技术领域：Technical field:
本发明涉及一种铁改性芦苇生物炭的制备，以及应用于处理低浓度含磷废水及污水深度除磷，属于水污染控制领域。The invention relates to the preparation of iron-modified reed biochar and its application to the treatment of low-concentration phosphorus-containing wastewater and deep phosphorus removal of sewage, belonging to the field of water pollution control.
背景技术：Background technique:
我国水资源人均占有量少，分布不平衡，随着经济发展和社会总体生活水平的提高，水资源的需求量日益增长，而水体污染严重。其中湖泊等地表水的水体污染半数以上是由氮、磷超标引起的水体富营养化。根据利贝格最小值定律：植物的生长取决于外界提供给它的所需养料中数量最小的那一种。藻类的经验分子式为C106H236O110N16P，可以发现，在藻类分子式中所占重量百分比最少的是氮和磷，尤其是磷。所以，控制生活污水中的磷对控制地表水的富营养化是至关重要的。根据《城镇污水处理厂污染物排放标准》（GB18918-2002）中一级A标准和B标准规定磷浓度限值为0.5mg/L和1mg/L。而一般城镇污水经过一定处理后中磷浓度一般在1-4mg/L，所以，除要对污染源头进行控制外，还需寻找一种经济有效的方法去除废水中磷，使其符合有关排放标准。The per capita possession of water resources in my country is small and the distribution is uneven. With the economic development and the improvement of the overall living standards of the society, the demand for water resources is increasing day by day, and the water pollution is serious. Among them, more than half of the water body pollution of lakes and other surface water is eutrophication caused by excessive nitrogen and phosphorus. According to Lieberg's minimum law: the growth of a plant depends on the smallest amount of nutrients provided to it by the outside world. The empirical molecular formula of algae is C106 H236 O110 N16 P. It can be found that nitrogen and phosphorus, especially phosphorus, account for the least weight percentage in the molecular formula of algae. Therefore, controlling phosphorus in domestic sewage is crucial to controlling eutrophication of surface water. According to the "Pollutant Discharge Standards for Urban Sewage Treatment Plants" (GB18918-2002), the first-level A standard and B standard stipulate that the phosphorus concentration limit is 0.5mg/L and 1mg/L. The concentration of phosphorus in general urban sewage after certain treatment is generally 1-4mg/L. Therefore, in addition to controlling the source of pollution, it is also necessary to find an economical and effective method to remove phosphorus in wastewater so that it meets the relevant discharge standards. .
常规的污水生物处理对低浓度含磷废水去除效率不高，通常的二级生化处理方法只能去除30%-50%的氮和磷，难以达标且机理复杂，过程不易控制。化学沉淀法除磷虽然去除率很高，应用也很广泛，但是需要向废水中投加絮凝剂，故而增加了处理成本，并会产生大量的化学污泥。吸附法除磷由于高效快速、无二次污染、易操作、可回收利用、金属氧化物活性点丰富且其成本低廉，已成为国内外除磷的研究热点。Conventional sewage biological treatment is not efficient in removing low-concentration phosphorus-containing wastewater. The usual secondary biochemical treatment method can only remove 30%-50% of nitrogen and phosphorus. It is difficult to meet the standard and the mechanism is complicated, and the process is difficult to control. Although the chemical precipitation method has a high removal rate and is widely used, it needs to add flocculants to the wastewater, which increases the treatment cost and produces a large amount of chemical sludge. Due to its high efficiency and rapidity, no secondary pollution, easy operation, recyclability, rich metal oxide active sites and low cost, adsorption phosphorus removal has become a research hotspot in phosphorus removal at home and abroad.
生物炭近年来被广泛用于固碳减排、土壤修复改良、污染水体净化等方面的研究和实践，具有成本低、环境友好等优点。现有相关学者研究表明水稻、小麦、玉米等制备的生物炭对水体中污染物有很好的吸附作用，刘进阁等[1]研究了豆角秸秆生物炭对中水铬的吸附效果显著，张慧等[2]研究了炭化水稻秸秆对水体中氨氮和磷的吸附，结果表明去除效果大于粉煤灰和炉渣，RenJing等[3]使用棉花秸秆生物炭负载铁去除水体中的磷，增加磷的去除率，生物炭净化水体这项技术有着广泛应用的潜力。用芦苇秸秆生物炭负载铁改性除磷有以下几大优势：①芦苇作为一种繁殖速度快，生物量大的水生植物，如果不及时去除任其自然腐烂分解，会造成污染，此发明利用芦苇为原料制备生物炭，将垃圾变废为宝，提高资源利用效率，减少污染；②生物炭具有固碳的特性，起到了大气碳库增汇减排作用，并且它的多孔结构增加了铁的负载率；③改性剂氯化铁价格便宜、无毒，磷酸根与负载在炭表面和孔隙中的铁离子反应发生作用，可达到很好的除磷效果，操作工艺简单，并无二次污染；④吸附后的吸附剂含有较丰富的磷，可作为植物生长肥料回用。In recent years, biochar has been widely used in the research and practice of carbon sequestration and emission reduction, soil remediation and improvement, and purification of polluted water bodies. It has the advantages of low cost and environmental friendliness. Existing studies by relevant scholars have shown that biochar prepared from rice, wheat, and corn has a good adsorption effect on pollutants in water bodies. Liu Jinge et al.[1] studied the remarkable adsorption effect of bean straw biochar on chromium in reclaimed water. Zhang Hui[2] studied the adsorption of carbonized rice straw to ammonia nitrogen and phosphorus in water, and the results showed that the removal effect was greater than that of fly ash and slag. RenJing et al.[3] used cotton straw biochar to load iron to remove phosphorus in water and increase phosphorus Removal rate, biochar water purification technology has the potential for wide application. The use of reed straw biochar to load iron to modify phosphorus removal has the following advantages: ① Reed is a fast-growing aquatic plant with large biomass. If it is not removed in time and allowed to rot and decompose naturally, it will cause pollution. This invention utilizes Reeds are used as raw materials to prepare biochar, turning waste into treasure, improving resource utilization efficiency, and reducing pollution; ②Biochar has the characteristics of carbon fixation, which plays a role in increasing carbon sinks and reducing emissions in the atmosphere, and its porous structure increases iron ③ The modifier ferric chloride is cheap and non-toxic, and the phosphate radical reacts with the iron ions loaded on the surface of the carbon and in the pores to achieve a good phosphorus removal effect. The operation process is simple and there is no difference Secondary pollution; ④The adsorbent after adsorption is rich in phosphorus, which can be reused as plant growth fertilizer.
发明内容：Invention content:
本发明针对传统除磷技术的不足之处，提供一种铁改性芦苇生物炭的制备方法，该方法在限氧和相对低温（<700℃）的条件下，由生物质原料热解产生的富碳、细颗粒、多孔材料。Aiming at the deficiencies of the traditional phosphorus removal technology, the present invention provides a preparation method of iron-modified reed biochar, which is produced by pyrolysis of biomass raw materials under the condition of limited oxygen and relatively low temperature (<700°C). Carbon-rich, fine-grained, porous materials.
本发明目的是提供上述制备方法得到的铁改性芦苇生物炭。The object of the present invention is to provide the iron-modified reed biochar obtained by the above preparation method.
本发明还提供利用铁改性芦苇生物炭作为吸附剂的应用，主要在处理低浓度含磷废水方面的应用。The invention also provides the application of the iron-modified reed biochar as an adsorbent, mainly in the treatment of low-concentration phosphorous-containing wastewater.
技术方案对应权利要求书即可，待定。The technical solution only needs to correspond to the claims, to be determined.
一种铁改性芦苇生物炭的制备方法，该方法的制备步骤如下：A preparation method of iron-modified reed biochar, the preparation steps of the method are as follows:
（1）先对芦苇秸秆进行预处理；(1) Pretreat the reed straw first;
（2）将步骤（1）预处理过的芦苇进行热解炭化；(2) Pyrolysis and carbonization of the reed pretreated in step (1);
（3）将步骤（2）热解炭化得到的生物炭冷却至室温，研磨过10-50目筛，用水清洗数次，去除表面灰分，烘干备用；(3) Cool the biochar obtained by pyrolysis and carbonization in step (2) to room temperature, grind it through a 10-50 mesh sieve, wash it with water several times, remove the surface ash, and dry it for later use;
（4）取FeCl3溶于水中，加入步骤（3）中烘干的生物炭搅拌混匀，保持铁炭质量比为0.56-1：1；置于烘箱中在85-105℃的温度下保持6-12h，将水分蒸干，再在300-500℃热处理2h；取出用水洗至洗液为中性，在85-105℃的温度下烘干6-12h，即得铁改性芦苇生物炭成品。(4) Dissolve FeCl3 in water, add the dried biochar in step (3), stir and mix well, keep the mass ratio of iron to carbon at 0.56-1:1; keep in an oven at a temperature of 85-105°C 6-12h, evaporate the water to dryness, and then heat-treat at 300-500°C for 2h; take it out and wash with water until the lotion is neutral, and dry at 85-105°C for 6-12h to obtain iron-modified reed biochar finished product.
本发明的进一步设计在于：A further design of the present invention is:
步骤(1)中预处理，将采摘的芦苇用水洗去表面灰尘，然后将洗净的芦苇放在烘箱中于85-105℃烘干至恒重，取出破碎成0.5-1cm长的段备用。Pretreatment in step (1), washing the picked reeds with water to remove surface dust, then drying the washed reeds in an oven at 85-105°C to constant weight, taking out and breaking into 0.5-1cm long segments for later use.
步骤（2）中，热解温度为300-500℃，升速温度为15℃/min，保持4-8h。In step (2), the pyrolysis temperature is 300-500° C., the rising rate temperature is 15° C./min, and the temperature is maintained for 4-8 hours.
步骤（3）中，烘干是在90-100℃烘箱中干燥。In step (3), drying is performed in an oven at 90-100°C.
步骤（4）中，热处理温度为350-450℃。In step (4), the heat treatment temperature is 350-450°C.
上述方法制备得到的铁改性芦苇生物炭。The iron-modified reed biochar prepared by the above method.
上述改性芦苇生物炭在处理低浓度含磷废水方面的应用。主要用于浓度范围为1-4mg/L的低浓度含磷废水处理及污水深度处理。The application of the above-mentioned modified reed biochar in the treatment of low-concentration phosphorus-containing wastewater. It is mainly used for the treatment of low-concentration phosphorus-containing wastewater with a concentration range of 1-4mg/L and the advanced treatment of sewage.
通过上述方法制得负载铁改性芦苇生物炭，可作为一种优良的吸附剂，并采用吸附的除磷工艺，吸附处理含磷废水，节省吸附剂用量的情况下并使出水水质达标。The iron-loaded modified reed biochar prepared by the above method can be used as an excellent adsorbent, and the adsorption phosphorus removal process is used to adsorb and treat phosphorus-containing wastewater, saving the amount of adsorbent and making the effluent water quality up to standard.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
（1）本发明采用芦苇秸秆为生物炭原料，来源广泛、价格低廉，本发明也为解决芦苇资源的处置问题提供了新的途径。芦苇秸秆中含有纤维素，可用来造纸，编织席、帘等；芦苇根也具有药用价值；芦苇叶可以用来包粽子。由于芦苇生命力强、生长速度快等特点，是景点旅游、水面绿化、河道管理、净化水质、护土固堤、改良土壤之首选。但是我国芦苇年产量大，据资料统计，我国芦苇面积约为130万hm2，年总产量在220万吨以上[4]，真正被用作造纸、药用等的芦苇量有限，仍有大部分的芦苇秸秆无法得到合理利用，如果不进行及时处理，会腐烂造成环境污染，所以进行湿地植物芦苇回收利用，寻求变废为宝的新途径，已成为亟待解决的热点问题。而本发明为其提供了一种有效的解决途径，实现资源化利用的目的。(1) The present invention uses reed straw as the raw material of biochar, which has a wide range of sources and low price. The present invention also provides a new way to solve the problem of reed resources disposal. Reed straw contains cellulose, which can be used to make paper, weave mats, curtains, etc.; reed roots also have medicinal value; reed leaves can be used to make zongzi. Due to the characteristics of strong vitality and fast growth of reed, it is the first choice for scenic spot tourism, water surface greening, river management, water purification, soil protection and embankment reinforcement, and soil improvement. But the annual output of reed in our country is large. According to statistics, the area of reed in our country is about 1.3 million hm2 , and the total annual output is more than 2.2 million tons[4] . Part of the reed straw cannot be used rationally. If it is not treated in time, it will rot and cause environmental pollution. Therefore, recycling wetland plant reeds and seeking new ways to turn waste into treasure has become a hot issue that needs to be solved urgently. However, the present invention provides an effective solution to achieve the purpose of resource utilization.
（2）本发明提供了一种铁改性芦苇生物炭的制备工艺，通过将芦苇秸秆与铁溶液混合烘干后煅烧的方法制备出改性芦苇生物炭，制备工艺简单易行，适合工业化生产。改性后的芦苇生物炭表面会负载铁的氧化物或羟基氧化物，与水体中的磷酸根通过化学反应发生作用，从而达到去除磷的效果，所以，除磷效果与负载的铁量有直接关系。(2) The present invention provides a preparation process of iron-modified reed biochar. Modified reed biochar is prepared by mixing reed straw with iron solution, drying, and then calcining. The preparation process is simple and easy, and is suitable for industrial production . The surface of the modified reed biochar will be loaded with iron oxides or oxyhydroxides, which will react with the phosphate in the water through a chemical reaction to achieve the effect of phosphorus removal. Therefore, the phosphorus removal effect is directly related to the amount of loaded iron. relation.
本发明提供的铁改性工艺相比于他人的铁改性工艺，如陆燕勤等用沸石负载铁，直接将沸石与硝酸铁溶液混合烘干，其负载量最大仅为8.325mg/g[6]，罗舒君研究了负载改性竹炭去除废水中磷，用反复蒸煮法将氯化铁负载于竹炭上，最大负载铁量为41.53mg/g[7]，本发明提供的改性方法负载铁量为53.94mg/g，铁的负载效果更好。Compared with the iron modification process provided by others, the iron modification process provided by the present invention, such as Lu Yanqin, etc. use zeolite to load iron, directly mix and dry the zeolite and ferric nitrate solution, and the maximum loading capacity is only 8.325 mg/g[6] , Luo Shujun studied the loading of modified bamboo charcoal to remove phosphorus in wastewater, and ferric chloride was loaded on the bamboo charcoal by repeated cooking method. The maximum loaded iron amount was 41.53mg/g[7] . 53.94mg/g, the loading effect of iron is better.
改性后的芦苇生物炭在温度为25℃下处理初始浓度为4mg/L的磷溶液时，平衡吸附量为1.55mg/g，而未改性芦苇生物炭平衡吸附量为0.019mg/g，改性芦苇生物炭吸附量是芦苇生物炭吸附量的81.6倍，改性后除磷效果显著。When the modified reed biochar was treated with a phosphorus solution with an initial concentration of 4 mg/L at a temperature of 25 °C, the equilibrium adsorption capacity was 1.55 mg/g, while that of the unmodified reed biochar was 0.019 mg/g. The adsorption capacity of modified reed biochar is 81.6 times that of reed biochar, and the phosphorus removal effect after modification is remarkable.
（3）本发明的吸附剂可应用于处理含磷生活污水，使其达标排放。吸附除磷后的生物炭内含丰富的铁和磷元素，还可以回收利用作为肥料还田，无二次污染产生，经济效益可观。该铁改性芦苇生物炭属于一种吸附性能优良、绿色环保型材料。(3) The adsorbent of the present invention can be applied to treat phosphorus-containing domestic sewage so that it can be discharged up to standard. The biochar after adsorption and removal of phosphorus is rich in iron and phosphorus elements, and can also be recycled as fertilizer and returned to the field without secondary pollution, and the economic benefits are considerable. The iron-modified reed biochar belongs to a green and environment-friendly material with excellent adsorption performance.
本发明将芦苇资源回收利用，制备成生物炭，将有机质中的碳元素封存下来，起到了增汇减排的作用，减少了温室气体的排放和大气污染。由于芦苇生物炭特殊的多孔结构，可以作用吸附剂，吸附大气、土壤和水体中的污染物质，如吸附去除水体中磷。多孔特性为土壤中微生物提供了迁移场所，并且生物炭本身含有的一些营养元素也为土壤提供了肥力，吸附后还可以用作土壤改良剂。因而，本发明的方法具有较高的环境和经济效益。相比水稻和小麦，三种秸秆的除磷效果上进行了比较与分析，如下：The invention recycles reed resources to prepare biochar, seals the carbon element in the organic matter, plays the role of increasing sink and reducing emission, and reduces greenhouse gas emission and air pollution. Due to the special porous structure of reed biochar, it can act as an adsorbent to adsorb pollutants in the atmosphere, soil and water, such as adsorbing and removing phosphorus in water. The porous property provides a migration site for microorganisms in the soil, and some nutrients contained in biochar itself also provide fertility for the soil, and can also be used as a soil improver after adsorption. Therefore, the method of the present invention has higher environmental and economic benefits. Compared with rice and wheat, the phosphorus removal effects of the three straws were compared and analyzed, as follows:
1）吴文清[5]用小麦秸秆经过碱液-超声波处理进行醚化反应，引入Fe3+制备出吸附剂，吸附剂投加量为0.1g的中性环境下，处理初始浓度为3mg/L的磷酸盐溶液24h，后剩余浓度为2.3mg/L，磷的去除率仅为23.3%，吸附量为0.23mg/g。而本发明制备的改性芦苇生物炭在相同条件下处理3mg/L的磷酸盐溶液6h，剩余浓度为0.467mg/L，磷的去除率达到84.4%，此时的吸附量为1.267mg/g，除磷效果明显优于小麦秸秆吸附剂。1) Wu Wenqing[5] carried out etherification reaction with wheat straw through lye-ultrasonic treatment, and introduced Fe3+ to prepare adsorbent. The initial concentration of adsorbent was 3mg/ L of phosphate solution for 24 hours, the remaining concentration was 2.3mg/L, the removal rate of phosphorus was only 23.3%, and the adsorption capacity was 0.23mg/g. However, the modified reed biochar prepared by the present invention treated 3 mg/L phosphate solution for 6 hours under the same conditions, the remaining concentration was 0.467 mg/L, and the removal rate of phosphorus reached 84.4%, and the adsorption capacity at this time was 1.267 mg/g , the phosphorus removal effect is obviously better than that of wheat straw adsorbent.
2）目前，利用水稻秸秆生物炭除磷的研究甚少，主要原因应是水稻秸秆生物炭所含色度较大，清洗时的水液为深黄色，这可能与水稻的生长过程有关。且水稻秸秆生物炭本身含磷量大，处理水体中的磷尤其是低浓度含磷废水时，有大量磷元素溶出的现象。2) At present, there are few studies on the use of rice straw biochar for phosphorus removal. The main reason should be that rice straw biochar contains a large chroma, and the water liquid during cleaning is dark yellow, which may be related to the growth process of rice. Moreover, rice straw biochar itself contains a large amount of phosphorus. When treating phosphorus in water, especially low-concentration phosphorus-containing wastewater, a large amount of phosphorus elements will dissolve.
综上所述，在解决芦苇资源的回收利用问题上，根据它的特殊的结构和节能减排优势，目前具有非常大的应用前景，故将芦苇秸秆制备成生物炭，为芦苇资源的回收利用，提供了有效的解决途径。并且本发明制备的吸附剂，除磷效果上与其他农作物秸秆相比，具有明显的优势，有利于处理低浓度含磷废水。To sum up, in solving the problem of recycling reed resources, according to its special structure and advantages of energy saving and emission reduction, it currently has a very large application prospect. , providing an effective solution. In addition, the adsorbent prepared by the invention has obvious advantages in phosphorus removal effect compared with other crop stalks, and is beneficial for treating low-concentration phosphorus-containing wastewater.
（4）本发明在处理低浓度含磷废水工艺上，采用了二次吸附工艺，将使用过后的吸附剂回用，再进行第二次吸附，相比于传统吸附工艺，在使出水水质达标的情况下，节省了吸附剂的使用量，是一种节能减排的除磷工艺。(4) In the process of treating low-concentration phosphorus-containing wastewater, the present invention adopts a secondary adsorption process, reusing the used adsorbent, and then performing the second adsorption. Compared with the traditional adsorption process, the effluent quality can reach the standard Under the circumstances, the use of adsorbent is saved, and it is a phosphorus removal process for energy saving and emission reduction.
附图说明:Description of the drawings:
图1为实例一制备的铁改性芦苇生物炭的XRD图谱。Figure 1 is the XRD spectrum of the iron-modified reed biochar prepared in Example 1.
具体实施方式：Detailed ways:
下面结合附图和具体实施例，对本发明中铁改性生物炭的制备和应用于处理低浓度的含磷废水做更详细的说明。The preparation and application of the iron-modified biochar in the present invention to treat low-concentration phosphorus-containing wastewater will be described in more detail below in conjunction with the accompanying drawings and specific examples.
制备实例：Preparation example:
实例一：Example one:
本发明铁改性芦苇生物炭的制作具体步骤如下：The making concrete steps of iron modified reed biochar of the present invention are as follows:
(1)芦苇秸秆采自南京市某湿地，用去离子水洗去表面灰尘，然后将洗净的芦苇放在烘箱中于100℃烘干至恒重，取出剪碎成长度约为0.5-1cm的小块。(1) Reed stalks were collected from a wetland in Nanjing City, washed with deionized water to remove surface dust, then dried in an oven at 100°C to constant weight, taken out and cut into pieces with a length of about 0.5-1cm small pieces.
（2）将第（1）步中破碎成小块的芦苇填满于坩埚，置于马弗炉中进行热解，热解温度为350℃，温度升速为15℃/min，保持6h。(2) Fill the crucible with the reeds broken into small pieces in step (1), and place it in a muffle furnace for pyrolysis. The pyrolysis temperature is 350°C, and the temperature rise rate is 15°C/min, and keep for 6h.
（3）将第（2）步中热解完成后取出坩埚冷却至室温，即为制备好的芦苇生物炭，将其研磨过10-50目筛，用去离子水清洗数次，去除热解过程中残余灰分，置于烘箱中于100℃下烘干至恒重备用。(3) After the pyrolysis in step (2) is completed, take out the crucible and cool it to room temperature, which is the prepared reed biochar, grind it through a 10-50 mesh sieve, wash it with deionized water several times, and remove the pyrolysis The residual ash in the process was dried in an oven at 100°C to constant weight for later use.
（4）称取FeCl3溶于去离子水中，配制铁离子浓度为1mol/L的溶液，加入第（3）步中烘干的生物炭搅拌混匀，保持铁与生物炭质量比为0.56：1。置于烘箱中在100℃的温度下将水分蒸干，再将其转入马弗炉中于350℃继续热处理2h。后取出用去离子水洗至滤液为中性，置于烘箱100℃中烘干10h，即得铁改性芦苇生物炭成品。(4) Weigh FeCl3 and dissolve it in deionized water to prepare a solution with an iron ion concentration of 1mol/L, add the dried biochar in step (3) and mix well, keeping the mass ratio of iron to biochar at 0.56: 1. Put it in an oven at a temperature of 100°C to evaporate the water to dryness, and then transfer it to a muffle furnace at 350°C to continue heat treatment for 2h. Finally, take it out and wash it with deionized water until the filtrate is neutral, and dry it in an oven at 100°C for 10 hours to obtain the finished iron-modified reed biochar.
制备的铁改性芦苇生物炭的XRD图谱如图1所示。XR谱图中有Fe2O3特征峰，说明改性后氧化铁主要以赤铁矿形式存在，而铁的氧化物中赤铁矿与芦苇生物炭的附着强度最高。所以与其他除磷改性吸附剂的制备工艺相比，铁的负载更牢固，负载量也更大，从而除磷效果更好。The XRD pattern of the prepared iron-modified reed biochar is shown in Figure 1. There is a characteristic peak of Fe2 O3 in the XR spectrum, indicating that the modified iron oxide mainly exists in the form of hematite, and the adhesion strength of hematite to reed biochar is the highest among iron oxides. Therefore, compared with the preparation process of other phosphorus removal modified adsorbents, the iron load is stronger and the loading capacity is larger, so the phosphorus removal effect is better.
实例二：本发明铁改性芦苇生物炭的制作具体步骤如下：Example two: the specific steps of making the iron-modified reed biochar of the present invention are as follows:
(1)芦苇秸秆采自南京市某湿地，用去离子水洗去表面灰尘，然后将洗净的芦苇放在烘箱中于90℃烘干至恒重，取出剪碎成长度约为0.5-1cm的小块。(1) Reed stalks were collected from a wetland in Nanjing, washed with deionized water to remove surface dust, then dried in an oven at 90°C to constant weight, taken out and cut into pieces with a length of about 0.5-1cm small pieces.
（2）将第（1）步中破碎成小块的芦苇填满于坩埚，置于马弗炉中进行热解，热解温度为450℃，温度升速为15℃/min，保持4h。(2) Fill the crucible with the reeds broken into small pieces in step (1), and place it in a muffle furnace for pyrolysis. The pyrolysis temperature is 450°C, the temperature rise rate is 15°C/min, and keep for 4h.
（3）将第（2）步中热解完成后取出坩埚冷却至室温，即为制备好的芦苇生物炭，将其研磨过10-50目筛，用去离子水清洗数次，去除热解过程中残余灰分，置于烘箱中于90℃下烘干至恒重备用。(3) After the pyrolysis in step (2) is completed, take out the crucible and cool it to room temperature, which is the prepared reed biochar, grind it through a 10-50 mesh sieve, wash it with deionized water several times, and remove the pyrolysis The residual ash in the process was dried in an oven at 90°C to constant weight for later use.
（4）称取FeCl3溶于去离子水，配制铁离子浓度为1mol/L的溶液，加入第（3）步中烘干的生物炭搅拌混匀，保持铁与生物炭质量比为1：1。置于烘箱中在90℃的温度下将水分蒸干，再将其转入马弗炉中于450℃继续热处理2h。后取出用去离子水洗至滤液为中性，置于烘箱90℃中烘干12h，即得铁改性芦苇生物炭成品。(4) Weigh FeCl3 and dissolve it in deionized water to prepare a solution with an iron ion concentration of 1mol/L, add the dried biochar in step (3) and mix well, keeping the mass ratio of iron to biochar at 1: 1. Put it in an oven at a temperature of 90°C to evaporate the water to dryness, and then transfer it to a muffle furnace at 450°C to continue heat treatment for 2h. Finally, take it out and wash it with deionized water until the filtrate is neutral, and dry it in an oven at 90°C for 12 hours to obtain the finished iron-modified reed biochar.
应用实例：将铁改性芦苇生物炭用于吸附处理低浓度含磷废水Application example: The use of iron-modified reed biochar for adsorption treatment of low-concentration phosphorus-containing wastewater
以下各测试以实例一制备的铁改性芦苇生物炭作为除磷的吸附剂，验证其对水体中磷的有较好的吸附效果，在吸附除磷的过程中，按照0.5-4g/L投加量处理浓度为1-4mg/L的含磷废水，废水pH值在6-8范围，温度在20-30℃之间，保持80-120r/min的转速吸附5-8h。通过三种不同的处理工艺比较了除磷效果，并通过处理的实际含磷废水，更具实际性的验证了铁改性生物炭除磷的效果，具体应用实施例如下：The following tests use the iron-modified reed biochar prepared in Example 1 as an adsorbent for phosphorus removal to verify that it has a good adsorption effect on phosphorus in water. Increase the amount to treat phosphorus-containing wastewater with a concentration of 1-4mg/L. The pH value of the wastewater is in the range of 6-8, the temperature is between 20-30°C, and the adsorption speed is maintained at 80-120r/min for 5-8h. The phosphorus removal effect was compared through three different treatment processes, and the phosphorus removal effect of iron-modified biochar was more practically verified through the actual phosphorus-containing wastewater treated. The specific application examples are as follows:
测试例1test case 1
分别称取0.05、0.05、0.1、0.1g改性生物炭投加到50ml浓度为1、2、3、4mg/L的含磷溶液中，用浓度都为1M的HCl和NaOH调节溶液pH为7，在25℃温度、转速为120r/min条件下，恒温振荡6h，用真空抽滤泵抽取全部水样A1（A11～A14），再将各A1水样依次再投加0.05、0.05、0.1、0.1g改性生物炭，进行上面同样的吸附过程，6h后抽滤，固液分离后的炭记为B1（B11～B14），并测定和计算滤液中的磷浓度C1（C11～C14）分别为0.084、0.462、0.342、0.470mg/L，可以看出，一定量的吸附剂经过两次分批吸附处理后，出水浓度均小于0.5mg/L，符合《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A排放标准。Weigh 0.05, 0.05, 0.1, 0.1g of modified biochar and add them into 50ml of phosphorus-containing solution with a concentration of 1, 2, 3, and 4mg/L, and adjust the pH of the solution to 7 with HCl and NaOH with a concentration of 1M. , at a temperature of 25°C and a rotational speed of 120r/min, oscillate at a constant temperature for 6 hours, extract all the water samplesA1 (A11 ~ A14 ) with a vacuum filter pump, and then add 0.05, 0.05, 0.1, 0.1g of modified biochar, carry out the same adsorption process as above, suction filtration after 6h, record the carbon after solid-liquid separation as B1 (B11 ~ B14 ), and measure and calculate the phosphorus concentration in the filtrate C1 (C11 ~C14 ) are 0.084, 0.462, 0.342, 0.470mg/L respectively. It can be seen that after a certain amount of adsorbent undergoes two batch adsorption treatments, the effluent concentration is less than 0.5mg/L, which meets the Class A discharge standard in "Pollutant Discharge Standards for Urban Sewage Treatment Plants" (GB18918-2002).
测试例2test case 2
处理初始浓度为1mg/L的含磷废水，先将测试例1中的炭B11回收利用，投加到50mL浓度为1mg/L的含磷废水中，用浓度都为1M的HCl和NaOH调节溶液pH为7，在25℃温度、转速为120r/min条件下，恒温振荡6h，用真空抽滤泵抽取全部水样A21，水样A21再投加新鲜的改性炭0.05g进行上面同样的吸附过程，6h后抽滤，并测定和计算滤液中的磷浓度C21为0.112mg/L。可以看出，经过吸附处理后，出水浓度虽然稍大于C11的值，但仍小于《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A标准值0.5mg/L，并且C21的值在0.2mg/L以下，已达到《地表水环境质量标准》（GB3838-2002）中Ⅲ类水总磷浓度限值。To treat phosphorus-containing wastewater with an initial concentration of 1mg/L, first recycle the charcoal B11 in Test Example 1, add it to 50mL of phosphorus-containing wastewater with a concentration of 1mg/L, and adjust it with HCl and NaOH with a concentration of 1M. The pH of the solution is 7. Under the conditions of 25°C and 120r/min, shake at a constant temperature for 6 hours, use a vacuum filter pump to extract all the water sample A21 , and add 0.05g of fresh modified carbon to the water sample A21 for the above In the same adsorption process, filter with suction after 6 hours, and measure and calculate the phosphorus concentrationC21 in the filtrate to be 0.112mg/L. It can be seen that after adsorption treatment, although the effluent concentration is slightly higher than the value of C11 , it is still lower than the first-class A standard value of 0.5mg/L in the "Pollutant Discharge Standard for Urban Sewage Treatment Plants" (GB18918-2002), and The value of C21 is below 0.2mg/L, which has reached the concentration limit of total phosphorus in Class III water in the "Environmental Quality Standards for Surface Water" (GB3838-2002).
测试例3Test case 3
处理初始浓度为2mg/L的含磷废水，先将测试例1中的后期吸附2mg/L含磷废水的吸附剂B12回收，再次投加到50mL浓度为2mg/L的含磷废水中，用浓度都为1M的HCl和NaOH调节溶液pH为7，在25℃温度、转速为120r/min条件下，恒温振荡6h，用真空抽滤泵抽取全部水样A22，在水样A22中再投加新鲜的改性炭0.05g进行上面同样的吸附过程，6h后抽滤，并测定和计算滤液中的磷浓度C22为0.498mg/L。经过吸附处理后，出水浓度大于C12的0.462mg/L，但仍小于《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A标准值0.5mg/L。Treat the phosphorus-containing waste water that initial concentration is 2mg/L, earlier the adsorbent B12 that absorbs 2mg/L phosphorus-containing waste water in the later stage in the test example 1 is reclaimed, add again in 50mL concentration and be 2mg/L in the phosphorus-containing waste water, Use 1M HCl and NaOH to adjust the pH of the solution to 7, shake at a constant temperature for 6 hours at a temperature of 25°C and a rotation speed of 120r/min, and extract all the water sample A22 with a vacuum filter pump. In the water sample A22 Then add 0.05g of fresh modified carbon to carry out the same adsorption process as above, filter with suction after 6h, and measure and calculate the phosphorus concentrationC22 in the filtrate to be 0.498mg/L. After adsorption treatment, the effluent concentration is greater than 0.462mg/L of C12 , but still less than the first-class A standard value of 0.5mg/L in the Discharge Standard of Pollutants for Urban Sewage Treatment Plants (GB18918-2002).
测试例4Test case 4
处理初始浓度为3mg/L的含磷废水，先将测试例1中的后期吸附3mg/L含磷废水的吸附剂B13回收，再次投加到50mL浓度为3mg/L的含磷废水中，用浓度都为1M的HCl和NaOH调节溶液pH为7，在25℃温度、转速为120r/min条件下，恒温振荡6h，用真空抽滤泵抽取全部水样A23，在水样A23中再投加新鲜的改性炭0.1g进行上面同样的吸附过程，6h后抽滤，并测定和计算滤液中的磷浓度C23为0.467mg/L。经过吸附处理后，出水浓度稍大于C13的0.342mg/L，但仍小于《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A标准值0.5mg/L。Treat the phosphorus-containing wastewater with an initial concentration of 3mg/L, first reclaim the adsorbent B13 that adsorbs 3mg/L phosphorus-containing wastewater in the later stage in Test Example 1, and add it to 50mL of phosphorus-containing wastewater with a concentration of 3mg/L again. Use HCl and NaOH with a concentration of 1M to adjust the pH of the solution to 7, shake at a constant temperature for 6 hours at a temperature of 25°C and a rotation speed of 120r/min, and extract all the water sample A23 with a vacuum filter pump. In the water sample A23 Then add 0.1g of fresh modified carbon to carry out the same adsorption process as above, filter with suction after 6h, and measure and calculate the phosphorus concentration C23 in the filtrate to be0.467mg /L. After adsorption treatment, the effluent concentration is slightly higher than 0.342mg/L of C13 , but still lower than the first-class A standard value of 0.5mg/L in the Discharge Standard of Pollutants for Urban Sewage Treatment Plants (GB18918-2002).
测试例5Test case 5
处理5m3磷浓度为1mg/L的含磷污水，将改性生物炭每0.5kg装进一个细孔网兜中，悬挂在水池中，共悬挂五个，投加铁改性生物炭共2.5kg，水池pH为7.3，水温为23℃，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭取出，继续以相同方式投加2.5kg改性炭，然后继续吸附反应7h后取出，此次取出的改性炭记为B21，并取水样测定计算剩余磷浓度为0.345mg/L。To treat 5m3 phosphorus-containing sewage with a phosphorus concentration of 1mg/L, put 0.5kg of modified biochar into a fine mesh bag, hang it in the pool, hang five in total, and add iron modified biochar for a total of 2.5kg , the pH of the pool is 7.3, the water temperature is 23°C, and the stirring speed is 100r/min to ensure full contact between the wastewater and the adsorbent, and after 7 hours of adsorption treatment. Take out the modified carbon, continue to add 2.5kg of modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. The modified carbon taken out this time is recorded as B21 , and the remaining phosphorus concentration is calculated as 0.345mg by taking a water sample. /L.
将B21回收后，再次投加到5m3磷浓度为1mg/L的含磷废水中，废水pH为7.1，水温为22℃，将B21每0.5kg装进一个细孔网兜中，悬挂在水池中，共悬挂五个，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭取出，继续以相同方式投加2.5kg新鲜的改性炭，然后继续吸附反应7h后取出，经过吸附处理后，出水浓度为0.407mg/L，依旧小于《城镇污水处理厂污染物排放标准》中的一级A标准值0.5mg/L，能够达标排放。After recovering B21 , add it again to 5m3 phosphorus-containing wastewater with a phosphorus concentration of 1mg/L. The pH of the wastewater is 7.1 and the water temperature is 22°C. Put 0.5kg of B21 into a fine mesh bag and hang it on the In the pool, a total of five are suspended, and the stirring speed is 100r/min to ensure full contact between the wastewater and the adsorbent, and after 7 hours of adsorption treatment. Take out the modified carbon, continue to add 2.5kg of fresh modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. After the adsorption treatment, the effluent concentration is 0.407mg/L, which is still lower than the pollutants in urban sewage treatment plants. The first-class A standard value in "Emission Standards" is 0.5mg/L, which can meet the emission standards.
测试例6Test case 6
处理5m3磷浓度为1.5mg/L的含磷污水，将改性生物炭每1kg装进一个细孔网兜中，悬挂在水池中，共悬挂四个，投加铁改性生物炭共4kg，水池pH为6.8，水温为23℃，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭取出，继续以相同方式投加4kg改性炭，然后继续吸附反应7h后取出，此次取出的改性炭记为B22，并取水样测定计算剩余磷浓度为0.444mg/L。To treat 5m3 phosphorus-containing sewage with a phosphorus concentration of 1.5mg/L, put 1kg of modified biochar into a fine-mesh bag, hang it in the pool, and hang four in total, and add 4kg of iron-modified biochar in total. The pH of the pool is 6.8, the water temperature is 23°C, and the stirring speed is 100r/min to ensure full contact between the wastewater and the adsorbent, and after 7 hours of adsorption treatment. Take out the modified carbon, continue to add 4kg of modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. The modified carbon taken out this time is recorded as B22 , and the remaining phosphorus concentration is calculated as 0.444mg/ L.
将改性炭B22回收后，再次投加到5m3磷浓度为1.5mg/L的含磷废水中，废水pH为7.1，水温为23℃，将改性炭B22每1kg装进一个细孔网兜中，悬挂在水池中，共悬挂四个，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭B22取出，继续以相同方式投加4kg新鲜的改性炭，然后继续吸附反应7h后取出，经过吸附处理后，出水浓度为0.479mg/L，依旧小于《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A标准值0.5mg/L。After recovering the modified carbon B22 , add it again to 5m3 phosphorus-containing wastewater with a phosphorus concentration of 1.5mg/L. The pH of the wastewater is 7.1 and the water temperature is23 °C. Hole net pockets, suspended in the pool, a total of four suspensions, the stirring speed is 100r/min, to ensure full contact between the wastewater and the adsorbent, after 7 hours of adsorption treatment. Take out the modified carbon B22 , continue to add 4kg of fresh modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. After the adsorption treatment, the effluent concentration is 0.479mg/L, which is still lower than the "pollution of urban sewage treatment plants" The first-level A standard value in the National Waste Emission Standard (GB18918-2002) is 0.5mg/L.
测试例7Test case 7
处理5m3磷浓度为2.8mg/L的含磷污水，将改性生物炭每1kg装进一个细孔网兜中，悬挂在水池中，共悬挂十个，投加铁改性生物炭共10kg，水池pH为6.5，水温为23℃，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭取出，继续以相同方式投加10kg改性炭，然后继续吸附反应7h后取出，此次取出的改性炭记为B23，并取水样测定计算剩余磷浓度为0.322g/L。To treat 5m3 phosphorus-containing sewage with a phosphorus concentration of 2.8mg/L, put every 1kg of modified biochar into a fine mesh bag, hang it in the pool, hang ten in total, and add 10kg of iron-modified biochar in total, The pH of the pool is 6.5, the water temperature is 23°C, and the stirring speed is 100r/min to ensure full contact between the wastewater and the adsorbent, and after 7 hours of adsorption treatment. Take out the modified carbon, continue to add 10kg of modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. The modified carbon taken out this time is recorded as B23 , and the remaining phosphorus concentration is calculated as 0.322g/ L.
继续将改性炭回收标记为B23回收后，再次投加到5m3磷浓度为2.8mg/L的含磷废水中，废水pH为6.7，水温为23℃，投放时将B23每1kg装进一个细孔网兜中，悬挂在水池中，共悬挂十个，搅拌转速为100r/min，保证废水与吸附剂充分接触，吸附处理7h后。将改性炭B23取出，继续以相同方式投加10kg新鲜的改性炭，然后继续吸附反应7h后取出，经过吸附处理后，出水浓度为0.467mg/L，依旧小于《城镇污水处理厂污染物排放标准》（GB18918-2002）中的一级A标准值0.5mg/L。After continuing to mark the modified carbon recovery as B23 recovery, add it again to 5m3 phosphorus-containing wastewater with a phosphorus concentration of2.8mg /L. The pH of the wastewater is 6.7 and the water temperature is 23°C. Put into a fine-mesh net bag, hang in the pool, hang ten in total, the stirring speed is 100r/min, ensure that the wastewater is in full contact with the adsorbent, and after 7 hours of adsorption treatment. Take out the modified carbon B23 , continue to add 10kg of fresh modified carbon in the same way, and then continue the adsorption reaction for 7 hours before taking it out. After the adsorption treatment, the concentration of the effluent is 0.467mg/L, which is still lower than the "pollution of urban sewage treatment plants". The first-level A standard value in the National Waste Emission Standard (GB18918-2002) is 0.5mg/L.
由以上可见：It can be seen from the above:
本发明应用测试例1中，将一定量的吸附剂分成两次投加进行吸附除磷，第二次投加的吸附剂可以再用于后续吸附。在测试例2至4中的方法将测试例1中第二次投加使用的吸附剂回收，进行二次吸附，在减少吸附剂使用量的情况下保证出水水质达标。测试例5至中7用改性生物炭处理实际含磷废水，处理结果表明，吸附剂可进行二次利用处理废水，出水浓度均小于0.5mg/L。In application test example 1 of the present invention, a certain amount of adsorbent is divided into two doses for adsorption and dephosphorization, and the adsorbent added for the second time can be used for subsequent adsorption. In the method in test examples 2 to 4, the adsorbent used for the second time in test example 1 is recovered and used for secondary adsorption, so as to ensure that the effluent water quality meets the standard while reducing the amount of adsorbent used. In Test Examples 5 to 7, the modified biochar was used to treat the actual phosphorus-containing wastewater. The treatment results showed that the adsorbent could be used for secondary treatment of wastewater, and the concentration of the effluent was all less than 0.5 mg/L.
本发明与现有除磷技术相比，不仅制备了一种具有良好除磷效果和环境友好型的改性生物炭做吸附剂，还找到了相应优化的吸附除磷工艺，拥有节能减排和资源循环利用的双重优势，并具有良好的应用前景。Compared with the existing phosphorus removal technology, the present invention not only prepares a modified biochar with good phosphorus removal effect and environmental friendliness as an adsorbent, but also finds a corresponding optimized adsorption and phosphorus removal process, which has energy saving and emission reduction and The dual advantages of resource recycling, and has a good application prospect.
对比分析：Comparative analysis:
芦苇生物炭和其他吸附剂材料相比的优势如下：The advantages of reed biochar compared with other adsorbent materials are as follows:
现有技术中，相关学者利用沸石或竹炭、小麦秸秆等制备成的生物炭对其负载铁进行除磷的研究，根据负载铁改性后的吸附剂除磷机理主要是水体中的磷与负载的铁发生化学反应和离子交换，从而达到从水中去除的效果，且磷的去除效果与吸附剂负载铁量有很大的关系。In the prior art, relevant scholars use biochar prepared from zeolite, bamboo charcoal, wheat straw, etc. to carry out phosphorus removal research on its loaded iron. The chemical reaction and ion exchange of iron occur in the water, so as to achieve the effect of removal from water, and the removal effect of phosphorus has a great relationship with the amount of iron loaded on the adsorbent.
陆燕勤等用沸石负载铁，直接将沸石与硝酸铁溶液混合烘干，其负载量最大仅为8.325mg/g[6]，目前用沸石做吸附剂去除水体中重金属有机物等污染物的研究较多，吸附后可进行再生利用，而用沸石吸附处理氮磷等，氮磷本身是营养元素可以还田用作肥料，如将吸附后的沸石进行再生处理，会增加了处理成本，故而不利于推广，所以相比而言，用生物炭负载铁除磷是一种变废为宝、循环利用的方法，避免了二次污染。Lu Yanqin et al. used zeolite to load iron, directly mixed and dried zeolite and ferric nitrate solution, and the maximum loading capacity was only 8.325 mg/g[6] . At present, there are many studies on using zeolite as adsorbent to remove heavy metal organic matter and other pollutants in water , can be recycled after adsorption, and nitrogen and phosphorus are treated with zeolite adsorption. Nitrogen and phosphorus itself are nutrients and can be used as fertilizers. If the adsorbed zeolite is regenerated, the treatment cost will increase, so it is not conducive to popularization. , so in comparison, using biochar to load iron to remove phosphorus is a method of turning waste into treasure and recycling, which avoids secondary pollution.
罗舒君研究了负载改性竹炭去除废水中磷，用反复蒸煮法将氯化铁负载于竹炭上，最大负载铁量为41.53mg/g[7]。反复蒸煮法比较麻烦，不适合推广。李际会用氯化铁改性小麦秸秆生物炭，探讨了其吸附磷酸盐的效果，将Fe3+与小麦秸秆生物炭以6种不同质量比进行混合，对其进行改性处理。确定Fe3+与生物炭的最佳混合质量比为0.7时吸附效果最好，但是此方法改性使得铁的负载效果较差[8]，从而影响其除磷效果。Luo Shujun studied the loading of modified bamboo charcoal to remove phosphorus in wastewater, and ferric chloride was loaded on bamboo charcoal by repeated cooking method, and the maximum loaded iron amount was 41.53mg/g[7] . The repeated cooking method is troublesome and is not suitable for popularization. Li Jihui modified wheat straw biochar with ferric chloride, and discussed its adsorption effect on phosphate. He mixed Fe3+ and wheat straw biochar in 6 different mass ratios to modify it. It is determined that the optimal mixing mass ratio of Fe3+ and biochar is 0.7, and the adsorption effect is the best, but the modification of this method makes the loading effect of iron poor[8] , thus affecting its phosphorus removal effect.
本发明中的选用的芦苇作为生物炭原材料制备成生物炭，并进行负载氯化铁改性，其负载铁量可达53.94mg/g，负载效果较上述的竹炭和小麦秸秆效果好。并且本发明在研究过程中，对水稻秸秆、芦苇秸秆、稻壳这三种年产量均较大的原料制备成的生物炭进行了吸附除磷比较，相同条件下制备的未进行负载铁改性的三种生物炭，在处理低浓度含磷废水时，水稻和稻壳生物炭均有较多的磷溶出现象，而本发明采用芦苇秸秆仅很少的磷溶出，这可能与植物在生长过程中，对土壤中营养物质的吸收和其本身的元素成分有关。所以将芦苇制备成生物炭，制备成吸附剂，与其他吸附剂材料的来源、预处理过程和负载铁效果相比，具有一定的优势。The reed selected in the present invention is used as the raw material of biochar to prepare biochar, which is modified by loading ferric chloride, and the loaded iron amount can reach 53.94mg/g, and the loading effect is better than that of the above-mentioned bamboo charcoal and wheat straw. And in the research process of the present invention, the biochar prepared from three kinds of raw materials with large annual output, namely rice straw, reed straw and rice husk, was compared for adsorption and dephosphorization. When treating low-concentration phosphorus-containing wastewater, rice and rice husk biochars have more phosphorus dissolution, but the present invention uses reed straw with only a small amount of phosphorus dissolution, which may be related to the growth process of plants. Among them, the absorption of nutrients in the soil is related to its own elemental composition. Therefore, the preparation of reed into biochar and adsorbent has certain advantages compared with the source of other adsorbent materials, pretreatment process and iron loading effect.
本发明将湿地植物芦苇秸秆在低温（350℃）低氧的环境下热解后，制备成芦苇生物炭，形成丰富的孔隙结构，再将生物炭与氯化铁溶液混合烘干后热处理，铁以赤铁矿的形态固载在生物炭上，整个除磷吸附剂的制备工艺简单，条件易控制，适合工业生产。且芦苇来源广泛，原材料丰富，氯化铁试剂属于常见化学品，价格低廉。整个铁改性吸附的制备过程工艺简单、成本低、无需耗费大量人力财力。In the present invention, after pyrolyzing wetland plant reed stalks in a low-temperature (350°C) and low-oxygen environment, reed biochar is prepared to form a rich pore structure. It is immobilized on biochar in the form of hematite, the preparation process of the whole phosphorus removal adsorbent is simple, the conditions are easy to control, and it is suitable for industrial production. Moreover, reeds come from a wide range of raw materials, and the ferric chloride reagent is a common chemical with a low price. The preparation process of the whole iron-modified adsorption is simple in technique, low in cost, and does not need to consume a lot of manpower and financial resources.
并且，经过吸附处理后，进行固液分离，将吸附剂从含磷废水中打捞出来，此时的吸附剂富含丰富的磷和铁元素，可施用于土壤中，给土壤增加肥力，生物炭本身特殊的结构也是一种优良的土壤改良剂。本发明不仅为芦苇资源的利用提供了新的途径，还采用了简单低成本的工艺方法制备出高效的除磷吸附剂，并使用二次循环吸附法二次利用吸附剂，最后，将使用后的吸附剂作为土壤改良剂，将芦苇资源变废为宝，实现循环利用，本发明的除磷吸附剂和除磷工艺是一种简单、低价、高效、环保的发明。Moreover, after the adsorption treatment, the solid-liquid separation is carried out, and the adsorbent is salvaged from the phosphorus-containing wastewater. At this time, the adsorbent is rich in phosphorus and iron elements, and can be applied to the soil to increase the fertility of the soil. Biochar Its special structure is also an excellent soil conditioner. The invention not only provides a new approach for the utilization of reed resources, but also adopts a simple and low-cost process to prepare an efficient phosphorus removal adsorbent, and uses the secondary cycle adsorption method to utilize the adsorbent for the second time. Finally, the used The adsorbent is used as a soil improver to turn reed resources from waste to treasure and realize recycling. The phosphorus removal adsorbent and phosphorus removal process of the present invention is a simple, low-cost, high-efficiency, and environmentally friendly invention.
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| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20151223 | |
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