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Traditional fertilizers are prone to causing excessive nutrient levels in the soil, and nutrient loss through surface runoff, denitrification, volatilization, and leaching not only harms the environment but also affects human health. Therefore, developing fertilizers that improve nutrient utilization efficiency and reduce pollution is crucial. Slow-release fertilizers provide an effective solution to this issue by precisely controlling the release of chemical components, and biochar-based slow-release fertilizers, in particular, have attracted increasing attention due to their unique properties. Various methods to enhance fertilizer efficacy have been studied in terms of preparation and application, including co-pyrolysis, impregnation, encapsulation, and granulation, with in-depth analyses of nutrient loading and release mechanisms. In recent years, significant progress has been made in research on biochar-based slow-release fertilizers, covering aspects such as raw material selection, preparation processes, and application effectiveness. These studies have demonstrated that biochar-based slow-release fertilizers can effectively improve nutrient use efficiency and significantly reduce environmental impacts. However, challenges remain in their practical application, and further optimization of preparation processes is necessary to enable the feasibility of large-scale implementation.

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传统肥料在土壤中易造成过量养分,通过地表径流、反硝化、挥发和沥滤导致的养分损失不仅危害环境,还会影响人类健康,开发能够提高养分利用效率并减少污染的肥料显得尤为重要.缓释肥料通过精确控制肥料中化学成分的释放为解决这一困境提供了有效的解决方案,尤其是生物炭基缓释肥料因其独特的性质逐渐受到关注.在制备和应用方面,研究了多种提高肥效的方法,包括共热解、浸渍、包埋、造粒等,并对养分负载和缓释机理进行了深入分析.近年来,对生物炭基缓释肥料的研究取得了显著进展,涵盖了原料选择、制备工艺及应用效果等方面,证明其能够有效提高养分利用效率并显著减少对环境的负面影响,但在实际应用中仍面临一些挑战,需要进一步优化制备工艺,以实现其大规模推广的可行性.

, correspAuthors=程红光, authorNote=null, correspAuthorsNote=
* 责任作者,教授,
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李璐(2002-),女,安徽铜陵人,北京师范大学硕士研究生,主要研究方向为生态修复..

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李璐(2002-),女,安徽铜陵人,北京师范大学硕士研究生,主要研究方向为生态修复..

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李璐(2002-),女,安徽铜陵人,北京师范大学硕士研究生,主要研究方向为生态修复..

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Science of The Total Environment2021792:148460., articleTitle=Mitigation of methane emission in a rice paddy field amended with biochar-based slow-release fertilizer, refAbstract=null)], funds=[Fund(id=1241116663437914316, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, awardId=41771496, language=CN, fundingSource=国家自然科学基金资助项目(41771496), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241116655338713640, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, xref=null, ext=[AuthorCompanyExt(id=1241116655347102250, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, companyId=1241116655338713640, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=College of Water Sciences, Beijing Normal University, Beijing 100875, China), AuthorCompanyExt(id=1241116655401628204, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, companyId=1241116655338713640, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=北京师范大学水科学研究院,北京 100875)])], figs=[ArticleFig(id=1241116660246049780, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Fig.1, caption=Various methods for the synthesis of biochar-based SRFs, figureFileSmall=AyDlklUiMA5MHBNswPZ0iw==, figureFileBig=C+fvC76S4tsvdCz5+bJn4w==, tableContent=null), ArticleFig(id=1241116660325740544, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=图1, caption=合成生物炭基缓释肥的各种方法, figureFileSmall=AyDlklUiMA5MHBNswPZ0iw==, figureFileBig=C+fvC76S4tsvdCz5+bJn4w==, tableContent=null), ArticleFig(id=1241116660589981734, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Fig.2, caption=Schematic of the synthesis of urea-infused biochar[58], figureFileSmall=1PUBhH5oEc5aDSvMbeLUHg==, figureFileBig=iVOe+q/DpFD0Opne/sogtw==, tableContent=null), ArticleFig(id=1241116660699033654, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=图2, caption=尿素注入生物炭的示意图[58], figureFileSmall=1PUBhH5oEc5aDSvMbeLUHg==, figureFileBig=iVOe+q/DpFD0Opne/sogtw==, tableContent=null), ArticleFig(id=1241116660787114048, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Fig.3, caption=Schematic illustration of the synthetic process of CSRFs[59], figureFileSmall=xz1bjg4k2zMLwtrWVCR1iQ==, figureFileBig=aC3ExHMnA04dIxvGX7TM2w==, tableContent=null), ArticleFig(id=1241116660887777355, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=图3, caption=包膜缓释肥的制备过程[59], figureFileSmall=xz1bjg4k2zMLwtrWVCR1iQ==, figureFileBig=aC3ExHMnA04dIxvGX7TM2w==, tableContent=null), ArticleFig(id=1241116661005217884, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Fig.4, caption=TEM images of a)BSRFs and b)CSRFs[59], figureFileSmall=dgo+YC/Wzei+qUfX+tZRFQ==, figureFileBig=/EBpFfLhDrWAT3MjOCeZVg==, tableContent=null), ArticleFig(id=1241116661118464100, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=图4, caption=a)缓释肥及b)包膜缓释肥的TEM[59], figureFileSmall=dgo+YC/Wzei+qUfX+tZRFQ==, figureFileBig=/EBpFfLhDrWAT3MjOCeZVg==, tableContent=null), ArticleFig(id=1241116661244293232, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Fig.5, caption=Mode of action of slow-release fertilizers[66], figureFileSmall=YDqw5lhEE0k/iZjeyqES3w==, figureFileBig=vyFsiPKp4du0+7q3WJSxAQ==, tableContent=null), ArticleFig(id=1241116662741659769, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=图5, caption=缓释肥料的作用方式[66], figureFileSmall=YDqw5lhEE0k/iZjeyqES3w==, figureFileBig=vyFsiPKp4du0+7q3WJSxAQ==, tableContent=null), ArticleFig(id=1241116662871683208, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Table 1, caption=

Raw material for biochar

, figureFileSmall=null, figureFileBig=null, tableContent=
类型生物质应用文献
农作物废料稻草影响微生物[15]
稻壳汞固定化[16]
玉米秸秆农业应用[17]
木材废料云杉咖啡因吸附[18]
杨木地下水修复[19]
柞木水修复[20]
畜禽粪便牛粪微塑料降解[21]
鸡粪去除有机物[22]
污泥城市污泥磷的形态转化[23]
自来水厂去除有机物[24]
药用污泥沼气提纯[25]
), ArticleFig(id=1241116662963957908, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=表1, caption=

生物炭的原料

, figureFileSmall=null, figureFileBig=null, tableContent=
类型生物质应用文献
农作物废料稻草影响微生物[15]
稻壳汞固定化[16]
玉米秸秆农业应用[17]
木材废料云杉咖啡因吸附[18]
杨木地下水修复[19]
柞木水修复[20]
畜禽粪便牛粪微塑料降解[21]
鸡粪去除有机物[22]
污泥城市污泥磷的形态转化[23]
自来水厂去除有机物[24]
药用污泥沼气提纯[25]
), ArticleFig(id=1241116663106564265, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=EN, label=Table 2, caption=

Advantages and disadvantages of BSRF methods

, figureFileSmall=null, figureFileBig=null, tableContent=
类型优点缺点
共热解工艺简单,易于控制营养成分N、P元素保留性差
浸渍法易制备,资源可回收利用营养低
造粒法操作简便,减少生物炭的流失需要粘合剂
营养保留差
包膜法营养元素可一步合成涂层降解性差
材料复杂且昂贵
集成法缓释性能优异制备工艺复杂
), ArticleFig(id=1241116663219810485, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241116650024530137, language=CN, label=表2, caption=

缓释肥制备方法的优缺点

, figureFileSmall=null, figureFileBig=null, tableContent=
类型优点缺点
共热解工艺简单,易于控制营养成分N、P元素保留性差
浸渍法易制备,资源可回收利用营养低
造粒法操作简便,减少生物炭的流失需要粘合剂
营养保留差
包膜法营养元素可一步合成涂层降解性差
材料复杂且昂贵
集成法缓释性能优异制备工艺复杂
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生物炭基缓释肥制备技术与农业应用的研究进展
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李璐 , 权蔚慈 , 吴雨茜 , 龚逸伟 , 程红光 *
中国环境科学 | 环境生态 2025,45(3): 1496-1506
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中国环境科学 | 环境生态 2025, 45(3): 1496-1506
生物炭基缓释肥制备技术与农业应用的研究进展
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李璐 , 权蔚慈, 吴雨茜, 龚逸伟, 程红光*
作者信息
  • 北京师范大学水科学研究院,北京 100875
  • 李璐(2002-),女,安徽铜陵人,北京师范大学硕士研究生,主要研究方向为生态修复..

通讯作者:

* 责任作者,教授,
Research progress on biochar-based slow-release fertilizer preparation technology and agricultural application
Lu LI , Wei-ci QUAN, Yu-xi WU, Yi-wei GONG, Hong-guang CHENG*
Affiliations
  • College of Water Sciences, Beijing Normal University, Beijing 100875, China
出版时间: 2025-03-20
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传统肥料在土壤中易造成过量养分,通过地表径流、反硝化、挥发和沥滤导致的养分损失不仅危害环境,还会影响人类健康,开发能够提高养分利用效率并减少污染的肥料显得尤为重要.缓释肥料通过精确控制肥料中化学成分的释放为解决这一困境提供了有效的解决方案,尤其是生物炭基缓释肥料因其独特的性质逐渐受到关注.在制备和应用方面,研究了多种提高肥效的方法,包括共热解、浸渍、包埋、造粒等,并对养分负载和缓释机理进行了深入分析.近年来,对生物炭基缓释肥料的研究取得了显著进展,涵盖了原料选择、制备工艺及应用效果等方面,证明其能够有效提高养分利用效率并显著减少对环境的负面影响,但在实际应用中仍面临一些挑战,需要进一步优化制备工艺,以实现其大规模推广的可行性.

缓释肥  /  共热解  /  浸渍  /  造粒  /  包膜

Traditional fertilizers are prone to causing excessive nutrient levels in the soil, and nutrient loss through surface runoff, denitrification, volatilization, and leaching not only harms the environment but also affects human health. Therefore, developing fertilizers that improve nutrient utilization efficiency and reduce pollution is crucial. Slow-release fertilizers provide an effective solution to this issue by precisely controlling the release of chemical components, and biochar-based slow-release fertilizers, in particular, have attracted increasing attention due to their unique properties. Various methods to enhance fertilizer efficacy have been studied in terms of preparation and application, including co-pyrolysis, impregnation, encapsulation, and granulation, with in-depth analyses of nutrient loading and release mechanisms. In recent years, significant progress has been made in research on biochar-based slow-release fertilizers, covering aspects such as raw material selection, preparation processes, and application effectiveness. These studies have demonstrated that biochar-based slow-release fertilizers can effectively improve nutrient use efficiency and significantly reduce environmental impacts. However, challenges remain in their practical application, and further optimization of preparation processes is necessary to enable the feasibility of large-scale implementation.

slow-release fertilizer  /  co-pyrolysis  /  impregnation  /  granulation  /  coating
李璐, 权蔚慈, 吴雨茜, 龚逸伟, 程红光. 生物炭基缓释肥制备技术与农业应用的研究进展. 中国环境科学, 2025 , 45 (3) : 1496 -1506 .
Lu LI, Wei-ci QUAN, Yu-xi WU, Yi-wei GONG, Hong-guang CHENG. Research progress on biochar-based slow-release fertilizer preparation technology and agricultural application[J]. China Environmental Science, 2025 , 45 (3) : 1496 -1506 .
由于全球人口的增加,对粮食和农产品的需求大幅增加.因此,现代农业在满足粮食和农产品需求方面发挥着重要作用[1],主要用于提高农业的作物生产率[2].尿素、氮肥、磷肥和钾肥等常规化肥的消费量逐步增加,部分化肥的过度使用降低了土壤的pH值,导致重金属的加速迁移.土壤退化会影响土壤质量,造成养分枯竭、盐碱化,降低土壤持水能力,制约粮食生产[3].
为了克服传统肥料用量大且利用率低的不足,生物炭基缓释肥应运而生.缓释肥经历了近百年的演变,其发展主要针对常规化肥的高溶解性问题,通过延缓养分释放速度并与作物生育期的需求相适应,减少环境污染并提高作物产量.最早的缓释肥概念起源于1920年左右,但直到20世纪60年代,缓释肥料的应用才逐渐扩大.随着农业可持续发展的需求,缓释肥料在21世纪得到了长足发展,并在2014年至2019年期间实现了6.5%的年增长率[3].目前,缓释肥料的研发集中在通过包膜技术和改性材料实现肥料的精准释放,以应对化肥使用过度导致的土壤退化和水体污染问题.
生物炭基肥是将肥料与生物炭基质复配后所得到.与传统肥料相比,生物炭基缓释肥料释放养分的速率低,延长了植物吸收养分的有效性,并减少了养分向环境中的流失[5]尿素具有水溶性,通常会被径流冲走,前期施用的肥料无法满足植物后期发育的需求[6].施用缓释肥可以减少与尿素肥料相关的氮损失,同时提高作物产量,有助于在全球范围内保持短期和长期的氮平衡.它们不仅可以用于控制氮的释放,而且理想情况下也可以适用于其他不同营养物质的持续释放,为作物提供稳定的养分供应[7].此外,缓释肥还可以固持农药、重金属和碳氢化合物,改善土壤质量[8].
目前,尽管生物炭基肥料表现出缓释性能,但其配方、营养成分和释放机制的研究进展缓慢.养分的缓释机理仍面临局限性,生物炭基缓释肥在实际应用中的效果需要进行更多的研究.
缓释肥有天然形式和合成形式,其区别在于,由天然材料制成的缓释肥在自然分解和腐败时将养分输送到土壤中,而合成肥料在水、热、阳光或微生物的作用下才会分解[9].缓释肥料可以根据不同的属性进行分类,例如包衣类型和所涉及的释放机制[10].根据以往的研究,缓释肥大致可以分为有机和无机两种形式[11].
常用的低溶解度无机缓释肥由标准式MeNH4PO4·xH2O化合物组成.其中“Me”代表铁、锌、镁或锰等金属的阳离子.这类无机材料有金属基磷酸铵,如磷酸铵镁(MgNH4PO4)、磷酸铵钾(KNH4PO4)和酸化磷矿.此外,部分酸化的磷矿石,也是一种低溶解度的磷酸盐,可以认为是一种缓释磷肥,主要用于微酸性或轻质地土壤.
有机缓释肥可以进一步分为两大类:天然和合成.有机天然缓释肥是植物和动物肥料(牛、鸡、家禽)、作物覆盖、堆肥、籽粉等[12].在将营养物质释放到土壤中之前,微生物会将其分解.缓释肥释放的养分量取决于土壤的微生物活性,而微生物活性受土壤含水量和温度的影响.因此,天然有机缓释肥通常需要比较长的时间来将营养物质释放至土壤中,而这些营养物质可能在植物最需要它们的时候无法获得.
有机合成缓释肥料通常制成颗粒状.土壤湿度、温度和微生物的活性决定了养分释放的速度[13].对于合成肥料,养分释放的周期从20d到18个月不等.合成有机肥分为基质型、无包膜型和包膜型三种.
在基质缓释肥中,活性成分,即营养成分,分散在由各种材料组成的基质中.活性成分通过载体孔隙、特别是表面微孔扩散至生长介质中.无包膜型的缓释肥由微小颗粒组成,在有或没有黏结剂的情况下烧结,主要用于维护绿地.与包膜肥料不同,它们的释放速率与覆盖层的厚度无关[14].包膜缓释肥不仅具有缓释特性,而且在某些特殊情况下也具有良好的释放特性.根据应用、要释放的营养物质的类型和营养物质的目标释放速率,可使用不同的包膜材料.
生物炭基肥主要由生物炭和肥料复配而来,部分生产工艺还会用到黏结剂.缓释肥的特性取决于营养元素组成、生物炭来源和制备方法.
生物炭是在缺氧或厌氧环境下制备的一种材料,可以作为一种载体,结合肥料中的养分,对土壤进行改良并提高原料利用率.其对营养物质具有很高的亲和力,包括水和土壤中的N和P.土壤施用生物炭增强了养分的缓释效应,在一定程度上可减轻常规肥料过量施用带来的环境负担.
生物炭的性质由原料决定.目前,丰富的生物质原料包括木材废料、植物废料、动物粪便、污水污泥和小球藻等,如表1所示.
从玉米芯和稻壳等作物残渣中生产的生物炭的氮和磷的含量往往较低[26].含有纤维素和木质素的木材废料可以通过腐败降解成小分子,为土壤提供有机质[27].与草炭或木炭相比,由粪便或家禽粪便制备的生物炭含有丰富的营养,N和P含量和pH值通常更高,比表面积也比从木材等高纤维素原料获得的生物炭更高[28].污泥中含有氮、硫等无机元素,由其制备的生物炭可显著改善土壤孔隙度[29].Kannari等[30]从食物垃圾产生的消化污泥中生产富钙生物炭.除了常见的废弃物,一些藻类或者菌类生物也可作为生物质原料.海藻生物炭含有大量的钾和氮.Chang等[31]以小球藻为基础的微藻残渣在400℃处理时产生的生物炭含有很高的N含量(>10%),其值随着温度的升高而下降.
与原料相比,生物质中的营养物质含量增加,因为热解过程中的浓缩作用造成了质量损失[32].尽管生物质有很大一部分在生物质炭生产过程中损失,但仍富含营养物质[33].由各种类型的生物质产生的生物炭含有腐殖质、生物可利用的氮、磷或钾等营养元.根据土壤的实际需求,选择合适的生物质原料制备生物炭,可有效提高土壤肥力[34].
除了生物炭,肥料和黏结剂也是缓释肥的重要原料之一.生物炭作为一种载体,结合肥料中的养分承担缓释养分、改良土壤和提高肥料利用率的作用,肥料承担补充养分、促进作物生产的作用.黏结剂是提高生物炭基肥机械强度的主要材料,影响生物炭基肥产品缓释、力学性能与成型效果,但具有一定的副作用,例如膨润土等天然矿物质,可增强生物炭基肥的物理强度和成型效果.但是黏结剂在高浓度使用时,可能影响肥料的缓释特性,阻碍养分的有效释放.
常规肥料大多是通过物理或化学合成制备,含有氮、磷、钾等养分,易溶于水、养分释放速度快且利用率低,如尿素、磷酸盐等.从生物质原料直接热化学处理获得的原始生物炭含有丰富的功能基团和高密度的微孔结构,有助于养分的吸附与释放,但缺乏作为肥料的营养物质.生物炭的优良性质为合成生物炭基缓释肥提供了良好的平台.共裂解[35]、浸渍[36]、造粒[37]、包膜[38]等已被广泛应用于生物炭基缓释肥的合成中,具体制备过程如图1所示.
生物质和化肥共热解是一种操作简单的生物可再生燃料的生产方法.通过物理吸附和化学键合的方式将营养物质负载到生物质中.共热解具有合成简单、营养负荷高等显著优点.
Liu等[39]采用微波共热解法,以棉秆为原料,添加K3PO4和MgO制备了缓释肥.研究发现,合成的高炉矿渣具有多层次的营养结构,包括水溶性磷、沉淀态磷和有机磷.此外,添加氧化镁还改善了高炉矿渣的孔结构和Zeta电位.Karim等[40]利用香蕉梗(700℃)与富磷废水污泥共热解得到缓释肥.结果表明,经过热解后,生物有效磷的含量由出水污泥的600mg/kg增加到5600mg/kg生物炭.由此种方式生产出的富含钾和磷的缓释肥,同样可用于非粮食作物的肥料和退化土壤的复垦.Carneiro等[41]将咖啡壳和家禽垫料与浓磷酸、氧化镁充分混合后,加水润湿样品,静置16h.在60℃下干燥后,在500℃下热解2h,咖啡壳中磷含量为201mg/g,家禽垫料中的磷浓度为178%.
共热解法工艺简单,易于控制营养成分,但是缓释肥所需的N、P元素的保留性较差,肥料效果有待提升.
浸渍法以生物质为载体,采用固/液/气吸附的方法与不同的肥料进行复合,生物质通过浸泡在液体肥料中获得养分的,可以重复利用水体中的营养物质.与原始生物质相比,浸渍法制备的生物炭能够提高对营养物质的吸附亲和力.通过生物炭浸渍回收废水中的营养物质,既减少了富营养化等废水对环境的污染,又充分利用了排放的营养物质,具有良好的应用前景[42].
但是浸渍法受到了原始生物炭对营养物的低吸附能力的显著限制.为了满足实际应用,人们开发了各种材料对生物炭进行改性,如氧化镁、K2O、膨润土和煤矸石等,以提高吸附能力[43].An等[44]发现番茄组织制备的生物炭可以有效地从水溶液中回收磷酸盐,其最大吸附容量超过100mg/g.氧化镁改性生物炭可显著增强废水中磷酸盐和铵的吸附[45].玉米秸秆为原料制备的富镁生物炭对沼气废水中的营养物质具有良好的回收效果.富镁生物炭的氮、磷累积释放比化肥低7倍和6倍.施用生物炭显著促进了玉米的养分吸收和生长,具有广阔的农业应用潜力[46].
在浸渍技术中,通过将生物炭浸入液体肥料中,随后干燥富含营养物的生物炭,将营养物添加到生物炭基质中.Lateef等[47]过将生物炭混合到大量营养素和微量营养素溶液中制备了生物炭基肥料.制备步骤包括将生物炭浸入肥料溶液中几个小时以允许最大吸收,和干燥养分浸渍的生物炭.
浸渍法具有操作简单、成本低等独特优点,在营养液中浸渍原始生物炭可以有效提高营养成分含量,从而延长了植物在生物炭中的养分有效性.但生物炭的吸附能力限制了缓释肥料的肥效.生物炭的改性可以提高对营养物质的吸附能力,多孔结构和大表面积为养分储存提供了容器和场所,但要考虑到改性过程的成本.化学改性常需酸、碱或金属氧化物等试剂,会增加材料费用.其次,改性工艺如高温处理、化学反应等,需要额外能源和设备,导致生产成本上升.
由于生物炭具有脆性、密度低、颗粒细小等特点,其在土壤中的储存和运输具有很高的挑战性.混合造粒是生物质炭与肥料混合的过程.混合物被粉碎成均匀的粉末颗粒,通过机械挤压或圆盘造粒机进行造粒[48].将生物炭与化肥按一定比例混合制成缓释肥料,常见比例为1:1~1:3.通过控制营养元素的比例,可以制备出一定形状的营养因子.此外,还可以添加黏土、金属氧化物和有机物,以适应农业应用[49].
富含营养素的生物炭通常为粉末形式,据报道,约30%的生物炭因强风吹散而损失,20%的生物炭粉末在施用于田地时因密集降雨而损失[50].小的生物炭会刺激人类的眼睛、皮肤和呼吸系统.利用造粒工艺可以减轻当施用到土壤中时富含营养物的生物炭的损失,由于生物炭具有疏水性,黏结剂常被用于辅助制粒和粒化过程[51].
Gwenzi等[52]过将锯末生物炭作为载体,淀粉-PVA作为黏结剂浸渍在NPK溶液中,开发了一种生物炭基肥料.然后将营养物浸渍的生物炭造粒以形成生物炭颗粒.
生物炭和营养素混合物的造粒通过增加扩散阻力有效地降低了养分的释放,是减少生物炭损失和土壤施用处理成本的有效选择,可以实现了在农业实践中的实际大规模应用.
包膜是将肥料包裹在无机或有机基质内,以减少养分损失,提高养分利用效率.采用膜覆法,将无机或有机疏水材料包覆在化肥颗粒上,制备出生物活性缓释肥料[52].疏水材料作为扩散屏障,减少营养损失.硫磺、沸石、石膏、白云石、硅藻土和膨润土通常用作缓释肥料配方中的包衣材料[53].然而,使用聚合物等材料制备缓释肥可能会导致农业系统的二次污染.涂层聚合物的积累会恶化土壤结构,抑制土壤养分循环,抑制微生物活动[54].因此,生物炭基涂层材料被引入到制备生物可再生肥料的原材料中.Chen等[55]以生物炭(玉米秸秆、稻草、森林凋落物为原料制备)和水性共聚物为包衣材料,对尿素进行包衣,制成缓释肥料.Jia等[56]研究了以醋炭、树脂、石蜡为包衣材料制备缓释肥料的效果,包膜完的缓释肥疏水性增加,水溶性降低.除此之外,他们还以稻草、醋液、毛竹为原料,选择生物炭和2种保护层(树脂,树脂及石蜡的组合)作为尿素颗粒的包衣材料,制备生物炭包膜尿素缓释肥[57].
包埋过程是复杂的,包括生物炭与营养物质的浸渍、不同组分(生物炭、矿物、黏结剂等)的混合和造粒.复杂而昂贵的封装工艺明显限制了包膜缓释肥在农业中的使用.在养分释放后,由于降解性差,包衣材料仍留在土壤中,导致潜在的环境威胁.绿色、可生物降解和廉价的包膜材料是未来的发展方向,有助于减少对环境的影响和促进可持续农业.绿色包膜材料避免了传统合成聚合物的微塑料污染和生态损害,同时提升了肥料的养分利用率,降低了养分流失及水体污染风险.
每种方法在制备生物炭基缓释肥方面都有不同的特点.共热解易于控制养分负荷,但高度依赖于N和P源.浸渍法由于原始生物炭对营养物质的吸附能力较低,通常需要对其进行改性,从而增加了工艺成本,但是可以考虑利用浸渍法从废水中回收营养物质.造粒在减少生物炭的损失和实际农业实践的处理成本方面是有效的,并且它通常与制造有效的生物炭基缓释肥的其他方法相结合.包膜法可以将营养物质包覆在生物炭上,对营养物质的缓释非常有利;但是复合的和昂贵的封装工艺限制了包膜肥料的应用.尽管通过单一方法制备的生物炭基肥料已被广泛证明是有前途的缓释肥料,但仍迫切需要进一步改进其缓释性能.考虑到低成本、易操作、高效率、环保等多重要求,很难找到一种满足所有应用的通用工艺.目前,集成方法获得了越来越多的研究兴趣.
集成法是指将缓释肥料的制备技术与其他多种材料或工艺(如聚合物涂层、生物材料、无机材料等)相结合,以控制肥料中养分的释放速度和方式的技术.这种方法通过集成不同的技术手段,优化肥料的施用效率,使养分缓慢、持续地释放,以满足作物在不同生长阶段的需求,减少肥料流失和对环境的负面影响.
Bakshi等[58]采用一体化工艺制备生物炭基缓释肥料,在500℃下通过快速裂解获得的松木生物炭与H3PO4溶液混合.在85℃下摇匀24h,充分干燥后,在N2和465℃下碳化2h.将活性生物炭与尿素的混合物磨碎,在137℃下加热,将尿素注入生物炭的孔隙中.以木质素磺酸钙溶液和液化石蜡为黏结剂,对输注尿素的生物炭进行造粒.制备过程如图2所示.
FTIR等分析显示,尿素通过尿素胺N和羰基C=O键接枝到生物炭上.生物炭基肥料具有优异的缓释效果,尿素缓释速度慢(4320min释放61%~90%),氮损失量低(68%~71%),NH3-N挥发量小(0.2%~0.9%).基于此开发的肥料有效地减少了土壤中N的流失,为植物提供了长期的NH4+-N供应.
An[59]利用耦合包膜与共热解技术制备包膜生物炭基缓释肥.先将棉花秸秆洗涤,用粉碎机粉碎,筛分,将棉花秸秆、Mg3(PO4)2和膨润土混合均匀,随后,将获得的样品转移到管式炉中,在500℃下热解2h得到缓释肥,粒径小于0.15mm.随后制备高疏水性乳状液,将1.0g的混合物转入挤出机,并保持恒定压力(0.8MPa),逐渐挤出至CaCl2液中,并不断搅拌,所产生的颗粒过滤,干燥,即可制备包膜生物炭基缓释肥.制备过程如图3所示.
图4a可见,缓释肥肥料颗粒(颜色较深的层),大部分颗粒在缓释肥内有规律的排列.由图4b可见,包膜缓释肥薄膜的典型结构特征,其中缓释肥在膜层结构中呈不规则排列,说明涂层材料在涂覆过程中可能会分散.
结果表明,在棉秆、Mg3(PO4)2和膨润土共热解生物炭基缓释肥料表面涂覆涂层可以显着改善其缓释性能.30d内缓释肥的P累积释放浓度为1.98g/L,而包膜缓释肥的P最大累积释放浓度仅为0.82g/L.P释放速率常数仅为缓释肥的一半左右.此外,包膜缓释肥还表现出优异的降解性.盆栽实验表明,施用包膜缓释肥施肥的辣椒幼苗长势更好,根长、鲜重和干重均明显高于未包膜缓释肥施肥的辣椒幼苗.
综上所述,不同类型的制备方法的优缺点如表2所示,虽然存在制备工艺简单等优点,但也存在一定缺陷;组合工艺制备缓释肥具有运行效果稳定,处理成本低的特点,是缓释肥制备的发展方向.在充分考虑经济性、可靠性和效率的基础上,应探索和开发新型组合工艺,发挥不同技术的协同作用,以期取得更好的施肥效果,满足农业可持续发展的需求.通过组合工艺,可以利用廉价原材料,如农业废弃物制成的生物炭和天然可降解涂层(如淀粉、蛋白质等)来降低生产成本.不同工艺的组合可提高缓释肥的性能稳定性.
养分释放机制是精准农业理念的一部分,它减少了经淋溶、挥发和地表径流损失的问题.常规肥料的养分释放机理包括物理、化学和生物过程.水分使肥料颗粒溶解,释放养分;养分与土壤成分反应,影响其有效性;土壤微生物分解有机物,转化养分为植物可吸收的形式.这些过程相互作用,决定了养分的释放速率和可利用性[60].缓释肥由于具有大的比表面积、多孔的微观结构和丰富的表面基团,可以通过络合、物理吸附、沉淀、静电吸引和离子交换等方式吸附无机元素.有机元素通过氢键、表面络合、孔隙填充和静电作用而固化.与传统肥料相比,生物炭基缓释肥中的无机和有机元素缓慢释放,提高了养分利用效率.目前已有一级释放动力学模型、Higuchi模型、Hixson-Crowell模型、Baker-Lansdale模型、抛物线扩散模型、Elovich模型和Korsmeyer-Peppas模型等数学模型用于研究生物炭基肥料的释放动力学和释放机理[61].
Shaviv等[62]提出了包膜肥料释放养分的详细概念模型.该模型识别出养分释放的三个不同阶段,如式(1)所述:
式中:r为颗粒半径;I为包覆厚度;gt时刻养分的释放量;Ps为溶质渗透率;A为颗粒表面积(考虑为球体);Csat为溶质或养分的饱和浓度;Q为颗粒中储存的肥料的总质量;t′为滞后期;t*为线性释放的持续时间;ρs为包膜材料的密度.
式(1)所阐述的3个阶段如下:
1.滞后期:将空隙填充到颗粒内的阈值水量所需的时间可称为滞后期.肥料颗粒的固体核与周围之间的蒸汽压力梯度产生驱动力,帮助水蒸气穿过膜涂层,占据核和涂层内部存在的空隙.在此之前很少或根本没有肥料释放.
2.线性释放的持续时期:在颗粒内达到饱和溶液的阈值体积后,养分不断地从肥料颗粒中释放出来.颗粒外的肥料运输是由内部饱和溶液和外部溶液中相对可忽略的浓度之间的恒定浓度梯度驱动的.在颗粒内保持饱和浓度,同时与未溶解的固体肥料保持平衡.只要保持饱和浓度,肥料中养分的释放速度就保持不变.
3.衰变阶段:在所有的肥料被溶解后,没有溶解的肥料和水不断进入核心,内部的浓度逐渐下降,肥料中营养物质向外部溶液的释放速度降低.
在最近由An等[63]进行的一项研究中,共裂解法制备的棉花秸秆/膨润土/K3PO4生物炭基肥料最符合Higuchi模型.研究表明,复合肥中磷、钾的释放应以扩散机制为主.另一项由An等[64]进行的研究发现棉花秸秆/磷酸三镁/膨润土生物炭基肥料符合Higuchi模型,磷的释放机制为溶解扩散机制.Hixson-Crowell模型较好地描述了包膜生物炭肥的磷素释放,其释放机制以肥料通过包膜材料的扩散为主,而不是以溶解为主.Wen[65]指出,合成生物炭基肥料的初始养分释放率高,是由于快速扩散和冲刷.平衡后,养分的释放一般较慢,可能受溶质从多孔固体生物炭相向水相扩散的影响.
缓释肥的作用方式如图5所示.缓释肥使养分逐渐释放,长期供应养分,避免淋失,提高肥料效率,减少对环境的潜在威胁.同时,利用生物炭吸附污染物已被广泛研究,并有报道对其吸附机制进行了深入讨论[66].生物炭对污染物的吸附与污染物和生物炭的性质密切相关.生物炭作为养分载体,由于其高表面积和多孔微观结构、有利的表面电荷、丰富的表面基团和活性碳,降低了养分的释放速率,提高了养分利用效率[67].
通过探究生物炭基缓释肥的基本特性和养分负荷机理,可以进一步提高其性能,有助于评估肥料在不同环境下的发展及应用前景.
土壤中的环境条件,包括温度、土壤条件、微生物种群和包膜厚度,都对缓释肥的养分释放有影响.下面对影响缓释肥料的因素进行讨论.
根据各种研究,温度是影响缓释肥释放其营养成分的重要因素[68].当土壤温度升高5~10℃时,土壤中影响缓释肥氮释放速率的微生物活性增加,导致养分释放速率增加[69].温度升高导致土壤内蒸汽压升高.在缓释肥释放养分的初始阶段,土壤中形成的水蒸气扩散到被涂覆的缓释肥中.一旦水蒸气凝结,缓释肥内的静水压力就会上升.由于缓释肥内强大的静水压力,营养液的释放加速,导致营养液大量流出[70].
研究表明,土壤的pH值不直接影响缓释肥的性能,而是影响微生物的数量和生长微生物的活动[71].细菌产生的酶是降解可生物降解缓释肥释放的营养物质所必需的,每种酶都有独特的pH值要求.一般当pH值低于3或高于10时,酶就不能有效地发挥作用.对于某些类型的肥料,如硫包覆尿素基肥料,较低的土壤pH值创造了有利于养分逐渐释放的环境[72].
其次是土壤质地,土壤砂、粉土和黏土颗粒的相对比例决定土壤质地.土壤质地通过影响土壤特性,例如保墒能力和温度,从而影响物质的养分释放速率,其本身不能影响养分释放速率[73].
影响从生物炭基缓释肥中释放养分的主要因素是土壤中的微生物种群.微生物在缓释肥的包衣表面形成菌落,然后分泌各种水解酶,分解包衣并释放营养物[74].土壤中的温度、pH值、湿度和其他环境因素,以及微生物的数量和活动,都有一定的作用[75].土壤的高温和高水分含量是微生物活动和发育的理想条件,有助于加快了包膜表面的代谢.
生物炭基缓释肥的包膜厚度在控制养分释放率方面起着重要作用.缓释肥核心周围的膜或涂层是营养物质在浓度梯度下扩散的屏障,根据菲克定律,跨越屏障的扩散速率与膜的厚度成反比[76].因此,涂层厚度的增加可以延长营养物质释放的滞后期,减缓营养物质的释放速度[77].当亲水性聚合物包膜肥料浸没在水中时,水在吸收过程中通过聚合物包膜而膨胀.当水穿过聚合物大分子之间的动态间隙时,缓释肥核心的营养物质会被水迅速溶解.
缓释肥的生产成本高于传统肥料,但它们的单一施用量部分弥补了这一成本.根据国际化肥工业协会(IFA)的一份报告,缓释肥的价格远远高于传统合成肥料的价格,甚至高出4~12倍[78].常规肥料每吨的价格范围因肥料种类和市场波动而异,一般在250~600美元.生物炭每吨的成本范围为80到1300美元[80],具体价格取决于所使用的生物质类型和处理方式.其中,稻壳、玉米秸秆等农作物废弃物被广泛用于生物炭的制备,这些生物质的来源相对较廉价,但其加工过程仍然需要大量的能源消耗,特别是在高温热解过程中.此外,后续的混合造粒和涂层过程(如将肥料颗粒包覆上有机或无机物质,以延长养分释放时间)也增加了生产成本.
虽然缓释肥的初期购买和生产成本高于常规化肥,但其长期使用可以减少总肥料的使用量,从而降低整体的施肥成本.此外,缓释肥能够通过改善肥料的利用效率来提高作物产量,从而增加经济收益.例如,研究表明,缓释肥能够提高45%的磷利用率,大大降低了施肥次数[81].由于目前能源成本上升和农业劳动力短缺的趋势,缓释肥将更具吸引力.
用于生产缓释肥的一些涂层材料不能生物降解,可能对土壤生物有毒[82].此外,缓释肥可降低土壤pH值,在大多数情况下,这是一个对植物生长和发育产生不利影响的过程.土壤酸化对养分供应造成干扰,从而导致例如钙和镁的缺乏[83].
在低温下,缓释肥可能是不充分的营养来源.当温度低于10℃时,肥料中的养分释放停止,而当温度高于32℃时,肥料中的养分释放过多.使用以生物碳为基础的化肥也可能带来环境风险[84].多环芳烃、挥发性有机化合物或重金属等有毒物质可从生物炭基质中释放出来,影响生物有机体.生物炭的毒性作用与生产所用的材料和热解温度有关.高pH值和高盐度也可能是观察到的毒性效应的原因[85].
生物炭基缓释肥的应用可以通过减少温室气体排放、固碳和改善土壤养分保留来缓解土壤退化和气候变化[86].Zhang等[87]报道,在中国旱作玉米田施用生物炭基缓释肥后,作物产量比常规肥料提高20%以上,N2O排放量减少30%以上.Fidel等[88]评估了生物炭改性土壤减少温室气体排放的潜力.在玉米生长的整个季节,生物炭可减少27%的土壤CO2排放,并且在连作系统中观察到NO2的减少.Dong等[89]发现,在水稻生长季节,添加生物炭基缓释肥可显著减少33.4%的CH4排放,这归因于缓释肥料中的N和土壤中速效钾的不同种类.应进一步研究与生物炭基缓释肥应用相关的温室气体排放的长期评估.
生物炭基缓释肥的发展旨在提高肥料利用效率,减少养分流失到环境中.为了提高营养物含量,通常会对生物炭进行改性,以提高吸附能力或营养物附着力.从生物质原料、制备方法、缓释模型、作用机理、成本与效益等方面进行了综述,为促进农业废弃物资源化利用提供参考.应用生物炭基缓释肥是促进可持续农业的一种可行方式.
(1)制备:生物质炭是一种重要的肥料,越来越复杂的工艺被用于制备高效的缓释肥.其肥效的提高主要通过共热解、浸渍、造粒和包膜等方法来实现,但每种制备方法都各有利弊.此外,目前的研究主要集中在提高肥效和降低养分释放上,但如何精确控制养分释放满足作物生长的要求,还需要在未来的工作中付出更多的努力.生物炭基缓释肥要求具有以下特点:①生产成本低,制造工艺简单;②环境友好;③营养物质缓释性能好,作物生长生物利用度高.因此,寻找一种合成符合这些要求的生物炭基缓释肥的策略,仍然是未来研究的当务之急.
(2)缓释机理:深入了解养分缓释机理对于肥料的合成和实际应用有重要意义.虽然对营养负荷机制的研究取得了进展,但对生物炭基缓释肥中营养物质的缓释机制仍缺乏深入的了解.营养屏障或化学反应也影响了生物炭对营养物质的吸收,应对生物炭基缓释肥的养分释放进行定量评价.可以在水或溶液介质中测定养分释放,也可以采用土壤或沙子中的柱淋失来检验养分的淋失.不同条件下的释放动力学提供了对养分捕获和淋失与生物利用度之间的关联性.此外,揭示养分与土壤环境之间的相互作用也是探明养分缓释机制的关键步骤.
(3)成本与效益:需要对缓释肥的经济效益进行更精确的评估.评估应该在不同缓释肥施用环境下进行,包括成本/效益比分析,以提供与传统肥料更合理的比较.此外,应将缓释肥料与复杂的农艺技术,以及农业实践相结合,以实现农艺效益和环境效益的最佳耦合.
(4)农业应用的研究进展:生物炭基缓释肥凭借其高比表面积和多孔结构,生物炭有可以有效吸附并缓释养分,提高养分利用率并减少流失,从而增强作物吸收和产量.使用缓释肥可减少肥料施用量和农业成本,同时改善土壤结构和水分保持,缓解酸化与盐渍化问题,吸附重金属,降低其毒性影响,有利于作物生长.其碳封存能力有助于减缓温室气体排放,推动农业可持续发展.未来研究聚焦于提升缓释性能和开发环保包膜材料,推动生物炭基缓释肥更广泛应用.
  • 国家自然科学基金资助项目(41771496)
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2025年第45卷第3期
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  • 接收时间:2024-08-30
  • 首发时间:2026-03-18
  • 出版时间:2025-03-20
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  • 收稿日期:2024-08-30
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国家自然科学基金资助项目(41771496)
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    北京师范大学水科学研究院,北京 100875

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2种不同金属材料的力学参数

Family
属数
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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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