污泥水热碳化中磷的形态变化及金属浸出行为

doi:10.11949/0438-1157.20200042

摘要/Abstract

摘要：

在不同温度下进行污泥水热碳化实验，利用Hedley顺序提取法探究水热炭中磷的形态变化，并结合钙、铁、铝的浸出行为进一步解释含磷物质的形态分布。结果表明，磷主要富集在水热炭中，水热碳化促进有机磷（P_o）向无机磷（P_i）转化，NaOH溶解态磷（NaOH-P）转化为HCl溶解态磷（HCl-P）和残渣态（Res-P）。污泥和水热炭中Ca、Fe主要以HCl溶解态为主；Al则由NaOH溶解态转化为 HCl溶解态。并且水热碳化过程促使污泥中磷形态从磷酸铝盐（Al-P）、磷酸铁盐（Fe-P）向磷酸钙盐（Ca-P）、磷酸镁盐（Mg-P）转化。通过理论分析，水热炭中Al-P可能以Al₂PO₄³⁺和AlHPO₄⁺络合物为主；羟基磷灰石是Ca-P的主要存在形态；部分磷酸盐可能被铁氧化物或氢氧化物固定。为后续水热炭的回收利用提供理论基础。

关键词: 污泥, 水热炭, 磷, 形态, 金属, 浸取

Abstract:

Hydrothermal carbonization (HTC) treatment of sewage sludge was conducted at different temperatures. The conventional fractionation of phosphorus in hydrochar was investigated by Hedley fractional extraction method, and to achieve a comprehensive understanding of the morphology of phosphorus-containing substances with consideration of Ca, Fe, Al. The results showed that phosphorus was mainly concentrated in the hydrochar. organophosphorus (P_o) almost transformed into inorganic phosphorus (P_i), and NaOH-extractable P (NaOH-P) converted to HCl-extractable P (HCl-P) and residue state (Res-P) in the process of HTC. Ca and Fe in the sludge and hydrochar were dominantly extracted by HCl whereas Al was transformed from NaOH-soluble to HCl-soluble. Moreover, the HTC process promoted the transformation of phosphorus form aluminum phosphate (Al-P) and iron phosphate (Fe-P) to calcium phosphate (Ca-P) and magnesium phosphate (Mg-P). Finally, a theoretical simulation of P-containing minerals suggested the existence of Al₂PO₄³⁺ and AlHPO₄⁺ complex in the hydrochar. Hydroxyapatite was the main existing form of Ca-P. Part of the phosphate may be fixed by iron oxides or hydroxides. This work provides a theoretical basis for the subsequent recycling of hydrochar.

Key words: sewage sludge, hydrochar, phosphorous, morphology, metal, extraction

中图分类号:

X 705

方俊华,唐琦,李杨,李遥瑶,吕秋颖,范准,周健,许劲. 污泥水热碳化中磷的形态变化及金属浸出行为[J]. 化工学报, 2020, 71(7): 3288-3295.

Junhua FANG,Qi TANG,Yang LI,Yaoyao LI,Qiuying LYU,Zhun FAN,Jian ZHOU,Jin XU. Morphology of phosphorus and metal extraction behavior in sewage sludge during hydrothermal carbonization treatment[J]. CIESC Journal, 2020, 71(7): 3288-3295.

图/表 10

表1 污泥基本性质

Table 1 Physicochemical characteristics of sewage sludge

高位热值/

( MJ·kg^-1)^③

表2 污泥矿物元素含量/(mg·g-1)

Table 2 Elements content of sewage sludge/(mg·g-1)

P	Fe	Al	Ca	Mg	Si	Na	K	S
11.88	57.90	34.47	23.55	5.82	57.04	3.17	10.14	2.79

表3 不同温度下水热炭中磷及金属的含量变化

Table 3 Major element content in hydrochar

样品	含量/(mg·g^-1)				回收率 /%
样品	P	Ca	Fe	Al	P	Ca	Fe	Al
HC-160	14.72	26.79	62.42	7.24	81.45	74.77	70.86	13.81
HC-180	16.35	33.75	74.20	10.40	82.49	85.91	76.80	18.08
HC-200	18.65	38.51	79.88	12.26	82.67	86.10	72.61	18.73
HC-220	19.55	40.93	84.74	13.12	83.41	88.09	74.17	19.29
HC-240	19.99	41.43	86.29	14.45	83.71	87.49	74.11	20.85
HC-260	20.92	41.82	87.63	15.65	84.74	85.46	72.82	21.84

表4 污泥及水热炭中磷的顺序提取分布含量/(mg·g-1)

Table 4 Amounts of P in hydrochar and sludge extracted by Hedley sequential method/(mg·g-1)

样品	H₂O-P	NaHCO₃-P	NaHCO₃-Pi	NaHCO₃-Po	NaOH-P	NaOH-Pi	NaOH-Po	HCl-P	P_i^①/%
HC-160	0.04	0.45	0.42	0.03	8.85	5.90	2.95	4.54	74.07
HC-180	0.03	0.42	0.38	0.04	8.22	5.64	2.59	5.45	70.27
HC-200	0.02	0.42	0.42	0.01	7.99	7.39	0.60	6.15	74.88
HC-220	0.03	0.36	0.34	0.02	6.37	6.01	0.36	7.41	70.54
HC-240	0.01	0.29	0.20	0.09	2.46	2.25	0.21	12.91	77.09
HC-260	0.01	0.06	0.05	0.01	1.04	0.91	0.13	15.20	77.30
污泥	0.20	0.90	0.81	0.09	6.40	3.17	3.23	2.57	56.83

图1 Hedley顺序提取法对P、Ca、Fe、Al的浸出能力分布

Fig.1 Distribution of P, Ca, Fe, Al in each step of Hedley’s sequential fraction with respect to extraction capacity

图2 Hedley顺序提取法对P、Ca、Fe、Al的浸出比例分布

Fig.2 Distribution of P, Ca, Fe, Al in each step of Hedley’s sequential fraction with respect to extraction ratio

图3 污泥及各温度下水热炭的XRD谱图

Fig.3 X-ray diffraction patterns of sewage sludge and hydrochar derived from different temperatures

表5 不同水热碳化温度下样品的pH

Table 5 pH of samples at different hydrothermal carbonization temperatures

污泥	HC-160	HC-180	HC-200	HC-220	HC-240	HC-260
6.6	5.9	6.1	6.6	6.9	7.1	7.3

图4 不同pH下各矿物相饱和指数

Fig.4 Saturation indices for minerals at different pH

图5 不同pH下磷及金属物质理论分布

Fig.5 Theoretical distribution of phosphorus and metals at different pH

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