市政污泥热化学处置中磷元素形态转变与回收利用研究进展

doi:10.16085/j.issn.1000-6613.2022-0760

摘要/Abstract

摘要：

我国市政污泥产量即将突破9000万吨，无害化、减量化和资源化处置非常迫切。干污泥中磷元素含量占2%～6%，回收磷资源的潜力巨大，其可以减少有限磷矿的消耗，缓解全球磷危机。本文从污泥处置技术、脱水污泥中磷元素含量与形态、热化学（热解、焚烧、气化和水热炭化）处理中磷元素形态转变、污泥灰/炭中磷元素回收方法和含磷矿物的植物可吸收性五个方面对污泥中磷资源回收与利用展开论述，详细对比分析了温度、添加剂成分、掺混燃料种类等因素对热处理产物中磷元素形态的影响。最后，归纳分析了热处理产物中磷元素的回收工艺和不同因素的影响以及含磷矿物的植物可吸收性，以期为我国未来污泥资源化利用提供参考。

关键词: 市政污泥, 磷元素, 热化学, 回收

Abstract:

The production of municipal sewage sludge in China is about to reach 90 million tons. Harmless, reduction and resource disposal for them is very urgent. The mass fraction of phosphorus in dried sewage sludge is 2%—6%. The potential is highly great for recycling phosphorus resource from sewage sludge. This not only reduces the consumption of phosphorus ore, but also alleviates global phosphorus crisis. The discussion about the recovery and utilization of phosphorus resource from sewage sludge focuses on five aspects, including sewage sludge disposal technologies, phosphorus content and speciation in dewatering sewage sludge, phosphorus speciation transformation during these thermal treatments (pyrolysis, incineration, gasification, hydrothermal carbonization), phosphorus recovery methods from sewage sludge ash/char and plant absorbability of phosphate minerals. It is also comparatively analyzed in detail that the effect of different factors including temperature, additive components and blending fuel types on phosphorus speciation in thermal treatment products. Finally, it is summarized and contrastively analyzed that the recovery processes of phosphorus from thermal treatment products and different factors influencing on the phosphorus recovery. Meanwhile, the plant availability for the recovered phosphate minerals were also discussed. This review could provide some suggestion for the resource utilization of phosphorus from sludge in China in the future.

Key words: municipal sewage sludge, phosphorus, thermal chemical treatment, recovery

中图分类号:

TK09

王毅斌, 冯敬武, 谭厚章, 李良钰. 市政污泥热化学处置中磷元素形态转变与回收利用研究进展[J]. 化工进展, 2023, 42(2): 985-999.

WANG Yibin, FENG Jingwu, TAN Houzhang, LI Liangyu. Research progress on phosphorus speciation transformation and recovery during thermal chemical conversion of municipal sewage sludge[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 985-999.

图/表 9

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城市	日产量（含水率80%）/t·d^-1	污泥处置技术路线	参考文献
广州市	约3313.97	浓缩+深度机械脱水+热干化+建材利用	[12-13]
北京市	6588～7684	中心城区以厌氧消化为主，周边城区以好氧发酵为主，多种工艺辅助。土地利用为主，建材利用为辅	[14]
上海市	4200	以焚烧为主，土地利用为辅，卫生填埋应急	[15]
武汉市	约1479.7	板框脱水+水泥/石灰炉窑混烧，建材利用为主，土地利用为辅，混合填埋保底	[16]
重庆市	约3191.59	水泥炉窑协同处置，建材利用	[17]
深圳市	5323	板框脱水+低温干化、外运处置	[18-19]
昆明市	1059	土地利用和建材利用并行，填埋处置应急	[20]

城市	日产量（含水率80%）/t·d^-1	污泥处置技术路线	参考文献
广州市	约3313.97	浓缩+深度机械脱水+热干化+建材利用	[12-13]
北京市	6588～7684	中心城区以厌氧消化为主，周边城区以好氧发酵为主，多种工艺辅助。土地利用为主，建材利用为辅	[14]
上海市	4200	以焚烧为主，土地利用为辅，卫生填埋应急	[15]
武汉市	约1479.7	板框脱水+水泥/石灰炉窑混烧，建材利用为主，土地利用为辅，混合填埋保底	[16]
重庆市	约3191.59	水泥炉窑协同处置，建材利用	[17]
深圳市	5323	板框脱水+低温干化、外运处置	[18-19]
昆明市	1059	土地利用和建材利用并行，填埋处置应急	[20]

材料	P₂O₅质量分数/%	单质P（干基）质量分数/%	备注
污泥	—	2～6	浙江嘉兴污泥（5.8%）^[11] 上海竹园干污泥（2.14%）^[51] 0.2～5.5（德国）^[10]
污泥灰（焚烧）	15.6～36^[53] （焚烧温度820～890℃）	3.6～13.3	850℃<焚烧温度<950℃^[50] 4.8%/5.7%（英国）^[50] 3.6%～13.3%（德国焚烧灰中磷元素平均值9%）^[46]
污泥炭（热解）	—	5～10.6	5.6%（西班牙）热解温度850℃^[50] 5.35%～7.08%热解温度300～500℃^[26] 9.99%～10.59%热解温度500℃/650℃/800℃^[54]
污泥灰（气化）	—	5.1～14.9	气化温度850～950℃^[55]
中国磷矿	33.8^[56] 我国磷矿中P₂O₅平均值为16.85^[3]	7.4（平均值）^[57]
埃及磷矿	28.5^[56]	—
摩洛哥磷矿	34.0^[56]	—
多哥磷矿	35.5^[56]	—

材料	P₂O₅质量分数/%	单质P（干基）质量分数/%	备注
污泥	—	2～6	浙江嘉兴污泥（5.8%）^[11] 上海竹园干污泥（2.14%）^[51] 0.2～5.5（德国）^[10]
污泥灰（焚烧）	15.6～36^[53] （焚烧温度820～890℃）	3.6～13.3	850℃<焚烧温度<950℃^[50] 4.8%/5.7%（英国）^[50] 3.6%～13.3%（德国焚烧灰中磷元素平均值9%）^[46]
污泥炭（热解）	—	5～10.6	5.6%（西班牙）热解温度850℃^[50] 5.35%～7.08%热解温度300～500℃^[26] 9.99%～10.59%热解温度500℃/650℃/800℃^[54]
污泥灰（气化）	—	5.1～14.9	气化温度850～950℃^[55]
中国磷矿	33.8^[56] 我国磷矿中P₂O₅平均值为16.85^[3]	7.4（平均值）^[57]
埃及磷矿	28.5^[56]	—
摩洛哥磷矿	34.0^[56]	—
多哥磷矿	35.5^[56]	—

磷酸盐	熔点/℃	参考文献
CaNaPO₄–Ca₃(PO₄)₂(β)	980	[70]
Ca₃(PO₄)₂–CaMg(SiO₃)₂	1300±5	[71]
Ca₃(PO₄)₂–Mg₃(PO₄)₂	1120	[72]
Ca₃(PO₄)₂	1810	[73]
K₃PO₄	1620	[74]
Na₃PO₄	1583	[73]
Mg₃(PO₄)₂	1357	[75]
MgNa₄(PO₄)₂	1655	[75]
AlPO₄	>1800	[76]
FePO₄	1208	[77]