effect of caco3 pretreatment on methane production from anaerobic digestion of rice straw

5
Effect of CaCO 3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw Benlin Dai 1, 2, a , Anfeng Zhu 2, b , Feihu Mu 1, 2, c , Ning Xu 1, d and Zhen Wu 1, e 1 Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology, Huaiyin Normal University, Huaian, Jiangsu, 223300, China 2 Jiangsu Key Laboratory for Chemistry of Low-Dimensional Material, Huaiyin Normal University, Huaian, Jiangsu, 223300, China a [email protected], b [email protected], c [email protected], d [email protected], e [email protected] Keywords: Anaerobic Digestion, Biogas, Methane Production, CaCO 3 Pretreatment, Rice Straw. Abstract. The chemical pretreatment of rice straw was achieved via the liquid-state dissolution of CaCO 3 . Pretreatment effects on the biodegradability and subsequent anaerobic production of methane were investigated. The results showed that the peak value of biogas production was attained of 4% CaCO 3 pretreatment on the 20 th day, which is 1 589 mL. The test daily methane content of different pretreatment conditions mainly ranges from 3.4% to 47.4%. The cumulative biogas production of 6% CaCO 3 pretreatment was the highest, about 19 917 mL. Introduction Straw is a kind of important lignocellulosic biomass resources, can provide biological transformation (such as bio-diesel, biogas, bio-ethanol, bio-hydrogen) provides polysaccharide rich [1]. In China, agriculture waste large quantity, variety, waste produced about 8 × 10 8 ton annual agricultural crops [2]. If the use of anaerobic fermentation into methane and biogas slurry or application of biogas residue recycling mode to make full use of the agricultural waste, not only ease the nervous energy in rural areas, but also can improve the ecological environment, contribute to the structural adjustment of our country agriculture, to achieve the transition to sustainable agriculture as soon as possible [3]. Straw cellulose and hemicellulose can be degraded biogas produced in the anaerobic fermentation conditions, while the lignin is difficult to be degraded and utilized. Because in the straw cellulose lignin and hemicellulose wrapped, lignin in the fiber, hindered the microbial and enzymatic degradation of cellulose and easy contact, causing resistance material on anaerobic digestion [4]. Visible damage, hydrolysis lignin structure and cellulose and hemicellulose are the raw material of biotransformation rate limiting step. The pretreatment methods to enhance the biogas yield were widely used in the conventional sole anaerobic digestion on the rice straw [5-6]. The objective of this study was to evaluate the biogas production and methane content enhancement capacity by using batch anaerobic reactors, when pretreating the rice straw substrate with four different weight percentages (2%, 4%, 6% and 8%) of CaCO 3 . The test pH value, biogas production and methane content were examined. It provides relevant technical reference to biogas production technology and equipment research and development of the rice straw during anaerobic digestion in this study. Materials and Methods Experimental Materials. Rice straw waste was used as the biodegradable substrate. The substrate was pulverized into particles of diameters of 2 - 3 mm. Anaerobic biogas slurry was collected from rural fecal pool in Xinji town, Huaian city, Jiangsu province, China. The substrate was washed and filtered before the experiment, and then cultured under mid-temperature for one week. No other strains were added in the experiment, and the components of the backfill material are illustrated in Table 1. Applied Mechanics and Materials Vols. 587-589 (2014) pp 208-211 Online available since 2014/Jul/04 at www.scientific.net © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMM.587-589.208 All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP, www.ttp.net. (ID: 130.207.50.37, Georgia Tech Library, Atlanta, USA-12/11/14,01:41:42)

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Page 1: Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw

Effect of CaCO3 Pretreatment on Methane Production from Anaerobic

Digestion of Rice Straw

Benlin Dai1, 2, a, Anfeng Zhu2, b, Feihu Mu1, 2, c, Ning Xu1, d and Zhen Wu1, e 1Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology, Huaiyin Normal

University, Huaian, Jiangsu, 223300, China

2Jiangsu Key Laboratory for Chemistry of Low-Dimensional Material, Huaiyin Normal University,

Huaian, Jiangsu, 223300, China

[email protected],

[email protected],

[email protected],

[email protected],

[email protected]

Keywords: Anaerobic Digestion, Biogas, Methane Production, CaCO3 Pretreatment, Rice Straw.

Abstract. The chemical pretreatment of rice straw was achieved via the liquid-state dissolution of

CaCO3. Pretreatment effects on the biodegradability and subsequent anaerobic production of methane

were investigated. The results showed that the peak value of biogas production was attained of 4%

CaCO3 pretreatment on the 20th

day, which is 1 589 mL. The test daily methane content of different

pretreatment conditions mainly ranges from 3.4% to 47.4%. The cumulative biogas production of 6%

CaCO3 pretreatment was the highest, about 19 917 mL.

Introduction

Straw is a kind of important lignocellulosic biomass resources, can provide biological transformation

(such as bio-diesel, biogas, bio-ethanol, bio-hydrogen) provides polysaccharide rich [1]. In China,

agriculture waste large quantity, variety, waste produced about 8 × 108 ton annual agricultural crops

[2]. If the use of anaerobic fermentation into methane and biogas slurry or application of biogas

residue recycling mode to make full use of the agricultural waste, not only ease the nervous energy in

rural areas, but also can improve the ecological environment, contribute to the structural adjustment

of our country agriculture, to achieve the transition to sustainable agriculture as soon as possible [3].

Straw cellulose and hemicellulose can be degraded biogas produced in the anaerobic fermentation

conditions, while the lignin is difficult to be degraded and utilized. Because in the straw cellulose

lignin and hemicellulose wrapped, lignin in the fiber, hindered the microbial and enzymatic

degradation of cellulose and easy contact, causing resistance material on anaerobic digestion [4].

Visible damage, hydrolysis lignin structure and cellulose and hemicellulose are the raw material of

biotransformation rate limiting step.

The pretreatment methods to enhance the biogas yield were widely used in the conventional sole

anaerobic digestion on the rice straw [5-6]. The objective of this study was to evaluate the biogas

production and methane content enhancement capacity by using batch anaerobic reactors, when

pretreating the rice straw substrate with four different weight percentages (2%, 4%, 6% and 8%) of

CaCO3. The test pH value, biogas production and methane content were examined. It provides

relevant technical reference to biogas production technology and equipment research and

development of the rice straw during anaerobic digestion in this study.

Materials and Methods

Experimental Materials. Rice straw waste was used as the biodegradable substrate. The substrate

was pulverized into particles of diameters of 2 - 3 mm. Anaerobic biogas slurry was collected from

rural fecal pool in Xinji town, Huaian city, Jiangsu province, China. The substrate was washed and

filtered before the experiment, and then cultured under mid-temperature for one week. No other

strains were added in the experiment, and the components of the backfill material are illustrated in

Table 1.

Applied Mechanics and Materials Vols. 587-589 (2014) pp 208-211Online available since 2014/Jul/04 at www.scientific.net© (2014) Trans Tech Publications, Switzerlanddoi:10.4028/www.scientific.net/AMM.587-589.208

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,www.ttp.net. (ID: 130.207.50.37, Georgia Tech Library, Atlanta, USA-12/11/14,01:41:42)

Page 2: Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw

Table 1 Composition of rice straw waste and anaerobic biogas slurry [%]

Digestive material Rice straw waste Anaerobic biogas slurry

Total solids (g TS g-1

wet) 91.2 8.3

Volatile solids (g VS g-1

TS) 83.3 3.2

C/N 69.3 25.8

Experimental Design. Semi-continuous anaerobic reaction was adopted in the experiment.

Different pretreated substrates, water and anaerobic biogas slurry at a certain proportion were put in a

sealed glass bottle with continuous stirring, the maximum volume of which is 2000 mL. The digester

was then put in a water bath, the temperature of which could be adjusted. The temperature was

maintained between 35.0±0.5℃. The test cycle was set to 30 d. The initial pH value was adjusted to

about 7. The mixture in the reactor was collected on time so that the indicators were monitored, and

the same amount of anaerobic biogas slurry was added.

Analytical Methods. Total solids (TS) and volatile solids (VS) were determined according to

Standard Methods 2540B, 2540E [7]. The pH was measured every day using a Leici PHS-3C pH

meter (Leici, Shanghai, China). Gas produced was collected daily in a 1000 mL volumetric bottle,

with biogas samples obtained on a daily basis and then analyzed. Biogas volumes were measured a

water displacement bottle containing acidified (pH = 2) tap water. Volumes were collected for

moisture content and converted to standard temperature and pressure (273 K, 105 Pa). Methane

content in the biogas (% CH4) was measured in a gas chromatograph fitted with flame ionization

detection (GC-FID-2014, Shimadzu, Japan). The analytical column, Rtx-WAX (30 m × 0.25 mm ×

0.25 um), was used for CH4 determination. A standard gas was used to calibrate the system and this

had the following composition: 30% CO2; 30% N2; 40% CH4.

Results and Discussion

The pH Value Variation. As seen in Fig. 1, the test of pH value of different pretreatment conditions

is roughly the same trend, also is the first appearance of a valley, and then slowly rising, then the

second peak and trough. For the substrates pretreated with 6% and 8% H3PO4, the pH value decreased

rapidly from the initial value of 7.20 and 7.26 to the minimum acid point of 5.10 and 5.12 around the

5th

day during the anaerobic digestion, respectively. The test pH values of different pretreatment

conditions mainly ranges from 5.10 to 7.60.

0 5 10 15 20 25 30

5.2

5.6

6.0

6.4

6.8

7.2

7.6

0.02CaCO3 0.04CaCO

3

0.06CaCO3 0.08CaCO

3

pH

Time (days)

Fig. 1 pH change of each pretreated substrate in the digester

Effect of CaCO3 Pretreatment on Daily Biogas Production and Methane Content. Fig. 2 and

3 show that the changes of daily biogas production and methane (CH4) content of each pretreated

substrate in the digester. The test using different CaCO3 pretreatment conditions on rice straw is very

Applied Mechanics and Materials Vols. 587-589 209

Page 3: Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw

slowly to enter the peak gas production of anaerobic digestion, the peak value of biogas production

was attained of 4% CaCO3 pretreatment on the 20th

day, which is 1 589 mL. In general, using CaCO3

pretreatment of rice straw biogas production is low. As seen in Fig. 3, the test of all the CaCO3

pretreated conditions show that similar variation trends in the methane content. The highest CH4

content was 47.4% for the 4% CaCO3- treated rice straw. The test daily methane content of different

pretreatment conditions mainly ranges from 3.4% to 47.4%.

0 5 10 15 20 25 300

300

600

900

1200

1500

1800 0.02CaCO3 0.04CaCO

3

0.06CaCO3 0.08CaCO

3

Bio

gas

pro

du

ctio

n (

mL

/d)

Time (days)

Fig. 2 Daily biogas production of each pretreated substrate in the digester

0 5 10 15 20 25 300

5

10

15

20

25

30

35

40

45

50

55 0.02CaCO3 0.04CaCO

3

0.06CaCO3 0.08CaCO

3

Rat

e o

f C

H4 (

%)

Time (days)

Fig. 3 CH4 content of each pretreated substrate in the digester

Effect of CaCO3 Pretreatment on Cumulative Biogas Production. The effect of the different

pretreatment on the cumulative biogas production in the digester is shown in Fig. 4. As seen in Fig. 4,

the cumulative biogas production of 6% CaCO3 pretreatment was the highest, about 19 917 mL,

which was followed by 4% CaCO3 (14 741 mL), 8% CaCO3 (9 562 mL), and 2% CaCO3 (9 240 mL).

The cumulative biogas production is increased significantly. This is due to the complex organic

compounds after CaCO3 pretreatment celluloses, hemicelluloses are degraded into soluble organic

matter, increase the substrate amount of acid producing bacteria, and the gas production increase.

210 Sustainable Cities Development and Environment Protection IV

Page 4: Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw

0 5 10 15 20 25 300

4000

8000

12000

16000

20000 0.02CaCO

3

0.04CaCO3

0.06CaCO3

0.08CaCO3

Cu

mu

lati

ve

bio

gas

pro

du

ctio

n (

mL

)

Time (days)

Fig. 4 Cumulative gas production of each pretreated substrate in the digester

Conclusions

Here we may derive the following conclusions,

(1) The test pH values of different pretreatment conditions mainly range from 5.10 to 7.60.

(2) The test using different CaCO3 pretreatment conditions on rice straw is very slowly to enter the

peak gas production of anaerobic digestion, the peak value of biogas production was attained of 4%

CaCO3 pretreatment on the 20th

day, which is 1 589 mL. The test daily methane content of different

pretreatment conditions mainly ranges from 3.4% to 47.4%.

(3) The cumulative biogas production of 6% CaCO3 pretreatment was the highest, about 19 917

mL, which was followed by 4% CaCO3 (14 741 mL), 8% CaCO3 (9 562 mL), and 2% CaCO3 (9 240

mL).

Acknowledgements

This work was financially supported by Huaian Municipal Science and Technology Support Program

of China (HAS2013088), the Open Foundation of Jiangsu Key Laboratory for Biomass-based Energy

and Enzyme Technology of China (JSBEET1216), the Open Founds of Jiangsu Key Laboratory for

Chemistry of Low-Dimensional Materials of China (JSKC12117).

References

[1] N. Mosier, C. Wyman, B. Dale, R. Elander, Y. Y. Lee and M. Holtzapple: Bioresour. Technol.

Vol. 96 (2005), p. 673

[2] J. Luo, Y. H. Zhang, L. Chen, C. J. Song, X. G. Li, Y. Qi and L. X. Zhao: T. Chinese Soc. Agr.

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[3] T. F. Carneiro, M. Pérez and L. I. Romero: Bioresour. Technol. Vol. 99 (2008), p. 6765

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Applied Mechanics and Materials Vols. 587-589 211

Page 5: Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw

Sustainable Cities Development and Environment Protection IV 10.4028/www.scientific.net/AMM.587-589 Effect of CaCO3 Pretreatment on Methane Production from Anaerobic Digestion of Rice Straw 10.4028/www.scientific.net/AMM.587-589.208

DOI References

[1] N. Mosier, C. Wyman, B. Dale, R. Elander, Y. Y. Lee and M. Holtzapple: Bioresour. Technol. Vol. 96

(2005), p.673.

http://dx.doi.org/10.1016/j.biortech.2004.06.025 [4] T. V. Fernandes, G. J. Klaasse Bos, G. Zeeman, J. P. M. Sanders and J. B. van Lier: Bioresour. Technol.

Vol. 100 (2009), p.2575.

http://dx.doi.org/10.1016/j.biortech.2008.12.012 [5] M. Taherdanak and H. Zilouei: Fuel Vol. 115 (2014), p.715.

http://dx.doi.org/10.1016/j.fuel.2013.07.094 [6] R. Chandra, H. Takeuchi, T. Hasegawa and R. Kumar: Energy Vol. 43 (2012), p.273.

http://dx.doi.org/10.1016/j.energy.2012.04.029