1 Supplementary Materials 2 3 4 5 6 7 8 9 Fouling analysis of membrane bioreactor (MBR) treating antibiotic production wastewater at different hydraulic retention times (HRTs) 10 Dawei YU a, Yutao CHEN a, Yuansong WEI a, *, Jianxing WANG a, Yawei WANG a, Kun LI a a State Key Joint Laboratory of Environmental Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085,China. * Corresponding author. E-mail: [email protected]; Tel: +86-10-62849690; Fax: +86-10-62849690. Contents: Table 1 Comparison of CAS wastewater treatment station and MBR Fig. 1 TOC concentration (a) and removal rates (b) in long term running Fig. 2 Effect of HRTs on COD (a) and NH4+-N (b) removals 11 12 Table 1 Comparison of CAS wastewater treatment station and MBR Equipment HRT MLSS Effluents Construction cost h g L-1 pH COD/mg L-1 NH4+-N/mg L-1 million (300 t d-1) CAS 72 1.61~2.76 6.55±0.63 709.93±62.75 40.13±9.00 ¥4.37 MBR 36 3.82±0.01 6.68±0.17 280±17.32 11.29±0.85 ¥3.91 13 14 Fig. 1 TOC concentration (a) and removal rates (b) in long term running 15 b 1 Fig. 2 Effect of HRTs on COD (a) and NH4+-N (b) removals 2 3 Long term performance of MBR system 4 The SRT of MBR treating antibiotic wastewater was chosen over 200 d to achieve both 5 accumulate sufficient sludge for refractory organic pollutants bio digestion, and avoid 6 non-biodegradables substance accumulate in sludge. The prolonged SRT remained unchanged all over 7 the 3 periods of 275 days, and 5 stages especially. To provide sufficient oxygen and ALK for 8 bio-digestion, DO and ALK was maintained around 4 mg L-1 and 2000 mg L-1 (Table 2). 9 For refractory organic wastewater, TOC is a reliable indicator of sludge and membrane removal of 10 refractory organics in the long term performance. Long term TOC removal rate is presented in Fig1b, 11 stabilize at 47.24%±12.35%. The TOC of influent, supernatant and permeate is 293.25±81.96mg L -1, 12 215.19±65.65mg L-1 and 151.84±47.82mg L-1 in 275days. Permeate were much more stable given a 13 fluctuant influent, show that membrane make TOC removal more stable than municipal 14 wastewater(Kappel et al. 2014). Permeate higher than influent in 85-120 days for NF concentration 15 recycling. Section removal rates are 23.40±23.89 %, 23.49±16.20 % and 47.24±12.35 % in sludge, 16 membrane and total. It is lower than refractory acrylonitrile-butadiene-styrene wastewater in both 17 removal rate and concentration (Chang et al. 2006). So according to organic pollutant removal, long 18 term performance of MBR was steady in the study. 19 Effects of HRT on COD removals 20 Throughout the HRT optimization period, the pH, DO, membrane flux and gas sparging rate were 1 controlled approximately constant to separate the influences of the HRT variation on system 2 performance from other factors. Although the growth/decay amounts are different at different HRT, 3 MLSS concentration was not correlated to HRT variations as municipal wastewater, which will be 4 discussed in later sections. As sludge discharging is very limit and roughly stable, OLR was a nature 5 result of HRT decrease. The influent COD concentrations are fluctuated from 800 to 2000 mg L-1. To 6 prevent inhibitions of oxygen, sufficient DO is provided besides membrane wash demands (Table. 2). 7 COD concentrations of the 5 stages were shown in Fig.2a. When HRT decline from 72 h to 60 h 8 and 48 h, COD removal rates stable at 60 %. In later stage, COD removal rate rise to 69 % at 36 h, and 9 then 73 % at 24 h respectively. Results show that HRT reductions consistent with higher COD removal 10 rate except for too short HRT. This result agrees with the observation in high strength 11 acrylonitrile-butadiene-styrene (ABS) wastewater (Chang et al. 2006). When HRT decreased too short 12 at 24 h, the COD removal rates in the MBR suddenly fall. Meanwhile, organic loading rate (OLR) 13 doubled from 0.19 kgCOD kgVSS-1 d-1 at 36 h of HRT to 0.38 kgCOD kgVSS-1d-1 at 24 h of HRT. But 14 effluent COD below than 500 mg L-1 in the whole time, more stable than removal efficiency. Average 15 effluent COD is 280 mg L-1 at 36 h especially, in spite of removal rate fluctuation. If we divided COD 16 removal to two part of sludge and membrane removal, Fig.4b shows that COD removal by membrane 17 is the lowest at 36 h, which agree with the supernatant COD and despite influent fluctuant. The 18 activated sludge removal results differ with MBR treating municipal wastewater (Tay et al. 2003), 19 sludge characters are the most significant difference between them in our observation, discussed in 20 section 3.4. Thus, if considering COD removal rate (69%) and lowest permeate COD (280 mg L-1), 36 21 h could be an optimized HRT. 22 Effects of HRT on NH4+-N removals 23 Ammonia is always efficient removed in municipal MBR. The major reasons regard to be that 24 membrane reserve the slowly growth ammonia-oxidizing bacteria (AOB), and ammonia oxygen are 25 rapid reacts. Fig.2b depicts the NH4+-N removals under different HRT. Ammonia removal rate is 26 rapidly fall down at middle of 72 h. There is synchronization among NH 4+-N and COD removal rate 27 fall down, TMP rise and effluent protein jump. So protein rise result in these effect at 72 h. In the next 3 28 stages, HRT decreased from 60 h to 36 h. NH4+-N removal rate maintained over 95% and effluent less 29 than 10 mg L-1, indicate that HRT decrease did not have bad effect on ammonia removal among the 1 range. But after HRT decreased to 24 h, removal rate begins to fall and rise. 2 Compared with municipal wastewater, antibiotic wastewater is much higher in antibiotic and 3 salty, as ALK is sufficient. But salty does not change rapidly with HRT (Jang et al. 2013). Meanwhile, 4 NH4+-N loading rate is not too high to inhibit removal at 0.094±0.02 gNH4+-N kgVSS-1 d-1. So more 5 antibiotic contact and accumulate in short period, might inhibited the ammonia oxygen, leading to the 6 NH4+-N removal rate wave. And as amounts of ammonia-oxidizing bacteria (AOB) could not change so 7 quick in a 100 L reactor(Munz et al. 2008). So, ammonia-oxidizing bacteria (AOB) activity inhibited 8 by antibiotic is a reasonable mechanism. 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 References Chang JS, Chang CY, Chen AC, Erdei L, Vigneswaran S (2006) Long-term operation of submerged membrane bioreactor for the treatment of high strength acrylonitrile-butadiene-styrene (ABS) wastewater: effect of hydraulic retention time Desalination 191:45-51 doi: 10.1016/j.desal.2005.07.020 Jang D, Hwang Y, Shin H, Lee W (2013) Effects of salinity on the characteristics of biomass and membrane fouling in membrane bioreactors Bioresource Technology 141:50-56 doi:10.1016/j.biortech.2013.02.062 Kappel C, Kemperman AJB, Temmink H, Zwijnenburg A, Rijnaarts HHM, Nijmeijer K (2014) Impacts of NF concentrate recirculation on membrane performance in an integrated MBR and NF membrane process for wastewater treatment Journal of Membrane Science 453:359-368 doi:10.1016/j.memsci.2013.11.023 Munz G, Gualtiero M, Salvadori L, Claudia B, Claudio L (2008) Process efficiency and microbial monitoring in MBR (membrane bioreactor) and CASP (conventional activated sludge process) treatment of tannery wastewater Bioresource Technology 99:8559-8564 doi:10.1016/j.biortech.2008.04.006 Tay JH, Zeng JL, Sun DD (2003) Effects of hydraulic retention time on system performance of a submerged membrane bioreactor Separ Sci Technol 38:851-868 doi:10.1081/Ss-120017630
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