International Journal of Environmental Science and Development, Vol. 4, No. 5, October 2013 Efficiencies of Mesophilic Two-Phase Anaerobic Digestion of Pretreated Surplus Sludge Guang Li, Jing Li, and Xiangkui Han of the first and second phase and the third phase were controlled within the two reactors, each form acid-producing bacteria, methanogens optimum environmental conditions acidogenic phase and methanogenic phase separation, can significantly improve system capacity and operational stability [1]. For two-phase anaerobic digestion process, the operational performance of the acidogenic phase methanogenic phase directly affects the subsequent operation stability. Ethanol type fermentation acid production phase is considered the best type of fermentation [2], [3]. It not only provides an easymethanogenic phase microbial transformation of organic substrates (ethanol and acetic acid -based short-chain fatty acids), while its fermentation process can also be a byproduct of hydrogen as a clean energy for recycling [4]. In this study, the temperature two -phase anaerobic digestion process, the acidogenic phase control in ethanol type fermentation stage, the high pressure combined with thermal hydrolysis pretreatment of sludge remaining after the stabilization process. Organic load can directly reflect the amount of organic pollutants and microbial relationship between the biological treatment systems is designed to run in one of the important parameters. Anaerobic biological treatment sludge dosing rate is usually represented by the system of organic load. However, due to the moisture content of sludge and organic matter content increased with treatment process and geographical changes are not consistent, the dosing rate can not reflect the actual organic load, so the use of organic load unit reactor volume per day to accept the weight of organic matter more accurate. This research into the mud by adjusting the amount of daily organic load control system was investigated in the temperature two -phase anaerobic digestion process sludge performance. In recent years, there is much research for surplus sludge two-phase anaerobic digestion technology, but less on acidogenic phase fermentation. Operation efficiency in acid directly influences the operation stability of subsequent methanogenic-phase. Ethanol-type fermentation is believed to be the optimal fermentation type in acidogenic phase [5], [6]. It not only supply organic substrate which could easy to transformation in methanogenic phase improve [7], the by-product hydrogen during the fermentation process could also act as a clean energy for recycling. This paper adopts mesophilic two-phase anaerobic digestion technology, controlling the acidogenic phase in ethanol-type fermentation; this study discussed the operating characteristic of mesophilic two-phase anaerobic digestion, researched the change of sludge VS, settling property and dewatering performance as well as species distribution of the Abstract—With surplus sludge after being treated for 30 minutes at 5MPa, 150℃ as matrix, the operating efficiency of mesophilic two-phase anaerobic digestion system was examined. The result showed that the removal rate of sludge VS decreased as organic load increased and the removal rate of the system VS was 59.4%, 54.7%, 50.21%, and 42.2% respectively when the organic load was 0.98, 1.57, 2.35 and 3.13kgVS/m3•d. If acidogenic phase controlled in ethanol-type fermentation period, the specific hydrogen production of acidogenic phase in this condition achieved 0.018 L•H2/g•VS. When the two phase anaerobic digestion system organic load at 3.13 kgVS/(m3•d), the removal rate of acidification phase and the two phase system VS removal is 15.7% and 42.2% respectively. In anaerobic digestion acidification stage portion EPS from activated sludge floc in vivo release, such as the release of methane-producing bacteria Extracelluler Polymer Substances (EPS) could not be timely use will result in the increase of sludge EPS impact sludge settling and dewatering performance. Index Terms—Surplus sludge, mesophilic anaerobic digestion, ethanol-type fermentation. two-phase I. INTRODUCTION Anaerobic digestion is the most widely used stabilizing sludge treatment process, in the absence of anaerobic digestion principle the presence of oxygen, anaerobic bacteria through degradation of the organic carbon in the sludge into CH4 and CO2, the sludge is stabilized. Anaerobic digestion is a complex biochemical process, the current is more recognized in 1979 by Bryant et al. proposed three-stage anaerobic digestion theoretical model will be divided into anaerobic digestion hydrolysis fermentation stage, the stage of hydrogen acetogenic and methanogenic phase. Conventional anaerobic digestion process will be three stages of reaction in a reactor for, but the three stages of strain generation cycle, the speed of degradation of organic matter and its environmental requirements vary, so that bacteria can not simultaneously each stage in the best physical condition, affecting the operational efficiency of the anaerobic digestion process. Poland, who in 1971 proposed a two -phase anaerobic digestion process, the anaerobic digestion process Manuscript received October 12, 2013; revised October 30, 2013. This work was supported in part by the financial support of the Jilin Architectural and Civil Engineering Institute. The doctoral scientific research fund and Youth Science and Technology Development Fund, Jilin province college students’ innovation and entrepreneurship training program.. Guang Li and Xiangkui Han are with the Key Laboratory of Songliao Aquatic Environment, Ministry of Education, Ji Lin Jian Zhu University, Changchun, China (e-mail: [email protected]; [email protected]). Jing Li is with Jilin Jian Yuan Design Group fifth Institute, Changchun, China (e-mail: [email protected]). DOI: 10.7763/IJESD.2013.V4.416 576 International Journal of Environmental Science and Development, Vol. 4, No. 5, October 2013 heavy metals in sludge after anaerobic digestion, built a dynamic model of surplus sludge anaerobic digestion and studied the property of surplus sludge after ethanol-type fermentation with supernatant as denitrifying carbon source. 10 10 5 5 2 II. EXPERIMENT MATERIALS AND METHODS 6 7 1 A. Surplus Sludge Properties Residual sludge used in this experiment from Beijing a sewage treatment plant, sludge in the investment and added to the original two-phase anaerobic digestion were carried out prior to pretreatment, pretreatment conditions 5MPa, 150 ℃ treatment 30min. Before and after pretreatment sludge properties are shown in Table I. 3 2 6 1 8 8 3 4 water seal mixer 9 inlet sludge outlet sludge water tank temperature controller acidogenic phase circulating water pump methanogenic phase wet gas meter TABLE I: SLUDGE PROPERTIES Parameters Original Sludge Pretreatment Sludge TS(g/L) 20.2~23.7 18.4~21.2 VS(g/L) 14.5~16.6 12.1~14.9 SS(g/L) 20.3~22.5 11.7~13.6 VSS(g/L) 10.4~14.5 5.5~6.9 TCOD(g/L) 21.8~23.9 20.6~22.4 SCOD(mg/L) 998~1145 6104~6539 NH3-N(mg/L) 98.4~118.4 326.4~367.7 TKN(g/L) 970.3~1233.6 876.2~1133.8 pH 6.65~7.32 6.54~6.93 Alkalinity (mg/L) 903.2~997.3 1547.6~1788.4 Fig. 1. Schematic diagram of experimental apparatus. B. Seed Sludge Properties Test two-phase anaerobic digestion process as seed sludge acidogenic phase test their own rich culture domesticated type of ethanol fermentation bacteria sludge, MLSS was 24.87g / L, MLVSS was 18.69g / L. Methanogenic sludge as inoculum Beijing Municipal Education Commission pilot school-enterprise cooperation projects hydrolysis acidification tank sludge and Gaobeidian sewage treatment plant sludge anaerobic digestion a mixed digester sludge. After mixing the sludge MLSS is 22.34g / L, MLVSS was 17.58g / L. D. Analysis Method Sludge TS and VS adopts gravimetric determination method; TCOD and SCOD adopts phosphoric acid distillation titration determination method; pH adopts pH meter; Alkalinity adopts using pH potentiometric titration method. Organic acid using phosphoric acid distillation titration determination; Volatile fatty acids (VFAs) the gas chromatography (GC) determination with FFAP capillary column (30m×0.32mm×0.5mm) Daojin - 2010, and detector is FID sludge samples operational controlling parameters are: 5,000 turn/min, 15min centrifugal, filtrate supernatant fluid by 0.45μm filter membrane, and then filtrate by 0.20μm filter membrane; using 6mol/L formic acid to control pH value below 2. During the determination, using 2μl nitrogen as the incoming sample carrier and control the injection temperature for 220 ℃,using program warming for detector temperature: initial temperature 120 ℃, maintain 5min, heating rate 10 / min, intermediate temperature 160 ℃ , maintain 1min. Component of anaerobic digestion gas production: gas chromatography (GC) - 2010 determination, TDX - 01 supporter, 60 - 80 order, the carrier for nitrogen, 0.1 MPa former pressure column, TCD detector, column temperature 70 ℃, inlet temperature 200 ℃, incoming sample content 80 ~ 100μl. III. RESULTS AND DISCUSSION A. The Change of pH Value and Alkalinity in Starting Process pH value in environment has a great influence on microbial activity, each microbial has its appropriate pH range. Under the optimal pH range and other appropriate conditions, the activity of microbial enzymes will reach the highest point and the growth rate also the fastest. Generally believed that the most suitable ethanol-type fermentation bacteria pH range between 4.0 and 4.5, and the most suitable methanogenic phase bacteria pH range between 6.8 and 7.2. After monitoring the changeable of pH value during the two phase starting periods, the results were shown in Fig. 2. C. Experimental Device and Operation Parameters Acidogenic phase and methanogenic phase reactor are made of a continuous stirred tank reactor (CSTR), CSTR reactor consists of glass processing, acidogenic phase reactor effective volume 9.0L, methanogenic phase reactor effective volume of 31.5L. Outside of the reactor with water bath sets, and with a water tank, submersible pump control tank and the water bath comprising water cycle, controlled by the temperature inside the reactor temperature in the range of 35 ± 1 ℃, the test apparatus shown in Fig. 1. During the two-phase anaerobic digestion system startup HRT remained at 16.20d, the system of organic load of 0.98 kgVS/m3 • d. 577 International Journal of Environmental Science and Development, Vol. 4, No. 5, October 2013 raised, with the extension of time, the alkalinity gradually stabilized in 2000 ~ 2200mg/L. Although acidogenic phase produce numerous volatile acid, but the alkalinity not reduced, it is mainly because sludge produced a great deal of volatile acid, at the same time protein hydrolysis into amino acids, which make alkalinity rise. The alkalinity of methanogenic phase is increasing gradually at the starting period, after running 27 days, and it stable at 2057~2660mg/L, the reason of alkalinity increases is that in methanogenic phase reactor methanogens bacteria turn liquid VFA into CH4, which make VFA restoration. methanogenic phase pH 7 6 5 4 3 0 10 20 30 40 50 running time(d) Fig. 2. The change of pH Value in two-phase system. Based on ethanol-type fermentation process of domestication, the author found that when water alkalinity reached more than 1500mg/L, because of stronger ability into the water cushion, ethanol fermentation bacteria can't maintain acidogenic phase in its appropriate scope of the pH value by itself. And after the pretreatment sludge alkalinity stable at 1500mg/L or so. Before put the sludge in the acidogenic phase reactor, the pH value should be adjust 5.2 ~ 5.8 in order to ensure acidogenic phase pH value in 4.0 ~ 4.5. At the first 7 days of the starting period, without any treatment, the acidogenic phase sludge enter the methanogenic phase, which make methanogenic phase pH value stable at less than 6.0. In order to guarantee the normal metabolism of methane bacteria, from the first 8d, we began to adjust acidogenic phase sludge pH value at 6.0 or so, and then put it into the methanogenic phase. From Fig. 2 we can see that from the first 12 days of methanogenic phase starting period, the pH value is stable at 6.5 ~ 7.3. Alkalinity refers to the neutralization reaction that can accept H+ ions and can carry on neutralizations reaction. For a buffer system, alkalinity can reflect the system's buffering capacity to acid, and it also can effectively relieve the pH value of rapid swings, which belongs to an important control parameters. Fig. 3 shows the change of alkalinity in two-phase system during the starting period. alkalinity (mgCaCO 3/L) inlet sludge 3000 acidogenic phase methanogenic phase 2500 2000 1500 500 0 10 20 30 running time(d) 40 acidogenic phase methanogenic phase removal rate of acidogenic phase removal rate of methanogenic phase 18 16 14 12 10 8 6 4 2 0 70 60 50 40 30 20 10 0 0 10 20 30 running time(d) 40 50 Fig. 4. The change of VS in two-phase system during the starting period. It can be seen from Fig. 4, at the first 18 days in starting period, the concentration of acidogenic phase VS gradually slow down, and it is stable at 12.73g/L after the system running 22d, the removal rate of acidogenic phase VS rang from 16.5% to 22.4% before it finished the starting period. At the first 18 days in the starting period, the concentration of methanogenic phase VS gradually slow down and it is sharply reduced after 9d. It is stable at 12.73g/L after the system running 32d, the removal rate of acidogenic phase VS rang from 59.4% to 61.6% before it finished the starting period. C. Gas Production Content and Gas Components Changes Fig. 5 and Fig. 6 reflect gas production content and gas components changes in starting period of two-phase anaerobic digestion system. It can be seen from Fig. 5, with time increased acidogenic phase gas production content and hydrogen content gradually increasing. After operation 23d, the content of gas production and hydrogen respectively stable at 2.3L/d and 36.6% or so, and the specific hydrogen production of acidogenic phase in this condition achieved 0.018 L•H2/g•VS. 1000 0 B. The Change of VS in Two-Phase System during the Starting Period This study adopts two-phase anaerobic digestion system to stabilize the surplus sludge. At the starting period, the system organic loading has been controlled at 0.98kgVS/m3•d, and the starting period is not finished until the removal rate of VS stops rising. Fig. 4 reflects the change of VS in two-phase system during the starting period. removal rate(%) acidogenic phase VS(mg/L) inlet 8 sludge 50 Fig. 3. The change of alkalinity in two-phase system. It can be seen from the Fig. 3, the alkalinity of inlet sludge is stable at 1400~1650mg/L, during the first 15 days of starting period, the alkalinity of acidogenic phase gradually 578 International Journal of Environmental Science and Development, Vol. 4, No. 5, October 2013 2 25 20 1.5 15 10 1 0.5 5 0 0 5 14 19 23 28 35 39 running time(d) 42 acidogenic phase 64 15 62 10 60 58 56 14 19 23 28 35 running time(d) 39 42 8 30 20 10 2 54 5 40 4 methane content of gas(%) gas production(L/d) 66 0 10 6 methane content of gas 68 5 50 12 46 20 60 14 It can be seen from Fig. 5, with time increased methanogenic phase gas production content gradually increasing. After operation 35d, the content of gas production is stable at 15L/d or so. The methanogenic phase gas production is stable at more than 58%, and after operation 35d, the content of methane production range from 63% to 68%. methanogenic phase removal rate of methanogenic phase 70 16 Fig. 5. Acidogenic phase gas production content and gas components changes. 25 methanogenic phase removal rate of acidogenic phase 18 removal rate(%) 35 30 2.5 VS(mg/L) gas production(L/d) acidogenic phase 40 hydrogen content of gas(%) hydrogen content of gas 3 the study of sludge VS removal rate lower than the results in this study, based on two-phase anaerobic digestion can obviously improve the removal efficiency of sludge VS [8]. 46 Fig. 6. Methanogenic phase gas production content and gas components changes. D. The Change of VS in Two-Phase System during the Running Period Anaerobic digestion is mainly through the degradation of organic matter in the sludge, the sludge stabilization. Sludge volatile solids content of organic matter available (VS) content expressed. Thus, during the trial investigated the anaerobic digestion of sludge VS changes, the results shown in Fig. 7. It can be seen from the Fig. 7, when the two phase anaerobic digestion system organic load of 0.98 kgVS/(m3•d), the acid production phase and two phase system VS average removal rate of 20.1% and 59.4% respectively, with the increase of organic load, after acidification phase and the two phase system VS removal rate are declining, organic load when the system reaches 3.13 kgVS/(m3•d), the removal rate of acidification phase and the two phase system VS 15.7% and 42.2% respectively. Wang Zhijun single-phase CSTR reactor by thermal hydrolysis and the joint treatment of residual sludge and organic load in the system of similar cases, 579 0 0 50 60 70 80 90 100 110 120 130 140 150 160 running time(d) Fig. 7. The change of VS in two-phase system during the runnting period. E. The Change of SV in Two-Phase System during the Running Period Anaerobic digestion of sludge settling and dewatering sludge stabilization is an important assessment indicator. Traditional theory holds that anaerobic digestion, anaerobic digestion of sludge in the sludge produced during the gap gas becomes large, thereby increasing the specific surface area of the sludge, changing the degree of integration of sludge and water, the sludge settling and dehydration is improved. However, studies have shown that treatment sludge settling and dewatering performance and anaerobic digestion for sludge retention time, within a certain range, sludge settling and dewatering performance as sludge retention time increased with the increase, when the sludge retention time reaches a certain value, which by the sludge retention time has little effect. Conversely, when the sludge retention time is insufficient, anaerobic digestion and dewatering sludge settling performance even worse than the original sludge [9]. Mainly because of the sludge settling and dewatering sludge addition to performance gaps related, but also with activated sludge extracellular polymeric substances (EPS) for [10], [11]. TABLE II: THE CHANGE OF EPS DURING THE RUNNING PERIOD OLR(kgVS/m3d) 1.57 2.35 3.13 EPS(mg/L) Pr Po Pr Po Pr inlet sludge 668 263 614 226 636 acidogenic phase 746 342 685 294 706 17. 47. 23. 55. 33. 8 4 6 7 6 methanogenic phase Po 25 2 31 5 78 EPS and activated sludge with a combination of a cation as a substrate, the microorganism containing, organic and inorganic substances, including the composition [12]. International Journal of Environmental Science and Development, Vol. 4, No. 5, October 2013 F. The Change of SV in Two-Phase System during the Running Period In this study, settlement ratio (SV, also known 30min sedimentation rate) indicates the sludge settling properties, Fig. 8 reflects the Central Plains during the test sludge, pretreated sludge acidogenic phase and methanogenic sludge SV, changes. Fig. 8 shows the original residual sludge SV average of 91%, by high pressure combined with thermal hydrolysis pretreatment significantly improved sludge settling properties, SV average of 53%, and after acidogenic phase fermented sewage mud settling performance degradation, and finally by the methanogenic phase digested sludge settling properties and a slight improvement, and the whole process of anaerobic digestion sludge settling properties are better than the original sludge. Can also be seen from the figure, with the increase of organic loading methanogenic sludge settling performance is getting worse. This is mainly because the heat treatment can be released from the sludge colloid bound water, while improving sludge settling [13], after fermentation by acidogenic phase release large amounts of dissolved organic matter in the sludge, resulting in deterioration of the sludge settling properties, and finally by the methanogenic phase digestion, sludge EPS dropped significantly (see Table II), methane phase sludge settling properties in acidogenic phase. inlet sludge 100 acidogenic phase methanogenic phase SV(%) 80 60 40 20 50 60 70 80 90 100 110 120 running time(d) 130 140 150 160 Fig. 8. The change of SV in two-phase system during the running period. two-phase anaerobic digestion of sludge dewatering performance deterioration, but still better than the original sludge. By observing the testing process sludge settling and dewatering of changes can be found in high pressure combined with thermal hydrolysis pretreatment can significantly improve the performance of residual sludge settling and dewatering performance, after the temperature two-phase anaerobic digestion of sludge settling properties and Although the dewatering performance deterioration, but are better than the original sludge. 50 inlet sludge acidogenic phase methanogenic phase 40 30 CST(s) Although most of the extracellular polymeric substances stored in the sludge floc body, but in the acidification stage anaerobic digestion part from the activated sludge floc EPS released from the body, such as the release of EPS can not be timely use of methane-producing bacteria, can cause EPS rises affecting sludge sedimentation and sludge dewatering performance. During the test sludge EPS of different organic load changes as shown in Table II. 20 10 0 50 60 70 80 90 100 110 120 running time(d) 130 140 150 160 Fig. 9. The change of CST in two-phase system during the running period. IV. CONCLUSIONS Using mesophilic two-phase anaerobic digestion system to process the excess sludge of high pressure combined with thermal hydrolysis. Controlling parameters are as follows: HRT 16.20d, system organic loading 0.98kgVS/m3•d, the VS removal rate can stable at 59.4 ~ 61.6%, which can be achieved the sludge stabilization. If acidogenic phase controlled in ethanol-type fermentation period, the specific hydrogen production of acidogenic phase in this condition achieved 0.018 L•H2/g•VS. When the two phase anaerobic digestion system organic load at 3.13 kgVS/(m3•d), the removal rate of acidification phase and the two phase system VS removal is 15.7% and 42.2% respectively. In anaerobic digestion acidification stage portion EPS from activated sludge floc in vivo release, such as the release of methane-producing bacteria EPS could not be timely use will result in the increase of sludge EPS impact sludge settling and dewatering performance. ACKNOWLEDGMENT G. The Change of CST in Two-Phase System during the Running Period This study adopts the capillary suction time (CST) sludge dehydration nature [14], a test during the sludge CST change as shown in Fig. 9. As can be seen from the figure, the sludge during the two-phase anaerobic digestion process dewatering performance and settling performance has a similar trend, i.e., after the high pressure combined with thermal hydrolysis pretreatment significantly improved sludge dewatering, the The authors gratefully acknowledge the financial support of the Jilin Architectural and Civil Engineering Institute The doctoral scientific research fund and Youth Science and Technology Development Fund (J201 11026). 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Ponsa et al., “Enhancement of thermophilic anaerobic sludge digestion by 70 ℃ pre-treatment: energy considerations,” J. Residuals Sci. Technol., vol. 6, no. 1, pp. 11-18, 2009. Guang Li was born in December 12, 1982, comes from Jilin, China, have full-time postgraduate education background, and have got Ph.D in China University of Geosciences in 2011. His major interest is Environmental Science and Engineering. His study orientation is technology of water treatment. Jin Li graduated from Ji Lin Jian Zhu University in 2005. She is an engineer of Jilin Jian Yuan Design Group fifth Institute, She's major interests are sustainable development and systems-level solutions in engineering and the environment, particularly in water resources, asset management and water distribution systems. Xiangkui Han is a dean of the school of municipal and environmental engineering, Jilin Jianzhu University, environmental science in Jilin province committee and deputy director of the secretary-general. He is the three northeast provinces council vice director of water supply and drainage technology and the international water association member and small wastewater treatment plant design and operation panel experts.
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