Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
Department of Chemistry and Bioscience, Aalborg University, Fredrik Bajers Vej 7H, 9220 Aalborg East, Denmark.
Water Res. 2019 Apr 15;153:208-216. doi: 10.1016/j.watres.2019.01.004. Epub 2019 Jan 21.
Phosphate, which contains the essential element phosphorous (P), is a necessary fertilizer for agriculture, but the current phosphate deposits are running out and alternative sources are needed. Sludge obtained from wastewater treatment plants contains high concentrations of phosphorus and represents an alternative, sustainable source. In this study, sludge obtained from a wastewater treatment plant with biological and chemical phosphorus removal was acidified (pH = 3, 4, 5 and 6) to release orthophosphate followed by sequestration of the orthophosphate by a zinc aluminum layered double hydroxide (ZnAl-LDH). Sulfuric acid (HSO), nitric acid (HNO), and hydrochloric acid (HCl) was tested, which showed that only sulfate anions compete with phosphate and results in reduced phosphate recovery (25-35%). The orthophosphate concentration in the liquid phase increased from 20% (raw sludge) to 75% of the total phosphorus concentration at a pH of 3, which enhanced the phosphate uptake by the ZnAl-LDH from 1.7 ± 0.2% to 60.3 ± 0.6%. During acidification, the competing anion carbonate is degassed as CO, which further improved the phosphate uptake. PXRD showed the intercalation of carbonate in the LDH in the raw sludge at pH = 8, whereas orthophosphate was intercalated at lower pH values. Al MAS NMR spectroscopy and powder X-ray diffraction (PXRD) proved preservation of the LDH at all pH values. Furthermore, about a fourth of the Al is present as an amorphous aluminum phosphate (AlPO) upon exposure to phosphate at low pH (pH = 3 and 5) based on Al MAS NMR spectroscopy. At a pH of 6 about a third of the P is present as brushite (CaHPO·2HO).
磷是一种含有必需元素磷(P)的肥料,是农业的必要肥料,但目前的磷矿储量正在枯竭,需要寻找替代来源。污水处理厂产生的污泥含有高浓度的磷,是一种替代的、可持续的来源。在这项研究中,对具有生物和化学除磷功能的污水处理厂产生的污泥进行酸化(pH=3、4、5 和 6),以释放正磷酸盐,然后用锌铝层状双氢氧化物(ZnAl-LDH)螯合正磷酸盐。测试了硫酸(HSO)、硝酸(HNO)和盐酸(HCl),结果表明只有硫酸根阴离子与磷酸盐竞争,导致磷酸盐回收减少(25-35%)。在 pH 值为 3 时,液相中的正磷酸盐浓度从 20%(原始污泥)增加到总磷浓度的 75%,这增强了 ZnAl-LDH 对磷的吸收,从 1.7±0.2%增加到 60.3±0.6%。在酸化过程中,竞争阴离子碳酸以 CO 的形式逸出,这进一步提高了磷的吸收。PXRD 表明在原始污泥的 pH 值为 8 时,碳酸盐在 LDH 中插层,而在较低 pH 值下,正磷酸盐插层。Al MAS NMR 光谱和粉末 X 射线衍射(PXRD)证明了在所有 pH 值下 LDH 的保存。此外,根据 Al MAS NMR 光谱,在低 pH(pH=3 和 5)下暴露于磷酸盐时,大约四分之一的 Al 以无定形的磷酸铝(AlPO)形式存在。在 pH 值为 6 时,大约三分之一的 P 以磷灰石(CaHPO·2HO)的形式存在。