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Using Taihu algal mud as the research subject, two common flocculants, polymeric ferric sulfate(PFS)and polyacrylamide(PAM), were selected to prepare different hydrochars at 180°C, 220°C, and 260°C. The results demonstrated that as the hydrothermal temperature increased, the carbon content in the algal mud hydrochar increased, while the hydrogen and nitrogen contents decreased. Decarboxylation and hydrolysis reactions were identified as the dominant processes during the hydrothermal conversion. The incorporation of PFS significantly enhanced the iron content in the hydrochar by 519.6% to 748.3%, and the rise in hydrothermal temperature facilitated the transformation of iron from Fe(III)to Fe(II), thereby improving its reducibility. PAM exhibited degradation at lower temperatures, generating oxygen-containing functional groups, while PFS promoted the degradation and carbonization of organic matter. The hydrochar prepared at 180°C showed higher nutrient retention. Rice cultivation experiments indicated that the application of algal mud-based hydrochar did not adversely affect rice growth;notably, PAM-based hydrochars increased rice plant biomass by 9.0%. Based on field survey data, it was estimated that converting Taihu algal mud into hydrochar could annually recover 3077.7 tons of total nitrogen and 776.7 tons of total phosphorus. The recovered total phosphorus accounted for 43.1% of the external phosphorus load input into Taihu Lake.

, correspAuthors=Hui-fang XIE, Yan-fang FENG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yi-meng WANG, Yun-yi LIANG, Bing-fa CHEN, Ya-xin MA, Zi-yu ZHOU, Shi-ying HE, Hui-fang XIE, Li-hong XUE, Yan-fang FENG), CN=ArticleExt(id=1241057222252360227, articleId=1241057218318102656, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=聚合硫酸铁和聚丙烯酰胺对藻泥水热炭特征的影响及产物应用潜力, columnId=1240689598737731645, journalTitle=中国环境科学, columnName=固体废物, runingTitle=null, highlight=null, articleAbstract=

以太湖藻泥为研究对象,选择聚合硫酸铁(PFS)和聚丙烯酰胺(PAM)两种常见絮凝剂,分别在180、220和260℃条件下制备得到不同水热炭.结果表明,随着水热温度升高,藻泥水热炭中碳含量增加,氢和氮含量减少,水热反应过程中脱羧和水解反应占主导地位.PFS的加入使水热炭中铁含量显著提高519.6%~748.3%,并且水热温度升高可使铁的形态由Fe(Ⅲ)逐渐向Fe(Ⅱ)转变,从而增加铁的还原性.PAM在较低温度即发生降解,生成含氧官能团,而PFS则促进了有机质的降解和碳化过程.180℃制备的藻泥基水热炭养分含量较高,水稻种植实验表明,施用藻泥基水热炭不会对水稻生长产生不利影响,其中PAM水热炭可以使水稻植株生物量增加9.0%.基于实地调研数据估算,太湖藻泥转化为水热炭,每年可回收总氮549.8t,总磷130.9t;其中总磷回收量占环太湖河流入湖磷负荷的7.3%.

, correspAuthors=谢慧芳, 冯彦房, authorNote=null, correspAuthorsNote=
* 责任作者,副教授,
** 研究员,
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王怡梦(2001-),女,河南许昌人,南京理工大学硕士研究生,主要研究方向为有机废弃物资源化和面源污染治理研究.发表论文1篇..

, authorsList=王怡梦, 梁韵仪, 陈丙法, 马亚鑫, 周紫瑜, 何世颖, 谢慧芳, 薛利红, 冯彦房)}, authors=[Author(id=1241057223238021789, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057218318102656, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=wym200108@163.com, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1241057223368045231, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057218318102656, authorId=1241057223238021789, language=EN, stringName=Yi-meng WANG, firstName=Yi-meng, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1.School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
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王怡梦(2001-),女,河南许昌人,南京理工大学硕士研究生,主要研究方向为有机废弃物资源化和面源污染治理研究.发表论文1篇..

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王怡梦(2001-),女,河南许昌人,南京理工大学硕士研究生,主要研究方向为有机废弃物资源化和面源污染治理研究.发表论文1篇..

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Report on the health status of Taihu Lake (2018)[R]. 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180HC、220HC、260HC分别代表其他研究中220℃、240℃、260℃温度下制备的水热炭

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不同的字母表明显著性差异(P<0.05)

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abc为同步图,def为异步图

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不同的字母表明显著性差异(P<0.05)

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Fed为游离氧化铁,Feo为无定形氧化铁,Fep为有机物络合氧化铁.不同的字母表明显著性差异(P<0.05)

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不同的字母表明显著性差异(P<0.05)

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(a)太湖年平均蓝藻打捞量,(b)太湖藻泥基水热炭的TN、TP储存总量,(c)占环太湖河流入湖TN、TP负荷的比重

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Basic physical and chemical properties of soil

, figureFileSmall=null, figureFileBig=null, tableContent=
pH值SOC(mg/g)TN(mg/g)TP(mg/g)TK(mg/g)
7.70±0.0513.41±0.571.23±0.040.74±0.0317.46±0.49
), ArticleFig(id=1241057235607024233, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057218318102656, language=CN, label=表1, caption=

土壤的基本理化性质

, figureFileSmall=null, figureFileBig=null, tableContent=
pH值SOC(mg/g)TN(mg/g)TP(mg/g)TK(mg/g)
7.70±0.0513.41±0.571.23±0.040.74±0.0317.46±0.49
), ArticleFig(id=1241057235724464757, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057218318102656, language=EN, label=Table 2, caption=

Yield and elemental analysis of different hydrochar and algal mud

, figureFileSmall=null, figureFileBig=null, tableContent=
处理Yield(%)N(%)C(%)H(%)S(%)O(%)1灰分(%)Mn(mg/g)Zn(mg/g)Cu(mg/g)Mg(mg/g)Cr(mg/g)
藻泥/5.7327.615.993.6018.8938.180.06±0.000.10±0.010.04±0.001.62±0.060.02±0.00
180AM72.003.9123.945.073.218.2155.650.06±0.000.16±0.040.07±0.001.36±0.060.02±0.00
220AM57.503.8025.384.653.356.3656.460.08±0.000.17±0.010.09±0.001.62±0.100.03±0.00
260AM50.582.1127.333.963.176.3357.100.10±0.000.22±0.010.11±0.002.39±0.160.04±0.01
180PFS79.253.7522.335.314.047.8456.750.13±0.000.19±0.030.07±0.001.00±0.050.03±0.00
220PFS64.582.8523.524.193.9310.7054.800.16±0.000.25±0.010.08±0.001.02±0.040.03±0.00
260PFS59.671.7625.814.003.1213.1552.160.28±0.000.28±0.010.10±0.001.38±0.030.04±0.00
180PAM80.835.2325.955.433.1816.2843.930.06±0.000.11±0.000.06±0.001.61±0.080.02±0.00
220PAM69.163.7626.954.633.1211.5749.970.07±0.000.16±0.000.08±0.002.37±0.030.02±0.00
260PAM62.233.0428.464.363.418.8151.930.08±0.000.17±0.010.08±0.002.85±0.010.03±0.00
), ArticleFig(id=1241057235837710980, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241057218318102656, language=CN, label=表2, caption=

藻泥基水热炭的元素分析及常见重金属含量

, figureFileSmall=null, figureFileBig=null, tableContent=
处理Yield(%)N(%)C(%)H(%)S(%)O(%)1灰分(%)Mn(mg/g)Zn(mg/g)Cu(mg/g)Mg(mg/g)Cr(mg/g)
藻泥/5.7327.615.993.6018.8938.180.06±0.000.10±0.010.04±0.001.62±0.060.02±0.00
180AM72.003.9123.945.073.218.2155.650.06±0.000.16±0.040.07±0.001.36±0.060.02±0.00
220AM57.503.8025.384.653.356.3656.460.08±0.000.17±0.010.09±0.001.62±0.100.03±0.00
260AM50.582.1127.333.963.176.3357.100.10±0.000.22±0.010.11±0.002.39±0.160.04±0.01
180PFS79.253.7522.335.314.047.8456.750.13±0.000.19±0.030.07±0.001.00±0.050.03±0.00
220PFS64.582.8523.524.193.9310.7054.800.16±0.000.25±0.010.08±0.001.02±0.040.03±0.00
260PFS59.671.7625.814.003.1213.1552.160.28±0.000.28±0.010.10±0.001.38±0.030.04±0.00
180PAM80.835.2325.955.433.1816.2843.930.06±0.000.11±0.000.06±0.001.61±0.080.02±0.00
220PAM69.163.7626.954.633.1211.5749.970.07±0.000.16±0.000.08±0.002.37±0.030.02±0.00
260PAM62.233.0428.464.363.418.8151.930.08±0.000.17±0.010.08±0.002.85±0.010.03±0.00
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聚合硫酸铁和聚丙烯酰胺对藻泥水热炭特征的影响及产物应用潜力
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王怡梦 1, 2 , 梁韵仪 2, 3 , 陈丙法 2 , 马亚鑫 1, 2 , 周紫瑜 1 , 何世颖 2 , 谢慧芳 1, * , 薛利红 2 , 冯彦房 2, **
中国环境科学 | 固体废物 2025,45(5): 2587-2597
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中国环境科学 | 固体废物 2025, 45(5): 2587-2597
聚合硫酸铁和聚丙烯酰胺对藻泥水热炭特征的影响及产物应用潜力
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王怡梦1, 2 , 梁韵仪2, 3, 陈丙法2, 马亚鑫1, 2, 周紫瑜1, 何世颖2, 谢慧芳1, * , 薛利红2, 冯彦房2, **
作者信息
  • 1.南京理工大学环境与生物工程学院,江苏 南京 210094
  • 2.江苏省农业科学院农业资源与环境研究所,农业农村部长江下游平原农业环境重点实验室,江苏 南京 210014
  • 3.南京林业大学材料科学与工程学院,江苏 南京 210037
  • 王怡梦(2001-),女,河南许昌人,南京理工大学硕士研究生,主要研究方向为有机废弃物资源化和面源污染治理研究.发表论文1篇..

通讯作者:

* 责任作者,副教授,
** 研究员,
Effects of polyferric sulfate and polyacrylamide on algal mud-based hydrochar and their application potential
Yi-meng WANG1, 2 , Yun-yi LIANG2, 3, Bing-fa CHEN2, Ya-xin MA1, 2, Zi-yu ZHOU1, Shi-ying HE2, Hui-fang XIE1, * , Li-hong XUE2, Yan-fang FENG2, **
Affiliations
  • 1.School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
  • 2.Key Laboratory of Agro-Environment in Downstream of Yangtze Plain, National Agricultural Experiment Station for Agricultural Environment, Ministry of Agriculture and Rural Affairs, Institute of Agricultural Resources and Environment, Jiangsu Academy of Agricultural Sciences, Nanjing 210014, China
  • 3.Material Science and Engineering College, Nanjing Forestry University, Nanjing 210037, China
出版时间: 2025-05-20
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以太湖藻泥为研究对象,选择聚合硫酸铁(PFS)和聚丙烯酰胺(PAM)两种常见絮凝剂,分别在180、220和260℃条件下制备得到不同水热炭.结果表明,随着水热温度升高,藻泥水热炭中碳含量增加,氢和氮含量减少,水热反应过程中脱羧和水解反应占主导地位.PFS的加入使水热炭中铁含量显著提高519.6%~748.3%,并且水热温度升高可使铁的形态由Fe(Ⅲ)逐渐向Fe(Ⅱ)转变,从而增加铁的还原性.PAM在较低温度即发生降解,生成含氧官能团,而PFS则促进了有机质的降解和碳化过程.180℃制备的藻泥基水热炭养分含量较高,水稻种植实验表明,施用藻泥基水热炭不会对水稻生长产生不利影响,其中PAM水热炭可以使水稻植株生物量增加9.0%.基于实地调研数据估算,太湖藻泥转化为水热炭,每年可回收总氮549.8t,总磷130.9t;其中总磷回收量占环太湖河流入湖磷负荷的7.3%.

水热炭化  /  絮凝剂  /  太湖藻泥  /  养分转化  /  稻田应用

Using Taihu algal mud as the research subject, two common flocculants, polymeric ferric sulfate(PFS)and polyacrylamide(PAM), were selected to prepare different hydrochars at 180°C, 220°C, and 260°C. The results demonstrated that as the hydrothermal temperature increased, the carbon content in the algal mud hydrochar increased, while the hydrogen and nitrogen contents decreased. Decarboxylation and hydrolysis reactions were identified as the dominant processes during the hydrothermal conversion. The incorporation of PFS significantly enhanced the iron content in the hydrochar by 519.6% to 748.3%, and the rise in hydrothermal temperature facilitated the transformation of iron from Fe(III)to Fe(II), thereby improving its reducibility. PAM exhibited degradation at lower temperatures, generating oxygen-containing functional groups, while PFS promoted the degradation and carbonization of organic matter. The hydrochar prepared at 180°C showed higher nutrient retention. Rice cultivation experiments indicated that the application of algal mud-based hydrochar did not adversely affect rice growth;notably, PAM-based hydrochars increased rice plant biomass by 9.0%. Based on field survey data, it was estimated that converting Taihu algal mud into hydrochar could annually recover 3077.7 tons of total nitrogen and 776.7 tons of total phosphorus. The recovered total phosphorus accounted for 43.1% of the external phosphorus load input into Taihu Lake.

hydrothermal carbonization  /  flocculant  /  Taihu algae mud  /  nutrient conversion  /  paddy field application
王怡梦, 梁韵仪, 陈丙法, 马亚鑫, 周紫瑜, 何世颖, 谢慧芳, 薛利红, 冯彦房. 聚合硫酸铁和聚丙烯酰胺对藻泥水热炭特征的影响及产物应用潜力. 中国环境科学, 2025 , 45 (5) : 2587 -2597 .
Yi-meng WANG, Yun-yi LIANG, Bing-fa CHEN, Ya-xin MA, Zi-yu ZHOU, Shi-ying HE, Hui-fang XIE, Li-hong XUE, Yan-fang FENG. Effects of polyferric sulfate and polyacrylamide on algal mud-based hydrochar and their application potential[J]. China Environmental Science, 2025 , 45 (5) : 2587 -2597 .
我国大型浅水湖泊,如太湖,近年来因富营养化而频繁爆发藻华危害[1].打捞是目前减轻藻华危害常用的应急控制手段之一.自2007年以来,已从太湖打捞出超过1000万t藻泥[2].打捞产生的藻泥由于含水量高、散发臭味、藻毒素普遍存在等原因,不宜直接还田应用,目前常用的堆肥、厌氧发酵等方法则需要较长的处理时间,不能满足及时处理藻华爆发期间巨大的打捞量[3].因此,亟需更加快速高效的藻泥资源化处理和产品利用技术[4].
水热炭化(HTC)是以水为溶剂,在较低的压力和温度条件(180~260℃)下[5],有机物经水解、缩合、脱羧和脱水反应[6],转化为液相产物(水热炭液)和固相产物(水热炭,HC),均具有较高附加值,当前受到广泛关注[7].HTC最大的优势在于原料无需脱水,避免因干燥原料带来的高成本,非常适合用于藻类等含水量高的废弃生物质的资源化再利用[8].水热炭用途广泛,可作为土壤改良剂、环境修复材料、碳捕集和储存材料等[9],由于原料中大部分磷都固定在水热炭中[10],还特别适合用作肥料管理[11].因此HTC是实现包括藻类在内的高湿有机废弃物高效资源化利用的有效措施.
近年来,有关藻泥水热处理的研究已有报道,但主要集中在不同种类和来源的藻类所制备的水热炭特性的研究上[12-14],并出现了多种水热过程改进技术,如两阶段顺序水热液化[15]、HTC-ZnCl2改性水热炭化等[16].目前在实际藻泥处理过程中,为提高藻泥的沉降及脱水效率,通常会添加絮凝剂[17-18],这不可避免地导致絮凝剂残留于藻泥中.聚合硫酸铁(PFS)和聚丙烯酰胺(PAM)是两种常用的絮凝剂,其残留可能显著影响藻泥的水热炭化过程及固相产物特性.有研究利用铁催化了微藻的HTL过程,获得了最高产率(36.2%)、能量密度(37.1MJ/kg)和最低杂原子含量(3.8% N和10.1% O)的生物原油[19].PAM本身作为一种有机高分子,也可能在水热条件下发生降解等反应,进而影响水热炭的化学组成和表面性质.然而,目前针对絮凝剂残留对藻泥水热转化过程中固相产物特性影响的研究仍较为匮乏,尚未见系统性报道.
为此,本文假设不同絮凝剂的添加可能改变水热炭化反应的路径、动力学过程及水热炭元素含量、官能团组成等特性,进而影响水热炭的应用性能.因此,选择了PFS和PAM两种典型藻类絮凝剂,探讨不同絮凝剂的加入对藻泥基水热炭结构组成、养分特征及其理化特性的影响,旨在为优化藻泥处理工艺和提高水热炭产品的应用性能提供科学依据.
研究采用太湖藻泥,于2023年7月5日取自江苏省常州市武进区藻水分离站(31°14′4″N,121°27′24″E).阳离子PAM(MW=3000000)购自阿达玛斯试剂有限公司(Adamas Reagent Co.,Ltd.),PFS购于上海麦克林生化科技股份有限公司(Shanghai Macklin Biochemical Co.,Ltd.),铁含量21%(质量分数).
将藻泥(AM)自然风干后通过60目筛,密封于阴凉处保存.风干藻泥与液相比例为1:10,即12g风干藻泥分别和120mL去离子水、2%PFS溶液、2%PAM溶液于150mL水热反应釜中混合均匀.设定不同反应温度(180、220和260℃)进行水热反应,保持时间为180min.水热反应结束后,待冷却至室温,过滤得到固相产物(即HC),冷冻干燥后避光储存.分别标记为180AM、220AM、260AM、180PFS、220PFS、260PFS、180PAM、220PAM和260PAM.
采用高温灼烧法测定样品灰分含量后,使用元素分析仪(Thermo FLASH 2000,美国)测定各水热炭中元素含量.使用傅里叶红外光谱仪(Thermo Fisher NICOLET 67,美国)得到水热炭红外光谱(Fourier Transform Infrared Spectra,FTIR);使用电子扫描显微镜观测水热炭的表面形貌;采用X射线光电子能谱(X-ray Photoelectron Spectroscopy,XPS,ESCALAB 250Xi,Thermo Fisher,美国)进行表面元素的定性、定量和价态分析.样品经高氯酸-氢氟酸-硝酸消煮后,使用电感耦合等离子体发射光谱仪ICP-OES(Thermo Fisher iCAP Pro,美国)测定其中总磷(TP)、总钾(TK)和主要金属的含量.
采用凯氏定氮法测量水热炭的总氮(TN)含量,使用流动分析仪(SKALAR SAN++SYSTEM,荷兰)测定铵态氮(NH4+-N)和硝酸盐(NO3--N)含量.用总有机碳分析仪(Multi N/C 3100,德国)测定水热炭中溶解性有机碳(DOC).采用顺序提取法[20]测定不同形态的P含量.采用邻菲罗啉比色法分别测定了Fe(II)和Fe(III)的含量,进而按Yao等[21]的方法分析了铁的形态分布,包括游离氧化铁(Fed)、无定形氧化铁(Feo)和有机物络合氧化铁(Fep).
为评估藻泥基水热炭部分替代化肥,用作土壤调理剂的可行性,选用180AM、180PFS、180PAM3种水热炭,进行为期30d的水稻苗期盆钵实验.实验在直径8cm、高10cm的透明塑料圆柱盆钵中进行.供试土壤采自江苏省农业科学院试验稻田,属马肝土,其基本性质如表1所示.
水热炭按用量0.3%(质量比)施加.将水热炭和土壤混合均匀后装填于盆钵中,选择生长状况近似一致的水稻幼苗,在每盆钵中移入三株(苗龄21d).实验处理分别命名为HC-AM、HC-PFS、HC-PAM,同时设置对照组,分别为:不施氮肥的空白对照组(CK0),常规施肥组(CKU),施用藻泥组(AM).
移栽后模拟田间施肥效果,分别于第3d和第17d施肥[22-23].CKU组施肥量按140kg/hm2TN、96kg/hm2P2O5、90kg/hm2K2O的施肥量进行,施加藻泥及藻泥基水热炭组则保持氮磷钾养分等量投入,即扣除水热炭所含养分后,用常规化肥补足至对照施肥水平.每个处理设有3个平行样本.水稻收获后,测量植株地上部和地下部的干重、叶绿素相对含量SPAD值及株高,以评估各处理对水稻生长的影响.
相关性分析使用IBM SPSS Statistics 27软件,使用单因素检验中Duncan检验分析其显著性(P<0.05).绘图采用Origin 2024和GraphPad Prism 8.XPS光谱由Avantage 6.8软件处理,并根据峰面积计算出不同价态元素的比例.
不同条件下制备水热炭的产率及其元素分析如表2所示.水热炭的产率随着温度升高而逐渐降低,这是由于温度升高将导致有机物的分解反应变得更加剧烈,更多的有机大分子经过水解、脱水、脱羧等反应分解为小分子物质转移到液相中,使水热炭的产率下降.在水热过程中,藻泥中的含氮有机物(如蛋白质)发生酰胺水解、脱羧等反应,导致氮转移到液相中,因此水热炭中的氮含量低于原料,且随着温度升高而降低,这表明水热温度是影响水热炭中氮含量的关键因素.藻泥中添加PAM则引入了外源有机氮,经水热处理后,产品的中N含量明显高于其他处理.在各组处理中,随着温度的升高,H/C值均降低,这与水热炭的芳香化程度增强有关[24].藻泥水热炭化过程中,温度升高导致水热炭O/C值下降,添加PAM时这一趋势相同,但添加PFS后,随着温度的升高,O/C值增加.如图1所示,与其他研究中典型水热炭比较[25-28],可以看出藻泥基水热炭的H/C较高,这是因为藻泥的芳香化程度较低,较为丰富的蛋白质、多糖、脂质等有机质在水热反应中可能分解不完全,形成较多的含氢基团(如羟基、烷基).高H/C比表明藻泥基水热炭具有更强的化学活性和功能化潜力,相对于高炭化材料,藻泥基水热炭可能更适合用作土壤改良剂.
不同水热炭金属元素含量如表2所示.相比于藻泥原料,水热炭中Mn、Zn含量略有增加且更高的水热温度导致更多的金属元素的沉淀富集在水热炭中,这与其他的研究结果一致[29].本研究中各水热炭的As、Pb、Cd低于检出限,检测到水热炭中含有微量的铬,但含量明显低于生物炭基有机肥农业行业标准(NY/T 3618-2020,Cr≤0.15mg/g)[30].
不同反应温度及絮凝剂对水热炭的pH值、Zeta电位及DOC浓度有显著影响(图2).在不同温度下制备的水热炭均呈酸性(pH<7,图2(c)),与之前研究结果一致[31].由于高温下藻泥脱羧在水热炭表面产生酸性物质[32],因此220AM的pH值显著低于180AM(P<0.05).酸性化合物在高于240℃的温度下分解,或生物质中某些物质,如蛋白质在较高的水热温度下反应,产生碱性化合物[33],因此260AM的pH值增至6.2.添加PFS后,pH值降低了0.4~1.4,由于PFS在水中会发生水解反应,生成氢氧化铁等产物,从而降低水热产物的pH值.在实际应用中,PFS水热炭在碱性土壤中能够有效降低土壤pH值,改善养分有效性.
Zeta电位是评估水热炭在土壤体系中表面电荷特性及其颗粒稳定性的重要参数(图2(a)).结果表明180AM、220AM、260AM的Zeta电位分别为-16.2,-0.6,-3.2mV,这是由于高温下表面官能团的重新排列、部分电荷的消散以及表面吸附的离子解吸等原因造成.PAM作为一种高分子聚合物,可以改变颗粒表面的电荷分布,同时还通过吸附、网捕等方式影响藻泥颗粒聚集状态和Zeta电位,土壤颗粒表面通常带负电荷,PAM水热炭的Zeta电位为负值且绝对值较大,表明其在土壤中的分散性较好,能够有效覆盖土壤颗粒表面,起到均匀改良的作用.
图2(b)所示,AM水热炭和PFS水热炭的DOC含量在220℃下达到峰值,而PAM水热炭的DOC含量较高且随温度的增加而降低.这是由于温度从180℃升高至220℃促进了藻泥中聚糖、脂肪酸等有机组分的分解,产生的较小的有机物被吸附富集在水热炭表面,导致DOC释放量增加[34],然而,当水热温度继续上升至260°C时,碳化作用加强及小分子有机物再聚合为大分子,因此DOC含量下降.在3种温度下,PFS水热炭的DOC含量均低于AM水热炭,这可能是因为铁离子与有机碳发生络合作用,使有机碳更加稳定.PAM在水热条件下会部分水解,产生一些小分子有机化合物,如酰胺类、羧酸类等,可以增加水热炭中DOC的含量,从而可以增加土壤碳含量,为微生物提供更多能力,增强其代谢活性.
水热炭的比表面积(SSA)可以评估其吸附能力、养分缓释性能及其在土壤改良和污染修复中的应用潜力(图2(d)).180PFS水热炭的SSA低于180AM水热炭;但当温度升高至220℃,PFS水热炭的SSA增加,高于相同温度下的AM水热炭,这说明高温条件下,PFS会促进有机质的分解,形成更多的微孔结构,提供更多活性表面位点.PAM的降解产物(如酰胺、羧酸等)会沉积在水热炭的表面和孔隙中,堵塞其表面微孔.180AM、220PFS、260PFS具有较大的比表面积,与土壤矿物和有机质颗粒相结合,促进土壤团聚体的形成,改善土壤结构和稳定性,并且更多的吸附位点可以延缓养分流失、提高肥效利用率.
通过XPS技术对水热炭表面含碳基团进行分析,结果如图3所示.180AM和180PFS中存在C-O和C-C,当温度升高至220℃,C-O键断裂消失,形成了更稳定的C=O键,随着温度升高至260℃,C=O键含量减少,260AM和260PFS的C=O键分别为14.2%、13.6%.180AM的C-C键从49.1%増至260AM中的85.8%,180PFS的C-C键从56.1%増至260PFS中的86.5%.添加PAM后,在180℃就出现了C=O且C-O键在260℃才消失.这可能由于PAM的酰胺基团在水热条件下容易发生水解,形成羧酸(-COOH)或羧酸盐.总体来说,在较高的温度下,含氧官能团变得不稳定并进行热降解,这些基团可能通过脱羧或脱水反应被去除,留下更热稳定的结构.随着温度的升高,碳结构进一步缩合,形成更稳定的芳环,这个过程减少了含氧键的数量,导致C-O的消失.C=O键的减少是因为脱羧反应,特别是来自羧酸或醛的基团,在高温下会分解,释放出二氧化碳.上述研究结果与生物质水热炭化的普遍趋势一致[35],即温度的升高使炭材料趋向于更凝聚的芳香结构,含氧基团更少.
基于FTIR的二维相关光谱(2D-COS)分析了不同温度下制备的水热炭的官能团变化.从图4中可以发现,AM水热炭在690cm-1、1140~1350cm-1和2070~2550cm-1之间出现了峰,分别代表了C=C、C-O、-NH2的振动[36-37].相比于AM水热炭,PFS水热炭在690cm-1的峰值强度有所减弱,可能是由于铁离子与C=C等官能团的相互作用减少了其自由振动.相比于AM水热炭,PAM同步图谱在1140~2550cm-1处的强度较弱,表明PAM对该区域官能团的振动有较大的影响,可能是由于PAM中的-NH2官能团参与了反应或相互作用.异步光谱是关于对角线反对称的,表示在两个给定波数处测量的光谱强度的顺序或不同步变化.在AM水热炭和PFS水热炭样品中,C=O和C-O的同步交叉峰为正,表明它们在水热反应(如水解和脱羧)过程中具有协同变化的趋势[38],这与XPS结果一致.根据Noda的光谱规则[39],在AM水热炭异步图中,C=O与C-O的交叉峰为正,与同步图一致,说明表明C=O随着反应温度的升高在时间上先于C-O变化,这可能是由于原料中有机物水解反应优先于脱羧[40].而PFS水热炭的C-O变化先于C=O,这可能是由于铁离子增强了某些特定反应的速率,导致羟基或醚类基团的转化.PAM水热炭由于酰胺基团的增加,改变了样品中的-NH2、C=O、C-O等官能团的变化趋势,同时引起了更多的交叉峰,表明其对水热反应中的多官能团体系产生了影响.
本研究使用SEM进一步观察了代表性水热炭样品形貌(图5).水热炭颗粒表面附着大量片状结构,温度越高,片状结构越多,表明样品的表面积较大,孔隙率较高,并且颗粒状物质间的结合变得疏松.从EDS(能量色散X射线光谱)的元素分布图可以发现,220AM和220PAM颗粒表面的Fe含量均为1.4%,180PFS、220PFS、260PFS的Fe含量分别为4.0%、4.6%、5.3%,这表明PFS促进铁在炭上的富集,且温度升高更有利于增加水热炭表面Fe含量.此外,PFS和PAM的添加均增加了水热炭表面的C含量.
在不同温度下,水热炭中TN含量变化如图6(a)所示.藻泥中蛋白质含量高,研究表明高温下蛋白质会发生水解[41].随着温度从180℃升高到260℃,水热炭中的TN含量逐渐降低,这是由于蛋白质的水解速率随着温度的升高而增加,水解后液体中溶解了更多的TN,降低了水热炭中的TN.这表明180℃制备的水热炭提高土壤有机氮库,促进作物生长,提升肥效.本研究水热炭中的TN大多以NH4+-N的形式存在(图6(b)),这与以前的研究一致[42].
图6(c)~(d)为水热炭中TP和各形态P的含量.P主要保留在水热炭中(图5(c)),与之前研究结果一致[43].180AM中P含量为8.6mg/g,220AM的P含量显著增加至13.1mg/g(P<0.05).加入PFS或者PAM降低了同温度条件下水热炭中的TP含量.从图5(d)可以发现,温度水热炭中的P主要以铁铝结合态形式存在,其次为钙结合态.随着反应温度的升高,铁铝结合态磷和钙结合态磷所占比例逐渐降低,残留态磷比例上升.HC可以逐渐释放P,其养分释放效率优于原料,可以持续为土壤提供P养分,它的应用既回收了废弃的P,又可以提高土壤肥力和P肥料的使用效率[44].
在水热反应中,TK易溶解在水热炭液中,因此,3种水热炭的钾含量均较低,其中,AM水热炭的TK含量为1.8~5.6mg/g(图6(e)).但PFS的添加会降低产品中的钾含量.添加PAM和增加水热温度均可以抑制TK的溶解.这可能是由于PAM改变钾的溶解平衡或在反应中形成有利于钾沉积的微环境,使钾更易被固定在水热炭的结构中,同时,在较高温度下,钾可与其他无机组分(如硅、铝等)发生反应,形成较为稳定的固态矿物相,导致钾更多地保留在水热炭中,减少钾离子的迁移或溶解.而PFS中的铁离子可能与钾离子在水热过程中产生竞争吸附,减少水热炭表面的吸附活性位点,使更多的钾留在液相产物中,导致PFS水热炭的钾含量低于AM水热炭.综上所述,低温条件下制备的水热炭总养分含量较高(图6(f)),有利于植株的生长,因此后续选择180AM,180PFS,180PAM进行了水稻盆钵实验.
水热炭化过程可以影响不同价态铁的相对比例,还具有促进土壤碳积累和肥力提升的潜力.从图7(a)中可以发现,AM水热炭和PAM水热炭中的铁主要以Fe(II)的形式存在,而且当水热温度从180℃升至260℃时,水热炭中的铁含量显著增加.由于PFS的添加,使PFS水热炭的铁含量明显增加,并且随着温度升高,Fe(II)占比有所增加,表明较高的温度下,Fe(III)还原为Fe(II),从而提高Fe的还原性.铁可以通过促进土壤聚集来促进土壤碳积累,Fe结合的有机碳是稳定碳的重要组成部分[45],因此对水热炭中的铁形态进行了分析.从图7(b)中可以发现,水热炭中铁大多以络合态形式存在,占38.2%~56.7%.络合态铁是指有机物质结合成络合物的铁,这种形态的铁在土壤中相对稳定,不易被氧化或沉淀,且可以增加铁在土壤中的溶解度.此外,AM经过水热炭化反应后,水热炭中的无定形Fe比例增加,无定形铁容易被植物根系吸收利用,对植物的生长和发育至关重要,且无定形铁能够吸附和固定土壤中的其他营养元素(如磷、钾等),减少养分的流失,提高土壤的肥力水平[46].温度升高,络合态氧化铁向无定型氧化铁和游离态氧化铁的转化,可能意味着水热炭在土壤调理中的功能更加显著.这种转化不仅提升了水热炭对养分的吸附和缓释能力,还增强了其对重金属的固定作用,同时有助于改善土壤结构和微生物环境,使其在农业应用中展现出更强的调理潜力.
藻泥基水热炭作为有机肥料在水稻种植中展现出提高作物生物量、氮素含量及N素利用率的潜力,可望为化肥减量施用提供新途径.如图8所示,通过显著性检验发现,与CKU相比,不同种类水热炭的施入在统计学上均未显著影响植株生物量,且HC-PAM处理显示出增加趋势,其植株总重比CKU高9.0%.HC-AM的株高(57cm)和SPAD(38.5)分别比CKU显著增加了9.2%、12.5%(P<0.05).SPAD值与植株中氮含量呈正相关[47],表明HC-AM可能增加了水稻的N素利用率,但要注意株高的显著增加可能会提高倒伏风险.由于PAM的成本较高,显著超过PFS,因此从经济性和稳定性角度综合考虑,HC-PFS是更具成本效益的选择.水稻盆钵实验的结果表明,藻泥基水热炭可以作为有机肥料部分替代化肥还田使用,在进行藻泥资源利用化的同时,可以减少化肥的投入,减少化肥使用对环境的影响.但尚需在更大实验体系和多季试验条件下进行验证.
本团队经过对太湖沿岸的藻水分离站进行实地调研,得到2015~2019年环太湖地区的年平均蓝藻打捞量(湿重)(图9(a)).每年打捞所得蓝藻经过处理后形成的藻泥通过使用水热炭化技术,基于本实验条件得到的产率,可以将这部分藻泥水热转化为1.0~1.5万t水热炭.藻泥基水热炭不仅具有良好的土壤改良潜力,同时还富含约4000t的养分,包括氮、磷、钾等多种对植物生长有益的成分.如图9(b)所示,将太湖藻泥通过HTC处理后,通过生产180AM、180PFS、180PAM水热炭每年可分别回收总氮430.6t、345.9t、549.8t.同时,藻泥基水热炭每年可回收总磷106.8 t~130.9t.环太湖入湖河流年均氮负荷为3.51万t,年均磷负荷为0.18万t(按江苏段2015~2018年均值计)[48],通过水热炭化藻泥,可回收环太湖河流1.6%入湖总氮负荷和7.3%的入湖总磷负荷(图9(c)).将获得的藻泥基水热炭作为有机肥料或土壤调理剂应用于农业生产,假设在正常施肥的基础上用藻泥水热炭替代20%氮肥,以当地推荐氮肥施用量240kg/hm2计,则这些藻泥基水热炭可为约1.1万hm2农田提供部分氮肥供应.而藻泥基水热炭对于磷肥的替代效益更为突出,按照当地96kg/hm2P2O5的稻田磷肥推荐施加量,同样假设20%的磷化肥替代率,太湖藻泥制备的水热炭可为当地约0.7万hm2农田提供磷肥.由此可见,通过对太湖沿岸的藻水分离站产生的藻泥进行水热炭化,制备水热炭产品并农田应用,可很大程度上减少传统化肥的施用,从而实现藻泥资源化利用,同时降低太湖沿岸化肥过量使用对土壤和环境的负面影响.建议未来开展藻泥基水热炭的中试生产和大田应用验证,同时对水热炭化液相产物进行系统分析和资源化潜力评估,进一步优化制备参数,并开展系统的经济环境效益综合分析,为藻泥的高值资源化利用和太湖地区农田面源污染风险减控提供有力支撑.
3.1 聚合硫酸铁通过降低pH值、增加比表面积和调控铁的化学形态,提高了水热炭中铁的还原性,促进有机质炭化.
3.2 聚丙烯酰胺在水热条件下共降解,调控了水热炭表面官能团.较低温度下制备的水热炭保留较多养分,藻泥基水热炭可替代部分化肥,显著提高株高和相对叶绿素含量.
3.3 计算表明,太湖藻泥水热炭化每年可回收TN TN549.8t和TP130.9t,表明其在藻泥资源化利用中的巨大潜力.
  • 国家重点研发计划(2024YFD1700300)
  • 江苏省自然科学基金项目(BK20221428)
  • 国家自然科学基金项目(42277332)
  • 江苏省产学研合作项目(BY20230288)
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2025年第45卷第5期
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  • 接收时间:2024-10-10
  • 首发时间:2026-03-18
  • 出版时间:2025-05-20
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  • 收稿日期:2024-10-10
基金
国家重点研发计划(2024YFD1700300)
江苏省自然科学基金项目(BK20221428)
国家自然科学基金项目(42277332)
江苏省产学研合作项目(BY20230288)
作者信息
    1.南京理工大学环境与生物工程学院,江苏 南京 210094
    2.江苏省农业科学院农业资源与环境研究所,农业农村部长江下游平原农业环境重点实验室,江苏 南京 210014
    3.南京林业大学材料科学与工程学院,江苏 南京 210037

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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