Shahgodari Shirin, Llorens Joan, Labanda Jordi
Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
Polymers (Basel). 2025 Jun 18;17(12):1696. doi: 10.3390/polym17121696.
This study examined total ammoniacal nitrogen (TAN) rejection by two reverse osmosis (RO) and two nanofiltration (NF) membranes as a function of pH for three ammonium salts to optimize conditions for a hybrid membrane system that can produce high-purity TAN streams suitable for reuse. The results showed that TAN rejection was significantly influenced by membrane type, feed pH, and the ammonium salt used. This study represents the first attempt to simulate real manure wastewater conditions typically found in pig manure. TAN rejection for (NH)SO and NHHCO reached up to 95% at pH values below 7, with the SW30 membrane showing the highest performance (99.5%), attributed to effective size exclusion and electrostatic repulsion of SO and HCO ions. In contrast, lower rejection was observed for NHCl, particularly with the MPF-34 membrane, due to its higher molecular weight cut-off (MWCO), which diminishes both exclusion mechanisms. TAN rejection decreased markedly with increasing pH across the BW30, NF90, and MPF-34 membranes as the proportion of uncharged NH increased. The lowest rejection rates (<15%) were recorded at pH 11.5 for both NF membranes. These results reveal a notable shift in separation behavior, where NH permeation under alkaline conditions becomes dominant over the commonly reported NH retention at low pH. This novel insight offers a new perspective for optimizing membrane-based ammonia recovery in systems simulating realistic manure wastewater conditions. TAN recovery was evaluated using a hybrid membrane system, where NF membranes operated at high pH promoted NH permeation, and the SW30 membrane at pH 6.5 enabled TAN rejection as (NH)SO. This hybrid system insight offers a new perspective for optimizing membrane-based ammonia recovery in systems simulating realistic manure wastewater conditions. Based on NH permeation and membrane characteristics, the NF90 membrane was operated at pH 9.5, achieving a TAN recovery of 48.3%, with a TAN concentration of 11.7 g/L, corresponding to 0.9% nitrogen. In contrast, the MPF-34 membrane was operated at pH 11.5. The NF90-SW30 system also achieved a TAN recovery of 48.3%, yielding 11.7 g/L of TAN with a nitrogen content of 1.22%. These nitrogen concentrations indicate that both retentate streams are suitable for use as liquid fertilizers in the form of (NH)SO. A preliminary economic assessment estimated the chemical consumption cost at 0.586 EUR/kg and 0.729 EUR/kg of (NH)SO produced for the NF90-SW30 and MPF-34-SW30 systems, respectively.
本研究考察了两种反渗透(RO)膜和两种纳滤(NF)膜对三种铵盐中总氨氮(TAN)的截留情况,该截留情况是pH值的函数,目的是优化混合膜系统的条件,以生产出适合回用的高纯度TAN物流。结果表明,TAN截留率受膜类型、进料pH值和所用铵盐的显著影响。本研究首次尝试模拟猪粪中常见的真实粪便废水条件。对于硫酸铵((NH)SO)和碳酸氢铵(NHHCO),在pH值低于7时,TAN截留率高达95%,其中SW30膜表现出最高性能(99.5%),这归因于硫酸根离子(SO)和碳酸氢根离子(HCO)的有效尺寸排阻和静电排斥作用。相比之下,氯化铵(NHCl)的截留率较低,尤其是使用MPF - 34膜时,这是由于其较高的截留分子量(MWCO)削弱了两种截留机制。随着pH值升高,在BW(苦咸水)30、NF90和MPF - 34膜中,由于不带电荷的氨(NH)比例增加,TAN截留率显著下降。两种纳滤膜在pH 11.5时记录到最低截留率(<15%)。这些结果揭示了分离行为的显著变化,即在碱性条件下氨(NH)的渗透变得比低pH值下通常报道的氨截留更为显著。这一新颖的见解为在模拟真实粪便废水条件的系统中优化基于膜的氨回收提供了新的视角。使用混合膜系统评估了TAN回收率,其中在高pH值下运行的纳滤膜促进了氨(NH)的渗透,而在pH 6.5时运行的SW30膜实现了对硫酸铵((NH)SO)的TAN截留。这种混合系统的见解为在模拟真实粪便废水条件的系统中优化基于膜的氨回收提供了新的视角。基于氨(NH)的渗透和膜特性,NF90膜在pH 9.5下运行,TAN回收率达到48.3%,TAN浓度为11.7 g/L,相当于0.9%的氮。相比之下,MPF - 34膜在pH 11.5下运行。NF90 - SW30系统也实现了48.3%的TAN回收率,产生11.7 g/L的TAN,氮含量为1.22%。这些氮浓度表明两种截留液流都适合用作硫酸铵((NH)SO)形式的液体肥料。初步经济评估估计,NF90 - SW30和MPF - 34 - SW30系统生产硫酸铵((NH)SO)时,化学消耗成本分别为0.586欧元/千克和0.729欧元/千克。