CN111495318B - 氨基嫁接改造专用猪粪炭、制备方法及其在农田退水氮回用方面的应用 - Google Patents
氨基嫁接改造专用猪粪炭、制备方法及其在农田退水氮回用方面的应用 Download PDFInfo
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Abstract
本发明涉及一种炭基肥的制备方法,特别涉及一种以氨基嫁接改造专用猪粪炭、制备方法及其在农田退水氮回用方面的应用。一种氨基嫁接改造专用猪粪炭的制备方法,该方法包括以下步骤:1)原料干燥:将原料猪粪脱水至含水率80%‑85%后依次进行酸洗、干燥、粉碎制得干猪粪粉;2)液氮预处理与高温炭化,制得膨胀型猪粪炭;3)羧基化处理得到羧基化猪粪炭;4)氨基嫁接:将步骤3)制得的羧基化猪粪炭加入氨水流体,200‑240℃油浴加热条件下搅拌20‑24h,冷却至室温后,将反应产物洗涤过滤,用N2吹干后将产物置于110±5℃条件下真空烘干12‑24h,研磨后得到氨基嫁接改造专用猪粪炭。
Description
技术领域
本发明涉及一种炭基肥的制备方法,特别涉及一种以氨基嫁接改造专用猪粪炭、制备方法及其在农田退水氮回用方面的应用,属于废弃物综合利用和农田氮磷面源污染防控领域。
背景技术
生物质炭材料因其具有多孔特性、巨大的比表面积以及在土壤改良调理、保水保肥等方面表现出优异的性能,因而在环境中的多个领域得到广泛应用。新时期农业技术的迅速发展导致种植业化肥、农药等要素的过量施用以及养殖业畜禽粪便的乱排乱放,超过了农田的养分负荷,过剩的氮素通过地表径流等途径而造成地下水污染,水体富营养化等问题。近年来,我国因化肥施用引致的总氮排放增加到600多万吨,总磷排放增加到50多万吨。农业退水氮超标不仅严重破坏水域景观,同时也导致生态***的失衡,以至于危害人类安全和发展。因此,减少土壤中氮流失、消减农田退水中氮污染以及畜禽粪便的资源利用对于控制农业面源污染十分重要,亟需研发一种定向高效吸附氮素的生物质炭材料,作为氮肥提升作物产量兼具土壤改良修复的作用。
生物质炭具有发达的孔隙结构、丰富的含氧官能团、稳定的芳香化结构,应用于土壤改良,能改善土壤孔隙度,增加土壤持水度,调节土壤pH等,更重要的是生物炭原料成本低廉且易再生。近年来,我国畜禽粪便产生量已经由2011年的21.21亿吨增加到28.75亿吨,预计到2023年将达到37.43亿吨。大量的禽畜粪便未得到及时有效的处理和利用,已严重制约我国禽畜养殖业持续高效发展。据全国第一次污染源普查数据显示,禽畜粪便已与工业源、生活源成为水污染的三大主要来源。因此,亟需寻找一种合适的方法对其进行资源化利用。
发明内容
本发明的目的在于提供一种氨基嫁接改造专用猪粪炭的制备方法,具有高的比表面积和孔隙、丰富稳定的含氨官能团,显著提升农田退水氮污染的吸附消减性能。
本发明还提供所述制备方法得到的氨基嫁接改造专用猪粪炭。
本发明解决其技术问题所采用的技术方案是:
一种氨基嫁接改造专用猪粪炭的制备方法,该方法包括以下步骤:
1)原料干燥:将原料猪粪脱水至含水率80%-85%后依次进行酸洗、干燥、粉碎制得干猪粪粉;
2)液氮预处理与高温炭化:将步骤1)制得的干猪粪粉进行液氮密闭处理,搅拌30-60min,加入无水乙醇快速挥发,随后过滤、洗涤、干燥,将烘干后的产物进行600-800℃的高温煅烧炭化,并通入纯度为98.99%-99.99%的高纯氮气,炭化处理后的产物经洗涤后于100±5℃的条件下真空烘干12-24h,制得膨胀型猪粪炭;
3)羧基化处理:将步骤2)制得的膨胀型猪粪炭采用超声分散于质量浓度为65%-68%的浓硝酸中,随后在微波辅助下搅拌4-6h,将产物洗涤、过滤、干燥得到羧基化猪粪炭;
4)氨基嫁接:将步骤3)制得的羧基化猪粪炭加入氨水流体,200-240℃油浴加热条件下搅拌20-24h,冷却至室温后,将反应产物洗涤过滤,用N2吹干后将产物置于110±5℃条件下真空烘干12-24h,研磨后得到氨基嫁接改造专用猪粪炭。
猪粪炭本身具有优良的性能,同时掺氮可以改善材料的浸润性、生物兼容性和导电性。氨基的嫁接保证了氨基的嫁接率,使材料具有较高的反应活性,进一步提高对水体中氮素的吸附性能,以便再次作为氮肥施于农田,兼具“以废治废”的废物资源化特点且成本低廉。
肥料中的氮主要有三种存在形式:铵态氮、硝态氮、尿素氮(或酰胺态氮)。其中,铵态氮和硝态氮是植物可以大量吸收的氮,铵态氮是还原态,为阳离子,硝态氮是氧化态,为阴离子。利用氨基嫁接猪粪炭可以吸附大量的铵态氮,而掺氮可以提高对阴离子的吸附,即该材料可通过化学反应和静电作用吸附大部分氮素,实现氮肥的重复利用。
本发明以废弃物猪粪为原料,通过液氮预处理、高温炭化和氨基嫁接等技术制备出氨基嫁接技术改造猪粪炭,可用来消减农田退水氮污染,并且农田回用。
作为优选,步骤1)中酸洗、干燥、粉碎为采用1-2mol/L的H3PO4或HNO3浸渍,搅拌器慢搅3-5h,转速为100-200r/min,快搅1-2h,转速为500-600r/min,烘箱85-110℃干燥12-24h后,粉碎至粒径<0.1mm。
作为优选,步骤2)中干猪粪粉与液氮的重量比为2:1-1.5,搅拌转速为200-400rpm;
乙醇分2-3次添加,每次添加时间间隔为1.5-2.5min,每次添加量与干猪粪粉的重量比为2:0.8-1.5,随后用水洗涤过滤。
作为优选,步骤2)中高温煅烧炭化在高温管式炉中进行,通入高纯氮气的流速为400-650mL/min,洗涤条件为无水乙醇和水交替洗涤,直至溶液pH呈中性。
作为优选,步骤3)中膨胀型猪粪炭采用超声分散于浓硝酸中,超声频率为40kHz,超声时间为0.5-2h。采用微波加热炉,在功率为200-300W条件下进行加热搅拌,搅拌转速为300-600r/min。洗涤条件为无水乙醇和水交替洗涤,直至溶液pH呈中性,随后在85-100℃下真空干燥。
作为优选,步骤4)中所述氨水流体为在温度320℃、压强10MPa条件下制得的氨水超临界流体,其浓度为2-3mol/L;
羧基化猪粪炭与氨水超临界流体的重量比为2:2-3,通入氮气的流速为300-600mL/min。用无水乙醇和水交替洗涤,直至溶液pH呈中性。
作为优选,步骤2)中掺氮含量为5-10%,步骤4)中氨基嫁接掺杂的氨基含量为10-15wt%。
步骤二中液氮处理是进行氮掺杂;步骤三中浓硝酸进行羧基化处理,增强碳材料表面的反应活性;步骤四中用氨水超临界流体是进行氨基嫁接。本发明方法中,氮掺杂是为了提高碳材料表面的电子密度,降低碳材料与氮之间的吸附能,提高吸附效率;氨基嫁接过程中氨基是吸附氮的功能基团。
一种采用本发明所述的方法制得的氨基嫁接改造专用猪粪炭,所述的氨基嫁接改造专用猪粪炭中,氨基含量为10-15wt%,掺氮含量为5-10%,比表面积为110-130m2/g。
一种所述的氨基嫁接改造专用猪粪炭在农田退水氮污染消减与回用方面的应用。
作为优选,农田退水进入猪粪炭高效吸附反应器,高效吸附反应器由三个依次连接的反应池组成,第一个反应池进行快速吸附,底部设有涡轮式搅拌器,转速300-600r/min,池中投入氨基嫁接改造专用猪粪炭,材料投加体积与反应器的体积比为1:15-20,反应池出水均通过底部的孔隙隔离网;第二个反应池进行截留吸附,截留猪粪炭的同时,底部也设有涡轮式搅拌器进行搅拌,待氨基嫁接改造专用猪粪炭充分吸附水体中的氮污染至超吸附平衡后,进入第三个反应池——斜板沉淀池,反应后收集沉淀物,晾干或烘干后得到缓释型炭基氮肥。
将吸附氮饱和的专用猪粪炭回收,得到缓释型炭基氮肥,应用于土壤肥力提升和改良,该缓释型炭基氮肥的施用比例为3-5wt%。
施用缓释型炭基氮肥时,测定含氮量,依据当地土壤的理化性质确定最佳施用量,在作物行间开沟,将此肥料施入其中覆土。
与现有技术相比,本发明具有以下有益效果:
1)本发明所述的氨基嫁接改造专用猪粪炭,具有高的比表面积和孔隙、丰富稳定的含氨官能团;
2)本发明所述的氨基嫁接改造专用猪粪炭,用于消减农田退水氮污染,性能高效稳定,经济环保,回收能源高,易于应用,适合于农田退水处理工程化应用或现有工程改良;
3)本发明的原料来自于废弃物猪粪,属于“以废治废”和可持续发展的制备技术,有效解决了猪粪的高附加值利用问题,具有良好的经济和环境效益;
4)吸附超饱和的专用猪粪炭作为缓释型炭基氮肥还田,不仅能改良土壤结构,而且提升土壤肥力等。
附图说明
图1为专用猪粪炭的电镜照片,左为普通猪粪炭,右为专用猪粪炭。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步的具体说明。应当理解,本发明的实施并不局限于下面的实施例,对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中,若非特指,所有的份、百分比均为重量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法,如无特别说明,均为本领域的常规方法。
实施例1
一种氨基嫁接改造专用猪粪炭的制备方法,该方法具体是:
1)原料干燥:将原料猪粪脱水至含水率80%-85%,采用1mol/L的HNO3进行酸洗,搅拌器慢搅3h,转速为100-200r/min,快搅1h,转速为500-600r/min,烘箱100℃干燥12h,粉碎至粒径<0.1mm,得干猪粪粉。
2)液氮预处理与高温炭化:
干猪粪粉进行液氮密闭处理,干猪粪粉与液氮的重量比为2:1,磁力搅拌转速为300rpm,搅拌40min,无水乙醇分2次添加,每次添加量与干猪粪粉的重量比为2:1,4分钟添加完毕,随后用水洗涤过滤,烘箱100℃干燥12h。烘干后的产物在高温管式炉中进行炭化,炭化温度为700℃,通入99.99%高纯氮气的流速为500mL/min,炭化处理后的产物经水洗涤后于100℃的条件下真空烘干15h,得到膨胀型猪粪炭。
3)羧基化处理:
将膨胀型猪粪炭超声分散于浓硝酸中,超声频率为40kHz,超声时间为1h,随后利用微波加热炉在功率为300W的条件下加热搅拌,搅拌转速为400r/min,搅拌5h,用无水乙醇和水交替洗涤,直至溶液pH呈中性,随后在85℃下真空干燥,得到羧基化猪粪炭。
4)氨基嫁接:
往羧基化猪粪炭中加入在温度320℃、压强10MPa条件下制得的浓度为2mol/L的氨水超临界流体,羧基化猪粪炭与氨水超临界流体的重量比为2:3,油浴加热温度达220℃,并磁力搅拌20h,冷却至室温后,将反应产物洗涤过滤。用流速为400mL/min的氮气吹干后,将产物置于110℃条件下真空烘干15h,研磨制得氨基嫁接改造专用猪粪炭。
对比例1
采用高温煅烧方法制备普通猪粪炭,具体过程同实施例1,但不进行步骤3)羧基化处理和步骤4)氨基嫁接及氮掺杂,该过程得到的即为普通猪粪炭。
采用X射线光电子能谱仪对专用猪粪炭进行检测分析,以确定专用猪粪炭表面的化学键合信息,经检测实施例1制得的专用猪粪炭氨基含量为11.5wt%,掺氮含量为6.7%,对比例1制得的猪粪炭氨基含量为2.1wt%,掺氮含量为1.3%。如图1电镜图片所示,相比于猪粪炭,专用猪粪炭孔隙更为丰富,比表面积高达115.3m2/g,显著高于普通猪粪炭7.2m2/g,具有更好的吸附物理结构。
实施例2
采用实施例1制得的氨基嫁接改造专用猪粪炭实现强化消减农田退水氮污染的方法,具体是:
高效吸附反应器由三个依次连接的反应池组成,第一、二、三三个反应池的体积比为3:1:2。第一个反应池中添加氨基嫁接改造专用猪粪炭。该方法中,农田退水进入猪粪炭高效吸附反应器进行处理,反应器连续流进水,水力停留时间48h。
第一个反应池进行快速吸附,底部设有涡轮式搅拌器,转速500r/min,池中投入氨基嫁接改造专用猪粪炭,材料投加体积与反应器的体积比为1:15,反应池出水均通过底部的孔隙隔离网;
第二个反应池进行截留吸附,截留猪粪炭的同时,底部也设有涡轮式搅拌器进行搅拌,待氨基嫁接改造专用猪粪炭充分吸附水体中的氮污染至超吸附平衡后,进入第三个反应池;
第三个反应池为斜板沉淀池,进行专用猪粪炭的固液分离,收集沉淀物,晾干或烘干后得到缓释型炭基氮肥。
施用缓释型炭基氮肥时,测定含氮量,依据当地土壤的理化性质确定最佳施用量,在作物行间开沟,将此肥料施入其中覆土。
应用实施例1
农田退水:用于实验的农田退水种植作物为单季稻,实验时期为施肥20天后,农田退水氮污染为氨氮浓度14.2±2.5mg/L、总氮浓度18.5±1.7mg/L,氮养分过多,水质恶化,有形成水体富营养化的潜在危险。
分别用普通猪粪炭(对比例1)和专用猪粪炭(实施例1),采用实施例2所述的方法进行农田退水处理试验,高效吸附反应器运行稳定后检测并分析两者的氮最大吸附量,结果见表1。
表1氨基嫁接改造专用猪粪炭对氮污染的吸附去除性能
表1数据表明氨基嫁接专用猪粪炭对农田退水的氨氮和总氮具有高效的吸附性,其最大吸附量分别高于普通猪粪炭的5.1倍和4.6倍,对氨氮和总氮的去除率稳定在90%与80%左右,处理后出水氮污染被高效回用至专用猪粪炭,水质得到明显改善,基本符合地表水环境质量标准基本项目标准限值(GB3838-2002)Ⅴ类,不存在对水环境造成富营养的潜在危害。通过氨基嫁接技术改造猪粪炭后,对农田退水氮污染吸附具有显著强化作用。
应用实施例2缓释型炭基氮肥对土壤的改良
以某养猪场附近的农田进行试验,猪粪厩肥取自于该养猪场,将吸附氮饱和的专用猪粪炭回收并应用于土壤肥力提升和改良,土壤中施用猪粪炭的重量百分比为3%。表2氨基嫁接改造专用猪粪炭对土壤改良与增产的效能如表2所示。
表2氨基嫁接改造专用猪粪炭对土壤改良与增产的效能
由表2可知,相比于原始土壤,施用专用猪粪炭有效的降低了土壤容重,提升了土壤持水和保肥能力,猪粪炭本身具有良好的营养元素,吸附饱和氮后其肥力也得到提升,具有缓释的功效,氮肥溶出率减少了31.1%,适宜于土壤改良的实际应用。施用专用猪粪炭提高了辣椒和番茄的产量,幅度达到40%-50%,因此,专用猪粪炭在改良土壤性质的同时也增加了植物产量,具有良好的实际应用价值。
综上所述,猪粪高温炭化后,灰分、有机炭、全磷、全钾和速效钾的含量较猪粪厩肥有所提高,而全氮、速效磷和碱解氮含量有所降低。将专用猪粪炭改造后吸附农田退水中的氮素作为缓释型炭基氮肥,正好又弥补了普通猪粪炭氮素不足的缺陷,对土壤增肥和植物减肥增产有显著作用。同时,节约了猪粪炭再生的处理成本,是一种变废为宝、循环利用的方法,也避免了二次污染。
本说明书中各个实施例采用递进的方式描述,每个实施例重点说明的都是与其它实施例的不同之处,各个实施例之间相同或相似部分互相参见即可。对于实施例公开的装置而言,由于其与实施例公开的方法相对应,所以描述的比较简单,相关之处参见方法部分说明即可。
以上对本发明所提供的氨基嫁接改造专用猪粪炭、制备方法及其在农田退水氮回用方面的应用进行了详细介绍。本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (9)
1.一种氨基嫁接改造专用猪粪炭的制备方法,其特征在于该方法包括以下步骤:
1)原料干燥:将原料猪粪脱水至含水率80%-85%后依次进行酸洗、干燥、粉碎制得干猪粪粉;
2)液氮预处理与高温炭化:将步骤1)制得的干猪粪粉进行液氮密闭处理,搅拌30-60min,加入无水乙醇快速挥发,随后过滤、洗涤、干燥,将烘干后的产物进行600-800℃的高温煅烧炭化,并通入纯度为98.99%-99.99%的高纯氮气,炭化处理后的产物经洗涤后于100±5℃的条件下真空烘干12-24h,制得膨胀型猪粪炭;
3)羧基化处理:将步骤2)制得的膨胀型猪粪炭采用超声分散于质量浓度为65%-68%的浓硝酸中,随后在微波辅助下搅拌4-6h,将产物洗涤、过滤、干燥得到羧基化猪粪炭;
4)氨基嫁接:将步骤3)制得的羧基化猪粪炭加入氨水流体,200-240℃油浴加热条件下搅拌20-24h,冷却至室温后,将反应产物洗涤过滤,用N2吹干后将产物置于110±5℃条件下真空烘干12-24h,研磨后得到氨基嫁接改造专用猪粪炭;
步骤2)中掺氮含量为5-10%,步骤4)中氨基嫁接掺杂的氨基含量为10-15wt%。
2.根据权利要求1所述的制备方法,其特征在于:步骤1)中酸洗、干燥、粉碎为采用1-2mol/L的H3PO4或HNO3浸渍,搅拌器慢搅3-5h,转速为100-200r/min,快搅1-2h,转速为500-600r/min,烘箱85-110℃干燥12-24h后,粉碎至粒径<0.1 mm。
3.根据权利要求1所述的制备方法,其特征在于:步骤2)中干猪粪粉与液氮的重量比为2:1-1.5,搅拌转速为200-400rpm;
乙醇分2-3次添加,每次添加时间间隔为1.5-2.5min,每次添加量与干猪粪粉的重量比为2:0.8-1.5,随后用水洗涤过滤。
4.根据权利要求1所述的制备方法,其特征在于:步骤2)中高温煅烧炭化在高温管式炉中进行,通入高纯氮气的流速为400-650 mL/min,洗涤条件为无水乙醇和自来水交替洗涤,直至溶液pH呈中性。
5.根据权利要求1所述的制备方法,其特征在于:步骤3)中膨胀型猪粪炭采用超声分散于浓硝酸中,超声频率为40kHz,超声时间为0.5-2h。
6.根据权利要求1所述的制备方法,其特征在于:步骤4)中所述氨水流体为在温度320℃、压强10MPa条件下制得的氨水超临界流体,其浓度为2-3mol/L;
羧基化猪粪炭与氨水超临界流体的重量比为2:2-3,通入氮气的流速为300-600 mL/min。
7.一种采用权利要求1所述的方法制得的氨基嫁接改造专用猪粪炭,其特征在于:所述的氨基嫁接改造专用猪粪炭中,氨基含量为10-15wt%,掺氮含量为5-10%,比表面积为110-130m2/g。
8.一种权利要求7所述的氨基嫁接改造专用猪粪炭在农田退水氮污染消减与回用方面的应用。
9.根据权利要求8所述的应用,其特征在于:农田退水进入猪粪炭高效吸附反应器,高效吸附反应器由三个依次连接的反应池组成,第一个反应池进行快速吸附,底部设有涡轮式搅拌器,转速300-600r/min,池中投入氨基嫁接改造专用猪粪炭,材料投加体积与反应器的体积比为1:15-20,反应池出水均通过底部的孔隙隔离网;第二个反应池进行截留吸附,截留猪粪炭的同时,底部也设有涡轮式搅拌器进行搅拌,待氨基嫁接改造专用猪粪炭充分吸附水体中的氮污染至超吸附平衡后,进入第三个反应池——斜板沉淀池,反应后收集沉淀物,晾干或烘干后得到缓释型炭基氮肥。
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