- Research Article
- Open Access
Wastewaters treatment containing phenol and ammonium using aerobic submerged membrane bioreactor
© The Author(s) 2018
Received: 21 March 2018
Accepted: 4 July 2018
Published: 9 July 2018
Phenolic wastewater was treated using anaerobic submerged membrane bioreactor (ASMBR). Effect of different solids retention times on MBR performance was studied. Various ratios of carbon to nitrogen were used in the synthetic wastewaters. During the operation, phenol concentration of feed was changed from 100 to 1000 mg L−1. Phenol concentration was increased stepwise over the first 30 days and kept constant at 1000 mg L−1, thereafter. For the first 100 days, a chemical oxygen demand (COD) to N ratio of 100:5.0 was used and this resulted in phenol and COD removal more than 99 and 95%, respectively. However, the ammonium removal decreased from 95 to 40% by increasing the phenol concentration of feed, from 100 to 1000 mg L−1. For the last 25 days, a COD to N ratio of 100:2.1 was used due to the ammonium accumulation in the ASMBR. This led to the complete ammonium removal and no ammonium was detected in the ASMBR permeate. These results suggest that in the ASMBR at high phenol loading of 1000 mg L−1, COD to N ratio of the phenolic wastewater must be 100:2.1 for ammonium removal, while at low phenol loading, COD to N ratio of 100:5.0 can be used.
Many industrial wastewaters are produced yearly in the world [1, 2]. Most of them contain ammonia [3, 4], phenolic and nitrogenous compounds at high concentrations, e.g. wastewaters from coke industries and refineries [5, 6]. Treatment methods such as liquid–liquid extraction , ultrasound , adsorption , membrane processes  and biological treatment methods have been used for phenolic wastewater renovation. The membrane separation processes can be used in the different process including gas separation [11–20], pervaporation [21–27], filtration in different configuration particularly hollow fiber membrane contactor [28–33]. Among these, biodegradation seems to be a suitable treatment method for phenol and ammonium removal due to the neutral compounds produced in this process . But, in biological systems, phenol has a negative effect on nitrogen removal . Previous studies have shown that real and synthetic phenolic wastewaters can be treated by biological systems . Effect of phenol concentration on nitrification process in batch systems and activated sludge reactors was investigated by Amor et al. . The results showed that the extent of nitrification decreases with initial phenol concentration above 1000 mg L−1, and also, increasing initial phenol concentration causes reduction of the nitrification along with the accumulation of nitrite and ammonium. Coke industries use activated sludge for wastewater treatment and revealed an inhibitory effect of phenol and p-cresol on nitrification. The results showed that no nitrification occurs at phenol concentrations above 500 mg L−l. In addition, effects of initial concentrations of ammonium, thiocyanate, free cyanide, ferric cyanide on nitrification were studied by . Other researchers also treated wastewaters of coke industries by conventional activated sludge process at several conditions and showed that phenol removal is more than 98% while ammonium removal is very low . Effects of phenol and formaldehyde on denitrification at anoxic conditions were studied and the results showed that removal of nitrogen decreases with increasing phenol .
The membrane bioreactor (MBR) is a technology which can be used in phenolic wastewater treatment . Different cultures were used as biological systems to remove phenol. Pseudomonas putida  and activated sludge  are usually used as a biological system in MBRs and the results showed suitable phenol biodegradation in both systems. Biodegradation of high loading phenol in MBRs was also studied and a population of biological systems was investigated . The results showed that floating biodegradative populations are observed and they may inhibit high efficiency and stability of the treatment performance. Researches showed that activated sludge must be acclimatized in presence of phenol to be used in MBR . Although the removal of phenol in membrane bioreactor has been studied, phenol to nutrients ratio (especially nitrogen) in feeds has not been investigated.
Membrane bioreactor performance also affected by many factors, i.e. hydraulic residence time (HRT), sludge retention time (SRT), temperature, feed to microorganism ratio (F/M), mixed liquor suspended solids (MLSS), aeration (as oxygen source and membrane fouling reducer) and biomass properties. The effects of these parameters on MBR performance and membrane fouling have been the subjects of some studies . Among these factors, HRT is one of the most influencing factors since it is directly related to the reactor volume and this, in turn, affects the capital and operational costs . Using ceramic membranes in external MBRs for phenol removal showed their ability to operate at low HRTs and high loadings of phenol . Real wastewater of a refinery containing phenol and ammonium was also treated by MBR and no phenol was detected in effluent but the effect of phenol on ammonium removal was not studied .
In this study, MBR has operated at different chemical oxygen demand (COD) to N ratios with phenol as a carbon source and three SRTs (infinite, 30, and 10 days) to evaluate ammonium accumulation inside the bioreactor.
Materials and methods
Activated sludge and synthetic wastewater
Activated sludge used in this study was supplied from Tehran oil refinery. A synthetic phenolic wastewater was prepared based on the mineral medium as described by Ahn et al. . Mineral medium contained 0.067 g CaCl2·2H2O, 0.248 g MgCl2·6H2O, 0.5 mg FeSO4·7H2O, 0.4 mg ZnSO4·7H2O, 0.002 mg MnCl2·4H2O, 0.05 mg COCl2·6H2O, 0.01 mg NiCl2·6H2O, 0.015 mg H3BO3, and 0.25 mg EDTA per liter. To this medium, NH4Cl as a nitrogen source as well as KH2PO4 and K2HPO4 as phosphorus sources were added at desired amounts. Glucose and/or phenol were used as carbon source and phenol at various concentrations.
The bioreactor was filled with activated sludge at initially MLSS of 3500 mg L−1. The SMBR was operated at 23–24 °C in a continuous flow mode throughout this study by introducing 10 mL min−1 feed to bioreactor resulting in an HRT of 16.6 h. Aeration was carried out such that DO remains above 2 mg L−1. Constant permeate flux was maintained using air backwashing during SMBR operation. Chemical cleaning was used when TMP reached 0.35–0.40 bar to completely remove the accumulated biomass from membrane skein and this allowed operation at TMPs of 0.05–0.10 bar.
ASMBR operational parameters
Operation interval (day)
Phenol (mg L−1)
MLSS (mg L−1)
Chemical oxygen demand and MLSS were measured according to the standard methods (ASTM D1426 for Ammonia Nitrogen In Water; ASTM D1783 for Phenolic Compounds in Water; Greenberg 5520 B for COD; Greenberg 2540 D for TSS). Phenol, N-NH4+, and COD were measured by spectrophotometry. COD was measured after centrifuging the mixed liquor for 10 min at 3000g. For measuring MLSS, three samples were taken each time. The samples were filtered through a 0.45 µm Millipore filter and dried in an oven at 105 °C until obtaining constant weights. The average values were then calculated.
Results and discussion
SMBR performance during acclimatization of activated sludge
Ammonium concentration in influent and permeate as well as ammonium removal during acclimation period are presented in Fig. 3. A constant COD:N ratio of 100:5 was used to provide enough carbon and nitrogen for growth of the microorganisms . Within the 1st days, when glucose was used as carbon source, almost all N-NH4+ was removed and nitrogen detected in the effluent was below 5%. To maintain a constant COD:N ratio while influent phenol concentration was raised, influent ammonium concentration was accordingly raised (Fig. 3). By introducing phenol to SMBR, ammonium removal started to decrease however after 10 days it increased showing similar trends to COD removal in Fig. 2.
By increasing influent phenol concentration to higher than 400 mg L−1, ammonium removal dropped to about 80% and further decreased to 75% at 500 mg L−1 influent phenol. This attributed to the fact that phenol reduced nitrification and excess ammonium did not be removed.
Effect of sudden phenol loading on SMBR performance
Despite the efficient COD and phenol removals observed at 1000 mg L−1 influent phenol in run 2 which are similar to those observed in acclimation period (Fig. 2), ammonium removal decreased sharply and leveled off after 6 days. Overall it can be seen that by increasing phenol concentration from around 300–500 (Fig. 2) and further to 1000 mg L−1 (Fig. 5), ammonium removal decreases from around 90–75 and 40%, respectively. This means that high loading of phenol adversely affects ammonium removal. This phenomenon has been reported to occur by some other researchers for conventional activated sludge processes  and it has mostly been attributed to inhibition of nitrifying bacteria converting ammonium ions to nitrate.
Effect of sludge retention time (SRT) on SMBR performance
Having increased the influent phenol concentration to 1000 mg L−1 in run 2 at infinite SRT (no sludge discharge), two further experiments were performed at SRTs of 30 and 10 days in runs 3 and 4 to examine the effect of SRT on SMBR performance at COD:N ratio of 20. Phenol and COD concentrations in permeate and their removals at the three examined SRTs are shown in Fig. 4.
As can be seen in Fig. 4, reduction of SRT had an insignificant effect on phenol and COD removals. Comparison of the results showed that at the three examined SRTs more than 99.5% of influent phenol and 95% of influent COD were removed. With regards to ammonium removal, Fig. 5 shows that by reducing SRT from infinity to 10 days ammonium removal undergoes a decrease from 40 to around 25%.
Effect of COD:N ratio on SMBR performance
COD to N ratios in influent and effluent of SMBR (phenol as carbon source)
COD (mg L−1)
Phenol (mg L−1)
NH4 (mg L−1)
NH4 (mg L−1)
To investigate the effect of SRT on ammonium accumulation in SMBR at COD:N ratio of 50, run 6 was performed at SRT of 10 days. Results in Fig. 4 showed that COD and phenol removals remain above 95 and 99%, respectively. However, ammonium removal rapidly grows such that ammonium removal reaches more than 90% after 4 days as shown in Fig. 6. The lower ammonium removal at SRT of 10 days can be attributed to the un-complete bacterial accrue in SMBR.
Transmembrane pressure (TMP)
As can be seen in Fig. 7, TMP was increased due to the reduction in membrane permeability. After 60 days, the membrane was severely fouled and chemical cleaning was used to remove the fouling. NaOH (0.4 wt%) was used to remove the organic materials and HCl (1%) was used for inorganic materials. The membrane was immersed in these solutions for 1 h and 30 min, respectively, according to the membrane manual. As observed, all of the fouling was removed by this method and the cleaned membrane operated similarly to the fresh membrane.
In this study, an ASMBR was operated for 125 days to treat a synthetic phenolic wastewater. The ASMBR was operated in 6 runs to investigate the effect of SRT and influent COD:N ratio at 1000 mg L−1 influent phenol on bioreactor performance. The following conclusions can be drawn from the present study: (I) It was demonstrated that different concentrations of phenol could be removed by the ASMBR confirming the high capability of the ASMBR in phenol removal. (II) Increasing ammonium as nitrogen source caused ammonium accumulation at phenol concentrations above 500 mg L−1, however, it had no effect on phenol and COD removals and COD to N ratio of 100:2.1, was capable of removing ammonium accumulation. (III) Using air backwashing for cleaning of the hollow fiber membrane module fairly reduced fouling and the membrane could be operated for 60 days without chemical cleaning. Chemical cleaning was then performed effectively.
The work is a product of the intellectual environment of the whole team; and that all members have contributed in various degrees to the analytical methods used, to the research concept, and to the experiment design. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
Availability of data and materials
The datasets generated and/or analysed during the current study are available from the corresponding author on reasonable request.
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- Shirazian S, Rezakazemi M, Marjani A, Moradi S (2012) Hydrodynamics and mass transfer simulation of wastewater treatment in membrane reactors. Desalination 286:290–295View ArticleGoogle Scholar
- Rezakazemi M, Ghafarinazari A, Shirazian S, Khoshsima A (2013) Numerical modeling and optimization of wastewater treatment using porous polymeric membranes. Polym Eng Sci 53:1272–1278View ArticleGoogle Scholar
- Rezakazemi M, Shirazian S, Ashrafizadeh SN (2012) Simulation of ammonia removal from industrial wastewater streams by means of a hollow-fiber membrane contactor. Desalination 285:383–392View ArticleGoogle Scholar
- Razavi SMR, Rezakazemi M, Albadarin AB, Shirazian S (2016) Simulation of CO2 absorption by solution of ammonium ionic liquid in hollow-fiber contactors. Chem Eng Process 108:27–34View ArticleGoogle Scholar
- Rezakazemi M, Khajeh A, Mesbah M (2018) Membrane filtration of wastewater from gas and oil production. Environ Chem Lett 16:367–388View ArticleGoogle Scholar
- Azimi A, Azari A, Rezakazemi M, Ansarpour M (2017) Removal of heavy metals from industrial wastewaters: a review. ChemBioEng Rev 4:37–59View ArticleGoogle Scholar
- Muhammad A, Younas M, Rezakazemi M (2017) Quasi-dynamic modeling of dispersion-free extraction of aroma compounds using hollow fiber membrane contactor. Chem Eng Res Des 127:52–61View ArticleGoogle Scholar
- Roudbari A, Rezakazemi M (2018) Hormones removal from municipal wastewater using ultrasound. AMB Express 8:91View ArticleGoogle Scholar
- Foroutan R, Esmaeili H, Abbasi M, Rezakazemi M, Mesbah M (2017) Adsorption behavior of Cu(II) and Co(II) using chemically modified marine algae. Environ Technol. https://doi.org/10.1080/09593330.2017.1365946 Google Scholar
- Asadollahzadeh M, Raoufi N, Rezakazemi M, Shirazian S (2018) Simulation of nonporous polymeric membranes using CFD for bioethanol purification. Macromol Theory Simul 27:1700084View ArticleGoogle Scholar
- Rezakazemi M, Shahidi K, Mohammadi T (2012) Sorption properties of hydrogen-selective PDMS/zeolite 4A mixed matrix membrane. Int J Hydrogen Energy 37:17275–17284View ArticleGoogle Scholar
- Rezakazemi M, Shahidi K, Mohammadi T (2012) Hydrogen separation and purification using crosslinkable PDMS/zeolite A nanoparticles mixed matrix membranes. Int J Hydrogen Energy 37:14576–14589View ArticleGoogle Scholar
- Sadrzadeh M, Rezakazemi M, Mohammadi T (2018) Fundamentals and measurement techniques for gas transport in polymers. In: Wilson R, Thomas S, Kumar A, George SC (eds) Transport properties of polymeric membranes, Chap 19. Elsevier, New York, pp 391–423. https://doi.org/10.1016/B978-0-12-809884-4.00019-7 View ArticleGoogle Scholar
- Rezakazemi M, Sadrzadeh M, Matsuura T (2018) Thermally stable polymers for advanced high-performance gas separation membranes. Progr Energy Combust Sci 66:1–41View ArticleGoogle Scholar
- Rezakazemi M, Ebadi Amooghin A, Montazer-Rahmati MM, Ismail AF, Matsuura T (2014) State-of-the-art membrane based CO2 separation using mixed matrix membranes (MMMs): an overview on current status and future directions. Prog Polym Sci 39:817–861View ArticleGoogle Scholar
- Rezakazemi M, Dashti A, Asghari M, Shirazian S (2017) H2—selective mixed matrix membranes modeling using ANFIS, PSO-ANFIS, GA-ANFIS. Int J Hydrogen Energy 42:15211–15225View ArticleGoogle Scholar
- Rezakazemi M, Vatani A, Mohammadi T (2016) Synthesis and gas transport properties of crosslinked poly(dimethylsiloxane) nanocomposite membranes using octatrimethylsiloxy POSS nanoparticles. J Nat Gas Sci Eng 30:10–18View ArticleGoogle Scholar
- Rezakazemi M, Vatani A, Mohammadi T (2015) Synergistic interactions between POSS and fumed silica and their effect on the properties of crosslinked PDMS nanocomposite membranes. RSC Adv 5:82460–82470View ArticleGoogle Scholar
- Sodeifian G, Raji M, Asghari M, Rezakazemi M, Dashti A (2018) Polyurethane-SAPO-34 mixed matrix membrane for CO2/CH4 and CO2/N2 separation. Chin J Chem Eng. https://doi.org/10.1016/j.cjche.2018.03.012 Google Scholar
- Dashti A, Harami HR, Rezakazemi M (2018) Accurate prediction of solubility of gases within H2-selective nanocomposite membranes using committee machine intelligent system. Int J Hydrogen Energy 43:6614–6624View ArticleGoogle Scholar
- Rezakazemi M, Razavi S, Mohammadi T, Nazari AG (2011) Simulation and determination of optimum conditions of pervaporative dehydration of isopropanol process using synthesized PVA–APTEOS/TEOS nanocomposite membranes by means of expert systems. J Membr Sci 379:224–232View ArticleGoogle Scholar
- Rezakazemi M, Shahverdi M, Shirazian S, Mohammadi T, Pak A (2011) CFD simulation of water removal from water/ethylene glycol mixtures by pervaporation. Chem Eng J 168:60–67View ArticleGoogle Scholar
- Rezakazemi M, Shahidi K, Mohammadi T (2014) Synthetic PDMS composite membranes for pervaporation dehydration of ethanol. Desalination Water Treat 54:1–8View ArticleGoogle Scholar
- Rezakazemi M, Sadrzadeh M, Mohammadi T (2018) Separation via pervaporation techniques through polymeric membranes. In: Wilson R, Thomas S, Kumar A, George SC (eds) Transport properties of polymeric membranes. Elsevier, New York, pp 243–263. https://doi.org/10.1016/B978-0-12-809884-4.00013-6View ArticleGoogle Scholar
- Baheri B, Shahverdi M, Rezakazemi M, Motaee E, Mohammadi T (2014) Performance of PVA/NaA mixed matrix membrane for removal of water from ethylene glycol solutions by pervaporation. Chem Eng Commun 202:316–321View ArticleGoogle Scholar
- Rezakazemi M, Iravaninia M, Shirazian S, Mohammadi T (2013) Transient computational fluid dynamics modeling of pervaporation separation of aromatic/aliphatic hydrocarbon mixtures using polymer composite membrane. Polym Eng Sci 53:1494–1501View ArticleGoogle Scholar
- Dashti A, Asghari M, Dehghani M, Rezakazemi M, Mohammadi AH, Bhatia S (2018) Molecular dynamics, grand canonical Monte Carlo and expert simulations and modeling of water–acetic acid pervaporation using polyvinyl alcohol/tetraethyl orthosilicates membrane. J Mol Liq 265:53–68View ArticleGoogle Scholar
- Rezakazemi M, Niazi Z, Mirfendereski M, Shirazian S, Mohammadi T, Pak A (2011) CFD simulation of natural gas sweetening in a gas–liquid hollow-fiber membrane contactor. Chem Eng J 168:1217–1226View ArticleGoogle Scholar
- Fasihi M, Shirazian S, Marjani A, Rezakazemi M (2012) Computational fluid dynamics simulation of transport phenomena in ceramic membranes for SO2 separation. Math Comput Model 56:278–286View ArticleGoogle Scholar
- Shirazian S, Marjani A, Rezakazemi M (2011) Separation of CO2 by single and mixed aqueous amine solvents in membrane contactors: fluid flow and mass transfer modeling. Eng Comput 28:189–198View ArticleGoogle Scholar
- Shirazian S, Rezakazemi M, Marjani A, Rafivahid MS (2012) Development of a mass transfer model for simulation of sulfur dioxide removal in ceramic membrane contactors. Asia Pac J Chem Eng 7:828–834View ArticleGoogle Scholar
- Shirazian S, Pishnamazi M, Rezakazemi M, Nouri A, Jafari M, Noroozi S, Marjani A (2012) Implementation of the finite element method for simulation of mass transfer in membrane contactors. Chem Eng Technol 35:1077–1084Google Scholar
- Muhammad A, Younas M, Rezakazemi M (2018) CFD simulation of copper(II) extraction with TFA in non-dispersive hollow fiber membrane contactors. Environ Sci Pollut Res 25:12053–12063View ArticleGoogle Scholar
- Amor L, Eiroa M, Kennes C, Veiga MC (2005) Phenol biodegradation and its effect on the nitrification process. Water Res 39:2915–2920View ArticleGoogle Scholar
- Viero AF, de Melo TM, Torres APR, Ferreira NR, Sant’Anna L Jr, Borges CP, Santiago VMJ (2008) The effects of long-term feeding of high organic loading in a submerged membrane bioreactor treating oil refinery wastewater. J Membr Sci 319:223–230View ArticleGoogle Scholar
- Kim YM, Park D, Lee DS, Park JM (2008) Inhibitory effects of toxic compounds on nitrification process for cokes wastewater treatment. J Hazard Mater 152:915–921View ArticleGoogle Scholar
- Vázquez I, Rodríguez J, Marañón E, Castrillón L, Fernández Y (2006) Simultaneous removal of phenol, ammonium and thiocyanate from coke wastewater by aerobic biodegradation. J Hazard Mater 137:1773–1780View ArticleGoogle Scholar
- Eiroa M, Vilar A, Amor L, Kennes C, Veiga MC (2005) Biodegradation and effect of formaldehyde and phenol on the denitrification process. Water Res 39:449–455View ArticleGoogle Scholar
- Rezakazemi M, Maghami M, Mohammadi T (2018) High Loaded synthetic hazardous wastewater treatment using lab-scale submerged ceramic membrane bioreactor. Period Polytech Chem Eng 62:299–304View ArticleGoogle Scholar
- Li Y, Wang C (2008) Phenol biodegradation in hybrid hollow-fiber membrane bioreactors. World J Microbiol Biotechnol 24:1843–1849View ArticleGoogle Scholar
- Ahn S, Congeevaram S, Choung Y-K, Park J (2008) Enhanced phenol removal by floating fungal populations in a high concentration phenol-fed membrane bioreactor. Desalination 221:494–501View ArticleGoogle Scholar
- Juang R-S, Tsai S-Y (2006) Role of membrane-attached biofilm in the biodegradation of phenol and sodium salicylate in microporous membrane bioreactors. J Membr Sci 282:484–492View ArticleGoogle Scholar
- Li Y, Loh K-C (2007) Continuous phenol biodegradation at high concentrations in an immobilized-cell hollow fiber membrane bioreactor. J Appl Polym Sci 105:1732–1739View ArticleGoogle Scholar
- Zhang F, Jing W, Xing W, Xu N (2009) Experiment and calculation of filtration processes in an external-loop airlift ceramic membrane bioreactor. Chem Eng Sci 64:2859–2865View ArticleGoogle Scholar
- Viero AF, Sant’Anna GL (2008) Is hydraulic retention time an essential parameter for MBR performance? J Hazard Mater 150:185–186View ArticleGoogle Scholar
- Goudar CT, Ganji SH, Pujar BG, Strevett KA (2000) Substrate inhibition kinetics of phenol biodegradation. Water Environ Res 72:50–55View ArticleGoogle Scholar
- Holman JB, Wareham DG (2005) COD, ammonia and dissolved oxygen time profiles in the simultaneous nitrification/denitrification process. Biochem Eng J 22:125–133View ArticleGoogle Scholar
- Morita M, Kudo N, Uemoto H, Watanabe A, Shinozaki H (2007) Protective effect of immobilized ammonia oxidizers and phenol-degrading bacteria on nitrification in ammonia- and phenol-containing wastewater. Eng Life Sci 7:587–592View ArticleGoogle Scholar