Potential of Untreated and Treated Paper Tubes: Batch Assays. Steam explosion pretreatments with four dierent setups with the addition of 02% NaOH at 190 C for 10 min were performed on the paper tubes, and the eects were evaluated by batch digestion assays (Table 4). Steam-exploded paper tubes with 0% NaOH resulted in about the same methane production as untreated paper tubes (about 270 N mL of CH4 g1 of VS compared to 250 N mL of CH4 g1 of VS), while 2% NaOH gave the highest methane output of approximately 400 N mL of CH4 g1 of VS, improving the methane potential by 50%. Samples treated with lower concentrations of NaOH gave higher yields of methane compared to that of untreated paper but less than the sample that was treated with 2% NaOH. Moreover, not only was the accumulated methane production increased, but the initial methane production rate was also enhanced as a result of the pretreatment. The digestion rate increased with an increasing NaOH concentration, from 25 N mL of CH4 g1 of VS day1 for untreated paper tubes to 41 N mL of CH4 g1 of VS day1 when 2% NaOH was added, which is an increment of 64% (Table 4). One-way ANOVA analysis showed that the concentration of NaOH is a signicant factor (p value of 0.048, with a 5% signicance level), aecting the accumulated methane yield. 3.2. Addition of Pretreated Paper Tubes in Continuous Co-digestion. Semi-continuous co-digestion assays were performed with three reactors in parallel to evaluate the longterm eects of the pretreatment. In reactor 1, BTS1 was
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digested exclusively; in reactor 2, untreated paper tubes (UP) were co-digested with BTS1; and in reactor 3, pretreated paper tubes (PP) were digested with BTS1. The pretreatment of the paper tubes were selected according to the best methane yield obtained in the batch digestion assay (steam explosion at 190 C for 10 min with 2% NaOH; Table 4). The pretreatment of the paper in co-digestion with BTS1 showed a higher methane potential (521 N mL of CH4 g1 of VS) compared to that when untreated papers were digested together with BTS1 (498 N mL of CH4 g1 of VS; Figure 1 and Table 5). The BTS1 alone produced 470 N mL of CH4 g1 of VS. This means a total increase of 6 or 11% of the methane yields when co-digesting BTS1 with UP or PP, respectively, compared to that obtained during the digestion of BTS1 alone. The concentration of methane in the biogas was 70% in reactors 1 and 2 and 69% in reactor 3, while the remaining part was carbon dioxide. The C/ N ratio of the digested mixture changed from 6.20 to 8.46 after the addition of paper, for both untreated and pretreated paper. The characteristics of euents, obtained after 3 HRTs, are shown in Table 6. The NH4+ level and the level of total VFA were lower in the reactors where BTS1 was co-digested with untreated or pretreated paper tubes, while the pH was stable at around 8 for all three reactors. Besides the higher methane yields followed by the codigestion of paper tubes and BTS, synergetic eects could be found (Table 5). The estimated theoretical methane yield (ETMY) for BTS1 + UP was calculated as the addition of the methane yield per BTS1 only (470 N mL of CH4 g1 of VS; Table 5), and the methane yield of untreated paper tubes was available from the batch assay (268 N mL of CH4 g1 of VS; Table 4). According to the VS ratio of 3:1, the expected ETMY value for BTS1 + UP was calculated as being 420 N mL of CH4 g1 of VS (Table 5). The obtained value of BTS1 + UP was 498 N mL of CH4 g1 of VS, and in comparison to the ETMY value, it is an increase of 19%. This synergy eect could also be seen for BTS1 + PP. The theoretical value of BTS1 + PP was calculated as 453 N mL of CH4 g1 of VS, and because the obtained value of BTS1 + PP reached 521 N mL of CH4 g1 of VS, there is an increase of 15% (Table 5). Consequently, synergy eects could be detected, because the co-digestion of dierent substrate streams resulted in elevated methane yields compared to those from the single streams. Furthermore, the eects of the pretreatment were evaluated by a comparison between the addition of untreated and pretreated paper tubes in co-digestion with BTS1. BTS1 + PP produced 521 N mL of CH4 g1 of VS compared to 498 N mL of CH4 g1 of VS for BTS1 + UP, corresponding to an increase in the total methane yield of 5%. The energy recovery calculated as the heating value of the produced methane35 divided by the heating value of the substrate36,37 is presented in Table 5. The energy balance of 61% for the digestion of BTS1 only is improved to 70 and 73% during the co-digestion process of BTS1 with UP and PP, respectively.
dx.doi.org/10.1021/ef301633x | Energy Fuels 2013, 27, 277284

Energy & Fuels


UP (g of VS L1 day1)

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Table 4. Accumulated Methane Production and Digestion Rate from Batch Anaerobic Digestion after Pretreatment with Dierent NaOH Concentrations
0.7 methane production pretreatment conditions untreated 0% NaOH 0.5% NaOH 1% NaOH 2% NaOH
a

20 HRT, VS ratioa of 2:1

operation set 3

yield (N mL g1 of VS) 268 251 295 352 403

SDb 48 70 57 66 20

digestion ratec (N mL g1 of VS day1) 25 22 26 32 41

BTS2 (g of VS L1 day1)

1.3 1.3

Accumulated methane yield after 43 days of digestion. bOne standard deviation on the accumulated yield. cDigestion rate calculated from the rst 4 days of digestion.

UP (g of VS L1 day1) BTS2 (g of VS L1 day1)

25 HRT, VS ratio of 3:1

operation set 2

Table 3. Operational Parameters in the Three Dierent Continuous Co-digestion Experiments

1.5 1.5

0.5

VS ratio = VSBTS/VSpaper (g/g). bBTS, buer tank substrate; UP, untreated paper; PP, pretreated paper.

PP (g of VS L1 day1)

Figure 1. Accumulated methane production from the co-digestion of untreated paper tubes (UP) and pretreated paper tubes (PP) with BTS1 at the HRT of 25 days. The OLR from BTS1 was 1.3 g of VS L1 day1 in all three reactors with the addition of 0.4 g of VS L1 day1 UP or PP, corresponding to the VSBTS/VSpaper (g/g) ratio of 3:1, in reactors 2 and 3, respectively.

0.4

3.3. Paper Tubes as a Stabilizer. In the second and third operation sets, a dierent buer tank substrate was used (BTS2) in the co-digestion with untreated paper tubes. The content of BTS2 can be found in Table 1. Figure 2 shows the methane production obtained in each reactor after a stable process was reached. In reactor 1, untreated paper tubes (UP) were added to BTS2, while in the control reactor, BTS2 was digested exclusively. Both reactors were operated at two dierent operation sets. At OLR of 2 g of VS L1 day1, HRT of 25 days, and a mixing ratio of 3:1 corresponding to VSBTS/VSpaper (g/g), the co-digestion of BTS2 and UP produced 444 N mL of CH4 g1 of VS (operation set 2). The control reactor with only BTS2 resulted in 354 N mL of CH4 g1 of VS at the same conditions. Consequently, a 25% higher methane yield (per gram of VS) could be achieved when co-digesting BTS2 with UP compared to that of the digestion of BTS2 alone. When the HRT was decreased to 20 days and the VSBTS/VSpaper (g/g) ratio was changed to 2:1, the methane production of BTS2 + UP increased to 482 N mL of CH4 g1 of VS. However, the control reactor with only BTS2 collapsed after a period of two retention times, and no methane yield could be obtained (Figure 2). The methane content in the produced biogas was 70% in all reactors, except reactor 2 in operation set 3. Prior to collapse, this reactor produced 58% methane. The euent characteristics of the reactors, after 3 HRT, can be found in Table 6. At the second operation set, the process in reactors 1 and 2 was stable and showed a similar pH of 7.9 and
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25 HRT, VS ratio of 3:1

UP (g of VS L1 day1) BTS1 (g of VS L1 day1) reactor substrateb

operation set 1

1 2 3

BTS UP + BTS PP + BTS

1.3 1.3 1.3

0.4

Energy & Fuels

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Table 5. Synergy Eects of Co-digestion of BTS and Untreated Paper Tubes Expressed in Methane Yields Per Gram of VS
operation seta 1 1 1 substrateb BTS1 BTS1 + UP BTS1 + PP obtained (N mL of CH4 g1 of VStotal) 470 498 521 C/N ratio 6.20 8.46 8.46 ETMYc (N mL of CH4 g1 of VS) 420 453 increased CH4 yield in co-digestion (%) 19 15 energy recoveryd (%) 61 70 73

a Operation set 1: HRT of 25, 1.3 g of VS L1 day1 from BTS1 and 0.4 g of VS L1 day1 from UP or PP respectively, and VS ratio of 3:1 VSBTS/ VSpaper (g/g). bUP, untreated paper; PP, pretreated paper; BTS, buer tank substrate. cETMY = estimated theoretical methane yield. dEnergy recovery calculated as the heating value of produced methane divided by the heating value of the dierent substrates.3537

Table 6. Euent Characterization in the Continuous Operation for All Three Sets after 3 HRTsa
operation setb 1 1 1 2 2 3 3
a

substrate BTS1 BTS1 BTS1 BTS2 BTS2 BTS2 BTS2 + UP + PP + UP + UP

pH 8.0 8.0 8.1 7.9 7.9 8.01 6.98

TS (%) 1.3 2.4 2.3 2.0 1.7 2.7 2.8

VS (%)

NH4+ (g/L) 3.1 2.5 2.1 1.92 1.92 1.68 1.66

total VFA (g/L) 3.65 2.47 3.25 1.92 4.49 1.81 5.98

acet (g/L) 1.08 0.97 1.02 1.29 2.30 1.24 1.98

prop (g/L) 2.42 1.48 2.17 0.34 0.97 0.44 2.25

but (g/L) 0.10

ibut (g/L)

isov (g/L) 0.054 0.019 0.061 <0.1 0.83

val (g/L)

1.5 1.2 2.0 2.0

0.14 0.62 0.15

0.74

0.29 0.25 0.13 0.22

HRT, hydraulic retention time; TS, total solids; VS, volatile solids; VFA, volatile fatty acids; acet, acetic acid; prop, propionic acid; but, butyric acid; ibut, isobutyric acid; isov, isovaleric acid; val, valeric acid. bOperation set 1: HRT of 25, 1.3 g of VS L1 day1 from BTS1 and 0.4 g of VS L1 day1 from UP or PP, respectively and VSBTS/VSpaper ratio of 3:1 (g/g), Operation set 2: HRT 25, 1.5 g of VS L1 day1 from BTS2 and 0.5 g of VS L1 day1 from UP and VSBTS/VSpaper ratio of 3:1 (g/g), Operation set 3: HRT 20, 1.3 g of VS L1 day1 from BTS2 and 0.7 g of VS L1 day1 from UP and VSBTS/VSpaper ratio of 2:1 (g/g).

Figure 2. Accumulated methane production from the co-digestion of untreated paper tubes (UP) with BTS2 at operation sets 2 and 3, with HRT of 25 and 20 days, respectively. The ORL from BTS2 was 1.5 g of VS L1 day1 for both reactors at operation set 2, with the addition of 0.5 g of VS L1 day1 of paper tubes in the second reactor, corresponding to the VSBTS/VSpaper (g/g) ratio of 3:1. The ORL from BTS2 was 1.3 g of VS L1 day1 for both reactors at operation set 3, with the addition of 0.7 g of VS L1 day1 of paper tubes in the second reactor, corresponding to the VSBTS/VSpaper (g/g) ratio of 2:1.

similar NH4+ levels of 1.92 g/L. The VFA levels were higher in the control reactor (4.49 g/L) (BTS2 alone) compared to that

when co-digesting BTS2 and untreated paper (1.92 g/L) (Table 6). However, when the operation conditions were changed to set 3 (Table 6), the control reactor, with only BTS2, showed a decrease in pH to 6.98 (Table 6) and high CO2 levels in the biogas were detected (3844%; data not shown). Eorts to restore the equilibrium of the process by feeding half or less of the organic load were not successful. The level of NH4+ in the two reactors was approximately 1.7 g/L; however, the VFA content was signicantly higher in the reactor digesting BTS2 only, reaching a level of approximately 6 g/L compared to 1.8 g/L in reactor 1 (BTS2 + UP; Table 6). The collapsed reactor, with BTS2 only, showed high concentrations of butyric acid (0.62 g/L), isobutyric acid (0.15 g/L), and isovaleric acid (0.74 g/L) compared to nondetectable levels of the same VFAs in the reactor digesting BTS2 together with UP at the same operating conditions. The C/N ratio of the BTS2 was measured as 5.98 because of a high content of a nitrogen-rich municipal solid waste fraction combined with slaughterhouse waste but with an absence of enough carbon-rich substrate fractions (Tables 1 and 2). However, when the paper tubes were added, the C/N ratio of the feedstock increased to 8.31 for operation set 2 and to 9.72 for operation set 3 (Table 7).

Table 7. Synergy Eects of Co-digestion of BTS and Untreated Paper Tubes Expressed in Methane Yields Per Gram of VS
operation seta 2 2 3 3
a

substrateb BTS2 + UP BTS2 BTS2 + UP BTS2

obtained (N mL of CH4 g1 of VStotal) 444 354 482 0

C/N ratio 8.31 5.98 9.72 5.98

ETMYc (N mL of CH4 g1 of VS) 333

increased CH4 yield in codigestion (%) 34

energy recoveryd (%) 66 48 74

Operation set 2: HRT of 25, 1.5 g of VS L1 day1 from BTS2 and 0.5 g of VS L1 day1 from UP, and VS ratio of 3:1 VSBTS/VSpaper (g/g). Operation set 3: HRT of 20, 1.3 g of VS L1 day1 from BTS2 and 0.7 g of VS L1 day1 from UP, and VS ratio of 2:1 VSBTS/VSpaper (g/g). bUP, untreated paper; PP, pretreated paper; BTS, buer tank substrate. cETMY = estimated theoretical methane yield. dEnergy recovery calculated as the heating value of produced methane divided by the heating value of the dierent substrates.3537
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Energy & Fuels Besides the stabilizing eects, the addition of the paper tube residuals resulted in signicantly higher methane production in the co-digestion with BTS2. The ETMY, is calculated as previously, with the addition of methane potentials determined for the two dierent streams digested separately. The yield for untreated paper tubes was determined during the batch experiment as 268 N mL of CH4 g1 of VS (Table 4), while BTS2 alone showed production of 354 N mL of CH4 g1 of VS. According to the mixing VS ratio of 3:1 for BTS2 and UP, the ETMY for the co-digestion was calculated to be 333 N mL of CH4 g1 of VS (Table 7). This means that the obtained value of 444 N mL of CH4 g1 of VS is 34% higher than the expected value. The energy recovery values can be found in Table 7 and show that this value for the digestion of BTS2 at operation set 2 was only 48%, which could be increased to 66% by the addition of paper tube residuals to the digestion process. At the operation set 3, the reactor with only BTS2 collapsed and no energy balance value could be calculated; however. when paper tubes where added, the energy balance value of 74% was obtained.

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4. DISCUSSION The addition of paper tube residuals to the nitrogen-rich buer tank substrates BTS1 and BTS2 resulted in elevated methane yields because of synergetic eects. The methane yields increased by 1534% when paper tubes were co-digested with BTS compared to the digestion of the single streams exclusively. Synergy eects have previously been found in codigestion of slaughterhouse waste, manure, and fruit and vegetable waste14 and co-digestion of dierent wastes from agro-industrial activities.17 A previous study found an almost doubled methane yield when the proportion of fruit and vegetable waste increased from 20 to 50%, in a co-digestion process with cattle slurry and chicken manure.16 Furthermore, the addition of paper tube residuals to the buer tank substrate BTS2 could prevent reactor failure. At lower retention times, the control reactor digesting BTS2 exclusively resulted in a reactor collapse, while the addition of paper tube residuals to BTS2 could stabilize the process. The addition of carbon-rich paper tubes prevented the accumulation of VFA at both higher and lower retention times (Table 6). The accumulation of VFA has shown to be toxic to the methanogens,25 where individual VFA have been found to be the most reliable indication of the process collapse.38 Increased concentrations of buturic and isobuturic acids were reported in a previous study,38 while an increase in concentrations of isobutyric acid and isovaleric acids was found by other authors as the main factors for process failure.39 Dierent anaerobic systems have dierent sensitivity and inhibition levels depending upon the specic substrates, the inoculum, and the operating conditions. A general concentration level of the VFA that causes inhibition can therefore not be determined. Thus, for a better understanding of the system, the relative change of VFA levels in the actual system should be studied.38 The collapsed reactor, with BTS2 only, showed high concentrations of the three mentioned VFAs compared to non-detectable levels of the same VFAs in the reactor where BTS2 was co-digested with UP (Table 6). The accumulation of VFA could be caused by the abundant nitrogen-rich feedstock streams compared to the carbon-rich streams making up the BTS2 mixture. The increase in the C/N ratio, after the addition of paper tubes from 5.98 to 9.72 for operation set 3, had an important eect in stabilizing the
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process and preventing the VFA accumulation. The C/N ratios should ideally be between 10:1 and 30:1;27 however, other authors state that the ideal C/N ratio should be between 20:1 and 30:1.25,40 Furthermore, the accumulation of VFA could be a consequence of the citrus waste content. About 5% of the feedstock content in BTS2 was citrus waste, which could aect the reactor performance negatively. Citrus waste has been found to be toxic to the microorganisms in the anaerobic digester, because of its content of limonene,41 where a feedstock of 30% citrus waste resulted in reactor failure. The BTS1 was a more robust feedstock in itself, and the digestion of BTS1 resulted in a higher methane yield than that of BTS2 (Figures 1 and 2). Thus, the addition of paper waste did not show as strong of stabilizing eects as it did in the case of BTS2. Moreover, in the case of BTS2, higher synergetic eects on the methane yields could be found within the codigestion with paper waste compared to the co-digestion of BTS1 and paper. The two buer tank substrates constituted dierent feedstock streams (Table 1), which explains their dierent behaviors. BTS1 had a marginally higher C/N ratio of 6.20 compared to 5.98 for BTS2 (Table 2); moreover, citrus waste with a toxic limonene content was absent in BTS1. The used pretreatment method resulted in a signicant improvement in the methane yield of paper tube residuals, evaluated by both batch and continuous mode of operation. While steam explosion results in a breakdown of the lignocellulosic structure as well as a decrease of the crystallinity, the added alkali hydrolyzes the hydrogen bonds between the lignin and the cellulose/hemicelluloses as well as the intralignin linkages.6,42,43 The best pretreatment condition evaluated by batch experiments improved the methane production by 50%. This number is higher than the dierence obtained when BTS1 + PP was compared to BTS1 + UP in the continuous codigestion assays. However, in these assays, only 25% of the VS was added in the form of paper tubes. Because the pretreatment was performed exclusively on the paper tube fraction, we can assume that the increment obtained in the methane production is due to the paper tubes only and can be calculated. The total increase in methane production per reactor when BTS1 + UP is compared to BTS1 + PP and divided per gram of VS of paper tubes added is calculated as being 98 N mL of CH4 g1 of VS. However, eventual additional synergy eects in the co-digestion are included in this number. This is comparable to the biochemical methane potential (BMP) test, where the pretreatment increased the methane production by 135 N mL of CH4 g1 of VS. Furthermore, the continuous co-digestion of pretreated paper tubes and BTS did not show any negative long-term eects, which further supports this pretreatment method as a highly interesting method for the future. Nevertheless, the economic advantages of the pretreatments of paper tube residuals for full-scale processes should be investigated.

5. CONCLUSION The addition of paper tube residuals to nitrogen-rich substrate mixtures used in a large-scale anaerobic digester plant had stabilizing eects on the process. The paper addition prevented the accumulation of VFA, which had otherwise caused reactor failure. Furthermore, the better nutritional balance in the system led to synergetic eects, and higher methane yields could be achieved. Many biogas plants are not working at their full capacity today because of the lack of suitable substrates, they could improve their economy by considering new
dx.doi.org/10.1021/ef301633x | Energy Fuels 2013, 27, 277284

Energy & Fuels substrates for use in biogas processes, and lignocellulosic substrates represent a great potential. It was proven in this study that the addition of pretreated or untreated paper tube residuals to nitrogen-rich feedstocks results in a more stable process with higher methane yields. When paper tubes were codigested with nitrogen-rich feedstock, synergetic eects were observed due to a better nutritional composition. Moreover, steam explosion pretreatment of paper tubes prior to biogas production led to a further increase in the methane production without showing any negative long-term eects during codigestion with BTS.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: anna.teghammar@hb.se.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS We thank Rakel Martinsson from Boras Energi and Miljo AB for providing information on the inoculums and the buer tank substrates. We also thank SP Technical Research Institute of Sweden for the characterization of the two buer tank substrates. This work was nancially supported by the Swedish Excellence Centre, Waste Renery. NOMENCLATURE BTS = buer tank substrate UP = untreated paper tubes PP = pretreated paper tubes TS = total solids VS = volatile solids VFA = volatile fatty acids C/N = carbon/nitrogen COD = chemical oxygen demand VSBTS/VSpaper = ratio of the volatile solids of the buer tank substrate over the volatile solids of the paper tubes HRT = hydraulic retention time SD = standard deviation ETMY = estimated theoretical methane yield ORL = organic loading rate REFERENCES

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