技术领域technical field
本发明属于废物处理领域，更具体地，涉及一种磁性生物炭吸附材料及其制备方法，尤其适用于植物基废料(如植物生物质，例如农林废弃物)的再回收利用，制备得到的磁性生物炭可作为吸附材料应用。The invention belongs to the field of waste treatment, and more specifically relates to a magnetic biochar adsorption material and a preparation method thereof, which is especially suitable for the recycling of plant-based waste (such as plant biomass, such as agricultural and forestry waste), and the prepared magnetic Biochar can be used as an adsorbent material.
背景技术Background technique
农林废弃物主要包括水果残渣、树皮、秸秆、稻壳等，是三大类生物质之一的植物生物质重要的组成部分(其他两大类生物质分别为动物生物质、以及微生物生物质)。我国每年产生大量的农林废弃物，在广大的农村，这些废弃物主要用于直接燃烧产热，还有一部分用作饲料、肥料和造浆造纸工业原料，但所占利用率不足农林废弃物的50％，每年仍有大部分农林废弃物被弃置于自然环境或露天焚烧，在造成环境污染的同时又造成资源的极大浪费。石油、煤炭等化石资源大量消耗所引发的资源危机，使得将农林废弃物等可再生资源用于工业生产成为了一种新的发展趋势，越来越多的国家特别是发达国家已经把农林生物质等可再生资源的转化利用列入社会经济可持续发展的重要战略。Agricultural and forestry waste mainly includes fruit residues, bark, straw, rice husk, etc., and is an important part of plant biomass, one of the three major types of biomass (the other two types of biomass are animal biomass and microbial biomass. ). A large amount of agricultural and forestry wastes are produced in my country every year. In the vast rural areas, these wastes are mainly used for direct combustion to produce heat, and some of them are used as feed, fertilizer and raw materials for pulp and paper industry, but the utilization rate is not enough for agricultural and forestry wastes. 50%, most of the agricultural and forestry wastes are still disposed of in the natural environment or burned in the open every year, causing environmental pollution and a great waste of resources at the same time. The resource crisis caused by the massive consumption of fossil resources such as oil and coal has made it a new development trend to use renewable resources such as agricultural and forestry wastes for industrial production. More and more countries, especially developed countries, have used agricultural and forestry waste The transformation and utilization of materials and other renewable resources is listed as an important strategy for the sustainable development of society and economy.
将农林废弃物资源转化为化工原料或新型工业材料有两种方式：一种是将农业林废弃物分离为纤维素、半纤维素和木质素后分别转化为工业产品，这种方法转化效率高，农林废弃物可以获得最大程度的高值化利用，但操作复杂，工艺繁琐；另一种是将农林废弃物全部组分直接转化为工业产品，这种方式不仅能够简化工艺，降低生产成本，而且可以减少农林废弃物组分分离过程中带来的环境压力。农林废弃物作为生物吸附剂可用于去除工业废水中油污、重金属离子，还可以处理有机污染物及放射性废水，甚至可以用来从海水中回收贵重金属，应用前景十分广阔。近年来随着工业的快速发展和城市现代化的进程加快，环境污染问题愈发严重，其中由重金属污染所引发的环境灾难性质恶劣，引发了各方关注。通过采用经济、有效、环保的方法来治理重金属污染已成为当前水处理领域的重要研究课题。There are two ways to convert agricultural and forestry waste resources into chemical raw materials or new industrial materials: one is to separate agricultural and forestry waste into cellulose, hemicellulose and lignin and then convert them into industrial products respectively. This method has high conversion efficiency , agricultural and forestry waste can obtain the maximum high-value utilization, but the operation is complicated and the process is cumbersome; the other is to directly convert all components of agricultural and forestry waste into industrial products. This method can not only simplify the process and reduce production costs, Moreover, the environmental pressure brought about in the separation process of agricultural and forestry waste components can be reduced. As a biosorbent, agricultural and forestry waste can be used to remove oil pollution and heavy metal ions in industrial wastewater, and can also treat organic pollutants and radioactive wastewater, and can even be used to recover precious metals from seawater. The application prospect is very broad. In recent years, with the rapid development of industry and the acceleration of urban modernization, the problem of environmental pollution has become more and more serious. Among them, the environmental disaster caused by heavy metal pollution is bad in nature and has aroused the attention of all parties. It has become an important research topic in the field of water treatment to control heavy metal pollution by adopting economical, effective and environmentally friendly methods.
直接应用农林废弃物作为重金属吸附材料存在吸附容量小、稳定性差、难以长期保存的缺点，将废物生物质进行活化制备生物炭是一种常用的改性方法。但是，为了保证较大比表面积，活化制备的生物炭多为粉末状，粒径小、机械强度低，其在实际应用过程中固液分离难度大、循环利用成本高，限制了生物炭吸附材料的规模化应用。The direct application of agricultural and forestry wastes as heavy metal adsorption materials has the disadvantages of small adsorption capacity, poor stability, and difficulty in long-term storage. Activation of waste biomass to prepare biochar is a commonly used modification method. However, in order to ensure a large specific surface area, the biochar prepared by activation is mostly in the form of powder, with small particle size and low mechanical strength. It is difficult to separate solid and liquid in the actual application process and the cost of recycling is high, which limits the biochar adsorption materials. large-scale application.
结合磁分离技术而制备的磁性生物炭在外加磁场的作用下可以实现生物吸附剂的快速分离，提高污水处置效率，是一种新型的吸附材料。已报道的磁性生物炭吸附剂制备方法包括浸渍法、共价交联法、包覆法以及化学共沉淀法。专利CN103480331A和专利CN104258823A采用浸渍法将农林废弃物浸泡在铁离子溶液中然后在无氧条件下焙烧得到磁性炭材料。专利CN103316636A以生物质为原材料制备活性炭，将酸洗后的活性炭浸渍在事先制备的四氧化三铁溶液中，通过吸附作用将四氧化三铁吸附于活性炭上得到磁性炭。专利CN104028214A将农林废弃物与三价铁离子超声混合负载，加入氢氧化钠沉淀后，经低温水热碳化反应得到生物质碳基磁性吸附材料。专利CN101314123A将磁性纳米粒子与黄孢原毛平革菌菌粉混合物加入到海藻酸钠溶液中，通过包埋固化的方法得到磁性生物吸附剂。The magnetic biochar prepared by combining magnetic separation technology can realize the rapid separation of biosorbent under the action of external magnetic field and improve the efficiency of sewage treatment. It is a new type of adsorption material. The reported preparation methods of magnetic biochar adsorbents include impregnation method, covalent cross-linking method, coating method and chemical co-precipitation method. Patent CN103480331A and patent CN104258823A adopt impregnation method to soak agricultural and forestry wastes in iron ion solution and then roast under anaerobic conditions to obtain magnetic carbon materials. Patent CN103316636A uses biomass as raw material to prepare activated carbon, soaks the acid-washed activated carbon in the pre-prepared ferric oxide solution, and absorbs ferric oxide on the activated carbon by adsorption to obtain magnetic carbon. In patent CN104028214A, agricultural and forestry wastes and ferric ions are ultrasonically mixed and loaded, and sodium hydroxide is added for precipitation, followed by low-temperature hydrothermal carbonization to obtain biomass carbon-based magnetic adsorption materials. Patent CN101314123A adds a mixture of magnetic nanoparticles and Phanerochaete chrysosporium powder into sodium alginate solution, and obtains a magnetic biosorbent by embedding and solidifying.
上述这些方法均存在不同程度的局限性：浸渍法依靠磁性粒子与生物质之间的物理吸附形成的联接稳定性不佳；共价交联法操作条件复杂，而且会消耗吸附材料表面官能团，降低材料吸附性能；包覆法需要添加藻酸钠等外加材料作为包埋介质；化学共沉淀法应用广泛但制备过程中容易堵塞生物材料孔隙结构降低比表面积，且磁核稳定性较差。The above-mentioned methods all have limitations to varying degrees: the impregnation method relies on the physical adsorption between the magnetic particles and the biomass to form a poor connection stability; Material adsorption performance; the coating method needs to add sodium alginate and other external materials as the embedding medium; the chemical co-precipitation method is widely used, but it is easy to block the pore structure of biological materials during the preparation process to reduce the specific surface area, and the stability of the magnetic core is poor.
发明内容Contents of the invention
针对现有技术的以上缺陷或改进需求，本发明的目的在于提供一种磁性生物炭吸附材料及其制备方法，其中通过对制备方法中关键的生物质原料的前处理工艺、溶剂热反应的具体条件(包括前驱体的组成与配比、溶剂类型、反应温度及时间等)进行改进，与现有技术相比能够有效解决磁性生物炭材料磁性粒子与生物质之间联接稳定性不佳的问题，并且该磁性生物炭吸附材料具有良好的吸附性能，分离速度快。In view of the above defects or improvement needs of the prior art, the object of the present invention is to provide a magnetic biochar adsorption material and its preparation method, wherein the key biomass raw material pretreatment process and solvothermal reaction in the preparation method are specifically Conditions (including the composition and proportion of the precursor, solvent type, reaction temperature and time, etc.) are improved, and compared with the existing technology, it can effectively solve the problem of poor connection stability between the magnetic particles of the magnetic biochar material and the biomass , and the magnetic biochar adsorption material has good adsorption performance and fast separation speed.
为实现上述目的，按照本发明的一个方面，提供了一种磁性生物炭吸附材料的制备方法，其特征在于，包括以下步骤：In order to achieve the above object, according to one aspect of the present invention, a kind of preparation method of magnetic biochar adsorption material is provided, it is characterized in that, comprises the following steps:
(1)生物炭的制备：(1) Preparation of biochar:
以植物生物质经过干燥处理、以及破碎处理得到的粉末为原材料，在200℃～1000℃的无氧条件下焙烧1h～4h，得到多孔状的生物炭；The powder obtained by drying and crushing plant biomass is used as raw material, and roasted under anaerobic conditions at 200°C to 1000°C for 1h to 4h to obtain porous biochar;
(2)三价铁前驱液的制备：(2) Preparation of trivalent iron precursor solution:
以乙二醇为分散剂，向该乙二醇中加入固态的三价铁盐，使所述三价铁盐与所述乙二醇的固体质量与液体体积之比为1:(20～100)mg/L，接着向该乙二醇中继续加入醋酸钠和表面活性剂，搅拌后形成分散系，该分散系即三价铁前驱液；该分散系中，所述三价铁盐、所述醋酸钠与所述表面活性剂三者的质量比为1:12:(3.5～21)；Using ethylene glycol as a dispersant, adding solid ferric salt to the ethylene glycol, so that the ratio of the solid mass and liquid volume of the ferric salt to the ethylene glycol is 1:(20～100 ) mg/L, then continue to add sodium acetate and surfactant in this ethylene glycol, form dispersion system after stirring, and this dispersion system is trivalent iron precursor solution; In this dispersion system, described ferric salt, the The mass ratio of sodium acetate and the surfactant three is 1:12:(3.5～21);
(3)溶剂热反应制备磁性生物炭吸附材料：(3) Preparation of magnetic biochar adsorption material by solvothermal reaction:
将所述步骤(1)得到的所述生物炭与所述步骤(2)得到的所述三价铁前驱液两者混合均匀得到混合物，该混合物中所述生物炭与铁元素的质量比为(0.5～10):1；接着，将所述混合物置于聚四氟乙烯水热反应釜中，并在200℃下进行溶剂热反应8h～12h，得到的溶剂热产物即磁性生物炭吸附材料。The biochar obtained in the step (1) is mixed with the ferric iron precursor solution obtained in the step (2) to obtain a mixture, and the mass ratio of the biochar to the iron element in the mixture is: (0.5～10): 1; Next, the mixture is placed in a polytetrafluoroethylene hydrothermal reaction kettle, and a solvothermal reaction is carried out at 200°C for 8h～12h, and the obtained solvothermal product is a magnetic biochar adsorption material .
作为本发明的进一步优选，所述步骤(1)中，所述植物生物质在进行所述干燥处理前还经过了洗涤处理；所述粉末的目数不小于60目；优选的，所述植物生物质为农林废弃物；优选的，所述农林废弃物为秸秆、树皮、果皮、果核、落叶、花生壳、玉米芯、锯末、甘蔗渣中的至少一种。As a further preference of the present invention, in the step (1), the plant biomass has also been washed before the drying treatment; the mesh number of the powder is not less than 60 mesh; preferably, the plant biomass The biomass is agricultural and forestry waste; preferably, the agricultural and forestry waste is at least one of straw, bark, fruit peel, fruit core, fallen leaves, peanut shells, corncobs, sawdust, and bagasse.
作为本发明的进一步优选，所述步骤(1)中，所述焙烧是在500℃下进行的。As a further preference of the present invention, in the step (1), the calcination is carried out at 500°C.
作为本发明的进一步优选，所述步骤(2)中，所述三价铁盐为氯化铁、硫酸铁、硝酸铁中的至少一种；所述三价铁盐与所述乙二醇的固体质量与液体体积之比为1:60mg/L。As a further preference of the present invention, in the step (2), the ferric salt is at least one of ferric chloride, ferric sulfate, and ferric nitrate; the ferric salt and the ethylene glycol The ratio of solid mass to liquid volume is 1:60mg/L.
作为本发明的进一步优选，所述步骤(2)中，所述表面活性剂为聚乙二醇、聚二甲基二烯丙基氯化铵、柠檬酸钠中的至少一种。As a further preference of the present invention, in the step (2), the surfactant is at least one of polyethylene glycol, polydimethyldiallylammonium chloride, and sodium citrate.
作为本发明的进一步优选，所述步骤(3)中，所述溶剂热产物是经过分离、洗涤、并在60℃下干燥至少6h，从而得到所述磁性生物炭吸附材料。As a further preference of the present invention, in the step (3), the solvothermal product is separated, washed, and dried at 60° C. for at least 6 hours, so as to obtain the magnetic biochar adsorption material.
作为本发明的进一步优选，所述步骤(3)中，所述混合物中所述生物炭与铁元素的质量比为5.5:1；所述溶剂热反应的时间为10h。As a further preference of the present invention, in the step (3), the mass ratio of biochar to iron in the mixture is 5.5:1; the solvothermal reaction time is 10 h.
作为本发明的进一步优选，所述步骤(2)中，加入的所述醋酸钠为无水醋酸钠。As a further preference of the present invention, in the step (2), the sodium acetate added is anhydrous sodium acetate.
按照本发明的另一方面，本发明提供了利用上述制备方法制备得到的磁性生物炭吸附材料。According to another aspect of the present invention, the present invention provides the magnetic biochar adsorption material prepared by the above preparation method.
通过本发明所构思的以上技术方案，与现有技术相比，由于采用溶剂热法制备磁性生物炭材料，首先是将原始生物质材料(即植物生物质)经过一定温度下的无氧焙烧处理得到生物炭，同时配制三价铁前驱液，并控制该三价铁前驱液中三价铁盐、醋酸钠、表面活性剂与乙二醇四者的比例，再将生物炭与该三价铁前驱液按一定比例混合得到溶剂热反应的前驱体，通过制备方法各个步骤的整体配合，使得制得的磁性生物炭材料具有良好的稳定性以及吸附效果。溶剂热法虽然被广泛用于磁性纳米材料合成，操作简便，所形成材料性能均一，但是利用该法制备磁性生物吸附剂的研究目前还未见报道；本发明采用溶剂热反应，通过溶剂热反应条件(包括前驱体的组成与配比、溶剂类型、溶剂热反应温度及时间等)与生物质的前处理工艺等其他步骤之间的相互配合，通过溶剂热法可以成功的制备出磁性生物吸附剂，具有良好的稳定性和吸附性能，克服了传统方法的局限性。Through the above technical scheme conceived by the present invention, compared with the prior art, since the magnetic biochar material is prepared by the solvothermal method, the original biomass material (i.e. plant biomass) is first subjected to anaerobic roasting treatment at a certain temperature Obtain biochar, prepare ferric iron precursor at the same time, and control the ratio of ferric salt, sodium acetate, surfactant and ethylene glycol in the ferric precursor, and then mix biochar with the ferric The precursor solution is mixed according to a certain ratio to obtain a solvothermal reaction precursor, and through the overall cooperation of each step of the preparation method, the prepared magnetic biochar material has good stability and adsorption effect. Although the solvothermal method is widely used in the synthesis of magnetic nanomaterials, it is easy to operate and the properties of the formed materials are uniform, but the research on the preparation of magnetic biosorbents by this method has not been reported yet; Conditions (including the composition and ratio of precursors, solvent type, solvothermal reaction temperature and time, etc.) and other steps such as biomass pretreatment process can be successfully prepared by solvothermal method. agent, has good stability and adsorption properties, and overcomes the limitations of traditional methods.
本发明制得的磁性生物炭吸附材料包括三维多孔结构的生物炭骨架和附着在生物炭骨架上的纳米四氧化三铁磁性粒子。本发明是将农林废弃物活化成具有三维多孔结构的生物炭，利用生物炭表面丰富的官能团吸附、螯合Fe3+，并在还原氛围下将其转化为固定在生物炭骨架上的纳米Fe3O4粒子，工艺操作简单。相比于化学共沉淀法，所负载的纳米Fe3O4磁性粒子结合稳定形貌均一，晶相纯度高，磁性优良。依靠表面活性剂的修饰作用，磁核的稳定性与吸附剂的吸附性能均得到了提升。The magnetic biochar adsorption material prepared by the invention comprises a three-dimensional porous structure biochar skeleton and nano ferroferric oxide magnetic particles attached to the biochar skeleton. The invention activates agricultural and forestry wastes into biochar with a three-dimensional porous structure, utilizes the abundant functional groups on the surface of biochar to absorb and chelate Fe3+ , and converts it into nano-Fe fixed on the skeleton of biochar under reducing atmosphere3 O4 particles, the process is easy to operate. Compared with the chemical co-precipitation method, the loaded nano-Fe3 O4 magnetic particles have a stable combination, uniform morphology, high crystal phase purity, and excellent magnetic properties. Relying on the modification of the surfactant, the stability of the magnetic core and the adsorption performance of the adsorbent have been improved.
本发明制备得到的磁性生物炭材料，结合了生物炭的吸附性能和磁性四氧化三铁的磁分离特性，对重金属离子具有吸附效率高和快速分离的优点，在重金属处理领域有广阔的应用前景。The magnetic biochar material prepared by the present invention combines the adsorption performance of biochar and the magnetic separation characteristics of magnetic ferroferric oxide, has the advantages of high adsorption efficiency and rapid separation of heavy metal ions, and has broad application prospects in the field of heavy metal treatment .
具体来说，本发明能够取得下列有益效果：Specifically, the present invention can obtain the following beneficial effects:
(1)本发明提供的磁性生物炭吸附材料的制备方法，采用农林废弃物为原料制备的生物炭与三价铁盐的前驱液混合经溶剂热反应制得，成本低、操作简便，制得的吸附材料形貌良好，结构优良，生物炭与纳米四氧化三铁颗粒紧密结合，依靠表面活性剂的修饰作用，磁核性能稳定。(1) The preparation method of the magnetic biochar adsorption material provided by the present invention is prepared by mixing the biochar prepared from agricultural and forestry wastes with the precursor solution of ferric salt through solvothermal reaction, which is low in cost and easy to operate. The adsorption material has a good shape and excellent structure, and the biochar is closely combined with the nanometer ferric oxide particles, relying on the modification effect of the surfactant, the magnetic core performance is stable.
(2)本发明提供的磁性生物炭吸附材料，成本低、吸附效率高、分离速度快，有广阔的应用前景，可用于废水中重金属离子、染料、色素等的去除。(2) The magnetic biochar adsorption material provided by the present invention has low cost, high adsorption efficiency and fast separation speed, and has broad application prospects, and can be used for the removal of heavy metal ions, dyes, pigments, etc. in wastewater.
附图说明Description of drawings
图1是本发明溶剂热法合成磁性生物吸附材料的机理示意图；Fig. 1 is the schematic diagram of the mechanism of the magnetic biological adsorption material synthesized by solvothermal method of the present invention;
图2是梧桐叶生物炭(即以梧桐叶作为反应的植物生物质原料，经无氧焙烧处理后得到的生物炭)的SEM图像(该SEM图像的放大倍数为2500倍)；Fig. 2 is the SEM image (the magnification of this SEM image is 2500 times) of sycamore leaf biochar (i.e. with sycamore leaf as the plant biomass raw material of reaction, the biochar obtained after anaerobic roasting process);
图3是本发明制得的磁性梧桐叶生物吸附材料SEM图像(该SEM图像的放大倍数为10000倍)；Fig. 3 is the SEM image (magnification of this SEM image is 10000 times) of the magnetic sycamore leaf biosorption material that the present invention makes;
图4是实施例1所制备的梧桐叶磁性生物炭吸附材料的XRD图谱；Fig. 4 is the XRD spectrum of the phoenix leaf magnetic biochar adsorption material prepared by embodiment 1;
图5是本发明制得的磁性梧桐叶生物吸附材料磁分离过程示意。Fig. 5 is a schematic diagram of the magnetic separation process of the magnetic sycamore leaf biosorbent material prepared in the present invention.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.
本发明中磁性生物炭吸附材料的制备方法，包括以下步骤：The preparation method of magnetic biochar adsorption material among the present invention, comprises the following steps:
(1)制备生物炭：以植物生物质(如，农林废弃物)经洗涤、干燥、破碎、过60目筛的粉末为原材料，在200-1000℃无氧条件下焙烧活化处理，焙烧时间控制在1-4h，得到生物炭。(1) Preparation of biochar: use plant biomass (such as agricultural and forestry waste) as raw material after washing, drying, crushing, and powder passing through a 60-mesh sieve, and roast and activate it at 200-1000°C under anaerobic conditions, and the roasting time is controlled In 1-4h, biochar is obtained.
(2)制备三价铁前驱液：三价铁盐通过磁力搅拌溶于乙二醇中，三价铁盐与乙二醇的固体质量和液体体积之比为1:(20-100)(单位mg/L)之间，优选1:60，随后加入无水醋酸钠和表面活性剂，持续搅拌形成均一的三价铁前驱液，所述前驱液中三价铁盐:无水醋酸钠:表面活性剂的质量比控制在1:12:3.5-21之间。(2) Preparation of ferric iron precursor solution: ferric salt is dissolved in ethylene glycol by magnetic stirring, and the ratio of solid mass and liquid volume of ferric salt to ethylene glycol is 1: (20-100) (unit mg/L), preferably 1:60, then add anhydrous sodium acetate and surfactant, continue stirring to form a uniform ferric precursor solution, ferric salt in the precursor solution: anhydrous sodium acetate: surface The mass ratio of active agent is controlled between 1:12:3.5-21.
(3)溶剂热反应制备磁性生物炭：生物炭与乳浊液充分混匀形成混合物，所述混合物中生物炭与铁元素的质量比为(10-0.5):1之间；(3) Preparation of magnetic biochar by solvothermal reaction: the biochar and the emulsion are fully mixed to form a mixture, and the mass ratio of biochar to iron in the mixture is between (10-0.5):1;
接着，将该混合物倒入聚四氟乙烯水热反应釜中，200℃下溶剂热反应8-12h，反应完成后自然冷却，得到的产品经分离洗涤，置于真空干燥箱中于60℃干燥6h得到磁性生物炭。Next, pour the mixture into a polytetrafluoroethylene hydrothermal reaction kettle, conduct solvothermal reaction at 200°C for 8-12 hours, cool naturally after the reaction is completed, separate and wash the obtained product, and dry it in a vacuum oven at 60°C 6h to obtain magnetic biochar.
上述制备方法得到的磁性生物吸附材料主要是通过溶剂热法在高温下发生成核反应使得Fe3O4纳米粒子生长在生物炭表面而形成的，其机理如图1所示。由于生物炭表面含有大量羧基、羟基等官能团，能够吸附、螯合三价铁前驱液中的Fe3+。而乙二醇是种高沸点的还原性溶剂，高温时在无水醋酸钠的协同作用下可以部分还原吸附在生物炭表面的Fe3+并在其表面形成Fe3O4纳米微晶。此外，无水醋酸钠作为静电稳定剂加入到反应体系中，在表面活性剂协同作用下可以控制晶体的生长过程，防止反应过程中纳米微晶发生大规模团聚，与此同时，通过表面活性剂对纳米粒子进行表面修饰，提升其稳定性。随着反应温度的升高，纳米微晶不断生长并最终在生物炭表面负载上形貌规则、磁性良好的Fe3O4纳米粒子。The magnetic biosorption material obtained by the above preparation method is mainly formed by nucleation reaction at high temperature by solvothermal method to make Fe3 O4 nanoparticles grow on the surface of biochar. The mechanism is shown in Figure 1 . Since the surface of biochar contains a large number of functional groups such as carboxyl and hydroxyl groups, it can adsorb and chelate Fe3+ in the ferric iron precursor. Ethylene glycol is a reducing solvent with a high boiling point. Under the synergistic effect of anhydrous sodium acetate at high temperature, Fe3+ adsorbed on the surface of biochar can be partially reduced and Fe3 O4 nanocrystals can be formed on the surface. In addition, anhydrous sodium acetate is added to the reaction system as an electrostatic stabilizer, which can control the crystal growth process under the synergistic effect of surfactants and prevent large-scale agglomeration of nanocrystals during the reaction process. Surface modification of nanoparticles to improve their stability. With the increase of the reaction temperature, the nano-crystallites continued to grow and finally supported the Fe3 O4 nanoparticles with regular morphology and good magnetic properties on the surface of biochar.
以下为具体实施例The following are specific examples
实施例1Example 1
本实施例中的磁性生物炭吸附材料的制备方法及其应用示例，包括以下步骤：The preparation method and application examples of the magnetic biochar adsorption material in this embodiment include the following steps:
(1)制备生物炭：农林废弃物为校园内收集的梧桐落叶，经洗涤、干燥、破碎、过60目后的粉末为原材料，置于马弗炉中在500℃无氧条件下焙烧2h，得到梧桐叶生物炭，图2为其SEM图像。(1) Preparation of biochar: the agricultural and forestry wastes are the fallen leaves of sycamore collected in the campus, and the powder after washing, drying, crushing and passing through 60 meshes is used as the raw material. The sycamore leaf biochar was obtained, and Fig. 2 is its SEM image.
(2)制备三价铁前驱液：取2.7g FeCl3·6H2O溶于80mL乙二醇溶液中，随后往其中加入7.2g无水醋酸钠和2g聚乙二醇(分子量为4000)，通过磁力搅拌持续搅拌30min，使其形成均一的乳浊液。(2) Preparation of ferric iron precursor solution: Dissolve 2.7g FeCl3 6H2 O in 80mL ethylene glycol solution, then add 7.2g anhydrous sodium acetate and 2g polyethylene glycol (molecular weight: 4000) to it, Stir continuously for 30 min by magnetic stirring to form a uniform emulsion.
(3)溶剂热反应制备磁性生物炭：往上述乳浊液加入0.77g梧桐基生物炭，通过磁力搅拌2h，使生物炭与乳浊液充分混匀。(3) Preparation of magnetic biochar by solvothermal reaction: add 0.77 g of sycamore-based biochar to the above emulsion, and stir for 2 hours by magnetic force to fully mix the biochar and emulsion.
(4)将混匀后的乳浊液倒入100mL聚四氟乙烯水热反应釜中，在室温下以3℃/min的升温速率使炉内温度升至200℃后在该温度下反应10h，反应结束后等溶剂热反应釜自然冷却，通过磁分离获得磁性生物炭并用乙醇和去离子水洗涤多次，最后将磁性生物炭置于真空干燥箱中于60℃下干燥6h得到磁性生物炭吸附材料。由于溶剂热反应中炭与铁元素质量比仅为1.375，其表面Fe3O4负载量较高，图3为其SEM图像。通过XRD分析所得吸附材料的晶型，结果如图4所示，其中6个主峰均为反式尖晶石结构的Fe3O4(JCPDS 75-1609)，样品噪音较大，表明样品中含有非晶态的生物炭成分。(4) Pour the mixed emulsion into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, raise the temperature in the furnace to 200°C at a rate of 3°C/min at room temperature and react at this temperature for 10h After the reaction, wait for the solvothermal reactor to cool naturally, obtain magnetic biochar by magnetic separation and wash it with ethanol and deionized water several times, and finally place the magnetic biochar in a vacuum drying oven at 60°C for 6 hours to obtain magnetic biochar Adsorbent material. Since the mass ratio of carbon to iron in the solvothermal reaction is only 1.375, the loading of Fe3 O4 on the surface is relatively high. Figure 3 shows its SEM image. The crystal form of the obtained adsorption material was analyzed by XRD, and the results are shown in Figure 4. The six main peaks were Fe3 O4 (JCPDS 75-1609) with a trans-spinel structure. The noise of the sample was relatively large, indicating that the sample contained Amorphous biochar component.
(5)取制备的磁性生物炭吸附材料20mg于10mL浓度为50mg/L的Cr(VI)溶液中，在室温下静态吸附24h，通过外加磁场进行固液分离操作，如图5所示。并通过分光光度法测定不同吸附时间时溶液中Cr(VI)的吸附率，得到磁性生物炭吸附材料对Cr(VI)离子的平衡吸附去除率为87.5％。(5) Take 20 mg of the prepared magnetic biochar adsorption material in 10 mL of Cr(VI) solution with a concentration of 50 mg/L, statically adsorb at room temperature for 24 h, and perform solid-liquid separation operation by applying an external magnetic field, as shown in Figure 5. The adsorption rate of Cr(VI) in the solution was measured by spectrophotometry at different adsorption times, and the equilibrium adsorption and removal rate of Cr(VI) ions by the magnetic biochar adsorption material was 87.5%.
实施例2Example 2
本实施例中的磁性生物炭吸附材料的制备方法及其应用示例，包括以下步骤：The preparation method and application examples of the magnetic biochar adsorption material in this embodiment include the following steps:
(1)制备生物炭：农林废弃物为校园内收集的梧桐落叶，经洗涤、干燥、破碎、过60目后的粉末为原材料，置于马弗炉中在500℃无氧条件下焙烧2h，得到梧桐叶生物炭。(1) Preparation of biochar: the agricultural and forestry wastes are the fallen leaves of sycamore collected in the campus, and the powder after washing, drying, crushing and passing through 60 meshes is used as the raw material. Get sycamore leaf biochar.
(2)制备三价铁前驱液：取2.7g FeCl3·6H2O溶于80mL乙二醇溶液中，随后往其中加入7.2g无水醋酸钠和2g聚乙二醇(分子量为4000)，通过磁力搅拌持续搅拌30min，使其形成均一的乳浊液。(2) Preparation of ferric iron precursor solution: Dissolve 2.7g FeCl3 6H2 O in 80mL ethylene glycol solution, then add 7.2g anhydrous sodium acetate and 2g polyethylene glycol (molecular weight: 4000) to it, Stir continuously for 30 min by magnetic stirring to form a uniform emulsion.
(3)溶剂热反应制备磁性生物炭：往上述乳浊液加入1.54g梧桐基生物炭，通过磁力搅拌2h，使生物炭与乳浊液充分混匀。(3) Preparation of magnetic biochar by solvothermal reaction: add 1.54 g of sycamore-based biochar to the above emulsion, and stir for 2 hours by magnetic force to fully mix the biochar and emulsion.
(4)将混匀后的乳浊液倒入100mL聚四氟乙烯水热反应釜中，在室温下以3℃/min的升温速率使炉内温度升至200℃后在该温度下反应10h，反应结束后等溶剂热反应釜自然冷却，通过磁分离获得磁性生物炭并用乙醇和去离子水洗涤多次，最后将磁性生物炭置于真空干燥箱中于60℃下干燥6h得到磁性生物炭吸附材料。(4) Pour the mixed emulsion into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, raise the temperature in the furnace to 200°C at a rate of 3°C/min at room temperature and react at this temperature for 10h After the reaction, wait for the solvothermal reactor to cool naturally, obtain magnetic biochar by magnetic separation and wash it with ethanol and deionized water several times, and finally place the magnetic biochar in a vacuum drying oven at 60°C for 6 hours to obtain magnetic biochar Adsorbent material.
(5)取制备的磁性生物炭吸附材料20mg于10mL浓度为50mg/L的Cr(VI)溶液中，在室温下静态吸附24h，通过外加磁场进行固液分离操作。并依靠分光光度法测定不同吸附时间时溶液中Cr(VI)的吸附率，得到磁性生物炭吸附材料对Cr(VI)离子的平衡吸附率为83.7％。(5) Take 20 mg of the prepared magnetic biochar adsorption material in 10 mL of Cr(VI) solution with a concentration of 50 mg/L, statically adsorb at room temperature for 24 h, and perform solid-liquid separation operation by applying an external magnetic field. And relying on spectrophotometry to measure the adsorption rate of Cr(VI) in the solution at different adsorption times, the equilibrium adsorption rate of Cr(VI) ion by the magnetic biochar adsorption material is 83.7%.
实施例3Example 3
本实施例中的磁性生物炭吸附材料的制备方法及其应用示例，包括以下步骤：The preparation method and application examples of the magnetic biochar adsorption material in this embodiment include the following steps:
(1)制备生物炭：农林废弃物为校园内收集的银杏落叶，经洗涤、干燥、破碎、过60目筛后的粉末为原材料，置于马弗炉中在500℃无氧条件下焙烧2h，得到银杏叶生物炭。(1) Preparation of biochar: The agricultural and forestry wastes are the fallen ginkgo leaves collected in the campus. The powder after washing, drying, crushing and passing through a 60-mesh sieve is used as the raw material, which is roasted in a muffle furnace at 500°C for 2 hours under anaerobic conditions. , to obtain ginkgo biloba biochar.
(2)制备三价铁前驱液：取2.7g FeCl3·6H2O溶于80mL乙二醇溶液中，随后往其中加入7.2g无水醋酸钠和2g聚乙二醇(分子量为4000)，通过磁力搅拌持续搅拌30min，使其形成均一的乳浊液。(2) Preparation of ferric iron precursor solution: Dissolve 2.7g FeCl3 6H2 O in 80mL ethylene glycol solution, then add 7.2g anhydrous sodium acetate and 2g polyethylene glycol (molecular weight: 4000) to it, Stir continuously for 30 min by magnetic stirring to form a uniform emulsion.
(3)溶剂热反应制备磁性生物炭：往上述乳浊液加入1.54g梧桐基生物炭，通过磁力搅拌2h，使生物炭与乳浊液充分混匀。(3) Preparation of magnetic biochar by solvothermal reaction: add 1.54 g of sycamore-based biochar to the above emulsion, and stir for 2 hours by magnetic force to fully mix the biochar and emulsion.
(4)将混匀后的乳浊液倒入100mL聚四氟乙烯水热反应釜中，在室温下以3℃/min的升温速率使炉内温度升至200℃后在该温度下反应10h，反应结束后等溶剂热反应釜自然冷却，通过磁分离获得磁性生物炭并用乙醇和去离子水洗涤多次，最后将磁性生物炭置于真空干燥箱中于60℃下干燥6h得到磁性生物炭吸附材料，平均粒径约为570nm。溶剂热反应中炭与铁元素质量比为2.75，负载的纳米粒子变少。(4) Pour the mixed emulsion into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, raise the temperature in the furnace to 200°C at a rate of 3°C/min at room temperature and react at this temperature for 10h After the reaction, wait for the solvothermal reactor to cool naturally, obtain magnetic biochar by magnetic separation and wash it with ethanol and deionized water several times, and finally place the magnetic biochar in a vacuum drying oven at 60°C for 6 hours to obtain magnetic biochar Adsorption material, the average particle size is about 570nm. In the solvothermal reaction, the mass ratio of carbon to iron was 2.75, and the supported nanoparticles became less.
(5)取制备的磁性生物炭吸附材料20mg于10mL浓度为50mg/L的Cr(VI)溶液中，在室温下静态吸附24h，通过外加磁场进行固液分离操作。并依靠分光光度法测定不同吸附时间时溶液中Cr(VI)的吸附率，得到磁性生物炭吸附材料对Cr(VI)离子的平衡吸附率为80.4％。(5) Take 20 mg of the prepared magnetic biochar adsorption material in 10 mL of Cr(VI) solution with a concentration of 50 mg/L, statically adsorb at room temperature for 24 h, and perform solid-liquid separation operation by applying an external magnetic field. And relying on spectrophotometry to measure the adsorption rate of Cr(VI) in the solution at different adsorption times, the equilibrium adsorption rate of Cr(VI) ion by the magnetic biochar adsorption material is 80.4%.
实施例4Example 4
本实施例中的磁性生物炭吸附材料的制备方法及其应用示例，包括以下步骤：The preparation method and application examples of the magnetic biochar adsorption material in this embodiment include the following steps:
(1)制备生物炭：农林废弃物为校园内收集的梧桐落叶，经洗涤、干燥、破碎、过60目后的粉末为原材料，置于马弗炉中在500℃无氧条件下焙烧2h，得到梧桐叶生物炭。(1) Preparation of biochar: the agricultural and forestry wastes are the fallen leaves of sycamore collected in the campus, and the powder after washing, drying, crushing and passing through 60 meshes is used as the raw material. Get sycamore leaf biochar.
(2)制备三价铁前驱液：取2.7g FeCl3·6H2O溶于160mL乙二醇溶液中，随后往其中加入7.2g无水醋酸钠和2g聚乙二醇(分子量为4000)，通过磁力搅拌持续搅拌30min，使其形成均一的乳浊液。(2) Preparation of ferric iron precursor solution: Dissolve 2.7g FeCl3 6H2 O in 160mL ethylene glycol solution, then add 7.2g anhydrous sodium acetate and 2g polyethylene glycol (molecular weight 4000) to it, Stir continuously for 30 min by magnetic stirring to form a uniform emulsion.
(3)溶剂热反应制备磁性生物炭：往上述乳浊液加入0.77g梧桐基生物炭，通过磁力搅拌2h，使生物炭与乳浊液充分混匀。(3) Preparation of magnetic biochar by solvothermal reaction: add 0.77 g of sycamore-based biochar to the above emulsion, and stir for 2 hours by magnetic force to fully mix the biochar and emulsion.
(4)将混匀后的乳浊液倒入100mL聚四氟乙烯水热反应釜中，在室温下以3℃/min的升温速率使炉内温度升至200℃后在该温度下反应10h，反应结束后等溶剂热反应釜自然冷却，通过磁分离获得磁性生物炭并用乙醇和去离子水洗涤多次，最后将磁性生物炭置于真空干燥箱中于60℃下干燥6h得到磁性生物炭吸附材料。相比于实施例3，由于溶液中Fe3+摩尔浓度降低，磁性粒子平均粒径约为370nm。(4) Pour the mixed emulsion into a 100mL polytetrafluoroethylene hydrothermal reaction kettle, raise the temperature in the furnace to 200°C at a rate of 3°C/min at room temperature and react at this temperature for 10h After the reaction, wait for the solvothermal reactor to cool naturally, obtain magnetic biochar by magnetic separation and wash it with ethanol and deionized water several times, and finally place the magnetic biochar in a vacuum drying oven at 60°C for 6 hours to obtain magnetic biochar Adsorbent material. Compared with Example 3, the average particle size of the magnetic particles is about 370nm due to the decrease in the molar concentration of Fe3+ in the solution.
(5)取制备的磁性生物炭吸附材料20mg于10mL浓度为50mg/L的Cr(VI)溶液中，在室温下静态吸附24h，通过外加磁场进行固液分离操作。并依靠分光光度法测定不同吸附时间时溶液中Cr(VI)的吸附率，得到磁性生物炭吸附材料对Cr(VI)离子的平衡吸附率为93.8％。(5) Take 20 mg of the prepared magnetic biochar adsorption material in 10 mL of Cr(VI) solution with a concentration of 50 mg/L, statically adsorb at room temperature for 24 h, and perform solid-liquid separation operation by applying an external magnetic field. And relying on spectrophotometry to measure the adsorption rate of Cr(VI) in the solution at different adsorption times, the equilibrium adsorption rate of the magnetic biochar adsorption material for Cr(VI) ions is 93.8%.
表1本发明各实施例实验参数一览表Table 1 list of experimental parameters of each embodiment of the present invention
各实施例结果表明不同条件下通过溶剂热反应合成的磁性生物炭吸附材料形貌良好，结构优良，生物炭与纳米四氧化三铁颗粒紧密结合，性能稳定，对Cr(VI)有优良的吸附效果。表1为以上各实施例的设计参数以及实验结果一览表，实施例1和实施例2的结果表明，生物炭和铁元素的比例不同，生物炭表面负载的磁性Fe3O4纳米粒子数量存在差异，适当提高铁元素比例有利于吸附材料对Cr(VI)的吸附效率；对比实施例1和实施例3可以发现，不同生物质材料表面官能团数量、性质存在差异，由此制备的磁性吸附材料对Cr(VI)的吸附效果存在差别；相对于实施例1，实施例4的吸附材料对Cr(VI)的吸附效率更高，这是由于实施例4中三价铁前驱液中Fe3+浓度较低，由此形成的Fe3O4粒径变小，导致吸附材料整体比表面积变大，提升吸附效率。The results of each example show that the magnetic biochar adsorption material synthesized by solvothermal reaction under different conditions has good appearance and excellent structure. Effect. Table 1 is a list of the design parameters and experimental results of the above examples. The results of Example 1 and Example 2 show that the ratio of biochar to iron is different, and the amount of magneticFe3O4 nanoparticles loadedon the surface of biochar is different. Appropriately increasing the proportion of iron element is conducive to the adsorption efficiency of the adsorption material to Cr(VI); Comparing Example 1 and Example 3, it can be found that there are differences in the number and properties of functional groups on the surface of different biomass materials, and the magnetic adsorption material thus prepared has a good effect on Cr(VI). There is a difference in the adsorption effect of Cr(VI); compared with embodiment 1, the adsorption material of embodiment 4 is higher to the adsorption efficiency of Cr(VI), this is due to the concentration ofFe in ferric iron precursor solution in embodiment 4 The lower the particle size of the Fe3 O4 formed, the larger the specific surface area of the adsorption material and the higher the adsorption efficiency.
本发明中生物炭的制备步骤、与三价铁前驱液的制备步骤顺序可以相互，既可以先制备生物炭、再制备三价铁前驱液，也可以先制备三价铁前驱液、再制备生物炭。本发明中的无氧条件可以是真空或保护气氛(如氮气气氛、或惰性气体气氛)下。本发明所使用的表面活性剂可以包括不同分子量的聚乙二醇、聚二甲基二烯丙基氯化铵、柠檬酸钠。In the present invention, the preparation steps of biochar and the preparation steps of trivalent iron precursor liquid can be mutually compatible, either biochar can be prepared first, and then ferric iron precursor liquid can be prepared, or ferric iron precursor liquid can be prepared first, and then biological carbon. The oxygen-free condition in the present invention can be under vacuum or protective atmosphere (such as nitrogen atmosphere, or inert gas atmosphere). The surfactant used in the present invention may include polyethylene glycol, polydimethyldiallylammonium chloride and sodium citrate with different molecular weights.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.
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| CN201610928550.9ACN106362690A (en) | 2016-10-31 | 2016-10-31 | Magnetic biochar adsorbing material and preparation method thereof |
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| CN201610928550.9ACN106362690A (en) | 2016-10-31 | 2016-10-31 | Magnetic biochar adsorbing material and preparation method thereof |
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| CN201610928550.9APendingCN106362690A (en) | 2016-10-31 | 2016-10-31 | Magnetic biochar adsorbing material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159123A (en)* | 2017-07-19 | 2017-09-15 | 合肥工业大学 | A kind of preparation method of magnetic active carbon and its magnetic active carbon of preparation |
| CN107262033A (en)* | 2017-06-30 | 2017-10-20 | 安徽工业大学 | The preparation and application of a kind of attapulgite/Fe3O4/ carbon composites |
| CN108380178A (en)* | 2018-03-12 | 2018-08-10 | 秋晓东 | A kind of preparation method of restoration of the ecosystem agent and its absorbing process to radionuclide |
| CN108483444A (en)* | 2018-04-19 | 2018-09-04 | 东北农业大学 | A kind of preparation method of the multiporous biological carbon composite of alpha-FeOOH nano-rod load |
| CN108821377A (en)* | 2018-06-14 | 2018-11-16 | 天津大学 | A kind of method that iron load yak dung charcoal synchronizes arsenic and fluorine in absorption water |
| CN108906082A (en)* | 2018-07-30 | 2018-11-30 | 陈蓉 | A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid |
| CN108927172A (en)* | 2018-08-01 | 2018-12-04 | 兰州大学 | A kind of preparation and its application of the magnetic green substance carbon material of load gold nano particle |
| CN108940320A (en)* | 2018-07-27 | 2018-12-07 | 李云军 | A kind of preparation method of micro/nano level solid acid |
| CN108940321A (en)* | 2018-07-30 | 2018-12-07 | 李云军 | A kind of preparation method of high dispersive iron oxide load sulfate ion type solid super-strong acid |
| CN109289787A (en)* | 2018-10-31 | 2019-02-01 | 山东大学 | A kind of preparation method of iron and cyclodextrin co-modified biochar composite material |
| CN109317095A (en)* | 2018-10-11 | 2019-02-12 | 温州医科大学 | A kind of composite material for removing hexavalent chromium and preparation method thereof |
| CN109592738A (en)* | 2019-02-18 | 2019-04-09 | 长沙如洋环保科技有限公司 | A kind of heavy metal waste water treatment process |
| CN109877143A (en)* | 2019-04-10 | 2019-06-14 | 黑龙江省农业科学院土壤肥料与环境资源研究所 | A kind of straw waste recycling and reusing processing method and adsorbent |
| CN110540188A (en)* | 2019-09-02 | 2019-12-06 | 大连理工大学 | A strip-shaped mesoporous nano-carbon material with high porosity and high graphitization degree and preparation method thereof |
| CN110652964A (en)* | 2019-11-06 | 2020-01-07 | 北京高能时代环境技术股份有限公司 | Magnetic iron-based biochar composite material, preparation method and application |
| CN111342100A (en)* | 2020-03-09 | 2020-06-26 | 广州市环境保护工程设计院有限公司 | Microbial fuel cell system |
| CN111408349A (en)* | 2020-04-30 | 2020-07-14 | 南阳师范学院 | Preparation method of straw-based magnetic porous biochar |
| CN111420975A (en)* | 2020-05-06 | 2020-07-17 | 浙江大学 | A kind of modified bagasse and its preparation method and application |
| CN111495331A (en)* | 2020-04-27 | 2020-08-07 | 中南林业科技大学 | Strong acid heteroatom-resistant magnetic biochar water treatment agent and preparation method and application thereof |
| CN112044408A (en)* | 2020-09-28 | 2020-12-08 | 东华理工大学 | Magnetic bamboo fiber and preparation process thereof |
| CN112058233A (en)* | 2020-09-22 | 2020-12-11 | 东北农业大学 | A kind of preparation method and application of lanthanum hydroxide modified magnetic porous biochar |
| WO2021004116A1 (en)* | 2019-07-05 | 2021-01-14 | 中国科学院南京土壤研究所 | Magnetic biomass carbon-quaternary phosphonium salt sterilization material, preparation method therefor and usage thereof |
| CN113457620A (en)* | 2021-05-25 | 2021-10-01 | 忻州师范学院 | Method for preparing magnetic meat and bone biochar by modifying magnetic fluid |
| CN113617333A (en)* | 2021-09-16 | 2021-11-09 | 茅台学院 | Magnetic charcoal adsorbent prepared from sorghum straws, and preparation method and application thereof |
| CN113714270A (en)* | 2020-05-25 | 2021-11-30 | 中国环境科学研究院 | Remediation device and remediation method for soil radioactive element pollution |
| CN113811388A (en)* | 2019-05-09 | 2021-12-17 | 阿布特克工业公司 | Compositions, articles and methods for reducing hydrocarbon, metal and organic pollutants |
| CN114515569A (en)* | 2022-01-30 | 2022-05-20 | 华南理工大学 | Biochar in-situ supported manganese dioxide catalyst and preparation method and application thereof |
| CN114904483A (en)* | 2022-04-18 | 2022-08-16 | 东北林业大学 | Preparation method of a wood-based carbon/Cu2O adsorbent for efficiently adsorbing anionic dyes |
| CN115414910A (en)* | 2022-07-29 | 2022-12-02 | 武汉轻工大学 | A kind of preparation method of magnetic porous bio-carbon material |
| CN119838568A (en)* | 2025-03-20 | 2025-04-18 | 中国农业科学院农业环境与可持续发展研究所 | Magnetic biochar and preparation method and application thereof, and preparation method of organic fertilizer |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614819A (en)* | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
| CN103949212A (en)* | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| KR101506094B1 (en)* | 2013-10-30 | 2015-03-26 | 울산대학교 산학협력단 | Heavy Metal Adsorbent Using Biochar-Alginate Capsule, Preparation Method Thereof and Removal Method ofHeavy Metal in Aqueous Solution Using the Same |
| CN104787831A (en)* | 2015-03-23 | 2015-07-22 | 湖南大学 | Method for removing hexavalent chromium in wastewater through magnetic adsorbent compounded by chitosan and magnetic biological carbon |
| CN105688804A (en)* | 2016-01-05 | 2016-06-22 | 鲁东大学 | Preparation of magnetic biomass charcoal and adsorption of magnetic biomass charcoal to dye |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614819A (en)* | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
| KR101506094B1 (en)* | 2013-10-30 | 2015-03-26 | 울산대학교 산학협력단 | Heavy Metal Adsorbent Using Biochar-Alginate Capsule, Preparation Method Thereof and Removal Method ofHeavy Metal in Aqueous Solution Using the Same |
| CN103949212A (en)* | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| CN104787831A (en)* | 2015-03-23 | 2015-07-22 | 湖南大学 | Method for removing hexavalent chromium in wastewater through magnetic adsorbent compounded by chitosan and magnetic biological carbon |
| CN105688804A (en)* | 2016-01-05 | 2016-06-22 | 鲁东大学 | Preparation of magnetic biomass charcoal and adsorption of magnetic biomass charcoal to dye |
| Title |
|---|
| HONGTAO GAO ET AL: ""The efficient adsorption removal of Cr(VI) by using Fe3O4 nanoparticles hybridized with carbonaceous materials"", 《RSC ADVANCES》* |
| 闫军锋，等: "《电子材料与器件试验教程》", 31 May 2016* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262033A (en)* | 2017-06-30 | 2017-10-20 | 安徽工业大学 | The preparation and application of a kind of attapulgite/Fe3O4/ carbon composites |
| CN107159123A (en)* | 2017-07-19 | 2017-09-15 | 合肥工业大学 | A kind of preparation method of magnetic active carbon and its magnetic active carbon of preparation |
| CN108380178A (en)* | 2018-03-12 | 2018-08-10 | 秋晓东 | A kind of preparation method of restoration of the ecosystem agent and its absorbing process to radionuclide |
| CN108483444A (en)* | 2018-04-19 | 2018-09-04 | 东北农业大学 | A kind of preparation method of the multiporous biological carbon composite of alpha-FeOOH nano-rod load |
| CN108483444B (en)* | 2018-04-19 | 2022-03-01 | 东北农业大学 | Preparation method of alpha-FeOOH nanorod-loaded porous biochar composite material |
| CN108821377A (en)* | 2018-06-14 | 2018-11-16 | 天津大学 | A kind of method that iron load yak dung charcoal synchronizes arsenic and fluorine in absorption water |
| CN108940320A (en)* | 2018-07-27 | 2018-12-07 | 李云军 | A kind of preparation method of micro/nano level solid acid |
| CN108906082A (en)* | 2018-07-30 | 2018-11-30 | 陈蓉 | A kind of method that precipitating-sulfuric acid acidization prepares iron oxide load sulfate ion type solid super-strong acid |
| CN108940321A (en)* | 2018-07-30 | 2018-12-07 | 李云军 | A kind of preparation method of high dispersive iron oxide load sulfate ion type solid super-strong acid |
| CN108927172B (en)* | 2018-08-01 | 2021-02-12 | 兰州大学 | Preparation and application of gold nanoparticle-loaded magnetic biomass carbon material |
| CN108927172A (en)* | 2018-08-01 | 2018-12-04 | 兰州大学 | A kind of preparation and its application of the magnetic green substance carbon material of load gold nano particle |
| CN109317095A (en)* | 2018-10-11 | 2019-02-12 | 温州医科大学 | A kind of composite material for removing hexavalent chromium and preparation method thereof |
| CN109289787A (en)* | 2018-10-31 | 2019-02-01 | 山东大学 | A kind of preparation method of iron and cyclodextrin co-modified biochar composite material |
| CN109592738A (en)* | 2019-02-18 | 2019-04-09 | 长沙如洋环保科技有限公司 | A kind of heavy metal waste water treatment process |
| CN109877143B (en)* | 2019-04-10 | 2021-11-30 | 黑龙江省农业科学院土壤肥料与环境资源研究所 | Straw waste recycling treatment method and adsorbent |
| CN109877143A (en)* | 2019-04-10 | 2019-06-14 | 黑龙江省农业科学院土壤肥料与环境资源研究所 | A kind of straw waste recycling and reusing processing method and adsorbent |
| CN113811388A (en)* | 2019-05-09 | 2021-12-17 | 阿布特克工业公司 | Compositions, articles and methods for reducing hydrocarbon, metal and organic pollutants |
| CN113811388B (en)* | 2019-05-09 | 2023-03-21 | 阿布特克工业公司 | Compositions, articles and methods for reducing hydrocarbon, metal and organic contaminants |
| US12121031B2 (en) | 2019-07-05 | 2024-10-22 | Institute Of Soil Science, Chinese Academy Of Sciences | Magnetic biomass carbon-quaternary phosphonium salt sterilization material, preparation method therefor and usage thereof |
| WO2021004116A1 (en)* | 2019-07-05 | 2021-01-14 | 中国科学院南京土壤研究所 | Magnetic biomass carbon-quaternary phosphonium salt sterilization material, preparation method therefor and usage thereof |
| CN110540188A (en)* | 2019-09-02 | 2019-12-06 | 大连理工大学 | A strip-shaped mesoporous nano-carbon material with high porosity and high graphitization degree and preparation method thereof |
| CN110540188B (en)* | 2019-09-02 | 2021-08-31 | 大连理工大学 | A strip-shaped mesoporous nano-carbon material with high porosity and high degree of graphitization and preparation method thereof |
| CN110652964A (en)* | 2019-11-06 | 2020-01-07 | 北京高能时代环境技术股份有限公司 | Magnetic iron-based biochar composite material, preparation method and application |
| CN111342100A (en)* | 2020-03-09 | 2020-06-26 | 广州市环境保护工程设计院有限公司 | Microbial fuel cell system |
| CN111342100B (en)* | 2020-03-09 | 2023-01-24 | 广州市环境保护工程设计院有限公司 | Microbial fuel cell system |
| CN111495331A (en)* | 2020-04-27 | 2020-08-07 | 中南林业科技大学 | Strong acid heteroatom-resistant magnetic biochar water treatment agent and preparation method and application thereof |
| CN111408349A (en)* | 2020-04-30 | 2020-07-14 | 南阳师范学院 | Preparation method of straw-based magnetic porous biochar |
| CN111420975A (en)* | 2020-05-06 | 2020-07-17 | 浙江大学 | A kind of modified bagasse and its preparation method and application |
| CN111420975B (en)* | 2020-05-06 | 2021-06-08 | 浙江大学 | A kind of modified bagasse and its preparation method and application |
| CN113714270A (en)* | 2020-05-25 | 2021-11-30 | 中国环境科学研究院 | Remediation device and remediation method for soil radioactive element pollution |
| CN112058233A (en)* | 2020-09-22 | 2020-12-11 | 东北农业大学 | A kind of preparation method and application of lanthanum hydroxide modified magnetic porous biochar |
| CN112044408A (en)* | 2020-09-28 | 2020-12-08 | 东华理工大学 | Magnetic bamboo fiber and preparation process thereof |
| CN113457620A (en)* | 2021-05-25 | 2021-10-01 | 忻州师范学院 | Method for preparing magnetic meat and bone biochar by modifying magnetic fluid |
| CN113617333A (en)* | 2021-09-16 | 2021-11-09 | 茅台学院 | Magnetic charcoal adsorbent prepared from sorghum straws, and preparation method and application thereof |
| CN114515569B (en)* | 2022-01-30 | 2024-01-19 | 华南理工大学 | Biochar in-situ supported manganese dioxide catalyst and preparation method and application thereof |
| CN114515569A (en)* | 2022-01-30 | 2022-05-20 | 华南理工大学 | Biochar in-situ supported manganese dioxide catalyst and preparation method and application thereof |
| CN114904483A (en)* | 2022-04-18 | 2022-08-16 | 东北林业大学 | Preparation method of a wood-based carbon/Cu2O adsorbent for efficiently adsorbing anionic dyes |
| CN114904483B (en)* | 2022-04-18 | 2023-07-07 | 东北林业大学 | A preparation method of wood-based carbon/Cu2O adsorbent for efficient adsorption of anionic dyes |
| CN115414910A (en)* | 2022-07-29 | 2022-12-02 | 武汉轻工大学 | A kind of preparation method of magnetic porous bio-carbon material |
| CN115414910B (en)* | 2022-07-29 | 2023-09-05 | 武汉轻工大学 | Preparation method of magnetic porous biological carbon material |
| CN119838568A (en)* | 2025-03-20 | 2025-04-18 | 中国农业科学院农业环境与可持续发展研究所 | Magnetic biochar and preparation method and application thereof, and preparation method of organic fertilizer |
| CN119838568B (en)* | 2025-03-20 | 2025-07-01 | 中国农业科学院农业环境与可持续发展研究所 | Magnetic biochar and preparation method and application thereof, and preparation method of organic fertilizer |
| Publication | Publication Date | Title |
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