Dou Wangab,
Hailong Huangab,
Fei Shen*ab,
Gang Yangab,
Yanzong Zhangb,
Shihuai Dengab,
Jing Zhangab,
Yongmei Zengb and
Yaodong Huc
aInstitute of Ecological and Environmental Sciences, Sichuan Agricultural University, 211 Huimin Road, Wenjiang District, Chengdu, Sichuan 611130, P. R. China. E-mail: fishen@sicau.edu.cn; Fax: +86-28-86293078; Tel: +86-28-86293078
bRural Environment Protection Engineering & Technology Centre of Sichuan Province, Sichuan Agricultural University, Chengdu, Sichuan 611130, P. R. China
cCollege of Animal Science and Technology, Sichuan Agricultural University, Chengdu, Sichuan 611130, P. R. China
First published on 19th September 2016
In order to elucidate the possibility of applying biomass densification in anaerobic digestion, pelleting and briquetting were typically investigated for biogas production, and the anaerobic digestion using densified biomass at higher solid content was discussed as well. In addition, the logistic cost, including harvest, transportation, and storage, was also evaluated to check the economic feasibility once biomass densification was employed for biogas production. The results demonstrated that the main composition, including cellulose, hemicellulose and lignin, of the pelleted and briquetted corn stover exhibited some degradation compared with their corresponding undensified corn stover. Both pellets and briquettes had no adverse impacts on anaerobic digestion. The cumulative biogas production from pellets was 349.9 mL g−1 VS (VS: volatile solid), which was 25.8% higher than unpelleted corn stover (278.1 mL g−1 VS, respectively), moreover, the cumulative CH4 production from pellets was 185.7 mL g−1 VS compared with 135.1 mL g−1 VS of unpelleted corn stover. Biogas production from briquettes was also slightly higher than that of the unbriquetted corn stover, however, improvement was not statistically significant. Increasing the organic loading, relatively higher biogas and CH4 production can be achieved from briquettes compared with the unbriquetted corn stover. This was mainly attributed to more free water in the anaerobic digestion of briquettes. Especially, there was 11.7% improvement on biogas production as the organic loading was increased to 80 g TS per kg (TS: total solid). As the briquettes were employed for biogas production with the digestor scale of 3000 m3, the logistic cost could be curtailed by 36.1%. Evidently, the biomass densification can be employed in anaerobic digestion for biogas production to potentially solve the extra high cost of logistic issues.
Currently, the leading technologies for biomass densification mainly includes pellet mill, briquette press, screw extruder, tablet press, and agglomerator. Among these, briquette press and pellet mill are 2 dominating technologies that can increase biomass densification and help in solving logistic issues.12,16–18 Pelleting is an agglomeration of ground particles into dense, free-flowing, durable pellets by means of mechanical or thermal processing.9,19 Pelleting of biomass involves size reduction (using grinders, choppers, and hammer mills), conditioning of the ground biomass by applying heat and/or moisture, and extrusion of the ground biomass through a die.20,21 The diameter and length of 6.3–6.4 mm and 13–19 mm pellets are the most common products with the unit density of 1125–1190 kg m−3 and cylindrical appearances.15 Briquetting is a mechanical process, in which biomass is first shredded with a low initial density and then submitted to high pressure, promoting its agglomeration and densification.17 Unlike the pelleting systems, briquetting can handle the biomass with larger-sized particles and wider moisture contents. The briquettes could be produced from various briquetting systems, such as piston press, tabletizer, cuber, roller press, and the produced briquettes have typical shapes of cylinder and cuboid. Generally, the cylindrical briquettes are 40–80 mm in diameter and 40–150 mm in length with unit density in the range of 800–1000 kg m−3.15 The cubic briquettes are from 12.7 × 12.7 mm to 38.1 × 38.1 mm in cross section, and from 25.4 to 101.6 mm in length with the unit density greater than 1000 kg m−3.15,22
It is also well known that the formation of solid bridges is the main binding mechanism during densification. These solid bridges are developed by chemical reactions and sintering solidification, hardening of the melted substances, or crystallization of the dissolved materials.16,23 During densification, the moisture in the biomass forms steam under high pressure and temperature, which may hydrolyze the hemicellulose and lignin into lower molecular carbohydrates, lignin products, sugar polymers, and other derivatives.24 In contrast to the undensified biomass, the densified biomass will result in different behaviors as they are employed for subsequent conversion for bio-methane by anaerobic digestion.17,25
However, as 2 leading densification technologies, the effect of briquetting and pelleting of agricultural residues on anaerobic digestion have been scarcely evaluated. In order to clarify the responses of pelleting and briquetting to the anaerobic digestion, pellets and briquettes made from corn stover were employed, and their corresponding undensified biomass were also anaerobically digested for comparison. Organic loading of 30, 50, and 80 g TS per kg were investigated for biogas production as well to elucidate the possibility of applying densified biomass for the digestion at higher solid content. Besides, the logistic cost, containing the streams of harvest, transportation, and storage, was evaluated to clarify the economic feasibility of applying biomass densification for biogas production.
The corn stalks were main raw materials for the pellets, which were produced by a ring die pelletizer with double rollers (FTHBCX350, Futen New-energy Technology Co., Ltd, Sanmenxia, Henan Province, China) with the capability of approximately 700–1200 kg h−1. The diameter of the die ring was 350 mm with die size of 10.0 mm. The raw materials should be grounded with size of 10–30 mm and the moisture was required in the range of 15–30% for pelleting. The produced pellets were cylindrical in shape with 10.0 mm in diameter and 15–20 mm in length, and the unit density was determined as 1176 kg m−3.
The determined moisture content of the briquettes and pellets and their corresponding raw materials were in the range of 8.4–10.27% (dry basis). The characteristics of the densified and undensified corn stover were presented in Table 1.
Composition (%) | Unpelleted corn stover | Pellets | Unbriquetted corn stover | Briquettes |
---|---|---|---|---|
a The values in the table were listed in the form of “Mean ± Standard deviation”. | ||||
Total solid | 89.7 ± 0.3a | 91.5 ± 0.0 | 90.97 ± 0.1 | 90.2 ± 0.0 |
Volatile solid | 96.4 ± 0.1 | 94.8 ± 0.0 | 94.9 ± 0.3 | 88.0 ± 1.1 |
Ash | 3.6 ± 0.1 | 5.2 ± 0.0 | 5.1 ± 0.3 | 12.0 ± 1.1 |
Cellulose | 35.2 ± 0.7 | 33.9 ± 1.5 | 34.5 ± 0.1 | 37.2 ± 1.1 |
Hemicellulose | 17.8 ± 0.3 | 15.6 ± 0.8 | 21.4 ± 1.9 | 19.1 ± 1.8 |
Acid-insoluble lignin | 17.1 ± 0.6 | 15.0 ± 2.0 | 17.7 ± 0.1 | 13.2 ± 0.1 |
Acid-soluble lignin | 4.1 ± 0.8 | 6.6 ± 0.4 | 5.4 ± 0.0 | 6.9 ± 0.1 |
Ethanol extractives | 6.5 ± 0.4 | 1.7 ± 0.8 | 2.2 ± 0.4 | 1.8 ± 0.7 |
Inoculum for the batch anaerobic digestion was obtained from Biogas Institute of Ministry of Agriculture, Chengdu, China. The inoculum was pre-incubated for 15 days at mesophilic temperature in order to deplete the residual biodegradable organic materials (degasification). The basic characteristics of inoculum were total solids (TS) of 3.7%, volatile solids (VS) of 52.2% (dry basis), ash content of 47.8% (dry basis), cellulose of 9.3% (dry basis), hemicellulose of 4.2% (dry basis), lignin of 19.4% (dry basis), C/N of 6.6 and pH of 7.42.
The degradation percentage of VS, cellulose, hemicellulose, and lignin after the anaerobic digestion were calculated according to the following equations.
(1) |
(2) |
(3) |
(4) |
The composition of the daily sampled biogas, including CH4, CO2, N2 and H2, were measured using a gas chromatograph (SP-2100A, Beifenruili Analytical Instrument Co., Ltd, Beijing, China) equipped with a molecular sieve packed stainless-steel column with the length and diameter of 2.0 m × 3.0 mm (TDX-01) and a thermal conductivity detector (TCD). The temperatures of the detector, injector, and oven were set at 100 °C, 50 °C, and 50 °C, respectively. The injection volume of sample to the column was 1.0 mL. A standard gas consisting of 52.81% (v/v) CH4, 32.27% (v/v) CO2, 4.93% (v/v) N2 and 9.99% (v/v) H2 was used for calibrating reads from the gas chromatograph.
Free water holdings of densified and undensified corn stover were estimated according to the unabsorbed water in a set duration. 12.0, 20.0 and 32.0 g densified and undensified corn stover were added in 400.0 g distilled water to simulate the organic loading of 30, 50 and 80 g TS per kg in the batch digestion. The water-absorbed biomass was filtered with a Buchner funnel for 2.0 h so that the unabsorbed water can be separated completely for collection. Afterwards, the unabsorbed water in each group was weighted to calculate the free water holding of densified and undensified corn stover. In this part, 3 repetitions were performed on each group.
As the richest fraction in lignocellulosic biomass, cellulose in the pellets was a little lower than the unpelleted corn stover. Unlike pellets, its content in briquettes presented to be a little higher comparing with the unbriquetted corn stover. The decrease of hemicellulose content could be observed after pelleting and briquetting. Similar results have been reported in reference, in which the mannan (mainly representing hemicellulose of softwood) in pellets of Doulas-fir was decreased obviously in contrast to the unpelleted chips.30 The hemicellulose was much more sensitive to thermo-shock than the fraction of cellulose and lignin and the degradation of hemicellulose will occur easily at high temperature and pressure during the process of briquetting and pelleting.12 Consequently, it was believed that degradation of hemicellulose was beneficial to natural bonding for densification due to the formation of adhesive products.16 Moreover, the relatively increased ash content after biomass densification also partially related to hemicellulose degradation. The decrease of acid-insoluble lignin content could be observed after the raw feedstocks were densified into briquettes and pellets. On the contrary, the acid-soluble lignin content was increased in some degree. The lignin content (the sum of acid-insoluble lignin and acid-soluble lignin) was decreased from 23.1% to 20.1% after briquetting, however, the changes of lignin before/after pelleting was not significant. This could be easily understood that densification intensity of briquetting was typical higher than that of pelleting resulting in higher pressure and temperature during briquetting process, and the lignin degradation may be intensified.12 Thereby, it can be deduced that the subsequent biological conversion in anaerobic digestion may be potentially affected by the changes of main composition of biomass after densification, which deserves a detailed investigation.
Furthermore, the cumulative methane yield of undensified and densified corn stover with a total solid loading of 30 g TS per kg was plotted in Fig. 1c. It could be found that the pellets yielded 185.7 mL g−1 VS over 46 days HRT (hydraulic retention time) comparing with the unpelleted corn stover of 135.1 mL g−1 VS, in which the difference was significant (p < 0.001). However, an obvious retard of special methane yield during the first 15 days can be observed on the pellets, which can be supported by the daily biogas production of pellets. As for the briquettes, methane yielded 131.7 mL g−1 VS, which was a slight higher than that of unbriquetted corn stover (129.3 mL g−1 VS), and the difference was not significant (p > 0.05). According to the above results, it was suggested that the biomass densification was feasible to be applied in anaerobic digestion as no negative effects on CH4 production.
As far as the technologies for biomass densification were concerned, the biomass need to be cut into smaller sizes for pellets production. Unlike pellet mills, briquetting machines can handle larger-sized particles, which meant more energy will be consumed for grinding biomass prior to densification for pellets.2,9,35 Moreover, the briquettes have been proved to be a promising low-cost, low-energy, high-capacity approach for densifying corn stover for renewable energy applications in contrast to the pellets.20 Thus, the briquetted corn stover was employed to investigate the digestion performances at the increasing organic loadings of 30, 50, and 80 g TS per kg. The daily biogas production, cumulative biogas production, and cumulative CH4 production were displayed in Fig. 2.
As presented in Fig. 2a, the biogas overall could be produced as the biomass was inoculated, and the biogas releasing exhibited a retard as the organic loading was increased, especially at 80 g TS per kg. The anaerobic digestion did not appear apparent difference between briquettes and the unbriquetted corn stover when the organic loading of 30 and 50 g TS per kg were employed. However, as the organic loading was enhanced to 80 g TS per kg, approximately a delay of 6 days can be observed (see the second peak and the third peak) as unbriquetted corn stover was employed. As the cumulative biogas production based on VS was evaluated (see Fig. 2b), it was no surprising that the biogas production decreased with the increase of organic loading. Moreover, the biogas production from briquettes with organic loading of 30 g TS per kg was improved by 0.6% comparing with the unbriquetted corn stover (p > 0.05). Furthermore, the improvement was intensified as the organic loading was increased. Especially, there was 11.7% improvement on biogas production from briquettes in contrast to the unbriquetted coren stover (p < 0.01) as 80 g TS per kg substrates were loaded. When the cumulative CH4 production based on VS was investigated (see Fig. 2c), the lower organic loading exhibited the higher CH4 production. However, the briquettes released more CH4 comparing with the unbriquetted corn stover. Moreover, the difference on CH4 production between briquettes and unbriquetted corn stover appeared to be more significant with the higher organic loading. According to these results, it was proved that the densification can promote the anaerobic digestion, although the biogas production generally reduced by increasing organic loading.
Apparently, the improvement on biogas releasing may relate to the higher bulk density of briquettes, in which water in anaerobic digestion could not be adsorbed too much, and more free water may potentially retain in the digestion system comparing the unbriquetted corn stover. Thus, it could be speculated that mass transfer and the accessibility of microorganisms and enzymes to substrates facilitating could be improved as briquettes were employed. In order to prove this speculation, the free water in the anaerobic digestion with different organic loadings was determined as displayed in Fig. 3. The retained free water in the anaerobic digestion was reduced with the increasing loading, which well responded to the decreased biogas production at higher loading. Moreover, the free water in the briquettes was also more than that of unbriquetted corn stover. When the weight differences of free water between briquettes and unbriquetted corn stover were correlated with the differences of biogas (CH4) production between briquettes and unbriquetted corn stover, the positive correlation could be observed with correlation coefficient (R2) of 0.77 and 0.86 for biogas and CH4 respectively, indicating the biogas production from anaerobic digestion may partially relate to the free water. Thus, it could be substantially proved the improvement on biogas production from briquettes was mainly due to the retained free water in the digestion slurry.
Fig. 3 Free water in anaerobic digestion using briquettes and unbriquetted corn stover at organic loading of 30, 50, and 80 g TS per kg. *** refers to p < 0.001; ** refers to p < 0.01. |
According to Table 2, the VS degradation after anaerobic digestion of the briquettes at organic loading of 30, 50, and 80 g TS per kg appeared to be higher than that of the unbriquetted corn stover. Moreover, increasing organic loading caused the decrease of VS degradation. This result could be a supplementary evidence for the intensified mass transfer and accessibility of microorganisms and enzymes to substrates in the digestion of briquettes. As the degradation of lignocellulosic fraction was calculated, the hemicellulose and cellulose were 2 dominant fractions for biogas conversion, which was consistent with the reported work.36 Moreover, the degradation of lignocellulosic fractions, including hemicellulose, cellulose and lignin, all decreased as the organic loading was promoted. Their degradation of briquettes after digestion at these 3 loadings were also higher than that of unbriquetted corn stover. These results also greatly responded to the results of retained free water in Fig. 3. Thus, the degradation of lignocellulosic fractions could be another supplementary proof that the anaerobic digestion was intensified by the more retrained free water during the anaerobic digestion. In addition to the free water, the thermal degradation during briquetting was attributed to the analysis of lignocellulosic fractions (see Table 1), which can be another important reason for improving the anaerobic digestion and biogas production.17,34
Degradation (%) | 30 g TS per kg | 50 g TS per kg | 80 g TS per kg | |||
---|---|---|---|---|---|---|
Unbriquetted corn stover | Briquettes | Unbriquetted corn stover | Briquettes | Unbriquetted corn stover | Briquettes | |
a The values in the table were listed in the form of “Mean ± Standard deviation”. | ||||||
Volatile solid | 55.8 ± 0.3a | 57.5 ± 0.2 | 41.9 ± 0.1 | 43.0 ± 1.0 | 32.5 ± 0.1 | 34.8 ± 0.1 |
Cellulose | 57.8 ± 0.1 | 87.3 ± 0.1 | 39.2 ± 0.0 | 51.3 ± 0.2 | 33.4 ± 0.2 | 50.5 ± 0.5 |
Hemicellulose | 63.3 ± 1.9 | 89.5 ± 0.0 | 49.1 ± 0.1 | 53.6 ± 0.9 | 43.6 ± 0.1 | 48.8 ± 0.2 |
Lignin | 51.6 ± 2.1 | 61.4 ± 0.4 | 30.2 ± 0.8 | 46.8 ± 2.1 | 25.4 ± 1.0 | 35.67 ± 0.3 |
Items in logistic cost | Unbriquetted corn stover | Briquettes | Comparison |
---|---|---|---|
a The detailed estimation for these items were listed in ESI. | |||
1. Harvest cost (¥ Yuan per ton) | 137.5 | 156.3 | ↑ 13.7% |
1.1 Collection from field | 80.0 | 80.0 | → 0.0% |
1.2 Size-reduction and densification | 7.5 | 26.3 | ↑ 250.7% |
1.3 Labour cost | 50.0 | 50.0 | → 0.0% |
2. Transportation cost (¥ Yuan per ton) | 17.8 | 7.5 | ↓ 57.9% |
3. Storage cost (¥ Yuan per ton) | 126.43 | 16.14 | ↓ 87.2% |
3.1 Construction for storage | 80.0 | 10.0 | ↓ 87.5% |
3.2 Fire-fighting equipment | 38.5 | 5.13 | ↓ 86.7% |
3.3 Land rent for storage | 2.0 | 0.25 | ↓ 87.5% |
3.4 Labour and operation cost | 5.93 | 0.76 | ↓ 87.2% |
Total cost (¥ Yuan per ton) | 281.73 | 179.94 | ↓ 36.1% |
As indicated in Table 3, it could be easily found that the harvest cost will be definitely increased by 13.7% due to 3.5-fold increase on size-reduction and densification as briquettes was employed. However, the transporting cost could be obviously reduced by 57.9% as the biomass volume can be densified to 1/8 comparing with the undensified corn stover. Even more importantly, the reduction of biomass volume also greatly curtailed the cost on construction and fire-fighting equipment in the stream of storage by 87.5% and 86.7%, respectively. Correspondingly, the land rent, labor and operation cost were also reduced by 87.5% and 87.2%, respectively. Overall the total logistic cost of briquettes for a 3000 m3 anaerobic digestor could be reduced to 179.94 ¥ Yuan per ton, which was decreased by 36.1% comparing with the unbriquetted corn stover. As a result, it was a feasible way to apply biomass densification in anaerobic digestion potentially to solve extra high cost of logistic issues.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra17298a |
This journal is © The Royal Society of Chemistry 2016 |