市政污泥热解耦合钙基添加剂改性生物炭的土地利用研究

随着经济发展、城市规模的日益扩大、城市污水处理效率逐年提高，城市生活污水处理厂产生了大量副产物—市政污泥。在现有处理处置方式与城市发展不匹配的严峻形势下，如何妥善处理处置污泥已成为当前城市环境污染治理领域的核心议题。与此同时，由于全球磷储备的迅速枯竭，采取热解手段回收污泥中丰富的磷资源并作为一种新型肥料越来越受到业界关注。本研究以城市污泥生物炭中磷的高效应用为目标，以热解改性为主要手段，全面揭示污泥热解特性以及挥发性产物释放规律；系统研究了不同钙基添加剂对污泥热解过程中磷的迁移转化机制的影响，揭示了污泥生物炭土地利用时对土壤理化性质以及土壤微生物群落的影响,提出了新的污泥生物炭改性策略。本文的研究成果，为实现市政污泥的减量化、稳定化以及清洁、高效利用提供了理论与技术基础。

本文首先利用热重-红外-质谱联用实时监测系统作为主要手段，研究了污泥与咖啡渣共热解的反应规律及污泥热解特性。研究发现，污泥热解挥发性产物释放集中在330~500 C，随着热解温度的升高整体上呈现出先增强后减弱的趋势。当掺混比（咖啡渣：污泥）为3:7时，此时共热解生成挥发性产物的释放会被抑制。咖啡渣的添加并未改变污泥热解产物的组成，但是会提升污泥最大失重效率；有利于污泥热解反应的热启动过程以及提高了污泥热解反应所需要的有效碰撞频率。另外，通过对生物炭总磷测定以及磷形态的分析，发现低温热解污泥生物炭中磷主要以有机磷形态存在，高温热解生物炭中磷主要以铝磷、焦磷酸盐等无机磷形态存在。研究表明，咖啡渣的掺混能增加总磷含量，且当掺混比为3:7，500 C热解时，生成生物炭中水溶性磷占比最高达到44%。因此，污泥与咖啡渣共热解生成的生物炭有作速效肥使用的潜力。

污泥热解过程中，三种常见钙基添加剂-氧化钙、氢氧化钙、磷酸钙-均能促进污泥中磷转化为植物可利用的钙磷形态（羟基磷酸钙），提出了一种从污泥中回收磷的有效策略。固态核磁结果显示，原始污泥中76.8%为Al₂(OH)₃PO₄，该形态磷不能被植物体利用；而在改性污泥生物炭中磷形态表征结果显示，添加10%氧化钙、5%氢氧化钙或者10%磷酸钙时生成的羟基磷酸钙的含量达到峰值。热力学模拟结果证明了添加剂的引入能增加该热解体系的焓值，且当添加剂为氧化钙时体系焓值最低，这也就表明了污泥热解过程中氧化钙的添加更有利于污泥中磷以羟基磷酸钙形式被回收利用。此外，当热解温度超过900 C时，生成的羟基磷酸钙不稳定，会急剧减少。因此，本研究证明了调控添加钙基添加剂（钙磷比）作为从市政污泥中以羟基磷酸钙形式回收磷的有效策略，这也就验证了城市污泥中回收磷从而实现全球磷资源可持续性途径的可行性。

通过系统的生物炭土地利用时对土壤理化性质和土壤微生物学的影响分析，提出了钙基改性污泥生物炭的有效改良技术及其清洁应用。研究发现，调节钙基添加剂促进污泥磷热解转化对黑麦草生长和土壤微生物多样性有促进作用。盆栽实验中，改性污泥生物炭主要是通过改变土壤有效磷和有机质含量，进而影响黑麦草的生长。添加氧化钙和氢氧化钙制备的污泥生物炭组土壤中，促进磷向羟基磷酸钙转化的Ramlibacter微生物占主导地位，而原始污泥生物炭处理组土壤中，能加速重金属吸收的Massilia微生物占主导地位。此外，钙基添加剂处理组黑麦草植株地上部分茎中Pb累积量小于3%，而在原始污泥生物炭处理组中黑麦草地上部分Pb累计量超过35%。基于宏观和微观信息分析，总结出磷增益污泥生物炭对黑麦草的生长有促进作用，对土壤理化性质特别是有效磷和有机质有改良效益，并阻碍了土壤中重金属向黑麦草植株的迁移。因此，本研究通过对污泥热解特性、污泥中磷迁移转化机制以及污泥生物炭应用时对土壤理化性质和微生物影响等方面的深入研究，设计了一种智能、简便以及绿色的污泥生物炭资源化应用手段。

With the development of economic, acceleration of urbanization, the efficiency of municipal sewage treatment has been improved year by year, large number of by-products-municipal sludge, are produced due to the treatment of municipal sewage. Considering the severe situation that the present treatment and disposal methods do not keep up with urban development, how to properly treat and dispose of sludge will become a core issue in the field of urban environmental pollution control. At the same time, reclaiming abundant phosphorus in sewage sludge to be used as a novel fertilizer via pyrolysis has gained increasing attention due to the rapid depletion of global phosphorus reserves. This study aimed at the efficient application of phosphorus in urban sludge pyrochar, and applied pyrolysis modification as the main method to comprehensively study the characteristics of sludge pyrolysis and the characteristics of volatile products release. By systematically studying the effects of different calcium-based additives on the migration of phosphorus during sludge pyrolysis, the effects of sludge pyrochar on soil physicochemical and microbial community were revealed when sludge pyrochar land utilization, and a novel sludge pyrochar modification strategy is proposed. The research results of this paper provide a theoretical and technical basis for realizing the reduction, stabilization, clean and efficient utilization of urban sewage sludge.

In this paper, the TG-FTIR-MS three-machine combined real-time monitoring system was used as the main means to study the co-pyrolysis of sludge and coffee grounds and the pyrolysis characteristic of sludge. The study found that the volatile products released during sludge pyrolysis was concentrated at 330 ~500 °C, and it showed a trend of increasing at first and then weakening with the increase of pyrolysis temperature. When the blending ratio (coffee grounds: sludge) is 3:7, it had a certain inhibitory effect on the release of volatile products. The addition of coffee grounds did not change the composition of sludge pyrolysis products, but increased the maximum weight loss efficiency of sludge; it was beneficial to the hot start process of sludge pyrolysis reaction and increased the effective collision frequency required for sludge pyrolysis reaction. In addition, through the determination of total phosphorus and the analysis of phosphorus species, it was found that phosphorus in low-temperature pyrolysis sludge pyrochar was mainly organic phosphorus, while phosphorus derived from high-temperature pyrolysis pyrochar was mainly inorganic phosphorus, such as Al-P and pyrophosphate. Studies showed that the blending of coffee grounds could increase the total phosphorus content, and when the blending ratio was 3:7, when pyrolysis is carried out at 500 °C, the proportion of water-soluble phosphorus in the biochar is up to 44%. Therefore, the biochar generated by co-pyrolysis of sludge and coffee grounds has the potential to be used as a quick-acting fertilizer.

During sludge pyrolysis, three common calcium-based additives—calcium oxide, calcium hydroxide, and calcium phosphate—promote the conversion of phosphorus in the sludge into a form of calcium and phosphorus available to plants (hydroxylapatite), and an efficient strategy for phosphorus recovery from sludge was proposed. The solid-state NMR results showed that 76.8% of the pristine sludge pyrochar was Al₂(OH)₃PO₄, and this form of phosphorus could not be used by plants; while the characterization results of phosphorus in the modified sludge pyrochar showed that the content of hydroxylapatite produced reached the peak by adding 10% CaO, 5% Ca(OH)₂ or 10% Ca₃(PO₄)₂. The thermodynamic simulation results show that the introduction of additives can increase the enthalpy of the pyrolysis system, and when the additive was CaO, the system enthalpy was the lowest, which showed that the addition of CaO during the sludge pyrolysis was more conducive to the recycling of phosphorus in the sludge as the form of hydroxylapatite. Moreover, when the pyrolysis temperature exceeds 900 °C, the generated calcium hydroxylapatite was unstable and decreases sharply. Therefore, this study demonstrates the regulation of calcium-based additives (Ca/P ratio) as an effective strategy to recover phosphorus in the form of hydroxylapatite from sewage sludge, which verified the feasibility of recycling phosphorus from urban sludge to achieve global phosphorus resource sustainability.

Through systematic analysis of soil physicochemical properties and soil microbiology during land-use of pyrochar, an effective improvement technology and cleaning application of calcium-based modified sludge pyrochar are proposed. The study found that adjusting calcium-based additives to promote the pyrolysis of sludge phosphorus positively affected ryegrass growth and soil microbial diversity. In the pot experiment, the modified sludge pyrochar mainly affected the growth of ryegrass by changing the content of available phosphorus and organic matter in the soil. In the groups treated with pyrochar prepared by CaO and Ca(OH)₂ addition, Ramlibacter was dominant, which can promote the conversion of phosphorus to hydroxylapatite; while in the groups treated with pristine sludge pyrochar addition, metal uptake-accelerating Massilia showed a high abundance in the group treated with pristine sludge pyrochar. In addition, the accumulation of Pb in the shoots of ryegrass plants in the calcium-based additive treatment group was less than 3%, but more than 35% of Pb was accumulated in shoots treated with pristine sludge pyrochar. Based on the analysis of macroscopic and microscopic information, it was concluded that phosphorus-enhanced sludge biochar can promote the growth of ryegrass, improve soil physicochemical properties, especially available phosphorus and organic matter, and prevent the metal transfer to ryegrass. Therefore, a smart, simple, and green application method of sludge pyrochar utilization was designed through in-depth research on the characteristics of sludge pyrolysis, the mechanism of phosphorus transfer and transformation in sludge, and the effect of sludge pyrochar on soil physicochemical properties and microorganisms.

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