CN111302340A - A kind of preparation method of biogas residue biochar - Google Patents
A kind of preparation method of biogas residue biocharDownload PDFInfo
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Abstract
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Description
Translated fromChinese技术领域technical field
本发明涉及一种生物炭的制备方法，具体地说是一种沼渣生物炭的制备方法，属于资源与环境技术领域。The invention relates to a method for preparing biochar, in particular to a method for preparing biochar from biogas residues, and belongs to the technical field of resources and environment.
背景技术Background technique
厌氧发酵制备生物甲烷产生的残余物沼渣的产量巨大，多数得不到合理的处理和利用。沼渣含有大量的植物生长的养分如有机物、N、P、K和微量元素等，同时也含有污染环境的物质。沼渣未经合理的处置直接土地利用有如下潜在的风险，一是未经腐熟的沼渣会与农作物争夺土壤中的氧气，影响作物的根系发育；二是沼渣中可能含有抗生素、重金属和病原菌等有毒有害物质，直接土地利用存在着通过食物链进入人体的风险。因此，沼渣的减量化处理和资源化利用已成为沼气工程产业化推广亟待解决的技术瓶颈问题。The output of biogas residue produced by anaerobic fermentation to produce biomethane is huge, and most of them cannot be properly treated and utilized. Biogas residue contains a lot of nutrients for plant growth such as organic matter, N, P, K and trace elements, etc., and also contains substances that pollute the environment. The direct land use of biogas residue without reasonable disposal has the following potential risks. First, the unripened biogas residue will compete with crops for oxygen in the soil and affect the root development of crops; second, the biogas residue may contain antibiotics, heavy metals and Toxic and harmful substances such as pathogenic bacteria, direct land use has the risk of entering the human body through the food chain. Therefore, the reduction treatment and resource utilization of biogas residues have become the technical bottleneck problems to be solved urgently for the industrialization of biogas projects.
沼渣因沼气发酵原料的不同，物质组成和性质有一定的差异，但沼渣富含碳源，正是制造生物炭所需原料的主要成分，将沼渣作为生物炭的生产原料，通过创新技术将其转变为高附加值的生物炭，不但解决了沼渣的出路问题，减少了环境污染，同时因沼渣的廉价而大大降低了现有生物炭产业的生产成本。Due to the different raw materials of biogas fermentation, the composition and properties of biogas residues are different, but biogas residues are rich in carbon sources, which are the main components of the raw materials required for the manufacture of biochar. Biogas residues are used as raw materials for biochar production. Converting it into high value-added biochar not only solves the problem of the exit of biogas residues and reduces environmental pollution, but also greatly reduces the production cost of the existing biochar industry due to the cheapness of biogas residues.
现有的沼渣制备生物炭的方法中，如专利CN107469768A中公开了一种畜禽粪沼渣生物炭的制备，以畜禽粪沼渣为原材料，风干过目后，限氧慢速热解炭化，制得畜禽粪沼渣生物炭。专利CN109809403A中公开了沼渣基活性炭的制备方法，包括以下步骤：(1)经厌氧发酵形成生物质沼渣，干燥，再经粉碎，得沼渣粉末；(2)将沼渣粉末在惰性气体氛围下与活化剂混合、共磨；(3)将步骤(2)所得沼渣粉末置于惰性气体氛围，于500～800℃温度条件下进行活化，经冷却，得到活化的沼渣；(4)将活化的沼渣漂洗至中性，再经干燥，即得所述沼渣基活性炭。Among the existing methods for preparing biochar from biogas residues, such as patent CN107469768A, a preparation of livestock and poultry manure biochar residues is disclosed. Livestock and poultry manure biochar residues are used as raw materials. , to obtain livestock and poultry manure biochar. Patent CN109809403A discloses a preparation method of biogas residue-based activated carbon, which includes the following steps: (1) anaerobic fermentation to form biomass biogas residue, drying, and then pulverizing to obtain biogas residue powder; (2) biogas residue powder in an inert Mixing and co-grinding with an activator under a gas atmosphere; (3) placing the biogas residue powder obtained in step (2) in an inert gas atmosphere, activating at a temperature of 500-800° C., and cooling to obtain an activated biogas residue; ( 4) The activated biogas residue is rinsed to neutrality, and then dried to obtain the biogas residue-based activated carbon.
但现有的制备方法存在如下问题：1.目前最常用的生物炭制备方式为直接热解法，在无氧条件下加热，使有机物产生热裂解，该方法形成的生物炭比表面积较低、孔隙结构与表面官能团的丰富度较差，不利于作为吸附材料的开发利用；2.高温炭化制备生物炭，使得生物炭碱度增加，阳离子交换能力减弱，较多官能团被氧化占据了较多的吸附位点。However, the existing preparation methods have the following problems: 1. The most commonly used biochar preparation method is direct pyrolysis, which is heated under anaerobic conditions to thermally crack organic matter. The biochar formed by this method has a relatively low specific surface area, The richness of pore structure and surface functional groups is poor, which is not conducive to the development and utilization of adsorption materials; 2. The preparation of biochar by high temperature carbonization increases the basicity of the biochar, weakens the cation exchange capacity, and more functional groups are occupied by oxidation. adsorption site.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了克服现有技术的不足，提供一种沼渣生物炭的制备方法，为一种高效的沼渣处置并且加工制造为生物炭的工艺流程。采用本发明的工艺可以使沼渣达到减量化处置、无害化处理和资源化利用，完全解决了沼渣处置难题，其生物炭成品质量完全符合污水处理标准，减少了沼渣处置的资金投入，并创造出可观的经济效益。The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a method for preparing biochar from biogas residue, which is an efficient process flow for disposing of biogas residue and processing and manufacturing it into biochar. By adopting the process of the invention, the biogas residue can be disposed of in a reduced amount, harmlessly treated and utilized as a resource, completely solving the problem of the disposal of the biochar residue, the quality of the finished biochar fully complies with the sewage treatment standard, and reducing the funds for the disposal of the biogas residue investment and create considerable economic benefits.
本发明的目的是通过以下技术方案实现的：The purpose of this invention is to realize through the following technical solutions:
本发明提供了一种沼渣生物炭的制备方法，该方法包括如下步骤：The invention provides a preparation method of biochar from biogas residue, which comprises the following steps:
步骤S1，向沼渣中投加药剂，进行高温高压反应；Step S1, adding chemicals into the biogas residue to carry out high temperature and high pressure reaction;
步骤S2，对步骤S1反应后得到的湿沼渣水热炭进行脱水干燥；Step S2, dehydrating and drying the wet biogas residue hydrothermal carbon obtained after the reaction in step S1;
步骤S3，将脱水干燥后的沼渣水热炭研磨过筛；Step S3, grinding and sieving the dehydrated and dried biogas residue hydrothermal carbon;
步骤S4，将过筛后的沼渣水热炭进行烧制，并通入活化保护气体；In step S4, the sieved biogas residue hydrothermal charcoal is fired, and activated protective gas is introduced;
步骤S5，将烧制后得到的产物放入活化剂中活化；Step S5, putting the product obtained after firing into an activator for activation;
步骤S6，对活化好的产物进行脱水干燥、研磨过筛；Step S6, dehydrating, drying, grinding and sieving the activated product;
步骤S7，对过筛后得到的活化产物进行冲洗干燥、研磨过筛，即得沼渣生物炭。In step S7, the activated product obtained after sieving is washed, dried, ground and sieved to obtain biogas residue biochar.
优选地，所述步骤S1中投加的药剂是1-3mol/L的盐酸溶液，使污泥的pH稳定在5.0。本发明的水热碳化原料会裂解形成大量羧酸、醛和呋喃类物质，进一步脱水缩合成芳香族化合物，进而形成碳材料，当体系中H+浓度过高，沼渣的水解过程不能全部消耗，过量则阻碍裂解，从而影响产物形貌结构，降低碳化程度。因此控制其pH在5.0能得到较高产率及有相对较高炭化程度。对于采用的药剂为盐酸溶液，是考虑到沼渣成分的复杂性，其中包括部分金属元素，使用如硫酸则有可能会造成堵孔的情况。Preferably, the agent added in the step S1 is a 1-3 mol/L hydrochloric acid solution to stabilize the pH of the sludge at 5.0. The hydrothermal carbonization raw material of the present invention will be cracked to form a large number of carboxylic acids, aldehydes and furans, which are further dehydrated and condensed into aromatic compounds to form carbon materials. When the H concentration in the system is too high, the hydrolysis process of the biogas residue cannot be fully consumed. , the excess will hinder the cracking, thereby affecting the morphology and structure of the product and reducing the degree of carbonization. Therefore, controlling its pH at 5.0 can obtain a higher yield and a relatively higher degree of carbonization. As the chemical used is hydrochloric acid solution, considering the complexity of biogas residue composition, including some metal elements, the use of sulfuric acid may cause pore blockage.
优选地，所述步骤S1中的反应温度为180℃、相对压力为0.6-1.7MPa、反应时间为1-4h，反应时采用的搅拌速度为30-120r/min。Preferably, the reaction temperature in the step S1 is 180° C., the relative pressure is 0.6-1.7 MPa, the reaction time is 1-4 h, and the stirring speed used in the reaction is 30-120 r/min.
本发明通过步骤S1的高温高压反应，使原料脱水脱羧形成可溶性产物，降低原料中的O、H含量，与此同时发生芳构化反应，进而形成表面含有丰富活性氧基团的材料。且该材料会具备挥发分含量增高，灰分较低，灰壳较薄的特性。In the present invention, through the high temperature and high pressure reaction in step S1, the raw material is dehydrated and decarboxylated to form a soluble product, the content of O and H in the raw material is reduced, and an aromatization reaction occurs at the same time, thereby forming a material rich in active oxygen groups on the surface. And the material will have the characteristics of higher volatile content, lower ash content and thinner ash shell.
优选地，所述步骤S2中的脱水干燥是在105℃下干燥8-10h。Preferably, the dehydration and drying in the step S2 is drying at 105° C. for 8-10 hours.
优选地，所述步骤S3中的研磨过筛为过30目筛。Preferably, the grinding and sieving in the step S3 is a 30-mesh sieve.
优选地，所述步骤S4中的烧制温度为400-750℃，升温速率为5℃/min，烧制时间为1-4h。所述烧制的热解过程中，热解产物的扩散和热传递需要一定时间，若升温速率过高，热解产生的焦油成分含量包括芳香族，脂环族和脂肪族含量达到最大值所对应的热解温度随升温速率的增加产生滞后现象，产生的气体成分释放速率也越快，会导致需要更高的热解温度使其彻底析出，造成能源浪费。而速率过低，则会增加反应时间。Preferably, the firing temperature in the step S4 is 400-750° C., the heating rate is 5° C./min, and the firing time is 1-4 h. During the pyrolysis process of the firing, the diffusion and heat transfer of the pyrolysis products require a certain time. If the heating rate is too high, the content of the tar components produced by the pyrolysis, including aromatic, alicyclic and aliphatic components, reaches the maximum value. The corresponding pyrolysis temperature produces a hysteresis phenomenon with the increase of the heating rate, and the faster the release rate of the generated gas components will be, which will lead to a higher pyrolysis temperature for complete precipitation, resulting in energy waste. If the rate is too low, the reaction time will be increased.
优选地，所述步骤S4中的活化保护气体为氮气，气体的流量为500mL/min。Preferably, the activated protective gas in the step S4 is nitrogen, and the flow rate of the gas is 500 mL/min.
优选地，所述步骤S5中的活化剂为1-6mol/L的FeCl3溶液(更优选为2mol/L)，所述产物与活化剂的固液体积比为1：2；所述活化时间为12-24h(更优选为12h)，活化在摇床上进行，摇床转速为150r/min。Preferably, the activator in the step S5 is1-6mol /L FeCl solution (more preferably 2mol/L), and the solid-liquid volume ratio of the product to the activator is 1:2; the activation time It is 12-24h (more preferably 12h), and the activation is carried out on a shaking table, and the rotating speed of the shaking table is 150r/min.
本发明通过采用活化剂为FeCl3，通过铁离子对生物炭改性显著提升了生物炭对重金属的修复效率；且将各种污染物以更加稳定、低毒性的形态固定下来，是一种极具潜力的生物炭改性方式。经试验表明，用FeCl3试剂对生物炭进行改性获得的生物炭对污染物氨氮，COD的吸附性能相比其他活化剂如HCl、NaOH、ZnCl2等最优。In the present invention, the activator is FeCl3 , and the biochar is modified by iron ions to significantly improve the remediation efficiency of the biochar to heavy metals; and various pollutants are fixed in a more stable and less toxic form, which is an extremely effective method. Potential biochar modification method. Experiments show that the biochar obtained by modifying biochar with FeCl3 reagent has the best adsorption performance for pollutants ammonia nitrogen and COD than other activators such as HCl, NaOH, ZnCl2 and so on.
优选地，所述步骤S6中的脱水干燥是在105℃下干燥8-10h，所述的研磨过筛为过30目筛。Preferably, the dehydration and drying in the step S6 is drying at 105° C. for 8-10 hours, and the grinding and sieving are 30 mesh sieves.
优选地，所述步骤S7中的冲洗是用体积浓度为30％的盐酸溶液浸泡1h，并用80℃的去离子水冲洗过滤5-10次；所述的干燥是在105℃下干燥8-10h；Preferably, the rinsing in the step S7 is to soak in a hydrochloric acid solution with a volume concentration of 30% for 1 hour, and to rinse and filter with deionized water at 80°C for 5-10 times; the drying is to dry at 105°C for 8-10 hours. ;
所述研磨过筛为过80目筛。The grinding and sieving are 80 mesh sieves.
本发明在热解之前进行了水热炭化处理，将有机物脱水缩合，促进炭骨架和孔道的形成及畅通形，为制备具有高比表面积的生物炭提供一个基础，并且可将重金属元素稳定于其水热过程所形成的晶体结构中，防止在使用过程中的析出，固定化效果好；本发明利用Fecl3试剂作为改性试剂，使生物炭表面增加正电荷官能团，提供了一种高吸附性能、环境友好、重金属残留量低的生物炭制备方法。The method performs hydrothermal carbonization treatment before pyrolysis, dehydrates and condenses organic matter, promotes the formation and smooth shape of carbon skeleton and pore channels, provides a basis for preparing biochar with high specific surface area, and can stabilize heavy metal elements in its In the crystal structure formed by the hydrothermal process, precipitation during use is prevented, and the immobilization effect is good; the present invention usesFecl3 reagent as a modification reagent to increase the surface of the biochar with positive charge functional groups, thereby providing a high adsorption performance. , Environmentally friendly, low heavy metal residue biochar preparation method.
现有技术相比，本发明具有如下的有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明方法工艺简单、操作方便、成本低，通过该方法制备的沼渣生物炭，可以使沼渣中的有机物碳化，完全杀灭病菌。1. The method of the present invention has the advantages of simple process, convenient operation and low cost, and the biochar from the biogas residue prepared by the method can carbonize the organic matter in the biogas residue and completely kill the germs.
2、本发明采用厌氧发酵的产物沼渣作为原料，原料来源广泛，有利于环境保护，制得的生物炭吸附效果好，整个过程符合无害化处理、减量化处置、资源化利用。2. The present invention adopts the biogas residue of anaerobic fermentation as raw material, which has a wide range of raw material sources, which is beneficial to environmental protection, and the obtained biochar has a good adsorption effect, and the whole process conforms to harmless treatment, reduction disposal and resource utilization.
3、本发明与现有制备方法相比多了水热的预处理过程，具有以下优势：3. Compared with the existing preparation method, the present invention has more hydrothermal pretreatment process, and has the following advantages:
(1)对于处理沼渣这种含水量高的废弃生物质时无需干燥，节约了预处理的成本；(1) There is no need to dry the waste biomass with high water content such as biogas residue, which saves the cost of pretreatment;
(2)传统制备过程呈弱碱化，而经过水热预处理则呈酸性化趋势，能提高后续处理的生物炭性能；(2) The traditional preparation process is weakly alkaline, but after hydrothermal pretreatment, it is acidic, which can improve the performance of biochar in subsequent treatment;
(3)保留大量生物质中的氧、氮元素，使炭化物表面含有丰富的含氧、含氮官能团；(3) Retain the oxygen and nitrogen elements in a large amount of biomass, so that the surface of the carbonized material is rich in oxygen-containing and nitrogen-containing functional groups;
(4)在固定重金属浸出风险上有明显优势；(4) It has obvious advantages in fixing the risk of heavy metal leaching;
(5)沼渣在水热碳化过程中释放粘性有机质，在高温高压的条件下，被大量水解脱水缩合形成碳微球，从而形成具有一定结构的炭骨架；并且在水热碳化的过程中部分有机质被分解，促进了炭骨架和孔道的形成及畅通；由此经水热碳化预处理后的沼渣能更好的与活化剂接触反应，在高温热解时能更好的渗透入炭骨架内部钻蚀孔道，增加生物炭的比表面积和孔道内部的活性基团；(5) Biogas residue releases viscous organic matter in the process of hydrothermal carbonization. Under the condition of high temperature and high pressure, it is hydrolyzed, dehydrated and condensed to form carbon microspheres, thereby forming a carbon skeleton with a certain structure; and in the process of hydrothermal carbonization, part of The organic matter is decomposed, which promotes the formation and smooth flow of carbon skeleton and pores; thus, the biogas residue after hydrothermal carbonization pretreatment can better contact and react with the activator, and can better penetrate into the carbon skeleton during high temperature pyrolysis Internal drilling and erosion of pores, increasing the specific surface area of biochar and active groups inside the pores;
(6)热解过后，使用FeCl3试剂作为活化剂浸泡生物炭，使生物炭中O和Fe的质量分数上升，极性增强，表面羟基含量增加，同时还具有静电相互作用，使其为吸附质提供了丰富的结合位点，提高对阴离子污染物的吸附；(6) After pyrolysis, use FeCl3 reagent as activator to soak biochar, so that the mass fraction of O and Fe in the biochar increases, the polarity is enhanced, the surface hydroxyl content increases, and it also has electrostatic interaction, making it an adsorption It provides abundant binding sites and improves the adsorption of anionic pollutants;
(7)铁的形态和分布影响着生物炭的物理化学性质，进而控制着铁改性生物炭在环境污染修复中的效果，氯化铁改性生物炭将各种污染物以更加稳定、低毒性、弱迁移性的形态固定下来，是一种很有潜力的生物炭改性方式；(7) The form and distribution of iron affect the physical and chemical properties of biochar, which in turn controls the effect of iron-modified biochar in the remediation of environmental pollution. The form of toxicity and weak mobility is fixed, which is a potential way of biochar modification;
(8)相对于其他金属改性试剂，金属Fe及其盐的成本最低。(8) Compared with other metal modification reagents, metal Fe and its salts have the lowest cost.
附图说明Description of drawings
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：Other features, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments with reference to the following drawings:
图1为本发明制备方法中步骤5中的活化剂浓度对沼渣炭吸附性能的影响；Fig. 1 is the influence of the activator concentration in
图2为本发明制备方法中步骤4中的活化温度对沼渣生物炭吸附性能的影响；Fig. 2 is the influence of activation temperature in step 4 in the preparation method of the present invention on the adsorption performance of biochar of biogas residue;
图3为本发明制备方法中步骤4中的活化时间对沼渣生物炭吸附性能的影响；Fig. 3 is the influence of activation time in step 4 in the preparation method of the present invention on the adsorption performance of biochar of biogas residue;
图4为本发明采用的原沼渣(a)和制备的沼渣生物炭(b)扫描电子显微镜图；Figure 4 is a scanning electron microscope image of the raw biogas residue (a) used in the present invention and the prepared biogas residue (b);
图5为本发明采用的原沼渣和制备的沼渣生物炭的FT-IR图谱。Figure 5 is the FT-IR spectrum of the raw biogas residue used in the present invention and the prepared biogas residue biochar.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
以下实施例提供了一种沼渣生物炭的制备方法，具体采用以下步骤：The following examples provide a preparation method of biogas residue biochar, which specifically adopts the following steps:
步骤1，向沼渣中投加体积浓度为2mol/L的盐酸溶液，使其pH稳定在5左右，将调节好pH后的沼渣放入密闭的高温高压反应釜，调节目标温度为180℃，调节转机在120r/min的转速下使沼渣充分反应4h，此时反应釜内的相对压力为0.6-1.7MPa。Step 1, add hydrochloric acid solution with a volume concentration of 2 mol/L to the biogas residue to stabilize its pH at about 5, put the adjusted biogas residue into a closed high temperature and high pressure reactor, and adjust the target temperature to 180°C , adjust the rotary machine to make the biogas residue fully react for 4h at the rotating speed of 120r/min, and the relative pressure in the reaction kettle is 0.6-1.7MPa at this time.
步骤2，将处理后的湿沼渣放入105℃的烘箱内进行脱水干燥8-10h。
步骤3，将所述脱水干燥后的沼渣粉碎并研磨，过30目筛。In step 3, the dehydrated and dried biogas residue is pulverized and ground, and passed through a 30-mesh sieve.
步骤4，将上述粉末状沼渣放入管式炉中烧制，设置5℃/min的升温速率，同时通入保护气体氮气(气体流量为500mL/min)，控制烧制温度为400-750℃，烧制时间为1-4h。Step 4, put the above-mentioned powdery biogas residue into the tube furnace for firing, set a heating rate of 5°C/min, and simultaneously feed the protective gas nitrogen (the gas flow rate is 500mL/min), and control the firing temperature to be 400-750 °C. ℃, the firing time is 1-4h.
步骤5，将高温热解且自然冷却过后的沼渣放入1-6mol/L的FeCl3溶液，固液体积比为1:2，将其放入摇床，转速为150r/min，震荡活化24h。
步骤6，将活化好的沼渣滤掉多余的活化剂，并放入105℃的烘箱内进行脱水干燥，将脱水干燥后的沼渣粉碎并研磨，过30目筛。In
步骤7，将干燥后的产物取出，加入体积浓度为30％的盐酸溶液200ml，并将其置于180r/min的摇床上震荡1h，将震荡好的沼渣生物炭进行过滤，并用过量的80℃的去离子水充分洗涤沼渣生物炭5-10次，浸洗出堵在沼渣生物炭孔中的灰分。将过滤好的沼渣生物炭置于105℃的烘箱内烘干，于干燥器中冷却至室温后取出研磨，研磨过80目筛，即得沼渣生物炭。Step 7, take out the dried product, add 200 ml of hydrochloric acid solution with a volume concentration of 30%, and place it on a shaking table at 180 r/min to shake for 1 hour, filter the shaken biogas residue, and use an excess of 80 ℃ deionized water fully wash the biochar of biogas residue for 5-10 times, leaching out the ash blocked in the biochar pores of biogas residue. The filtered biogas residue biochar was dried in an oven at 105°C, cooled to room temperature in a desiccator, taken out and ground, and ground through an 80-mesh sieve to obtain biogas residue biochar.
对于步骤4和步骤7中的活化过程属于化学活化，对沼渣生物炭的吸附效果有着较大的影响，下面我们将分别从活化温度、热解时间、活化剂浓度几个方面分别介绍化学活化过程中各个条件要素的选取。The activation process in steps 4 and 7 belongs to chemical activation, which has a great influence on the adsorption effect of biochar residues. Below we will introduce chemical activation from the aspects of activation temperature, pyrolysis time, and activator concentration. The selection of each condition element in the process.
如图1：对于步骤5中的活化剂浓度，通过单因素实验我们发现，在相同的烧制条件下(温度650℃、烧制2h)，在活化剂浓度在1-3mol/L时的变化对沼渣生物炭对COD的去除率差距不明显。随着FeCl3浓度的升高，沼渣生物炭的COD、氨氮去除率和比表面积呈下降趋势，当FeCl3浓度高于3mol/L后，随着活化剂浓度的增大，生物炭的COD、氨氮去除率明显下降。活化剂浓度的增加导致生物炭的吸附能力呈后下降的趋势，其原因在于，一方面当有充足的活化剂参加反应时，可形成发达微孔结构，使生物炭的比表面积和微孔体积逐渐提高，但是当活化剂浓度过大时，会造成活化反应过于剧烈，活化中生成的部分微孔转化为中孔。另一方面活化剂浓度过高时，在热解过程中会堵塞微孔且会污染环境。同时，投加过量的FeCl3导致在洗涤沼渣生物炭时，难以完全洗净，从而导致其比表面积的降低。Figure 1: For the activator concentration in
如图2：对于步骤4的烧制温度，通过单因素实验我们发现，在相同的烧制时间(2h)和活化剂浓度(FeCl3浓度2mol/L)条件下，温度的变化对沼渣生物炭的吸附性能影响较大。当热解温度为400-650℃时，随着温度増高，沼渣生物炭产物的COD、氨氮去除率和比表面积显著提高，吸附性能明显増高，表示内部空隙正在形成；当热解温度达650℃时沼渣生物炭的沼渣生物炭的比表面积为72.58m2/g，对COD的去除率为57.2％，对氨氮的去除率为36.8％。但当热解温度高于650℃时，随着温度的増高，产物的吸附性能、孔隙率和产率显著降低。这是由于温度过高时，深度碳化，使产物中含碳量减少，灰分含量的増加堵塞了孔隙，大量物质挥发，原料完全分解。Figure 2: For the firing temperature of step 4, we found through single-factor experiments that under the same firing time (2h) and activator concentration (FeCl3 concentrationof 2mol/L), the change of temperature had an adverse effect on biogas residue biogas The adsorption performance of carbon is greatly affected. When the pyrolysis temperature is 400-650 °C, as the temperature increases, the COD, ammonia nitrogen removal rate and specific surface area of biochar residues are significantly improved, and the adsorption performance is significantly improved, indicating that internal voids are being formed; when the pyrolysis temperature When the temperature reaches 650℃, the specific surface area of the biochar is 72.58m2 /g, the removal rate of COD is 57.2%, and the removal rate of ammonia nitrogen is 36.8%. However, when the pyrolysis temperature was higher than 650 °C, the adsorption performance, porosity and yield of the product decreased significantly with the increase of temperature. This is because when the temperature is too high, deep carbonization reduces the carbon content in the product, the increase in ash content blocks the pores, a large amount of substances are volatilized, and the raw materials are completely decomposed.
如图3：对于步骤4的烧制停留时间，通过实验我们发现，在相同的活化温度(650℃)和活化剂浓度(FeCl3浓度2mol/L)条件下，时间的变化对沼渣生物炭的吸附性能影响较小。当热解停留时间为1-2h时，随着热解时间延长，可以明显的看出产物的吸附性能开始増大；当热解停留时间达到2h时，产物的比表面积为73.20m2/g，对COD的去除率为52.6％，对氨氮的去除率为35.5％。在热解2h之后，随着热解时间继续延长，吸附性能开始逐渐降低。沼渣生物炭在热解过程中，随着时间増长，其内部的空隙发展到一定程度后，孔的増长由原先的加深变为拓宽，同时在孔的内壁上又生成新的孔，使得孔的密度大大増大从而増大了产物的吸附性能。但随着活化时间继续増长，孔壁进一步扩大，表面的孔开始合并消失，形成大量大孔，并且孔壁变薄消失，热解初期形成的微孔被烧穿，导致生物炭结构强度下降，吸附性能和生物炭的比表面积进一步下降。Figure 3: For the firing residence time of step 4, we found through experiments that under the same activation temperature (650 °C) and activator concentration (FeCl3 concentration of 2 mol/L), the change of time had a significant effect on biochar residues. The adsorption performance has little effect. When the residence time of pyrolysis is 1-2h, with the extension of pyrolysis time, it can be clearly seen that the adsorption performance of the product begins to increase; when the residence time of pyrolysis reaches 2h, the specific surface area of the product is 73.20m2 /g, The removal rate of COD was 52.6%, and the removal rate of ammonia nitrogen was 35.5%. After 2 h of pyrolysis, as the pyrolysis time continued to prolong, the adsorption performance began to decrease gradually. During the pyrolysis process of biochar residues, as time increases, the internal voids develop to a certain extent, and the length of the pores changes from the original deepening to widening, and new pores are formed on the inner wall of the pores at the same time. The density of the pores is greatly increased to increase the adsorption performance of the product. However, as the activation time continues to increase, the pore wall further expands, the pores on the surface begin to merge and disappear, forming a large number of macropores, and the pore wall thins and disappears. , the adsorption performance and the specific surface area of biochar further decreased.
通过正交分析影响生物炭制备的各工艺条件，在活化温度650℃、活化时间2h、活化剂浓度2mol/L条件下制备的沼渣生物炭，比表面积为74.23m2/g，对COD的去除率为53.6％，对氨氮的去除率为36.2％。活化因素对生物炭吸附性能上各因素影响程度结果为：热解温度>活化剂浓度>热解停留时间。Through orthogonal analysis of the various process conditions affecting the preparation of biochar, the biochar from biogas residues prepared under the conditions of activation temperature of 650 °C, activation time of 2 h, and activator concentration of 2 mol/L has a specific surface area of 74.23 m2 /g, which has a significant impact on COD. The removal rate was 53.6%, and the removal rate of ammonia nitrogen was 36.2%. The effect of activation factors on the adsorption performance of biochar was as follows: pyrolysis temperature > activator concentration > pyrolysis residence time.
表1是原沼渣和沼渣生物炭的元素分析和工业分析，其中挥发分的含量是判断沼渣是否适合制备成生物炭的一个重要指标，这是因为挥发分在热解的过程中能被分解从而形成孔洞结构。从表1可以看出，原沼渣具有较高的挥发分，说明该沼渣是一种良好的制备活性炭的前驱物。且原沼渣中碳的含量较高，由于金属离子对某些污染物具有较强的吸附能力，负载铁改性是比较常用的方法，应用性强，对氮磷的吸附均很好。因此，采用负载Fe金属盐对生物炭进行改性，得到的沼渣生物炭比表面积和总孔容有所增大，增强了其吸附能力。表1元素分析结果表明，原污泥及污泥活性炭主要由C、N、H和S组成，这些元素对生物炭的表面化学性能具有重要影响。Table 1 shows the elemental analysis and industrial analysis of the raw biogas residue and biochar. The content of volatile matter is an important indicator for judging whether the biogas residue is suitable for preparing biochar. This is because the volatile matter can is decomposed to form a pore structure. It can be seen from Table 1 that the raw biogas residue has high volatile content, indicating that the biogas residue is a good precursor for preparing activated carbon. In addition, the carbon content in the raw biogas residue is relatively high. Since metal ions have strong adsorption capacity for certain pollutants, iron-loaded modification is a commonly used method, which has strong applicability and good adsorption of nitrogen and phosphorus. Therefore, the biochar was modified by loading Fe metal salt, and the specific surface area and total pore volume of the biochar obtained from biogas residues increased, which enhanced its adsorption capacity. The elemental analysis results in Table 1 show that the raw sludge and sludge activated carbon are mainly composed of C, N, H and S, and these elements have an important influence on the surface chemical properties of biochar.
表1原沼渣和沼渣生物炭的元素及工业分析(％)Table 1 Elements and industrial analysis of raw biogas residue and biochar (%)
从图4(a)可以看出，原沼渣的表面有大量微生物的死体结构及类似于植物纤维的结构存在，说明沼渣泥中含有大量有机质成分，能作为制备生物炭的前驱物。比较图4(a)、4(b)可以看到，原沼渣经过水热预处理—高温热解—Fecl3溶液活化后，材料表面发生了较大的变化，表面有机物明显减少，表面粗糙度显著增大，孔隙分布不规则，孔洞明显增多且变小，这是由于在碳化的过程中有机物的蒸发以及有机物的固定所造成的。From Figure 4(a), it can be seen that there are a large number of dead microbial structures and structures similar to plant fibers on the surface of the raw biogas residue, indicating that the biogas residue sludge contains a large amount of organic matter, which can be used as a precursor for the preparation of biochar. Comparing Figures 4(a) and 4(b), it can be seen that after the original biogas residue was subjected to hydrothermal pretreatment - high temperature pyrolysis - Fecl3 solution activation, the surface of the material changed greatly, the surface organic matter was significantly reduced, and the surface was rough The degree of porosity increases significantly, the pore distribution is irregular, and the pores increase and become smaller, which is caused by the evaporation of organic matter and the fixation of organic matter in the process of carbonization.
图5为原沼渣和沼渣生物炭的FT-IR图谱。由红外光谱图可以看出，生物炭含有相同的官能团种类，但官能团含量却随着不同的活化方式略有改变。不同的生物炭在波长为3500nm附近时出现吸收峰，此峰代表酚羟基的收缩振动，波长2900nm处，制备的生物炭均没有峰，此除有峰代表饱和脂肪烃基团，此位置的峰消失，表明此时制备的生物炭中只含有芳香结构，含有大量饱和脂肪烃的半纤维素和纤维素分解较为完全。波长1500-2000cm-1处有一系列尖锐的吸收峰，代表气态水变角振动，1580-1700cm-1处的峰宽较为明显，代表结晶水的变角振动。1000-1100cm-1范围内有多个峰，代表糖类C-OH收缩振动。1610-1450cm-1范围内为苯环或芳香族的特征峰值区间，不同生物炭峰值明显，表明含有苯环类物质。1252-1102cm-1波数范围内一般认为是酚、醚、醇的-C＝O伸缩振动及-C＝C伸缩和-OH面弯曲振动吸收峰。图中原沼渣在3415cm-1处的吸收带表示N-H和O-H伸缩振动峰，在沼渣炭的图谱中移到3416cm-1处，且强度减弱，吸收带变宽，这是由于在热解的过程中元素H被去除，并且通入的气体将部分有机基团氧化生成了少量的羧基；同时，原沼渣在3269cm-1处出现CH2的伸缩振动峰移动到3249cm-1处，进一步说明了在热解的过程中大量的H元素被去除；从图5还可以看到，原沼渣在1618cm-1处出现仲酰胺的CO伸缩振动峰，1424cm-1处出现仲酰胺的C-N伸缩振动峰，在沼渣生物炭中分别分别迁至1617cm-1，甚至消失，并且峰的强度减弱，说明热解使仲酰胺断键从而分解挥发；并且1043cm-1处的C-O伸缩振动峰移到1099cm-1处，可能是微波使醚键断裂。以上分析显示，在沼渣生物炭的制备过程中，沼渣中的有机质主要是通过仲酰胺基团的断键而被分解或是分解挥发，同时一部分有机基团被氧化生成了少量的羧基。Figure 5 shows the FT-IR spectra of raw digestate and biochar. It can be seen from the infrared spectrum that the biochar contains the same functional group species, but the functional group content slightly changes with different activation methods. Different biochars have absorption peaks around the wavelength of 3500nm, which represents the contraction vibration of the phenolic hydroxyl group. At the wavelength of 2900nm, the prepared biochars have no peaks. Except for the peaks representing saturated aliphatic hydrocarbon groups, the peaks at this position disappear. , indicating that the biochar prepared at this time only contains aromatic structures, and the decomposition of hemicellulose and cellulose containing a large amount of saturated aliphatic hydrocarbons is relatively complete. There are a series of sharp absorption peaks at the wavelength of 1500-2000cm-1 , representing the variable angle vibration of gaseous water, and the peak width at 1580-1700cm-1 is more obvious, representing the variable angle vibration of crystal water. There are multiple peaks in the range of 1000-1100 cm-1 , which represent the C-OH contraction vibration of sugars. The range of 1610-1450cm-1 is the characteristic peak range of benzene rings or aromatics, and the peaks of different biochars are obvious, indicating that they contain benzene ring substances. In the wavenumber range of 1252-1102cm-1 , it is generally considered to be the absorption peaks of -C=O stretching vibration, -C=C stretching and -OH plane bending vibration of phenol, ether and alcohol. In the figure, the absorption band at 3415cm-1 of the original biogas residue represents the NH and OH stretching vibration peaks, which moved to 3416cm-1 in the map of biogas residue carbon, and the intensity weakened and the absorption band became wider. During the process, element H was removed, and some organic groups were oxidized to generate a small amount of carboxyl groups by the gas; at the same time, the stretching vibration peak of CH2 appeared at 3269 cm-1 and moved to 3249 cm-1 , which further explained In the process of pyrolysis, a large amount of H element is removed; it can also be seen from Fig. 5 that the CO stretching vibration peak of the secondary amide appears at 1618 cm-1 , and the CN stretching vibration of the secondary amide appears at 1424 cm-1 . The peaks moved to 1617cm-1 in the biochar, respectively, and even disappeared, and the intensity of the peaks weakened, indicating that pyrolysis caused the secondary amide to break bonds and decompose and volatilize; and the CO stretching vibration peak at 1043cm-1 moved to 1099cmAt -1 , it may be that the microwave breaks the ether bond. The above analysis shows that in the preparation process of biochar from biogas residue, the organic matter in the biogas residue is mainly decomposed or decomposed and volatilized by the cleavage of secondary amide groups, and at the same time, some organic groups are oxidized to form a small amount of carboxyl groups.
实施例1Example 1
取南京本地秸秆沼渣作为原料，按前述沼渣生物炭的制备方法中的步骤1-3对沼渣进行预处理，将处理好的沼渣放入管式炉中烧制，5℃/min的升温速率，同时通入保护气体氮气(气体流量为500mL/min)，控制烧制温度为650℃，烧制时间为2h，然后冷却至室温，将热解过后的产物放入2mol/L的FeCl3溶液，固液体积比为1:2，将其放入摇床，转速为150r/min，震荡活化24h、干燥研磨，得到活化产物，对产物进行酸浸、水洗、干燥，最后过80目筛，即得沼渣生物炭。Take Nanjing local straw biogas residue as raw material, pretreat the biogas residue according to steps 1-3 in the aforementioned preparation method of biogas residue and biochar, and put the treated biogas residue into a tube furnace for firing at 5°C/min At the same time, the protective gas nitrogen (the gas flow rate is 500mL/min) was introduced, the control firing temperature was 650°C, and the firing time was 2h, then cooled to room temperature, and the pyrolyzed product was put into 2mol/L FeCl3 solution, the volume ratio of solid to liquid is1 :2, put it into a shaker, the rotating speed is 150r/min, vibrate and activate for 24h, dry and grind to obtain an activated product, pickle the product, wash with water, dry, and finally pass 80 Mesh sieve to obtain biogas residue biochar.
实验测得，沼渣生物炭的比表面积为72.58m2/g，对COD的去除率为57.2％，对氨氮的去除率为36.8％。Experiments show that the biochar has a specific surface area of 72.58m2 /g, the removal rate of COD is 57.2%, and the removal rate of ammonia nitrogen is 36.8%.
实施例2Example 2
取猪粪沼渣作为原料，按前述沼渣生物炭的制备方法中的步骤1-3对沼渣进行预处理，将处理好的沼渣放入管式炉中烧制，5℃/min的升温速率，同时通入保护气体氮气(气体流量为500mL/min)，控制烧制温度为650℃，烧制时间为2h，然后冷却至室温，将热解过后的产物放入2mol/L的FeCl3溶液，固液体积比为1:2，将其返给摇床，转速为150r/min，震荡活化24h、干燥研磨，得到活化产物，对产物进行酸浸、水洗、干燥，最后过80目筛，即得沼渣生物炭。Take pig manure biogas residue as a raw material, pretreat the biogas residue according to steps 1-3 in the aforementioned preparation method of biogas residue and biochar, and put the treated biogas residue into a tube furnace for firing at a temperature of 5°C/min. The heating rate, while feeding the protective gas nitrogen (the gas flow rate is 500mL/min), the control firing temperature is 650 ° C, the firing time is 2h, then cooled to room temperature, and the pyrolyzed product is put into 2mol/L FeCl3 solution, the volume ratio of solid to liquid is 1:2, return it to the shaker, the rotation speed is 150r/min, vibrate and activate for 24h, dry and grind to obtain an activated product, pickle the product, wash with water, dry, and finally pass 80 mesh Sieve to obtain biochar from biogas residue.
实验测得，沼渣生物炭的比表面积为57.24m2/g，对COD的去除率为47.3％，对氨氮的去除率为31.3％。Experiments show that the biochar has a specific surface area of 57.24m2 /g, a removal rate of 47.3% for COD and 31.3% for ammonia nitrogen.
实施例3Example 3
取鸡粪沼渣作为原料，按前述沼渣生物炭的制备方法中的步骤1-3对沼渣进行预处理，将处理好的沼渣放入管式炉中烧制，5℃/min的升温速率，同时通入保护气体氮气(气体流量为500mL/min)，控制烧制温度为650℃，烧制时间为2h，然后冷却至室温，将热解过后的产物放入2mol/L的FeCl3溶液，固液体积比为1:2，将其返给摇床，转速为150r/min，震荡活化24h、干燥研磨，得到活化产物，对产物进行酸浸、水洗、干燥，最后过80目筛，即得沼渣生物炭。Take chicken manure biogas residue as a raw material, pretreat the biogas residue according to steps 1-3 in the aforementioned preparation method of biogas residue and biochar, and put the treated biogas residue into a tube furnace for firing at a temperature of 5°C/min. The heating rate, while feeding the protective gas nitrogen (the gas flow rate is 500mL/min), the control firing temperature is 650 ° C, the firing time is 2h, then cooled to room temperature, and the pyrolyzed product is put into 2mol/L FeCl3 solution, the volume ratio of solid to liquid is 1:2, return it to the shaker, the rotation speed is 150r/min, vibrate and activate for 24h, dry and grind to obtain an activated product, pickle the product, wash with water, dry, and finally pass 80 mesh Sieve to obtain biochar from biogas residue.
实验测得，沼渣生物炭的比表面积为61.25m2/g，对COD的去除率为49.9％，对氨氮的去除率为30.1％。Experiments show that the biochar has a specific surface area of 61.25m2 /g, the removal rate of COD is 49.9%, and the removal rate of ammonia nitrogen is 30.1%.
对比例1Comparative Example 1
本对比例与实施例1的方法基本相同，不同之处仅在于：本对比例不进行步骤1的高温高压反应，直接将秸秆沼渣进行步骤2的处理。The method of this comparative example is basically the same as that of Example 1, and the difference is only that: this comparative example does not carry out the high temperature and high pressure reaction in step 1, and directly carries out the treatment of
实验测得，本对比例制备的沼渣生物炭的比表面积为40.72m2/g，对COD的去除率为34.5％，对氨氮的去除率为21.9％。通过对比发现步骤1即沼渣的高温高压反应对沼渣生物炭的性能有很大的提升。Experiments show that the specific surface area of the biochar prepared by this comparative example is 40.72 m2 /g, the removal rate of COD is 34.5%, and the removal rate of ammonia nitrogen is 21.9%. Through comparison, it was found that step 1, the high temperature and high pressure reaction of biogas residue, greatly improved the performance of biochar from biogas residue.
对比例2Comparative Example 2
本对比例与实施例1的方法基本相同，不同之处仅在于：本对比例不进行步骤5的活化处理，直接将步骤4烧制后的沼渣进行步骤6的脱水干燥处理。The method of this comparative example is basically the same as that of Example 1, the only difference is that the activation treatment of
实验测得，本对比例制备的沼渣生物炭的比表面积为47.41m2/g，对COD的去除率为23.9％，对氨氮的去除率为15.2％。通过对比发现步骤5即沼渣生物炭的活化反应对沼渣生物炭的性能有很大的提升。Experiments show that the specific surface area of the biochar prepared by this comparative example is 47.41 m2 /g, the removal rate of COD is 23.9%, and the removal rate of ammonia nitrogen is 15.2%. Through comparison, it was found that the activation reaction of biochar residue in
本发明具体应用途径很多，以上所述仅是本发明的优选实施方式。应当指出，以上实施例仅用于说明本发明，而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进，这些改进也应视为本发明的保护范围。There are many specific application ways of the present invention, and the above are only the preferred embodiments of the present invention. It should be noted that the above embodiments are only used to illustrate the present invention, but not to limit the protection scope of the present invention. For those skilled in the art, without departing from the principle of the present invention, several improvements can also be made, and these improvements should also be regarded as the protection scope of the present invention.
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