CN115301236A - A method for preparing iron mud-based catalytically active granular biochar by in-situ iron modification - Google Patents
A method for preparing iron mud-based catalytically active granular biochar by in-situ iron modification Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 113
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 abstract description 20
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 abstract description 19
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- 229960005404 sulfamethoxazole Drugs 0.000 description 20
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
Description
技术领域:Technical field:
本发明属于危废资源化处理处置和功能材料合成领域,具体属于生物质危险固体废弃物资源化制备功能性催化材料即高含铁污泥制备催化活性颗粒生物炭。The invention belongs to the field of hazardous waste resource treatment and functional material synthesis, and specifically belongs to the preparation of functional catalytic materials from biomass hazardous solid waste resources, that is, the preparation of catalytically active granular biochar from high-iron-containing sludge.
背景技术:Background technique:
剩余污泥处置和资源化,尤其是含金属工业污泥的安全处置和高值化是科学研究和技术攻关的重点目标。当前,国内外对于污泥的处理技术路线主要有四种,分别是:污泥深度脱水-填埋路线、好氧发酵-土地利用路线、厌氧发酵-土地利用路线、污泥干化-焚烧-灰渣填埋或建材利用路线。以上四种路线中,污泥的填埋和污泥发酵后再土地利用是比较简单且经济成本低的处理方式,是我国污泥处理处置中重要的选择方案。但是,由于空间和土地利用范围的限制,特别是在农业部发布了禁止将污泥用做有机肥原料的新标准,并且工业污水污泥被列为《国家危险废物名录》之后。前面三种污泥处理方式就受到了很大的限制。而污泥焚烧后再填埋的方式,对于污泥的处置虽然节约了土地,但是却增加了成本,并且对于污泥的资源化利用程度有限。所以,寻找一种新的污泥处理及资源化路径方案,对于当下特别是在“碳达峰及碳中和”时代目标背景下的我们来说,具有非常重要的意义。The disposal and recycling of surplus sludge, especially the safe disposal and high-value conversion of industrial sludge containing metals, is the key goal of scientific research and technical research. At present, there are mainly four technical routes for sludge treatment at home and abroad, namely: sludge deep dehydration-landfill route, aerobic fermentation-land use route, anaerobic fermentation-land use route, sludge drying-incineration -Ash landfill or construction material utilization route. Among the above four routes, sludge landfill and land use after sludge fermentation are relatively simple and low-cost treatment methods, and are important options for sludge treatment and disposal in my country. However, due to the limitations of space and land use, especially after the Ministry of Agriculture issued new standards prohibiting the use of sludge as organic fertilizer raw materials, and industrial sewage sludge was listed in the "National Hazardous Waste List". The first three sludge treatment methods have been greatly restricted. The way of sludge incineration and then landfill saves land for sludge disposal, but increases the cost, and the utilization of sludge as a resource is limited. Therefore, it is very important for us to find a new path for sludge treatment and resource utilization, especially in the context of the era of "carbon peaking and carbon neutrality".
生物炭是一种将生物质在缺氧条件下高温热解而得到的富炭固体物质,具有较大的比表面积和发达的孔隙结构,可以用于污染修复,土壤改良以及固碳缓解气候变化等。而污泥作为一种含炭量丰富的生物质,是制备生物炭很好的原材料。在现有技术中,已经有了相关的探索工作。然而,大多数污泥基生物炭制备技术都是以常规城市污水处理产生的污泥为基本原料,通过人为加入铁盐进行改性的应用效果和制备成本均存在短板。本发明CN112410047A公开了一种载铁污泥生物炭及其制备方法和应用[1],专门向污泥中掺铁粉,这样不仅提高了制作成本,而且是为了作出含铁的生物炭而研究。更多的负铁污泥生物炭是采用后负载方法,即制备出生物炭后浸渍铁盐溶剂,通过化学结合和粘合剂的作用负载上过渡态铁盐,工艺复杂,成本较高。Biochar is a carbon-rich solid material obtained by pyrolyzing biomass at high temperature under anoxic conditions. It has a large specific surface area and a well-developed pore structure, and can be used for pollution remediation, soil improvement, and carbon sequestration to mitigate climate change. Wait. Sludge, as a kind of biomass rich in carbon, is a good raw material for the preparation of biochar. In the prior art, there have been related exploration works. However, most sludge-based biochar preparation technologies use the sludge produced by conventional urban sewage treatment as the basic raw material, and there are shortcomings in the application effect and preparation cost of modification by artificially adding iron salts. The present invention CN112410047A discloses a kind of iron-loaded sludge biochar and its preparation method and application [1] , which is specially mixed with iron powder in the sludge, which not only improves the production cost, but also researches for making iron-containing biochar . More iron-negative sludge biochars adopt the post-loading method, that is, after the biochar is prepared, the iron salt solvent is impregnated, and the transition state iron salt is loaded through chemical bonding and the action of the binder. The process is complicated and the cost is high.
目前,芬顿工艺常被用于处理难降解污染物,而且在很多市政污水处理厂也经常用到聚合硫酸铁等铁盐絮凝剂进行脱水调理,这导致脱水污泥中含有大量的高价铁,在工业废水处理体系产生的该类污泥被划分为危废。因此,选择高含铁的脱水污泥作为资源化处理对象,一方面可以实现含铁污泥的无害化处理,另一方面可以利用其过渡金属的属性进行原位改性制成催化性功能材料,进而构建变废为宝、以废治废的新型污染物去除方法。At present, the Fenton process is often used to treat refractory pollutants, and iron salt flocculants such as polyferric sulfate are often used in many municipal sewage treatment plants for dehydration conditioning, which leads to a large amount of high-priced iron in the dewatered sludge. This type of sludge produced in industrial wastewater treatment systems is classified as hazardous waste. Therefore, choosing dewatered sludge with high iron content as the resource treatment object can realize the harmless treatment of iron-containing sludge on the one hand, and on the other hand, it can use its properties of transition metals for in-situ modification to make catalytic functions Materials, and then build a new pollutant removal method that turns waste into treasure and treats waste with waste.
发明内容:Invention content:
本发明的目的是通过提供一种原位铁改性制备铁泥基催化活性颗粒生物炭的方法,以针对污泥脱水中大量使用铁盐絮凝剂和含芬顿氧化工艺的污水处理厂中作为危废产生的高含铁脱水污泥处理困难,同时其兼具生物质和过渡金属具有资源化潜力的实际矛盾,给出可行性高,应用价值高的方案。The purpose of the present invention is to provide a method for preparing iron mud-based catalytically active granular biochar by providing a kind of in-situ iron modification, so as to use a large amount of iron salt flocculant and Fenton oxidation process in sewage treatment plants for sludge dewatering as It is difficult to treat the high-iron-containing dewatered sludge produced by hazardous waste. At the same time, it has the actual contradiction that biomass and transition metals have potential for resource utilization. A solution with high feasibility and high application value is proposed.
为实现上述目的,本发明提供一种原位铁改性制备铁泥基催化活性颗粒生物炭的方法,其主要包括三个阶段:In order to achieve the above object, the present invention provides a method for preparing iron mud-based catalytically active granular biochar by in-situ iron modification, which mainly includes three stages:
(1)脱水污泥调质造粒,包括:水分减除,掺杂活化剂和改性剂,混合后造粒;(1) Conditioning and granulation of dewatered sludge, including: moisture reduction, doping with activators and modifiers, and granulation after mixing;
(2)高温热解活化制备生物炭,包括:在氨气作为还原氛围气的同时控制升温速率、热解温度及热解时间;(2) Preparation of biochar by high-temperature pyrolysis activation, including: controlling the heating rate, pyrolysis temperature and pyrolysis time while ammonia gas is used as the reducing atmosphere;
(3)清洗纯化烘干制取成品颗粒炭,包括:采用盐酸酸洗和特定温度清水洗炭,并特定温度烘干。(3) Washing, purifying, and drying to produce finished granular carbon, including: pickling with hydrochloric acid, washing the charcoal with water at a specific temperature, and drying at a specific temperature.
优选的,对高含铁脱水污泥调质造粒前,对含水率80%左右的高含铁脱水污泥减除含水率至60%-70%。其中,高含铁范围为10%-27%,含水率控制在60%-70%的选择依据主要有二:一是造粒易成型,压缩后出水分较少,颗粒度较高;二是对掺杂颗粒活化剂的溶解性较低,易保持颗粒活化剂的形态,对于热解过程造孔有一定帮助。该参数的选择是经过试验比较得出的。Preferably, before conditioning and granulating the high-iron-containing dewatered sludge, the moisture content of the high-iron-containing dewatered sludge with a moisture content of about 80% is reduced to 60%-70%. Among them, the range of high iron content is 10%-27%, and the water content is controlled at 60%-70%. The solubility of the doped particle activator is low, it is easy to maintain the shape of the particle activator, and it is helpful for the formation of pores in the pyrolysis process. The selection of this parameter is obtained through experiments and comparisons.
优选的,使用粒径为20-200微米的颗粒态尿素同时作为活化剂和改性剂,掺杂比例为20-50mg/gTSS。对于尿素的选择依据主要有三:一是尿素作为含氮有机物在本发明涉及的热解温度范围易高温分解为氨气等还原性气体,可以对内含高价态铁进行高温下的还原同时可以对生物炭起到掺氮的作用;二是颗粒态的尿素在热解前期对于颗粒态污泥内部有一定的造孔作用,分解产气的过程中,气体溢出将进一步产生更多的微孔结构;三是尿素掺杂量的选择根据内含铁中三价铁的含量进行化学反应的电子衡量计算所得(Fe3+→Fe0;N3-→N0)。Preferably, granular urea with a particle size of 20-200 microns is used as both an activator and a modifier, and the doping ratio is 20-50 mg/gTSS. There are three main basis for the selection of urea: one is that urea, as a nitrogen-containing organic matter, is easily pyrolyzed into reducing gases such as ammonia in the pyrolysis temperature range involved in the present invention. Biochar plays the role of nitrogen doping; the second is that granular urea has a certain pore-forming effect on the interior of granular sludge in the early stage of pyrolysis. During the process of decomposition and gas production, gas overflow will further produce more microporous structures ; The third is that the choice of urea doping amount is calculated according to the electronic measurement of the chemical reaction of the ferric iron content in the contained iron (Fe 3+ →Fe 0 ; N 3- →N 0 ).
优选的,造粒时控制污泥粒径为0.8-1.0cm直径。污泥历经的选择依据有二:一是热解过程污泥成炭过程水分和挥发性有机物的释放会使颗粒紧缩,体积减小,最终成品颗粒炭直径范围为0.4-0.8cm;二是成品炭的颗粒体积控制主要为其作为吸附性颗粒态非均相催化剂和床层吸附材料做的考量,一般非均相催化剂的生物炭的颗粒度范围较广,一般在50-5×103微米;而作为床层材料,方便成床分层且防止流失,颗粒度一般在0.5-5cm。Preferably, the sludge particle size is controlled to be 0.8-1.0 cm in diameter during granulation. There are two basis for the selection of sludge process: one is that the release of water and volatile organic compounds in the process of sludge charcoal pyrolysis will shrink the particles and reduce the volume, and the diameter of the final product granular carbon is 0.4-0.8cm; the other is the finished product The particle volume control of charcoal is mainly considered as an adsorption granular heterogeneous catalyst and bed adsorption material. Generally, the particle size range of biochar for heterogeneous catalysts is relatively wide, generally at 50-5×10 3 microns ; As a bed material, it is convenient to form a bed layer and prevent loss. The particle size is generally 0.5-5cm.
优选的,高温热解制备生物炭时以氨气作为还原性氛围气体,开始以氮气排除空气,后将氨气充满石英管,维持30-60min。Preferably, ammonia gas is used as the reducing atmosphere gas during high-temperature pyrolysis to prepare biochar, nitrogen gas is used to remove air at first, and then ammonia gas is filled into the quartz tube for 30-60 minutes.
优选的,高温热解的参数为:升温速率3-5℃/min,热解温度900℃,热解时间60min,热解结束后取出粗品生物炭之前采用氮气排空氨气残余。Preferably, the parameters of high-temperature pyrolysis are: heating rate 3-5°C/min, pyrolysis temperature 900°C, pyrolysis time 60min, after pyrolysis, nitrogen gas is used to exhaust residual ammonia gas before taking out crude biochar.
试验过程热解过程的升温速率、热解温度和热解时间范围选择分别为 1/3/5/10℃/min;400/600/900℃;30/60/120min。本发明中选取参数为经以生物炭的比表面积为目标的均匀设计试验优化所得。相比常规所用甲烷氢气混合气,尿素产生的氨气同时具有还原性和掺氮属性,而采用氮气排空主要是为了防治氨气造成大量泄露污染环境和对操作人员造成健康损伤。The heating rate, pyrolysis temperature and pyrolysis time ranges of the pyrolysis process during the test were selected as 1/3/5/10°C/min; 400/600/900°C; 30/60/120min. The parameters selected in the present invention are obtained through the optimization of the uniform design experiment with the specific surface area of the biochar as the target. Compared with the conventional methane-hydrogen mixture, the ammonia produced by urea has both reducing and nitrogen-doped properties, and the use of nitrogen for evacuation is mainly to prevent large amounts of ammonia leakage from polluting the environment and causing health damage to operators.
优选的,在纯化制取成品催化性颗粒生物炭时,水洗温度和烘干温度都维持在70±5℃。Preferably, when purifying and preparing the finished catalytic granular biocoke, both the water washing temperature and the drying temperature are maintained at 70±5°C.
优选的,盐酸酸洗是指2.5-3.5mol/L的盐酸浸洗20-30min;水洗是指去离子水反复水洗至中性。清洗条件的选择依据也主要有二:一是该浓度下的盐酸洗涤对于生物炭中灰分和其他金属氧化物具有就较高的化学溶解作用;二是3mol盐酸30min的洗涤对于生物炭中铁元素的含量造成的损失最多为17-25%,过低的浓度不利于灰分的洗出和过长的酸洗时间造成效率降低且铁元素损失较多。因此控制在2.5-3.5mol/L,洗涤时间不超过30min,对于本发明产品质量的保持具有最佳效果。Preferably, hydrochloric acid pickling refers to 2.5-3.5mol/L hydrochloric acid immersion for 20-30min; water washing refers to repeated washing with deionized water until neutral. There are two main basis for the selection of cleaning conditions: one is that washing with hydrochloric acid at this concentration has a relatively high chemical dissolution effect on ash and other metal oxides in biochar; The loss caused by the content is at most 17-25%. Too low concentration is not conducive to the washing out of ash content and too long pickling time causes efficiency reduction and more iron element loss. Therefore, it is controlled at 2.5-3.5mol/L, and the washing time is no more than 30min, which has the best effect on maintaining the quality of the product of the present invention.
本发明提供了一种原位铁改性制备铁泥基催化活性颗粒生物炭,其通过前述制备方法制备得到。The invention provides an in-situ iron modification to prepare iron mud-based catalytically active granular biochar, which is prepared by the aforementioned preparation method.
本发明还提供了一种降解磺胺甲恶唑的方法,采用前述原位铁改性制备铁泥基催化活性颗粒生物炭和过硫酸钠混合,作为降解试剂,优选的,过硫酸钠和生物炭的质量比为1:5。The present invention also provides a method for degrading sulfamethoxazole, using the aforementioned in-situ iron modification to prepare iron mud-based catalytically active granular biochar and mixing sodium persulfate as a degradation reagent, preferably sodium persulfate and biochar The mass ratio is 1:5.
本发明的科学原理是利用颗粒态尿素高温分解气化生产氨气的过程及水分气化的过程对污泥炭化过程进行多级造孔,利用氨气的还原性对污泥中赋存的高价态铁盐在高温下进行还原反应生成低价态铁化合物,同时利用氨气与铁盐、氮素与碳素在高温下的反应形成氮铁键、碳氮键等具有催化功能的化学基团,从而实现生物炭制备过程的原位铁改性,制备出具有高效催化活性的颗粒态生物炭材料。The scientific principle of the present invention is to use the process of pyrolysis and gasification of granular urea to produce ammonia and the process of water gasification to carry out multi-stage pore-forming in the sludge carbonization process, and use the reducing property of ammonia to reduce the high price of ammonia in the sludge. Iron salts undergo reduction reaction at high temperature to form low-valent iron compounds, and at the same time, chemical groups with catalytic functions such as nitrogen-iron bonds and carbon-nitrogen bonds are formed through the reaction of ammonia gas and iron salts, nitrogen and carbon at high temperatures , so as to realize the in-situ iron modification in the biochar preparation process, and prepare granular biochar materials with high catalytic activity.
与现有技术相比,本发明的有益效果为:Compared with prior art, the beneficial effect of the present invention is:
1.本发明设计的制备方法采用了创新的原位铁改性方法,采用颗粒态尿素同时作为活化剂和改性剂并制备中以氨气为还原性氛围将生物炭中高价态铁还原至二价、一价甚至零价,结合其丰富的孔隙结构,赋予了本发明制备的生物炭极高的催化活性。1. The preparation method designed by the present invention adopts an innovative in-situ iron modification method, adopts granular urea as an activator and a modifier at the same time, and uses ammonia as a reducing atmosphere to reduce high-valent iron in biochar to Bivalent, monovalent or even zero-valent, combined with its rich pore structure, endows the biochar prepared by the present invention with extremely high catalytic activity.
2.本发明设计的颗粒态催化性生物炭,具有一定的稳定结构,经过搅拌洗涤后依然维持较高的颗粒态,使其具有较高的非均相催化和成为催化性床层材料的潜力。2. The granular catalytic biochar designed by the present invention has a certain stable structure, and after stirring and washing, it still maintains a relatively high granular state, so that it has a higher potential for heterogeneous catalysis and becoming a catalytic bed material .
3.本发明设计方法制备的原位铁改性催化颗粒生物炭具有较已报道的文献中更高的比表面积和更高的催化活性[2,3]。3. The in-situ iron-modified catalytic granular biochar prepared by the design method of the present invention has a higher specific surface area and higher catalytic activity than those reported in the literature [2,3] .
4.本发明针对危废进行资源化并赋予其更高的附加值以进行其他危废的处理,实现了变废为宝,以废治废,以危治危的效果,具有显著的经济效益和环境效益。4. The present invention recycles hazardous waste and endows it with higher added value for the treatment of other hazardous waste, realizing the effects of turning waste into treasure, treating waste with waste, and treating danger with danger, and has significant economic benefits and environmental benefits.
5.本发明制备得到的生物炭,具有432.41±33.54㎡/g(R2=0.991)的比表面积和丰富的微介孔结构,含有大量铁催化活性位点,表面活化能为157㎡/g·K,可高效催化活化过硫酸钠降解磺胺类抗生物,实现了危废的资源化利用。结果表明,采用500ppm生物炭可吸附19.22mg/L的磺胺抗生素,活化100ppm过硫酸钠,30min可催化降解磺胺抗生素29.31mg/L(63.44%),说明以本发明制备的铁泥基催化性颗粒生物炭具有明显的催化活性,能带来显著的经济和环境效益。5. The biochar prepared by the present invention has a specific surface area of 432.41±33.54㎡/g (R 2 =0.991) and rich micro-mesoporous structure, contains a large number of iron catalytic active sites, and has a surface activation energy of 157㎡/g K, can efficiently catalyze and activate sodium persulfate to degrade sulfonamide antibiotics, realizing the resource utilization of hazardous waste. Result shows, adopt the sulfonamide antibiotic of 500ppm biochar can adsorb 19.22mg/L, activate 100ppm sodium persulfate, 30min can catalytically degrade sulfonamide antibiotic 29.31mg/L (63.44%), illustrate with the iron mud base catalytic particle prepared by the present invention Biochar has obvious catalytic activity and can bring significant economic and environmental benefits.
附图说明:Description of drawings:
图1为本发明设计生物炭制备系统工艺图。Figure 1 is a process diagram of the biochar preparation system designed in the present invention.
图2为本发明设计方法操作流程图。Fig. 2 is the flow chart of the operation of the design method of the present invention.
图3为本方法制备铁泥基催化性多级孔颗粒生物炭成品及对照组样品图。Figure 3 is a sample diagram of the iron mud-based catalytic hierarchical porous granular biochar finished product and the control group prepared by this method.
图4为本方法制备的原位铁改性多级孔催化性生物炭表观形貌(FSEM)图Figure 4 is the appearance (FSEM) figure of the in-situ iron-modified hierarchically porous catalytic biochar prepared by this method
图5为本发明中制备生物炭的吸脱附曲线,其中A为原位铁改性FN-SBC生物炭;B为空白组氮气氛围生物炭CK-SBC。Figure 5 is the adsorption-desorption curve of the biochar prepared in the present invention, where A is the in-situ iron-modified FN-SBC biochar; B is the blank group nitrogen atmosphere biochar CK-SBC.
图6为方法制备的催化性多级孔铁泥生物炭的100nm以下的孔径分布及表面活化能分布。其中,a和a’为掺杂尿素氨气氛围制得FN-SBC的孔径分布和表面活化能;b和b’为氨气氛围不掺杂尿素活化的F-SBC的孔径分布和表面活化能; c和c’为氮气氛围不掺杂尿素活化的CK-SBC的孔径分布和表面活化能。Fig. 6 is the pore size distribution and surface activation energy distribution below 100nm of the catalytic hierarchical porous iron sludge biochar prepared by the method. Among them, a and a' are the pore size distribution and surface activation energy of FN-SBC prepared in an ammonia atmosphere doped with urea; b and b' are the pore size distribution and surface activation energy of F-SBC activated without doping urea in an ammonia atmosphere ; c and c' are the pore size distribution and surface activation energy of CK-SBC activated without doping urea in nitrogen atmosphere.
图7为原位改性催化生物炭FN-SBC(FSBC-urea)与空白对照CK-SBC (FSBC-ori)的XRD谱图,其中低价态的铁化合物晶体明显增多。Figure 7 shows the XRD patterns of the in-situ modified catalytic biochar FN-SBC (FSBC-urea) and the blank control CK-SBC (FSBC-ori), in which the crystals of iron compounds in the low-valence state increased significantly.
图8为本发明制备原位铁改性催化颗粒生物炭FN-SBC活化过硫酸钠催化降解磺胺甲恶唑(SMX)的效果。Fig. 8 shows the effect of preparing in-situ iron-modified catalytic granular biochar FN-SBC activated by sodium persulfate to catalyze the degradation of sulfamethoxazole (SMX) according to the present invention.
具体实施方式:Detailed ways:
下面结合附图和实施例对本发明做进一步说明。应当理解,此处所描述的具体实施例是为了更好的解释本发明,而并不是用于限定本发明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are for better explaining the present invention, but not for limiting the present invention.
<实施例1><Example 1>
本实施为用脱水含铁剩余污泥热解制备具有催化活性的生物炭,其步骤如下:This implementation is to prepare biochar with catalytic activity by pyrolysis of dehydrated iron-containing excess sludge. The steps are as follows:
(1)含芬顿工艺和铁盐絮凝剂处理工艺的污水处理厂80%含水率的剩余污泥(含铁量17.4%),烘除水分至65%并掺杂尿素颗粒(50mg/gTSS)充分混匀,然后制成0.8-1.0cm的污泥颗粒。(1) The remaining sludge with 80% moisture content (iron content 17.4%) of the sewage treatment plant containing Fenton process and iron salt flocculant treatment process, dried to 65% and doped with urea particles (50mg/gTSS) Mix well, and then make sludge particles of 0.8-1.0cm.
(2)氨气氛围中进行热解活化制备生物炭。开始以氮气排除空气,后将氨气充满石英管,维持30min,在程控管式炉内,氨气氛围中以5℃/min的升温速率至900℃,并在维持热解60min。冷却后取出,得到热解生物炭。(2) Biochar was prepared by pyrolysis activation in an ammonia atmosphere. Start to remove the air with nitrogen, and then fill the quartz tube with ammonia gas and keep it for 30 minutes. In the program-controlled tube furnace, the heating rate is 5 ℃/min in the ammonia atmosphere to 900 ℃, and the pyrolysis is maintained for 60 minutes. Take it out after cooling to obtain pyrolysis biochar.
(3)酸洗水洗纯化生物炭并烘干为成品颗粒炭。3mol/L的盐酸浸洗30min; 70℃的去离子水反复水洗至中性;70℃烘箱内烘干,制得原位铁改性的催化活性铁泥基颗粒生物炭。(3) Pickling and water washing to purify the biochar and drying it into finished granular carbon. Immerse with 3mol/L hydrochloric acid for 30min; wash with deionized water at 70°C repeatedly until neutral; dry in an oven at 70°C to prepare in-situ iron-modified catalytically active iron-sludge-based granular biochar.
图1和图2展示了本发明制备原位铁改性催化炭的制备系统工艺和操作流程图。Figure 1 and Figure 2 show the process and operation flow chart of the preparation system of the present invention for preparing in-situ iron-modified catalytic carbon.
对本发明制备的生物炭材料采用BET测定其比表面积,孔隙率及其孔尺寸。得到本发明的生物炭材料的BET比表面积为432.41±33.54㎡/g(R2=0.991),表面活化能为157㎡/g·K。The specific surface area, porosity and pore size of the biochar material prepared by the present invention are measured by BET. The BET specific surface area of the obtained biochar material of the present invention is 432.41±33.54㎡/g (R 2 =0.991), and the surface activation energy is 157㎡/g·K.
其中,图5为生物炭在300℃下进行氮气吸脱附曲线。Among them, Fig. 5 is the nitrogen adsorption and desorption curve of biochar at 300°C.
图3,4,6,7分别从采用本发明制备的生物炭的成品状态、表观形貌(孔隙及铁元素分布)、铁改性后表面活化能的提升情况,以及最明显的经原位铁改性制备的生物炭中低价态铁化合物晶型的丰富情况等方面给出了本发明的实际效果。Figures 3, 4, 6, and 7 show the finished product state, appearance (pore and iron element distribution) of the biochar prepared by the present invention, the improvement of the surface activation energy after iron modification, and the most obvious effect of the raw material. The actual effect of the present invention is given in terms of the richness of crystal forms of low-valent iron compounds in the biochar prepared by bit-iron modification.
<实施例2><Example 2>
用本发明所制备的催化生物炭活化过硫酸钠降解磺胺甲恶唑,其步骤如下:The catalytic biochar prepared by the present invention activates sodium persulfate to degrade sulfamethoxazole, and its steps are as follows:
(1)配制50mg/L的磺胺甲恶唑溶液。由于磺胺甲恶唑极难溶于水,所以配置溶液时可以先将其在少量去离子水中超声5min,然后再转移至容量瓶中,再用磁力搅拌器,在800rpm/min的转速下,搅拌十个小时,保证其充分溶解。(1) Prepare 50mg/L sulfamethoxazole solution. Since sulfamethoxazole is extremely difficult to dissolve in water, when preparing the solution, it can be ultrasonicated in a small amount of deionized water for 5 minutes, then transferred to a volumetric flask, and then stirred with a magnetic stirrer at a speed of 800rpm/min. Ten hours to ensure that it is fully dissolved.
(2)在150ml的锥形瓶中进行降解实验。首先取已配好的浓度为50mg/L 磺胺甲恶唑溶液100ml与锥形瓶中,再向锥形瓶中同时加入10mg的过硫酸钠(即过硫酸钠浓度为100mg/L)和50mg的生物炭(即生物炭浓度为500mg/L)。(2) The degradation experiment was carried out in a 150ml Erlenmeyer flask. First take 100ml of sulfamethoxazole solution with a prepared concentration of 50mg/L and put it in the conical flask, then add 10mg of sodium persulfate (that is, the concentration of sodium persulfate is 100mg/L) and 50mg of sodium persulfate to the conical flask at the same time Biochar (that is, the concentration of biochar is 500mg/L).
(3)用磁力搅拌器在200rpm/min的转速下搅拌反应,每隔十分钟取样1 mL,用0.22微米的滤头过滤,打到棕色试样瓶。在24h内利用高效液相色谱仪定量分析SMX的含量。(3) Stir the reaction with a magnetic stirrer at a speed of 200 rpm/min,
经过高效液相色谱测样后得出结果为,用本发明制备得到的生物炭材料活化过硫酸钠降解磺胺甲恶唑,在30min降解效果为63.44%,降解含量为29.31mg/L,比降解效率为117.24mg/g/h。After the high-performance liquid chromatography sample measurement, the result is that the biochar material prepared by the present invention activates sodium persulfate to degrade sulfamethoxazole, and the degradation effect in 30min is 63.44%, and the degradation content is 29.31mg/L, the specific degradation The efficiency is 117.24 mg/g/h.
[对比例1][Comparative Example 1]
本对比例为本发明制备的催化活性生物炭单独吸附去除磺胺甲噁唑,具体步骤如下:This comparative example is that the catalytically active biochar prepared by the present invention adsorbs and removes sulfamethoxazole separately, and the specific steps are as follows:
(1)在150ml的锥形瓶中进行降解实验。首先取已配好的浓度为50mg/L 磺胺甲恶唑溶液100ml与锥形瓶中,再向锥形瓶中加入50mg的生物炭(即生物炭浓度为500mg/L)。(1) The degradation experiment was carried out in a 150ml Erlenmeyer flask. Firstly, take 100ml of sulfamethoxazole solution with a prepared concentration of 50mg/L and put it in the conical flask, then add 50mg of biochar into the conical flask (that is, the concentration of biochar is 500mg/L).
(2)用磁力搅拌器在200rpm/min的转速下搅拌反应,每隔十分钟取样1 mL,用0.22微米的滤头过滤,打到棕色试样瓶。在24h内利用高效液相色谱仪定量分析SMX的含量。(2) Stir the reaction with a magnetic stirrer at a speed of 200 rpm/min,
经过高效液相色谱测样后得出结果为,单纯用生物炭降解磺胺甲恶唑,其效果为在30min降解39.49%,吸附量为19.22mg/L,比吸附率为76.88mg/g/h,虽表明其吸附性较强,但是生物炭本身去除作用与催化活化过硫酸钠相去甚远。After the high-performance liquid chromatography test sample, the result is that, simply using biochar to degrade sulfamethoxazole, the effect is to degrade 39.49% in 30 minutes, the adsorption capacity is 19.22mg/L, and the specific adsorption rate is 76.88mg/g/h , although it shows that its adsorption is strong, but the removal effect of biochar itself is far from that of catalytic activation of sodium persulfate.
[对比例2][Comparative example 2]
对比例2为单独采用过硫酸钠降解磺胺甲恶唑溶液,具体步骤如下:Comparative example 2 is to adopt sodium persulfate to degrade sulfamethoxazole solution alone, and concrete steps are as follows:
(1)在150ml的锥形瓶中进行降解实验。首先取已配好的浓度为50mg/L 磺胺甲恶唑溶液100ml与锥形瓶中,再向锥形瓶中加入10mg的过硫酸钠(即过硫酸钠浓度为100mg/L)。(1) The degradation experiment was carried out in a 150ml Erlenmeyer flask. Firstly, take 100ml of sulfamethoxazole solution with a prepared concentration of 50mg/L and place it in the conical flask, then add 10mg of sodium persulfate to the conical flask (that is, the concentration of sodium persulfate is 100mg/L).
(2)用磁力搅拌器在200rpm/min的转速下搅拌反应,每隔十分钟取样1 mL,用0.22微米的滤头过滤,打到棕色试样瓶。在24h内利用高效液相色谱仪定量分析SMX的含量。(2) Stir the reaction with a magnetic stirrer at a speed of 200 rpm/min,
经过高效液相色谱测样后得出结果为,单纯用过硫酸钠降解磺胺甲恶唑,其效果仅为在30min降解8.37%。其降解效果远小于实施例1。The result obtained after the high-performance liquid chromatography test sample is that, simply using sodium persulfate to degrade sulfamethoxazole, its effect is only to degrade 8.37% in 30 minutes. Its degradation effect is far less than
图8为实施例2及其对比例中本发明涉及生物炭材料活化过硫酸钠降解磺胺甲恶唑的降解曲线。Fig. 8 is the degradation curve of sulfamethoxazole by activating sodium persulfate activated by biochar material according to the present invention in Example 2 and its comparative example.
根据实施例2,对比实施例1和2,证实了本发明涉及生物炭材料活化过硫酸钠降解磺胺甲恶唑发挥了协同效果。According to Example 2 and Comparative Examples 1 and 2, it is confirmed that the present invention relates to the biochar material activated sodium persulfate to degrade sulfamethoxazole and exerts a synergistic effect.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干简单推演或替换,都应当视为属于本发明的保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be assumed that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field of the present invention, without departing from the concept of the present invention, some simple deduction or replacement can be made, which should be regarded as belonging to the protection scope of the present invention.
参考文献:references:
[1]邵莹莹,李兆轶,李琬聪,许斌,张伟屹,邵艳秋,朱英.一种载铁污泥生物炭及其制备方法和应用[P].山东省:CN112410047A,2021-02-26.[1] Shao Yingying, Li Zhaoyi, Li Wancong, Xu Bin, Zhang Weiyi, Shao Yanqiu, Zhu Ying. A kind of iron-loaded sludge biochar and its preparation method and application [P]. Shandong Province: CN112410047A, 2021-02-26.
[2]申敏.赤泥改性污泥生物炭活化过一硫酸盐降解磺胺甲恶唑的研究[D]. 华中科技大学,2020.[2] Shen Min. Research on Red Mud Modified Sludge Biochar Activated Peroxosulfate to Degrade Sulfamethoxazole [D]. Huazhong University of Science and Technology, 2020.
[3]桑瑞,孟宪荣,许伟,施维林.污泥基生物炭活化过硫酸钠降解水中萘的研究[J].现代化工:1-14[2022-06-05]. 。[3] Sang Rui, Meng Xianrong, Xu Wei, Shi Weilin. Research on the Degradation of Naphthalene in Water by Activation of Sodium Persulfate by Sludge-Based Biochar [J]. Modern Chemical: 1-14 [2022-06-05].
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