技术领域Technical field
本发明属于水体修复技术领域，具体涉及用于处理由磷酸盐引起水体富营养化的球磨零价铁掺杂硫/生物炭及其制备方法。The invention belongs to the technical field of water body restoration, and specifically relates to ball-milled zero-valent iron-doped sulfur/biochar used to treat water body eutrophication caused by phosphate and its preparation method.
背景技术Background technique
营养物质特别是磷的过度排放导致的富营养化已经发生成为世界范围内一个严峻的环境问题。高浓度磷酸盐会刺激生物体，尤其是藻类在水体中的生长，从而恶化环境Eutrophication caused by excessive discharge of nutrients, especially phosphorus, has become a serious environmental problem worldwide. High concentrations of phosphate can stimulate the growth of organisms, especially algae, in water bodies, thereby deteriorating the environment
水生生态系统的质量。大量的藻类将耗尽水中所有的溶解氧，危及动植物的生存。此外，水生植物进行光合作用所需的阳光会被大量的海藻团块阻挡在水中。值得注意的是，即使是相对较小的磷酸盐水平，也能在淡水水体中引发重大的藻华事件，导致富营养化现象。根据中国科学院的调查研究结果，我国的湖泊和水库等缓流水体的富营养化问题正日趋严重，有50％以上的主要湖泊存在着不同程度的水生生态系统退化现象。可以预见在未来一段时间内，水体的富营养化仍然是我们面临的重大环境问题之一。Aquatic ecosystem quality. Large amounts of algae will deplete all dissolved oxygen in the water, endangering the survival of animals and plants. In addition, the sunlight needed for photosynthesis by aquatic plants is blocked by large clumps of algae in the water. It is worth noting that even relatively small phosphate levels can trigger major algal bloom events in freshwater bodies, leading to eutrophication. According to the survey results of the Chinese Academy of Sciences, the eutrophication problem of slow-flowing water bodies such as lakes and reservoirs in my country is becoming increasingly serious. More than 50% of major lakes have varying degrees of aquatic ecosystem degradation. It is foreseeable that in the future, eutrophication of water bodies will still be one of the major environmental problems we face.
因此发展高效低能的降磷技术对缓解水体富营养化至关重要。到目前为止，已经研究了许多技术来去除废水中的磷，主要分为三类：化学沉淀法、生物法和吸附法。化学除磷会产生大量的污泥，因为磷的沉淀可能会导致新的污染。生物除磷对操作参数比较敏感，因此其除磷效率较不稳定。此外，生物处理涉及活性污泥或其他预处理会增加成本。而吸附法具有能耗低、效率高和易操作的优点，在水体除磷领域有广阔应用前景。近年来，零价铁因具有很高的反应活性和优越的吸附性能，被认为是一种新兴环境功能材料，现已有大量零价铁对磷酸盐去除的研究。但由于零价铁具有较高还原活性，使其易被氧化进而老化失活，此外零价铁易于团聚、分散性差，无法表现出理想的反应活性，在实际应用中老化和团聚问题均会引起反应活性降低，对其工程应用产生较大限制。因此对磷酸盐引起水体富营养化的修复材料仍有很大的提升空间。Therefore, the development of high-efficiency and low-energy phosphorus reduction technology is crucial to alleviate eutrophication of water bodies. So far, many technologies have been studied to remove phosphorus from wastewater, mainly divided into three categories: chemical precipitation, biological methods and adsorption methods. Chemical phosphorus removal will produce large amounts of sludge because the precipitation of phosphorus may lead to new pollution. Biological phosphorus removal is sensitive to operating parameters, so its phosphorus removal efficiency is unstable. In addition, biological treatment involving activated sludge or other pretreatment increases costs. The adsorption method has the advantages of low energy consumption, high efficiency and easy operation, and has broad application prospects in the field of phosphorus removal from water bodies. In recent years, zerovalent iron has been considered an emerging environmental functional material due to its high reactivity and superior adsorption performance. There have been a large number of studies on the removal of phosphate by zerovalent iron. However, due to the high reducing activity of zero-valent iron, it is easily oxidized and deactivated due to aging. In addition, zero-valent iron is easy to agglomerate and has poor dispersion, and cannot show ideal reactivity. In practical applications, aging and agglomeration problems will occur. The reactivity is reduced, which greatly limits its engineering application. Therefore, there is still a lot of room for improvement in repair materials for water eutrophication caused by phosphate.
针对零价铁老化问题，硫化物改性零价铁最近引起广泛关注。零价铁的硫化作用可控制零价铁的腐蚀速率，从而提高零价铁的反应活性，延长其反应寿命。另外，人们越来越关注使用环保材料作为零价铁的载体材料，解决零价铁的团聚问题。其中具有理想固定化、经济绿色等优点的生物炭成为近年来的研究热点。生物炭是指生物质材料在缺氧或厌氧条件经高温热解所生成的一种稳定物质。生物炭具有巨大比表面积、丰富的孔隙结构和含氧基团，因此，生物炭在吸附重金属和有机物方面得到很多应用，同时由于生物炭的多功能性，也被用为分散载体和稳定纳米粒子的支撑材料。制备复合材料的传统方法通常依赖于化学过程，尤其是合成一定比例的铁化合物时，浸渍需要过量的化学溶液，这会浪费试剂和提高成本，限制了材料的大规模应用。In response to the aging problem of zero-valent iron, sulfide-modified zero-valent iron has attracted widespread attention recently. The sulfidation of zero-valent iron can control the corrosion rate of zero-valent iron, thereby improving the reactivity of zero-valent iron and extending its reaction life. In addition, people are paying more and more attention to the use of environmentally friendly materials as carrier materials for zero-valent iron to solve the agglomeration problem of zero-valent iron. Among them, biochar, which has the advantages of ideal immobilization, economy and greenness, has become a research hotspot in recent years. Biochar refers to a stable substance generated by high-temperature pyrolysis of biomass materials under anoxic or anaerobic conditions. Biochar has a huge specific surface area, rich pore structure and oxygen-containing groups. Therefore, biochar has many applications in adsorbing heavy metals and organic matter. At the same time, due to its versatility, biochar is also used as a dispersion carrier and stabilized nanoparticles. support material. Traditional methods for preparing composite materials usually rely on chemical processes, especially when synthesizing a certain proportion of iron compounds. Impregnation requires excessive chemical solutions, which wastes reagents and increases costs, limiting the large-scale application of materials.
发明内容Contents of the invention
发明目的：本发明所要解决的技术问题是针对现有技术的不足，提供一种球磨零价铁掺杂硫/生物炭复合材料的制备方法及其应用，该方法绿色节能、简便，可大规模生产，制备的材料能够快速有效处理水体中的磷酸盐，且材料长期具有有效反应活性。Purpose of the invention: The technical problem to be solved by this invention is to provide a preparation method and application of ball milling zero-valent iron-doped sulfur/biochar composite materials in view of the shortcomings of the existing technology. This method is green, energy-saving, simple, and can be used on a large scale. The materials produced and prepared can quickly and effectively treat phosphates in water bodies, and the materials have effective reactivity for a long time.
为了实现上述目的，本发明采取的技术方案如下：In order to achieve the above objects, the technical solutions adopted by the present invention are as follows:
一种球磨零价铁掺杂硫/生物炭复合材料，包括生物炭载体，以及负载在生物炭载体上的有硫掺杂的零价铁。A ball-milled zero-valent iron-doped sulfur/biochar composite material includes a biochar carrier, and sulfur-doped zero-valent iron loaded on the biochar carrier.
优选地，该复合材料的粒径不超过100目；所述生物炭载体所使用的生物质原材料包括但不限定于秸秆类农业废弃物，特别是玉米秸秆。Preferably, the particle size of the composite material does not exceed 100 mesh; the biomass raw materials used in the biochar carrier include but are not limited to straw agricultural waste, especially corn straw.
进一步地，本发明还提供上述球磨零价铁掺杂硫/生物炭复合材料的制备方法，包括如下步骤；Further, the present invention also provides a method for preparing the above-mentioned ball-milled zerovalent iron-doped sulfur/biochar composite material, which includes the following steps;
(1)将生物质原材料洗涤，烘干，粉碎，过筛，获得生物质原材料粉末；(1) Wash, dry, crush and sieve the biomass raw materials to obtain biomass raw material powder;
(2)将步骤(1)得到的生物质原材料粉末在氮气气氛下热解，然后自然冷却至室温，经盐酸浸泡后，水洗至中性，烘干得到生物炭载体；(2) Pyrolyze the biomass raw material powder obtained in step (1) under a nitrogen atmosphere, then naturally cool to room temperature, soak in hydrochloric acid, wash with water until neutral, and dry to obtain a biochar carrier;
(3)将步骤(2)得到的生物炭载体置于球磨罐中，然后加入单质硫粉以及零价铁粉，在惰性气体或氮气保护条件下，于20～25℃球磨3～48h，即得。(3) Place the biochar carrier obtained in step (2) into a ball mill tank, then add elemental sulfur powder and zero-valent iron powder, and ball-mill at 20 to 25°C for 3 to 48 hours under inert gas or nitrogen protection conditions, that is have to.
步骤(1)中，洗涤采用去离子水；烘干的温度为50～80℃，烘干时间为12～24h；粉碎采用高速破碎机，粉碎时间为1～10min；粉碎后过20～100目筛。In step (1), deionized water is used for washing; the drying temperature is 50 to 80°C, and the drying time is 12 to 24 hours; a high-speed crusher is used for crushing, and the crushing time is 1 to 10 minutes; after crushing, it is passed through 20 to 100 mesh screen.
步骤(2)中，氮气以300～400mL/min的流速通入；以4～5℃/min的升温速率升温至400～800℃，热解1.5～3h；采用1mol/L盐酸水溶液浸泡24h后，用去离子水洗至中性。In step (2), nitrogen is introduced at a flow rate of 300 to 400 mL/min; the temperature is raised to 400 to 800°C at a heating rate of 4 to 5°C/min, and pyrolysis is carried out for 1.5 to 3 hours; soaked in 1 mol/L hydrochloric acid aqueous solution for 24 hours. , wash with deionized water until neutral.
步骤(3)中，所述生物炭载体、单质硫粉以及零价铁粉三者质量比为3:(0.5～1):(1～3)，优选比例为3:1:1。In step (3), the mass ratio of the biochar carrier, elemental sulfur powder and zero-valent iron powder is 3: (0.5-1): (1-3), and the preferred ratio is 3:1:1.
步骤(3)中，球磨采用的研磨球包括直径为15mm的大球、直径10mm的中球和直径5mm的小球，大球、中球和小球的质量比为1:1:1；生物炭载体与研磨球总质量比为1:(20～100)。In step (3), the grinding balls used in the ball mill include large balls with a diameter of 15mm, medium balls with a diameter of 10mm, and small balls with a diameter of 5mm. The mass ratio of the large balls, medium balls, and small balls is 1:1:1; Biology The total mass ratio of carbon carrier to grinding ball is 1:(20~100).
步骤(3)中，所述球磨罐放入行星球磨机以300～600rpm的公转转速球磨3～48h；球磨过程中，每间隔30min，停止5min，转换公转方向后继续下一轮球磨。In step (3), the ball mill jar is put into a planetary ball mill and milled for 3 to 48 hours at a revolution speed of 300 to 600 rpm; during the ball milling process, stop for 5 minutes every 30 minutes, change the direction of revolution, and continue with the next round of ball milling.
进一步地，本发明还提供上述球磨零价铁掺杂硫/生物炭复合材料在用于修复污染水体中的应用，尤其是磷酸盐过量导致的污染水体，或者四环素类抗生素过量导致的污染水体。Further, the present invention also provides the application of the above-mentioned ball-milled zero-valent iron-doped sulfur/biochar composite material in repairing polluted water bodies, especially polluted water bodies caused by excess phosphate, or polluted water bodies caused by excessive tetracycline antibiotics.
有益效果：Beneficial effects:
1、本发明利用秸秆废弃物等廉价易得的原材料，通过球磨生物炭、负载成本较低的零价铁和硫粉快速的制备了球磨零价铁掺杂硫/生物炭复合材料，制备方法简易，适合工业化生产，且制备过程不产生污染，为球磨零价铁掺杂硫/生物炭复合材料的制备、废弃生物质的资源化利用提供了新的思路；1. The present invention utilizes cheap and easily available raw materials such as straw waste to quickly prepare ball-milled zero-valent iron-doped sulfur/biochar composite materials by ball-milling biochar, zero-valent iron and sulfur powder with low loading costs. Preparation method It is simple, suitable for industrial production, and the preparation process does not produce pollution. It provides new ideas for the preparation of zero-valent iron-doped sulfur/biochar composite materials by ball milling and the resource utilization of waste biomass;
2、本发明制备的球磨零价铁掺杂硫/生物炭复合材料具有高效吸附性能、抗老化性能和回收潜力，可有效去除水溶液和实际水体中过量磷酸盐污染目的。本发明既弥补了单纯使用生物炭和零价铁颗粒材料的局限性，又可解决实际应用过程中零价铁改性生物炭易老化失活的难题，具有广阔的应用前景。2. The ball-milled zero-valent iron-doped sulfur/biochar composite material prepared by the present invention has efficient adsorption performance, anti-aging performance and recycling potential, and can effectively remove excessive phosphate pollution in aqueous solutions and actual water bodies. The invention not only makes up for the limitations of simply using biochar and zero-valent iron granular materials, but also solves the problem that zero-valent iron-modified biochar is prone to aging and deactivation during practical application, and has broad application prospects.
附图说明Description of the drawings
下面结合附图和具体实施方式对本发明做更进一步的具体说明，本发明的上述和/或其他方面的优点将会变得更加清楚。The above and/or other advantages of the present invention will become more clear when the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1中a、b、c和d分别为原始生物炭、球磨生物炭、球磨零价铁/生物炭和球磨零价铁掺杂硫/生物炭的扫描电镜图。In Figure 1, a, b, c, and d are the scanning electron microscopy images of original biochar, ball-milled biochar, ball-milled zerovalent iron/biochar, and ball-milled zerovalent iron-doped sulfur/biochar, respectively.
图2为实施例1～6和对比例1～3对磷酸盐的吸附容量图。Figure 2 is a diagram showing the adsorption capacity of phosphate in Examples 1 to 6 and Comparative Examples 1 to 3.
图3为球磨零价铁掺杂硫/生物炭在不同温度下对磷酸盐的吸附动力学图。Figure 3 shows the adsorption kinetics of phosphate on ball-milled zerovalent iron-doped sulfur/biochar at different temperatures.
图4为球磨零价铁掺杂硫/生物炭在不同温度下对磷酸盐的吸附等温线图。Figure 4 shows the adsorption isotherm of phosphate at different temperatures by ball-milled zerovalent iron-doped sulfur/biochar.
图5为球磨零价铁掺杂硫/生物炭在不同老化时间后对磷酸盐的吸附容量图。Figure 5 shows the adsorption capacity of ball-milled zerovalent iron-doped sulfur/biochar for phosphate after different aging times.
图6为球磨零价铁掺杂硫/生物炭在实际水体中对磷酸盐的吸附等温线图。Figure 6 shows the adsorption isotherm of phosphate by ball-milled zerovalent iron-doped sulfur/biochar in actual water.
图7中a、b、c和d分别为原始生物炭、球磨生物炭、球磨零价铁/生物炭和球磨硫化载铁生物炭的扫描电镜图。Figure 7 a, b, c and d are the scanning electron microscopy images of original biochar, ball milled biochar, ball milled zero-valent iron/biochar and ball milled sulfide-loaded iron biochar, respectively.
图8为实施例7与对比例4～6对四环素的吸附容量图。Figure 8 is a graph showing the adsorption capacity of tetracycline in Example 7 and Comparative Examples 4 to 6.
图9为球磨硫化载铁生物炭在不同温度下对四环素的吸附动力学图。Figure 9 shows the adsorption kinetics of tetracycline on ball-milled sulfide-loaded iron biochar at different temperatures.
图10为球磨硫化载铁生物炭在不同温度下对四环素的吸附等温线图。Figure 10 shows the adsorption isotherms of tetracycline on ball-milled sulfide-loaded iron biochar at different temperatures.
图11为球磨硫化载铁生物炭在空气和水中老化后对四环素的吸附容量图。Figure 11 is a graph showing the adsorption capacity of ball-milled sulfide iron-loaded biochar for tetracycline after aging in air and water.
图12为球磨硫化载铁生物炭在实际水体中对四环素的吸附等温线图。Figure 12 is the adsorption isotherm diagram of tetracycline by ball-milled sulfide-loaded iron biochar in actual water.
具体实施方式Detailed ways
根据下述实施例，可以更好地理解本发明。The present invention can be better understood from the following examples.
实施例1～6Examples 1 to 6
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在60～80℃下烘干24h，然后通过植物粉碎机粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 60-80°C for 24 hours, then crush it through a plant crusher and pass through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于管式炉中，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至600℃，热解2h后自然冷却至室温取出，经1mol/L盐酸浸泡24h后，用去离子水洗至中性，并于60～80℃烘干，得到生物炭载体；Step 2: Place the straw powder obtained in Step 1 into a tube furnace, pass nitrogen into the tube furnace at a flow rate of 400 mL/min, then raise the temperature to 600°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to Take it out at room temperature, soak it in 1 mol/L hydrochloric acid for 24 hours, wash it with deionized water until neutral, and dry it at 60-80°C to obtain the biochar carrier;
步骤三：将步骤二得到的生物炭载体放置于球磨罐中，再在球磨罐中放入研磨球、单质硫粉和零价铁粉，球磨珠大、中、小(直径15、10、5mm)比例为1:1:1，共150g。在氮气保护条件下，密封球磨罐，在室温20～25℃下，将球磨罐放入行星球磨机以380rpm运转205min，每30min改变一次旋转方向。按质量份数计，生物炭、硫粉和铁粉的比为3:X:Y，三者总质量4.5～7g。X、Y值见表1。Step 3: Place the biochar carrier obtained in Step 2 into a ball milling tank, and then put grinding balls, elemental sulfur powder and zero-valent iron powder into the ball milling tank. The ball milling beads should be large, medium and small (diameter 15, 10, 5mm) ) ratio is 1:1:1, total 150g. Under nitrogen protection conditions, seal the ball mill jar, place the ball mill jar into a planetary ball mill and run it at 380 rpm for 205 minutes at room temperature of 20 to 25°C, changing the direction of rotation every 30 minutes. In terms of parts by mass, the ratio of biochar, sulfur powder and iron powder is 3:X:Y, and the total mass of the three is 4.5-7g. See Table 1 for X and Y values.
表1Table 1
对比例1～3Comparative Examples 1 to 3
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在60～80℃下烘干24h，然后通过植物粉碎机粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 60-80°C for 24 hours, then crush it through a plant crusher and pass through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于管式炉中，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至600℃，热解2h后自然冷却至室温取出，经1mol/L盐酸浸泡24h后，用去离子水洗至中性，并于60～80℃烘干，得到生物炭载体；Step 2: Place the straw powder obtained in Step 1 into a tube furnace, pass nitrogen into the tube furnace at a flow rate of 400 mL/min, then raise the temperature to 600°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to Take it out at room temperature, soak it in 1 mol/L hydrochloric acid for 24 hours, wash it with deionized water until neutral, and dry it at 60-80°C to obtain the biochar carrier;
步骤三：将步骤二得到的生物炭载体放置于球磨罐中，再在球磨罐中放入研磨球、单质硫粉和零价铁粉，球磨珠大、中、小(直径15、10、5mm)比例为1:1:1，共150g。在氮气保护条件下，密封球磨罐，在室温20～25℃下，将球磨罐放入行星球磨机以380rpm运转205min，每30min改变一次旋转方向。按质量份数计，生物炭、硫粉和铁粉的比为3:X:Y，X、Y值见表2。Step 3: Place the biochar carrier obtained in Step 2 into a ball milling tank, and then put grinding balls, elemental sulfur powder and zero-valent iron powder into the ball milling tank. The ball milling beads should be large, medium and small (diameter 15, 10, 5mm) ) ratio is 1:1:1, total 150g. Under nitrogen protection conditions, seal the ball mill jar, place the ball mill jar into a planetary ball mill and run it at 380 rpm for 205 minutes at room temperature of 20 to 25°C, changing the direction of rotation every 30 minutes. In terms of parts by mass, the ratio of biochar, sulfur powder and iron powder is 3:X:Y. The X and Y values are shown in Table 2.
表2Table 2
通过SEM可看出生物炭是多孔粗糙的块，没有规则的形状，参见图1(a)。球磨生物炭(对比例1)是较均匀的超细颗粒，可为零价铁提供均匀分布的载体位置，参见图1(b)。球磨零价铁/生物炭(对比例3)成功负载了零价铁，由于强烈的团聚效应，裸露的零价铁聚集形成链结构或团簇，参见图1(c)。仅负载零价铁的改性生物炭团聚现象严重，而经过硫化后的实施例3团聚现象明显减弱，参见图1(d)。It can be seen from SEM that biochar is a porous rough block with no regular shape, see Figure 1(a). Ball-milled biochar (Comparative Example 1) is relatively uniform ultra-fine particles and can provide evenly distributed carrier locations for zero-valent iron, see Figure 1(b). Ball-milled zerovalent iron/biochar (Comparative Example 3) successfully loaded zerovalent iron. Due to the strong agglomeration effect, the exposed zerovalent iron aggregated to form chain structures or clusters, see Figure 1(c). The agglomeration phenomenon of the modified biochar loaded with only zero-valent iron was serious, while the aggregation phenomenon of Example 3 after sulfide was significantly weakened, see Figure 1(d).
将实施例1～6和对比例1～3进行磷酸盐吸附对比，吸附剂用量为2g/L，磷酸盐浓度为30mg P/L，在25℃的条件下使用300rpm速度震荡6h，结果显示，单独的球磨生物炭(BMBC，对比例1)吸附磷的效果最差，吸附量仅为1.00mg/g，BMBC负载硫或零价铁后对磷的吸附都有所改善，3:1:0(对比例2)的吸附量为2.08mg/g，3:0:1(对比例3)的吸附量为5.15mg/g，说明硫和零价铁对生物炭吸附磷有一定促进作用。从3:0.5:1(实施例1，13.57mg/g)与3:0.5:2(实施例2，8.96mg/g)的吸附量对比可知，S/Fe0比降低，吸附量下降，3:1:1(实施例3，14.78mg/g)、3:1:2(实施例4，13.96mg/g)以及3:1:3(实施例5，12.34mg/g)的吸附量变化也证明了这一点；另外从3:0:1(对比例3，5.15mg/g)、3:0.5:1(实施例1，13.57mg/g)以及3:1:1(实施例3，14.78mg/g)对比可看出S/Fe0比升高，吸附量上升，并且硫起到很大的促进作用，参见图2。表明S/Fe0比在磷酸盐的去除中起着关键作用，其中S/Fe0比为1时(实施例3)吸附量最大。3:2:2(实施例6)的S/Fe0比虽也为1，但其铁硫质量超过了生物炭，吸附量大幅下降，仅有8.36mg/g。The phosphate adsorption was compared between Examples 1 to 6 and Comparative Examples 1 to 3. The adsorbent dosage was 2g/L, the phosphate concentration was 30 mg P/L, and the phosphate was shaken at 300 rpm for 6 hours at 25°C. The results showed that: Ball-milled biochar (BMBC, Comparative Example 1) alone has the worst effect on adsorbing phosphorus, with an adsorption capacity of only 1.00 mg/g. The adsorption of phosphorus by BMBC is improved after loading sulfur or zero-valent iron, 3:1:0 The adsorption capacity of (Comparative Example 2) is 2.08 mg/g, and the adsorption capacity of 3:0:1 (Comparative Example 3) is 5.15 mg/g, indicating that sulfur and zero-valent iron have a certain promoting effect on the adsorption of phosphorus by biochar. From the comparison of the adsorption amounts of 3:0.5:1 (Example 1, 13.57 mg/g) and 3:0.5:2 (Example 2, 8.96 mg/g), it can be seen that the S/Fe0 ratio decreases and the adsorption amount decreases. 3 : Changes in adsorption amount of 1:1 (Example 3, 14.78mg/g), 3:1:2 (Example 4, 13.96mg/g) and 3:1:3 (Example 5, 12.34mg/g) This has also been proven; in addition, from 3:0:1 (Comparative Example 3, 5.15mg/g), 3:0.5:1 (Example 1, 13.57mg/g) and 3:1:1 (Example 3, 14.78 mg/g), it can be seen that the S/Fe0 ratio increases, the adsorption amount increases, and sulfur plays a great promoting role, see Figure 2. It shows that the S/Fe0 ratio plays a key role in the removal of phosphate, and when the S/Fe0 ratio is 1 (Example 3), the adsorption amount is the largest. Although the S/Fe0 ratio of 3:2:2 (Example 6) is also 1, its iron-sulfur mass exceeds that of biochar, and the adsorption capacity drops significantly, only 8.36 mg/g.
采用吸附动力学试验了解球磨零价铁掺杂硫/生物炭在不同温度下对磷酸盐的吸附速度，取实施例3制备的球磨零价铁掺杂硫/生物炭0.05g，放入离心管中，加入25ml的30mg/L的磷酸盐，分别在25℃、35℃和45℃条件下使用300rpm速度震荡10min，30min，60min，90min，120min，240min和360min。结果显示，球磨零价铁掺杂硫/生物炭对磷酸盐的吸附量在初始阶段迅速增加，动力学吸附90min后，生物炭对磷酸盐的吸附过程逐渐放缓，150min后基本平衡，360min吸附完全，吸附量不再增加，参见图3。An adsorption kinetics test was used to understand the adsorption speed of ball-milled zero-valent iron-doped sulfur/biochar at different temperatures. Take 0.05g of ball-milled zero-valent iron-doped sulfur/biochar prepared in Example 3 and put it into a centrifuge tube. , add 25ml of 30mg/L phosphate, and shake at 300rpm for 10min, 30min, 60min, 90min, 120min, 240min and 360min at 25℃, 35℃ and 45℃ respectively. The results show that the adsorption amount of phosphate by ball-milled zero-valent iron-doped sulfur/biochar increases rapidly in the initial stage. After kinetic adsorption for 90 minutes, the adsorption process of biochar for phosphate gradually slows down. It is basically balanced after 150 minutes and adsorbed after 360 minutes. Completely, the adsorption capacity no longer increases, see Figure 3.
采用吸附等温线试验确定了球磨零价铁掺杂硫/生物炭在不同温度下对磷酸盐的最大吸附量，取实施例3制备的球磨零价铁掺杂硫/生物炭0.05g于6支离心管中，分别加入5～150mg/L不同浓度的磷酸盐溶液25mL，分别在25℃、35℃和45℃条件下使用300rpm速度震荡6h并测定剩余磷酸盐含量。为得到球磨零价铁掺杂硫/生物炭对磷酸盐的最大吸附量，采用Langmuir模型进行数据拟合，结果显示，球磨零价铁掺杂硫/生物炭对磷酸盐在25℃、35℃和45℃条件下的最大吸附量分别为25.00mg/g、28.49mg/g和39.72mg/g，参见图4。随着温度的升高，球磨零价铁掺杂硫/生物炭对磷酸盐的吸附量有一定提升，说明吸附过程是吸热的过程，升高温度有利于吸附的进行。The adsorption isotherm test was used to determine the maximum adsorption capacity of ball-milled zero-valent iron-doped sulfur/biochar at different temperatures. Take 0.05g of ball-milled zero-valent iron-doped sulfur/biochar prepared in Example 3 and add it to 6 tubes. In the centrifuge tube, add 25 mL of phosphate solutions with different concentrations of 5 to 150 mg/L, shake at 300 rpm for 6 hours at 25°C, 35°C, and 45°C, and measure the remaining phosphate content. In order to obtain the maximum adsorption capacity of phosphate by ball-milled zero-valent iron doped with sulfur/biochar, the Langmuir model was used for data fitting. The results showed that the adsorption capacity of ball-milled zero-valent iron-doped sulfur/biochar with phosphate at 25°C and 35°C The maximum adsorption capacities at 45℃ and 45℃ are 25.00mg/g, 28.49mg/g and 39.72mg/g respectively, see Figure 4. As the temperature increases, the amount of phosphate adsorbed by ball-milled zerovalent iron-doped sulfur/biochar increases to a certain extent, indicating that the adsorption process is an endothermic process, and increasing the temperature is conducive to the adsorption.
为进一步确定球磨零价铁掺杂硫/生物炭能否以及如何减缓老化，选取实施例1～6制备的对磷吸附效果较好的4种球磨零价铁掺杂硫/生物炭，实施例1、实施例3、实施例4和实施例5在空气中老化一定时间后用于磷酸盐吸附实验。在老化0天、3天、7天、14天、30天和60天时，取老化后的球磨零价铁掺杂硫/生物炭0.05g，放入离心管中，分别加入25ml的30mg/L的磷酸盐，使用300rpm速度震荡6h并测定剩余磷酸盐含量。可以看到老化0天时各实施例的球磨零价铁掺杂硫/生物炭对磷的吸附效果相差不大，老化14天时的影响较小，老化30天时除了实施例5，其他3种球磨零价铁掺杂硫/生物炭均能保持65％以上的去除率。老化60天后实施例1、实施例4和实施例5的去除率分别为59.7％、45％以及19.2％，而实施例3对磷的去除率仍保持在84.4％，参见图5。因此球磨零价铁掺杂硫/生物炭具有较好的抗老化效果，氧气的侵蚀无法显著影响其反应活性。In order to further determine whether and how ball-milled zero-valent iron-doped sulfur/biochar can slow down aging, four kinds of ball-milled zero-valent iron-doped sulfur/biochar prepared in Examples 1 to 6 with better phosphorus adsorption effects were selected. Examples 1. Example 3, Example 4 and Example 5 were used for phosphate adsorption experiments after aging in air for a certain period of time. At 0 days, 3 days, 7 days, 14 days, 30 days and 60 days of aging, take 0.05g of aged ball-milled zero-valent iron-doped sulfur/biochar, put it into a centrifuge tube, and add 25 ml of 30 mg/L respectively. of phosphate, shake at 300 rpm for 6 hours and determine the remaining phosphate content. It can be seen that the phosphorus adsorption effects of the ball-milled zero-valent iron-doped sulfur/biochar of each embodiment are similar at 0 days of aging, and the impact is smaller at 14 days of aging. Except for Example 5, the other three ball-milled zero-valent iron-doped sulfur/biochars have little effect on aging for 30 days. Valent iron-doped sulfur/biochar can both maintain a removal rate of more than 65%. After aging for 60 days, the removal rates of Example 1, Example 4 and Example 5 were 59.7%, 45% and 19.2% respectively, while the phosphorus removal rate of Example 3 still remained at 84.4%, see Figure 5. Therefore, ball-milled zero-valent iron doped sulfur/biochar has a good anti-aging effect, and the erosion of oxygen cannot significantly affect its reactivity.
为进一步确定球磨零价铁掺杂硫/生物炭的实际应用价值，测试了球磨零价铁掺杂硫/生物炭在实际不同水体中的吸附效果。磷酸盐溶液分别使用去离子水、自来水、人工湖水和自然河水配制。将实例3制备的0.05g球磨零价铁掺杂硫/生物炭于6支离心管中，分别加入5～150mg/L不同浓度的磷酸盐溶液25mL，在300rpm速度震荡6h后测定剩余磷酸盐含量。对实验数据进行Langmuir模型，可以看到去离子水中球磨零价铁掺杂硫/生物炭对磷的最大饱和吸附量为25.00mg/g，自来水为24.42mg/g，河水为22.67mg/g，湖水为20.53mg/g，参见图6。表明球磨零价铁掺杂硫/生物炭在各种水体中对磷均有较好的吸附效果，这意味着球磨零价铁掺杂硫/生物炭对实际水体的修复是可行的。In order to further determine the practical application value of ball-milled zero-valent iron-doped sulfur/biochar, the adsorption effect of ball-milled zero-valent iron-doped sulfur/biochar in actual different water bodies was tested. Phosphate solutions were prepared using deionized water, tap water, artificial lake water and natural river water. Put 0.05g of ball-milled zero-valent iron-doped sulfur/biochar prepared in Example 3 into 6 centrifuge tubes, add 25 mL of phosphate solutions of different concentrations from 5 to 150 mg/L, and measure the remaining phosphate content after shaking at 300 rpm for 6 hours. . Applying the Langmuir model to the experimental data, we can see that the maximum saturated adsorption capacity of phosphorus for ball-milled zerovalent iron-doped sulfur/biochar in deionized water is 25.00mg/g, tap water is 24.42mg/g, and river water is 22.67mg/g. The lake water is 20.53mg/g, see Figure 6. It shows that ball-milled zero-valent iron-doped sulfur/biochar has a good adsorption effect on phosphorus in various water bodies, which means that ball-milled zero-valent iron-doped sulfur/biochar is feasible to remediate actual water bodies.
实施例7Example 7
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在50～80℃下烘干24h，然后粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 50-80°C for 24 hours, then crush it through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于管式炉中，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至400℃，热解2h后自然冷却至室温取出，经1mol/L盐酸浸泡24h后，用去离子水洗至中性，并于60～80℃烘干，得到生物炭载体；Step 2: Place the straw powder obtained in Step 1 into a tube furnace, pass nitrogen into the tube furnace at a flow rate of 400 mL/min, then raise the temperature to 400°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to Take it out at room temperature, soak it in 1 mol/L hydrochloric acid for 24 hours, wash it with deionized water until neutral, and dry it at 60-80°C to obtain the biochar carrier;
步骤三：将步骤二得到的生物炭载体放置于球磨罐中，然后再向罐中加入零价铁粉和单质硫粉，还原铁粉、单质硫粉与生物炭载体质量比为1:1:3，总质量为5g。球磨罐中放入玛瑙研磨球，球磨球大、中、小(直径15、10、5mm)比例为1:1:1，共150g。在氮气保护条件下，密封球磨罐，在室温20～25℃下，将球磨罐放入行星球磨机以380rpm运转205min，每30min改变一次旋转方向，3h后得到球磨零价铁掺杂硫/生物炭复合材料(球磨硫化载铁生物炭)。Step 3: Place the biochar carrier obtained in step 2 into a ball mill tank, and then add zero-valent iron powder and elemental sulfur powder into the tank. The mass ratio of reduced iron powder, elemental sulfur powder and biochar carrier is 1:1: 3. The total mass is 5g. Put agate grinding balls into the ball milling tank. The ratio of large, medium and small ball milling balls (diameter 15, 10, 5mm) is 1:1:1, totaling 150g. Under nitrogen protection conditions, seal the ball mill jar, put the ball mill jar into a planetary ball mill and run it at 380 rpm for 205 minutes at room temperature of 20 to 25°C, changing the direction of rotation every 30 minutes. After 3 hours, ball-milled zero-valent iron-doped sulfur/biochar is obtained. Composite material (ball-milled sulfide-loaded iron biochar).
对比例4Comparative example 4
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在50～80℃下烘干24h，然后粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 50-80°C for 24 hours, then crush it through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于气氛炉内，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至400℃，热解2h后自然冷却至室温取出，经1mol·L-1的HCl浸渍24h后，用去离子水洗至中性，并于60～80℃烘干，得到原始生物炭。Step 2: Place the straw powder obtained in Step 1 into an atmosphere furnace, pass nitrogen into the tubular furnace at a flow rate of 400 mL/min, then raise the temperature to 400°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to room temperature. Take it out, soak it in 1 mol·L-1 HCl for 24 hours, wash it with deionized water until it becomes neutral, and dry it at 60-80°C to obtain the original biochar.
对比例5Comparative example 5
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在50～80℃下烘干24h，然后粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 50-80°C for 24 hours, then crush it through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于气氛炉内，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至400℃，热解2h后自然冷却至室温取出，经1mol·L-1的HCl浸渍24h后，用去离子水洗至中性，并于60～80℃烘干，得到生物炭；Step 2: Place the straw powder obtained in Step 1 into an atmosphere furnace, pass nitrogen into the tubular furnace at a flow rate of 400 mL/min, then raise the temperature to 400°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to room temperature. Take it out, soak it in 1 mol·L-1 HCl for 24 hours, wash it with deionized water until neutral, and dry it at 60-80°C to obtain biochar;
步骤三：将步骤二得到的生物炭3g放置于球磨罐中，球磨罐中放入玛瑙研磨球，球磨球大、中、小(直径15、10、5mm)比例为1:1:1，共150g。在氮气保护条件下，密封球磨罐，在室温20～25℃下，将球磨罐放入行星球磨机以380rpm运转205min，每30min改变一次旋转方向，3h后得到球磨生物炭。Step 3: Place 3g of the biochar obtained in step 2 into a ball milling tank, and put agate grinding balls into the ball milling tank. The ratio of large, medium and small ball milling balls (diameter 15, 10, 5mm) is 1:1:1, total 150g. Under nitrogen protection conditions, seal the ball mill jar, put the ball mill jar into a planetary ball mill and run it at 380 rpm for 205 minutes at room temperature of 20-25°C, changing the direction of rotation every 30 minutes, and obtain ball-milled biochar after 3 hours.
对比例6Comparative example 6
步骤一：将玉米秸秆去除杂质后，用去离子水充分洗净，放入烘箱中在50～80℃下烘干24h，然后粉碎过100目筛，获得秸秆粉末；Step 1: After removing impurities from the corn straw, wash it thoroughly with deionized water, place it in an oven and dry it at 50-80°C for 24 hours, then crush it through a 100-mesh sieve to obtain straw powder;
步骤二：将步骤一得到的秸秆粉末置于气氛炉内，以400mL/min的流速向管式炉内通入氮气，然后以4℃/min升温至400℃，热解2h后自然冷却至室温取出，经1mol·L-1的HCl浸渍24h后，用去离子水洗至中性，并于60～80℃烘干，得到生物炭载体；Step 2: Place the straw powder obtained in Step 1 into an atmosphere furnace, pass nitrogen into the tubular furnace at a flow rate of 400 mL/min, then raise the temperature to 400°C at a rate of 4°C/min, and pyrolyze for 2 hours before naturally cooling to room temperature. Take it out, soak it in 1 mol·L-1 HCl for 24 hours, wash it with deionized water until neutral, and dry it at 60-80°C to obtain the biochar carrier;
步骤三：将步骤二得到的生物炭载体放置于球磨罐中，然后再向罐中加入还原铁粉，还原铁粉与生物炭质量比为1:3，共4g。球磨罐中放入玛瑙研磨球，球磨球大、中、小(直径15、10、5mm)比例为1:1:1，共150g。在氮气保护条件下，密封球磨罐，在室温20～25℃下，将球磨罐放入行星球磨机以380rpm运转205min，每30min改变一次旋转方向，3h后得到球磨零价铁生物炭。Step 3: Place the biochar carrier obtained in Step 2 into a ball mill tank, and then add reduced iron powder to the tank. The mass ratio of reduced iron powder to biochar is 1:3, totaling 4g. Put agate grinding balls into the ball milling tank. The ratio of large, medium and small ball milling balls (diameter 15, 10, 5mm) is 1:1:1, totaling 150g. Under nitrogen protection conditions, seal the ball mill jar and place it into a planetary ball mill at room temperature of 20 to 25°C and run it at 380 rpm for 205 minutes, changing the direction of rotation every 30 minutes. After 3 hours, ball-milled zero-valent iron biochar is obtained.
图1为原始生物炭(对比例4)、球磨生物炭(对比例5)、球磨零价铁/生物炭(对比例6)和球磨硫化载铁生物炭(实施例7)的SEM。图7a、图7b为球磨前后形貌差异，生物炭颗粒主要呈块状结构且大小不均，经过球磨后的生物炭，由于摩擦碰撞导致断裂和变形，形成了细小且相对均匀的颗粒。从图7c可看出，球磨零价铁/生物炭成功负载上了零价铁，同时零价铁生物炭引入球磨生物炭后，能够一定程度抑制零价铁的团聚。由图7d可知，与零价铁生物炭相比球磨硫化载铁生物炭进一步提高了零价铁的分散性。这可能是硫的添加与球磨生物炭产生协同作用，使得零价铁呈现出更加均匀的分布，参见图7。Figure 1 is an SEM of original biochar (Comparative Example 4), ball-milled biochar (Comparative Example 5), ball-milled zerovalent iron/biochar (Comparative Example 6) and ball-milled sulfide iron-loaded biochar (Example 7). Figure 7a and Figure 7b show the difference in morphology before and after ball milling. The biochar particles are mainly in block structure and uneven in size. After ball milling, the biochar breaks and deforms due to friction and collision, forming small and relatively uniform particles. It can be seen from Figure 7c that the ball milled zerovalent iron/biochar was successfully loaded with zerovalent iron. At the same time, the introduction of zerovalent iron biochar into the ball milled biochar can inhibit the agglomeration of zerovalent iron to a certain extent. It can be seen from Figure 7d that compared with zero-valent iron biochar, ball-milled sulfide-loaded iron biochar further improves the dispersion of zero-valent iron. This may be due to the synergistic effect of the addition of sulfur and the ball-milled biochar, making the zerovalent iron more evenly distributed, see Figure 7.
为了确定对四环素的最佳吸附材料，将实施例7与对比例4～6进行四环素吸附量的对比。吸附剂用量为400mg·L-1，四环素浓度为100mg·L-1，在20℃的条件下使用300rpm速度震荡6h，结果显示，原始生物炭(对比例4)吸附四环素的效果最差，吸附量仅为4.3mg·g-1，经球磨改性后球磨生物炭(对比例5)的对四环素的吸附量有一定提升，为37.3mg·g-1。结合SEM分析可知，球磨后MBC的粒径减小，增加了其比表面积以及孔径，提高了对四环素的吸附量。球磨零价铁/生物炭(对比例6)在6h内对四环素的吸附量为102.7mg·g-1，相较于零价铁生物炭，通过引入球磨生物炭和单质硫后，球磨硫化载铁生物炭(实施例7)在对四环素的吸附量提高到245.6mg·g-1，是零价铁生物炭吸附量的2.4倍。表明球磨生物炭和单质硫的引入可以有效提升零价铁的吸附量，因此选择球磨硫化载铁生物炭作为一下研究对象，参见图8。In order to determine the best adsorbent material for tetracycline, Example 7 was compared with Comparative Examples 4-6 in terms of tetracycline adsorption capacity. The adsorbent dosage was 400 mg·L-1 , the tetracycline concentration was 100 mg·L-1 , and the tetracycline was shaken at 300 rpm for 6 hours at 20°C. The results showed that the original biochar (Comparative Example 4) had the worst adsorption effect on tetracycline. The amount of tetracycline adsorbed by the ball-milled biochar (Comparative Example 5) after ball milling modification has been improved to 37.3mg·g-1 . Combined with SEM analysis, it can be seen that the particle size of MBC decreases after ball milling, increasing its specific surface area and pore size, and increasing the adsorption capacity of tetracycline. The adsorption capacity of ball-milled zero-valent iron/biochar (Comparative Example 6) for tetracycline within 6 hours is 102.7mg·g-1 . Compared with zero-valent iron biochar, after the ball-milled biochar and elemental sulfur are introduced, the ball-milled sulfide loading capacity is 102.7 mg·g -1 . The adsorption capacity of iron biochar (Example 7) for tetracycline was increased to 245.6 mg·g-1 , which is 2.4 times the adsorption capacity of zero-valent iron biochar. It shows that the introduction of ball-milled biochar and elemental sulfur can effectively increase the adsorption capacity of zero-valent iron. Therefore, ball-milled sulfide iron-loaded biochar was selected as the research object, see Figure 8.
采用吸附动力学试验了解球磨硫化载铁生物炭在不同温度下对四环素的吸附速度，取实施例制备的球磨硫化载铁生物炭10mg，放入离心管中，加入25ml的100mg·L-1的四环素，分别在293K、303K和313K条件下使用300rpm速度震荡10min，30min，60min，90min，120min，240min和360min。结果显示，球磨硫化载铁生物炭对四环素的吸附过程均可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段。在快速吸附阶段，四环素分子迅速占据球磨硫化载铁生物炭表面丰富的结合位点，随后球磨硫化载铁生物炭表面活性位点逐渐减少，对四环素的吸附速率减缓，参见图9。Adsorption kinetics test was used to understand the adsorption speed of ball-milled sulfide iron-loaded biochar on tetracycline at different temperatures. Take 10 mg of ball-milled iron-loaded sulfide biochar prepared in the example, put it into a centrifuge tube, and add 25 ml of 100 mg·L-1 For tetracycline, shake at 300rpm for 10min, 30min, 60min, 90min, 120min, 240min and 360min respectively under conditions of 293K, 303K and 313K. The results show that the adsorption process of tetracycline by ball-milled sulfide-loaded iron biochar can be divided into rapid adsorption stage, slow adsorption stage and equilibrium adsorption stage. In the rapid adsorption stage, tetracycline molecules quickly occupy the abundant binding sites on the surface of ball-milled iron-loaded sulfide biochar. Then, the active sites on the surface of ball-milled iron-loaded sulfide biochar gradually decrease, and the adsorption rate of tetracycline slows down, see Figure 9.
采用吸附等温线试验确定了球磨硫化载铁生物炭在不同温度下对四环素的最大吸附量，取实施例制备的球磨硫化载铁生物炭10mg于9支离心管中，分别加入150～1500mg·L-1不同浓度的四环素溶液25mL，分别在293K、303K和313K条件下使用300rpm速度震荡6h并测定剩余四环素含量。为得到球磨硫化载铁生物炭对四环素的最大吸附量，采用Langmuir模型进行数据拟合，结果显示，球磨硫化载铁生物炭对四环素在293K、303K和313K条件下的最大吸附量分别为387.2mg·g-1、425.6mg·g-1和505.7mg·g-1。随着温度的升高，球磨硫化载铁生物炭对四环素的吸附量有一定提升，说明吸附过程是吸热的过程，升高温度有利于吸附的进行，参见图10。The adsorption isotherm test was used to determine the maximum adsorption capacity of ball-milled iron-loaded sulfide-loaded biochar for tetracycline at different temperatures. Take 10 mg of ball-milled iron-loaded sulfide-loaded biochar prepared in the example and put it into 9 centrifuge tubes. Add 150 to 1500 mg·L respectively.-1 25 mL of tetracycline solutions of different concentrations were shaken at 300 rpm for 6 hours under conditions of 293K, 303K and 313K respectively and the remaining tetracycline content was measured. In order to obtain the maximum adsorption capacity of tetracycline by ball-milled sulfide-loaded iron-loaded biochar, the Langmuir model was used for data fitting. The results showed that the maximum adsorption capacity of tetracycline by ball-milled sulfide-loaded iron-loaded biochar under the conditions of 293K, 303K and 313K was 387.2mg respectively. ·g-1 , 425.6mg·g-1 and 505.7mg·g-1 . As the temperature increases, the adsorption capacity of ball-milled iron-loaded sulfide-loaded biochar for tetracycline increases to a certain extent, indicating that the adsorption process is an endothermic process, and increasing the temperature is conducive to the progress of adsorption, see Figure 10.
零价铁自身具有极高的反应活性，可以预见在实际的应用过程中易老化失活。为此，针对性的设计实验以探究球磨硫化载铁生物炭在空气中和水中的抗氧化能力和稳定性。Zero-valent iron itself has extremely high reactivity, and it can be expected that it will easily age and become deactivated in actual applications. To this end, experiments were specifically designed to explore the antioxidant capacity and stability of ball-milled sulfide-loaded iron biochar in air and water.
将球磨硫化载铁生物炭在空气中老化，0、5、10、20、40、60天后，分别取老化第0、5、10、20、40、60天后的老化样品10mg于6支离心管中，分别加入100mg·L-1浓度的四环素溶液25mL，在293K条件下使用300rpm速度震荡6h并测定剩余四环素含量；将球磨硫化载铁生物炭在水中老化，0、5、20、40、80、120小时后，分别取老化第0、5、20、40、80、120小时后的老化样品10mg于6支离心管中，分别加入100mg·L-1浓度的四环素溶液25mL，在293K条件下使用300rpm速度震荡6h并测定剩余四环素含量。Aging the ball-milled sulfide iron-loaded biochar in the air. After 0, 5, 10, 20, 40, and 60 days, take 10 mg of the aged samples after aging for 0, 5, 10, 20, 40, and 60 days respectively in 6 centrifuge tubes. , add 25 mL of tetracycline solution with a concentration of 100 mg·L-1 respectively, shake at 300 rpm for 6 hours at 293K, and determine the remaining tetracycline content; age the ball-milled sulfide-loaded iron biochar in water at 0, 5, 20, 40, and 80 , 120 hours later, take 10 mg of the aging samples after aging for 0, 5, 20, 40, 80, and 120 hours respectively into 6 centrifuge tubes, add 25 mL of tetracycline solution with a concentration of 100 mg·L-1 , and heat at 293K Shake at 300 rpm for 6 hours and determine the remaining tetracycline content.
在空气中老化20天后球磨硫化载铁生物炭对四环素的吸附量基本保持不变，可达到239.7mg·g-1；将空气中老化时间进一步延长至40天和60天后发现球磨硫化载铁生物炭对四环素的吸附量都有一定程度降低；分别是217.4mg·g-1和213.5mg·g-1。而未经硫化的零价铁在空气中老化5天后基本失活，对四环素的吸附量仅有14.6mg·g-1，说明该复合材料在空气中具有较高的稳定性，氧气的入侵无法显著影响球磨硫化载铁生物炭的反应活性。在水中老化5小时后，球磨硫化载铁生物炭对四环素的吸附量降低至223.1mg·g-1；在5～80h的老化时间段中可以发现球磨硫化载铁生物炭对四环素的吸附量出现缓慢下降趋势；当球磨硫化载铁生物炭对四环素在水中老化时间继续延长至120小时后，球磨硫化载铁生物炭对四环素的吸附量降低至171.6mg·g-1。而未经硫化处理的零价铁在水中老化5小时后基本失活，吸附量仅为12.7mg·g-1，表明球磨硫化载铁生物炭在水中同样具备较高的稳定性。综合以上分析，相较于未经硫化处理的零价铁，球磨硫化载铁生物炭不仅能够提高对四环素的吸附量，同时具有抗氧化性、稳定性和长时间储存的优点，参见图11。After aging in the air for 20 days, the adsorption capacity of ball-milled sulfide iron-loaded biochar for tetracycline remained basically unchanged and could reach 239.7mg·g-1 ; after further extending the aging time in air to 40 days and 60 days, it was found that ball-milled sulfide iron-loaded biochar The adsorption capacity of tetracycline on carbon decreased to a certain extent; they were 217.4mg·g-1 and 213.5mg·g-1 respectively. However, unsulfated zero-valent iron is basically deactivated after aging in the air for 5 days, and the adsorption capacity of tetracycline is only 14.6mg·g-1 , indicating that the composite material has high stability in the air and cannot be invaded by oxygen. Significantly affects the reactivity of ball-milled sulfide-loaded iron biochar. After aging in water for 5 hours, the adsorption capacity of ball-milled sulfide-loaded iron-loaded biochar for tetracycline decreased to 223.1 mg·g-1 ; during the aging period of 5 to 80 hours, it can be found that the adsorption capacity of ball-milled sulfide-loaded iron-loaded biochar for tetracycline increased. Slow downward trend; when the aging time of tetracycline on ball-milled iron-loaded sulfide biochar in water continued to extend to 120 hours, the adsorption capacity of tetracycline on ball-milled iron-loaded sulfide biochar decreased to 171.6 mg·g-1 . The zero-valent iron that has not been sulfided is basically deactivated after aging in water for 5 hours, and the adsorption capacity is only 12.7mg·g-1 , indicating that ball-milled sulfide iron-loaded biochar also has high stability in water. Based on the above analysis, compared with zero-valent iron without sulfidation treatment, ball-milled sulfide-loaded iron biochar can not only increase the adsorption capacity of tetracycline, but also has the advantages of oxidation resistance, stability and long-term storage, see Figure 11.
为进一步确定球磨硫化载铁生物炭的实际应用价值，测试了球磨硫化载铁生物炭在实际不同水体中的吸附效果。四环素溶液分别使用去离子水、人工湖水和河水配制。取实施例制备的球磨硫化载铁生物炭10mg于9支离心管中，分别加入150～1500mg·L-1不同浓度的四环素溶液25mL，在293K条件下使用300rpm速度震荡6h并测定剩余四环素含量。为得到球磨硫化载铁生物炭对四环素的最大吸附量，采用Langmuir模型进行数据拟合，可以看到去离子水中球磨硫化载铁生物炭对四环素的最大饱和吸附量为387.2mg·g-1，湖水为266.09mg·g-1，河水为246.29mg·g-1，参见图12。表明球磨硫化载铁生物炭在实际水体中对四环素均有较好的吸附效果，这意味着球磨硫化载铁生物炭对实际水体的修复是可行的。In order to further determine the practical application value of ball-milled sulfide iron-loaded biochar, the adsorption effect of ball-milled sulfide iron-loaded biochar in actual different water bodies was tested. Tetracycline solutions were prepared using deionized water, artificial lake water and river water respectively. Take 10 mg of the ball-milled sulfide iron-loaded biochar prepared in the example and put it into 9 centrifuge tubes. Add 25 mL of tetracycline solutions of different concentrations from 150 to 1500 mg·L-1 respectively. Shake at 300 rpm for 6 hours under 293K conditions and measure the remaining tetracycline content. In order to obtain the maximum adsorption capacity of tetracycline by ball-milled sulfide-loaded iron-loaded biochar, the Langmuir model was used for data fitting. It can be seen that the maximum saturated adsorption capacity of tetracycline by ball-milled sulfide-loaded iron-loaded biochar in deionized water is 387.2mg·g-1 . The lake water is 266.09mg·g-1 and the river water is 246.29mg·g-1 , see Figure 12. It shows that ball-milled sulfide iron-loaded biochar has a good adsorption effect on tetracycline in actual water bodies, which means that ball-milled sulfide iron-loaded biochar is feasible to remediate actual water bodies.
本发明提供了一种球磨零价铁掺杂硫/生物炭复合材料及其制备方法与应用的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，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，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。The present invention provides a ball-milled zero-valent iron-doped sulfur/biochar composite material and its preparation method and application ideas and methods. There are many methods and approaches to specifically implement this technical solution. The above is only the preferred implementation of the present invention. method, it should be pointed out that for those of ordinary skill in the art, several improvements and modifications can be made without departing from the principles of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented using existing technologies.
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