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ISSN : 1226-0088(Print)
ISSN : 2288-7253(Online)
Membrane Journal Vol.32 No.3 pp.173-180

Zeolite Based Membrane for Removal of Ammonium: A Review

Joo Yeop Lee*, Rajkumar Patel**
*Nano Science and Engineering, Underwood International College, Yonsei University, Incheon 21983, South Korea
**Energy and Environmental Science and Engineering, Integrated Science and Engineering Division, Underwood International College, Yonsei University, Incheon 21983, South Korea
Corresponding author(e-mail:;
June 4, 2022 ; ; June 13, 2022


Presence of ammonia in drinking water is very toxic to human health. Soluble ammonia contaminates ground water due to activities such as the use of fertilizer in crop, industrial effluents and burning of fossil fuel. Even low concentration of ammonia present in water will damage aqua environment such as marine organism. Membrane technology is an important process to remove ammonia from effectively from water. Flat sheet membrane, membrane contactor and membrane distillation are some of the methods used for water purification from ammonia. Membrane contractor is an efficient process in which ammonia is removed through liquid-gas or liquid-liquid mass transfer without change of phase unlike membrane distillation. However, the cost of ammonia removal in this method is high due to maintenance of very high pH. Zeolite has excellent ion exchange ability that enhances its ability to interact with ammonia and adsorb from wastewater. Mixed matrix membranes containing zeolite enhance the efficiency of ammonia adsorption and separation from wastewater. In this review the above discussed issues are summarized in detail.

효소 고정화막의 응용에 대한 총설

이 주 엽*, 라즈쿠마 파텔**
*연세대학교 언더우드학부 융합과학공학부 나노과학공학
**연세대학교 언더우드학부 융합과학공학부 에너지환경융합전공


음용수 속 암모니아의 존재는 인간의 건강에 매우 해롭다. 농작물에서의 비료 사용, 산업 폐수, 화석 연료의 연소 와 같은 활동으로 인해 가용성 암모니아는 지하수를 오염시킨다. 물에 존재하는 암모니아 농도가 낮더라도 해양생물 등의 수 생환경을 훼손한다. 막 기술은 암모니아를 물로부터 효과적으로 제거하기 위한 매우 중요한 과정이다. 평평한 시트 막, 막 접 촉기, 그리고 막 증류법은 암모니아를 제거하여 물을 정화하는 데 사용되는 방법들 중 하나이다. 막 접촉기는 막 증류법과는 달리 상변화 없이 액체와 가스 간의 또는 액체와 액체간의 질량 전달을 통해 암모니아를 제거하는 효율적인 공정이다. 다만 이 방법은 pH가 매우 높아 암모니아 제거에 비용이 많이 든다. 제올라이트는 우수한 이온 교환 능력을 가지고 있는데, 이는 암모니아와의 상호작용을 향상시켜 폐수로부터 흡착하는 능력을 향상시킨다. 제올라이트를 함유한 혼합 매트릭스 막은 암모 니아 흡착 및 폐수로부터의 분리 효율을 향상시킨다. 이 리뷰에서는 위에서 소개된 내용이 자세히 논의될 것이다.

    1. Introduction

    All forms of life need nitrogen compounds to live. However, too much nitrogen compounds in receiving water bodies could cause problems. Eutrophication makes algae to grow excessively and leads degradation of water quality. Soluble ammonia is also a problem since it is very toxic even at low concentration and hard to remove. Water bodies with high nitrogen compounds which is made from human activities such as using fertilizers and fossil fuels and raising livestock is not only a wastewater but also an abundance of water resources, energy, and nutrients. Therefore, we should recover these resources from sewage for sustainable development[1-7].

    Various studies and research spotlight zeolite membranes since zeolite, an inorganic porous material, has a highly ordered porous structure. Moreover, zeolite has valuable ion exchange capacity and thus has good ammonium ion selectivity, which make zeolite good for ion exchange[8-10]. This advantage is acquired because zeolites are aluminosilicates with crystalline micropore and well-defined framework of SiO4 and AlO4. The isomorphous substitution of Al3+ for Si4+ in the tetrahedra create negatively charged zeolite framework which can be by exchangeable cations.

    Removal of NH4+ ion by ion exchange and adsorption method showed tremendous propospect through low energy process. Metal cations can be easily exchanged which is essential to selectively remove aqueous phase NH4+[11].

    Zeolite can be applied for enhancing microalgal growth as well as for removal of pollutants such as residual ammonia, phosphorus, and carbon dioxide [12-13]. While zeolite-based membranes have many applications, this review is focused on pollutants removal, especially on nitrogen compounds removal, which can be divided into four types: i) membrane contactor, ii) mixed matrix membrane, iii) ion exchange membrane, and iv) ceramic membrane. The schematic and performance of zeolite-based membranes for NH3 removal are shown in Fig. 1 and Table 1, respectively.

    2. Membrane Contactor

    Membrane contactor contains a ceramic or porous polymer membrane, zeolite-based membrane for example. The membrane is used to promote better contact between two phases. Since membrane contactors can be applied widely, their practical importance continuously increases. E. E. Licon Bernal et al. reported about hollow fibre liquid–liquid membrane contactors (HF-LLMCs) used for concentrating and purifying ammonia effluents which make ammonium nitrate and (NH4)2(HPO4) solutions that can be potentially used as liquid fertilizers[14]. They conduct this experiment with a closed-loop setup to find the effect of various operational process such as flow rate, initial concentration of ammonia, and concentration of stripping acid. It was found when HNO3 and H3PO4 uses as stripping solution, the recovery capacity of ammonia higher than 95–98%. Since only gas can be conveyed via the hydrophobic membrane, the ammonium salts made have high purity. Moreover, the ammonium-exhausted zeolite filters can be regenerated by reusing the exhausted NH3/NaOH streams after removing NH3.

    Various operational parameters on the efficiency of the HF-LLMC process were investigated for ammonia recovery by utilizing a concentrated NH3 stream that is recovered from wastewater treated with zeolites and NaOH[15]. It was found that the best ammonia recovery and liquid fertilizer composition in N (from NH4+) which are over 96% and around 4.6% respectively by optimizing the parameters as using 2 vertical membrane contactors in one-step configuration; utilizing HNO3 as stripping solution; feed and acid streams suplied to the HF-LLMC as shell and lumen sides respectively. The optimized HF-LLMC process can be applied to the recovery of ammonia in an urban wastewater treatment plant (WWTP) and to production ammonium salts for liquid fertilizers in irrigation applications simultaneously.

    I. Sancho et al. evaluated zeolite adsorption method as a post-treatment for the excellent up-concentration processes instead removal by biological process[16]. A natural clinoptilolite zeolites was used as precursor for selective sorption of ammonium from treated effluents and was studied in batch as well as fixed bed experiments. The improvement in equilibrium and kinetic parameters were handled after converting the natural zeolite to the sodium form. Ammonia recovery ratio is over 98%, and NH4NO3 and di-ammonium phosphate have 2–5% wt. of N. Nitric and phosphoric acids was incorporated in hollow fiber membrane contactors and found that recovery capacity of nitrogen over 95% when there is presence of free acid in excess in the stripping stream. The purity of NH4NO3 and di-ammonium phosphates byproducts is high, since they are transported on the hydrophobic hollow fibre membrane contactors with restriction of the properties of the membrane which only support solutes in gas phases. The exhausted ammonia/alkali streams after NH3 removal can be used again for regeneration of the NH4+ exhausted zeolites filters.

    X. Vecino et al. reported about making a valuable product for fertilizing applications by treating ammonia- rich streams from a regeneration step with zeolites using 70–80 g NaOH/L containing possibly up to 3.5– 4.5 g NH3/L as well as other ionic species and dissolved organic matter (DOM)[17]. Remaining amount of DOM was removed and membrane fouling reduced before treating with HF-LLMC by a pre-treatment process. To extract NH3 selectively, polypropylene HF-LLMC in single or two-step configurations was utilized by applying different acid stripping solutions like H3PO4, HNO3 or a mixture of HNO3/H3PO4. H3PO4 is the excellent acid solution to strip by one-step HF-LLMC, resulting 76% of the NH3 removal with an ammonia mass transfer coefficient (Km(NH3)) of 8.8×10−7 m/s. NH3 was concentrated 26 times and recovered it as multi-nutrient liquid fertilizer composed of 7.8% N and 21.6% phosphorus pentoxide. Recovery of NH3 increased to 94% by two-step HF-LLMC.

    3. Mixed Matrix Membrane

    Mixed matrix membranes (MMMs) are used for gas purification applications. MMMs improve the properties of polymeric membranes by combining the characteristics of polymers and inorganic materials, which are easy processability and the superior selectivity respectively. MMMs are studied in both academic and industrial purpose thanks to their unique properties of combining inherent characteristics. MMMs, composite fibers, and pore-filled membranes were synthesized by mixing natural zeolite nanoparticles with polysulfone polymer matrices and evaluated their performance[18]. Among them, mixed matrix membranes have the highest total ammonia nitrogen (TAN) removal capacity followed by pore-filled membranes and then composite fibers. They found out that PEG addition to mixed matrix membranes resulted in higher permeability but lower nitrogen removal capacity, while presence of higher zeolite particle resulted in a lower permeability but higher removal capacity of ammonia. These membranes are stable and can be easily regenerated by NaCl solution without reduction in performance. They found out that IP capping the pore-filled membranes decreased flux and TAN removal capacity significantly whereas PEM capping did not reduce TAN removal capacity.

    Several mixed-matrix electrospun membranes were preapared by incorporating particles made from the cheap zeolites such as zeolite 13X, zeolite Y, and zeolite 3A and 4A and evaluated their performance[19].

    The MMM have high ammonium removal capacity which is over 55 mg/g zeolite and high permeability which can be easily regenerated by filtering with 2M NaCl. The membranes removed over 90% of ammonia from low TAN wastewaters (i.e., aquaculture wastewaters). Finally, they found that TAN removal capacity is affected by particle type, loading and the level of its dispersion.

    P. Moradihamedani et al. synthesized PSf/zeolite membrane with different weight ratios to study their performance of low-concentration ammonia (1–10 ppm) removal from aquaculture wastewater[20].

    They used FTIR spectroscopy to inspect the interactions between PSf and zeolite particles, AFM to investigate the surface roughness, and SEM to analyze the surface pore blockage, the big cavities, and macrovoids. They discovered that PSf/zeolite (80/20) is the most efficient membrane among the MMMs. Increasing presence of zeolite in the membrane matrix decreased pure water flux and ammonia elimination from water because of zeolite particles blocking the surface pore and formation of defects such as cavities and macrovoids in the membrane.

    4. Ion Exchange Membrane

    Ion-exchange membrane is electrically conductive. It blocks the flow of ion with similar charge or neutral molecule which allow the flow of opposite charged ion. Ion-exchange membranes are mainly used in desalination and chemical recovery since ion can move ions cam move easily with little passage of water. The performance of ion exchange columns was studied in which nitrifying bacteria cultivated to get a “combined” process of simultaneous ion-exchange and nitrification which were enhanced by in-situ aeration with a novel membrane module[21]. It was found out that both addition of the nitrifiers and column operation with membrane aeration significantly enhanced the ammonia removal. Among polyethersulfone membrane (PES), polypropylene membrane (PP), nylon, and polytetra- fluoroethylene membrane (PTFE), PES showed the best improvement of the ammonia removal, while PTFE was the best aeration performance. The breakthrough capacities were greatly improved in the biologically active ion exchange columns embedded with membrane aeration through the four porous membranes. PP showed the best improvement followed by PES and then PTFE. Unlike the others, the nylon column showed a reduction in breakthrough capacity, and they were not able to explain this. Combined nitrification and ion-exchange is greatly enhanced in packed columns by in-situ aeration utilizing a membrane module.

    S. Guida et al. reported an ion exchange process for its ability to eliminate variable ammonium (NH4+-N) loads and proved that it has benefits to the environment through a life cycle assessment (LCA)[22]. NH4+-N concentration in the effluent of secondary processes ranges from 0 to 26 mg/L and experiments conducted with these concentrations which showed the NH4+-N exchange capacity of Zeolite-N ranging from 0.9 to 17.7 mg NH4+-N/g media. The Zeolite-N released the NH4+-N into the wastewater with influent concentration below 2.5 mg NH4+-N/L. This is because there is equilibrium of NH4+ exchange between the media and the wastewater. The LCA showed that the optimal scenario is the IEX-NaCl-MEM scenario which reduced 25% cumulative energy demand.

    5. Ceramic Membrane

    Ceramic membranes are synthesized by depositing colloidal suspensions of metal hydroxides on porous supports and used for liquid filtration. They have excellent thermal stability, therefore, could be used in high-temperature membrane processes. They can be used even with the existence of corrosive media such as acids or strong solvents. M.R. Adam et al. tried to synthesize natural zeolite based hollow fiber ceramic membrane (HFCM) through phase inversion and sintering process to remove NH3 in wastewater[23]. They discovered that the HFCM synthesized with containing 45 wt.% of natural zeolite and by spinning at 5 cm of air– gap distance and 15 ml/min of bore fluid flowrate and sintering at 1050◦C shows the best performance which are mechanical strength of 50.92 MPa, permeation flux of 249.57 L/m2·h, and ammonia removal of 90%. They suggested that this hybrid adsorptive HFCM can be potentially used in other systems such as membrane distillation, membrane contactor and other processes. SEM is used to see the difference in the morphology of membranes before and after the modification of surface. Same group synthesized natural zeolite based HFCM through extrusion-based on phase inversion and sintering techniques to remove NH3 in wastewater[24]. They found out that 1050 °C is the ideal sintering temperature for the performance of the HFCM, the permeation flux of 249.57 L/m2h and the NH3 removal of nearly 90%. They explained that this high performance is due to the synergistic effect of the two processes, adsorption and separation, in the HFCM system. They suggested that natural zeolite based HFCM can potentially be used in wastewater treatment as a single – step NH3 removal.

    6. Conclusions

    Even low concentration of ammonia in water body cause harmful effect to human as well as marine organism. One of the important traditional removal method is chlorination process. But the removal of excess ammonia by this mean leads to large amount of side product like trihalomethans and chlorinated side products. Nitrification followed by denitrification is another traditional method of ammonia removal which has problem of excess nitrite presence in water. Biological method of removal is another solution but it is not as efficient and only solution to remove less concentrated ammonia. Membrane separation technology is one of the best alternative way for removal of ammonia. Membrane distillation, membrane contractor and flat sheet membrane are various suitable process. Mixed matrix membrane containing zeolite are another successful method for removal of ammonia. In this review the above processes are discussed in detail.



    Schematic presentation of classification of the review.


    SEM images of cross-sectional surfaces (top panel) and top surfaces (bottom panel) of fabricated mixed matrix membrane (20%PES-100%Zeolite13X) with increased left to right magnifications (Reproduced from Chen et al., 19, MDPI).


    The percentage of TAN removal as a function of the filtrate collected for mixed matrix membranes incorporating different zeolite particles of 13X, 3A, 4A, and Y. The membranes have the same mass composition of 20%PES-100% Zeolite (Reproduced from Chen et al., 19, MDPI).


    SEM micrographs from cross-section of (a) neat PSf, (b) PSf/Z (80/20) and (c) PSf/Z (60/40) (Reproduced from Moradihamedani et al., 20, IWA Publishing).


    Pure water flux of prepared membranes (Reproduced from Moradihamedani et al., 20, IWA Publishing).


    Summary of the Separation Membrane


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