WO2024083260A1 - 一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用 - Google Patents

一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用 Download PDF

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WO2024083260A1
WO2024083260A1 PCT/CN2023/126748 CN2023126748W WO2024083260A1 WO 2024083260 A1 WO2024083260 A1 WO 2024083260A1 CN 2023126748 W CN2023126748 W CN 2023126748W WO 2024083260 A1 WO2024083260 A1 WO 2024083260A1
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red mud
straw
straw biochar
biomass ash
biochar material
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English (en)
French (fr)
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林晓晨
张后虎
张圣虎
许一凡
孙孜菲
郭宏基
李学健
许元顺
张大鹏
王莉莉
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生态环境部南京环境科学研究所
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J20/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

Definitions

  • the invention belongs to the field of solid waste resource recycling, and specifically relates to a preparation method and application of a red mud-enhanced magnetic straw biochar material.
  • Biochar or activated carbon is a commonly used adsorption material with high value, but ordinary straw biochar has low value due to its weak adsorption capacity.
  • Straw and agricultural and forestry waste are partially used as biomass fuel to generate energy, and the secondary waste in this process is mainly biomass ash.
  • Biomass ash is alkaline and rich in nutrients such as phosphorus, magnesium, and soluble silicon. It can be used as a fertilizer and improve acidic soil. However, for alkaline soils in large areas of western and northern my country, direct application of biomass ash will aggravate soil salinization and inhibit the comprehensive utilization of biomass ash.
  • Red mud is the largest non-ferrous metal waste in my country. 95% of red mud is produced by the Bayer process, with an annual output of about 120 million tons. Although Bayer red mud contains a certain amount of iron oxide, it is difficult to sort and enrich, has no refining value, and has a comprehensive utilization rate of less than 5%. The stockpiling of red mud occupies a large amount of land, causing environmental and safety hazards. It is urgent to find a way to comprehensively utilize red mud. provinces such as Shandong and Henan are not only major red mud production areas, but also major grain-producing provinces. If straw and red mud can be used synergistically, it can greatly alleviate the pressure of solid waste disposal.
  • Fluoroquinolone antibiotics are inexpensive, have a broad spectrum of antibacterial properties, and are not prone to drug resistance. They are a class of drugs commonly used in humans and animals. However, fluoroquinolone antibiotics are difficult to degrade in water bodies. Their large-scale use causes these antibiotics to accumulate in the environment, posing a great threat to the environment. Commonly used fluoroquinolone antibiotics include ofloxacin, norfloxacin, ciprofloxacin, pefloxacin, enoxacin, etc. Adsorption is an important means of removing fluoroquinolone antibiotics.
  • Straw biochar has high ash content, low specific surface area, weak adsorption capacity and low economic value.
  • the iron in red mud is difficult to enrich by sorting, has no smelting value and is difficult to utilize comprehensively.
  • Red mud has a small specific surface area and extremely low adsorption capacity for organic pollutants such as antibiotics. Therefore, adsorption materials prepared using red mud are mainly for inorganic pollutants such as heavy metals, and organic pollutants are rarely involved.
  • CN110586038B and CN109847697B proposed a method for loading nano zero-valent iron on biochar to achieve efficient removal of pollutants, but these methods require the use of iron salts or ferrous salts as raw materials for zero-valent iron, and the manufacturing cost is high.
  • CN107051413B and CN108543517B show a method of mixing red mud, carbon source and binder and calcining them in oxygen isolation to generate magnetic materials for enriching and recovering heavy metal ions in wastewater, showing the possibility of using red mud to make magnetic adsorbents.
  • Chinese invention patent publication number CN106362685A also discloses a method for removing arsenic from water bodies using co-pyrolysis products of red mud and biomass.
  • CN113522238A introduces a red mud-based iron-carbon composite material and its preparation method and application for removing heavy metals from wastewater, but in this method, the red mud needs to be treated with acid solution for pre-dealkalization, forming a large amount of acidic wastewater, and it does not show that the adsorption performance of the composite material is improved compared with the original biochar.
  • the above-mentioned biochar materials have the defects of complicated preparation process and high cost, which is not conducive to the resource utilization of solid wastes such as straw and red mud.
  • the prepared biochar materials mainly target heavy metals.
  • the technical problem to be solved by the present invention is to provide a preparation method of red mud-enhanced magnetic straw biochar material in view of the shortcomings of the prior art.
  • red mud, biomass ash and straw Through the coordinated utilization of red mud, biomass ash and straw, the quality and value of the comprehensive utilization products are improved, the solid waste recycling is realized, and economic benefits are generated.
  • a method for preparing a red mud-enhanced magnetic straw biochar material comprises the following steps:
  • step (3) mixing the crushed straw in step (1) and the powdered red mud in step (2) by ball milling to obtain a straw-red mud mixed powder;
  • step (5) The paste mixture of step (5) is co-pyrolyzed under a protective atmosphere at a pyrolysis temperature of 400-1000° C. (preferably 500-850° C.) and a heat preservation time of 10 min-5 h (preferably 30 min-3 h); the magnetic straw biochar generated by the co-pyrolysis is washed with water until it is neutral, thereby obtaining a red mud-enhanced magnetic straw biochar material.
  • step (1) the straw is naturally air-dried or dried to a moisture content of less than 5wt%, and then crushed to a size of less than 120 mesh; in step (2), the red mud has a Fe2O3 content of ⁇ 30wt%, and is dried to a moisture content of less than 2wt%.
  • the red mud and straw are dried before ball milling to avoid sticking to the pot due to residual moisture, which affects the effect.
  • step (3) the powdered red mud is ball-milled and mixed with straw at a mass ratio of 5% to 85% of the total mixture, preferably 10% to 65%; the mixing time is 4 to 72 hours, preferably 12 to 24 hours.
  • the mixing and nesting of the two material particles is achieved in the mechanical process of ball milling.
  • the alkali metal-rich biomass ash is selected from any one of broad-leaved tree ash, wheat straw ash, rice husk ash, cotton stalk ash, and sunflower stalk ash, or a mixture of two or more thereof; the biomass ash and water are mixed in a mass ratio of 1:0.5 to 4 (preferably 1:1 to 1.5), and the extraction is performed by filtering and separating after solid-liquid mixing, or by column percolation extraction; the biomass ash extract produced after the extraction is rich in alkaline substances and is used for modification to improve the quality of straw biochar; the remaining low-alkali solid is rich in phosphorus, magnesium and soluble silicon, with less soluble substances, and the produced dealkalized biomass ash solid residue is used as a fertilizer to reduce the risk of soil salinization.
  • step (5) the straw-red mud mixed powder and the biomass ash extract are mixed in a mass ratio of 1:0.2 to 4, the straw-red mud mixed powder and the biomass ash extract are stirred evenly to form a paste mixture, and the mixture is allowed to stand for 0.5 to 2 hours to allow the solid and liquid to react fully, so that the ions in the biomass ash extract and the soluble alkali metals in the red mud diffuse into the interior of the straw particles with the help of water.
  • the protective atmosphere is nitrogen, and the nitrogen flow rate per minute is 3%-30% of the furnace volume, so as to prevent oxygen from entering the furnace to oxidize the product, and to prevent excessively high flow rate from causing a decrease in production.
  • alkali reacts with carbon to promote the development of biochar pores; iron oxide in red mud is reduced to produce ferroferric oxide and elemental iron, which are the source of the material's magnetism and give the biochar material magnetism.
  • alkali metals and elements such as Fe, Si, Al, Na, and Ti in red mud react with biochar in the solid phase to form a submicron homogeneous structure, which increases the adsorption points of straw biochar.
  • red mud enhanced magnetic straw biochar material prepared by the above preparation method is also within the protection scope of the present invention.
  • the present invention also claims to protect the use of the above-mentioned red mud enhanced magnetic straw biochar material as an adsorbent for sewage treatment.
  • the present invention claims to protect the use of the above-mentioned red mud enhanced magnetic straw biochar material as an adsorbent for removing fluoroquinolone antibiotics in water in sewage treatment, which specifically includes the following steps:
  • step S4 The red mud-enhanced magnetic straw biochar material regenerated by pyrolysis in step S3 is reused to adsorb fluoroquinolone antibiotics in wastewater.
  • step S3 the temperature of pyrolysis regeneration should be lower than the initial preparation temperature of red mud enhanced magnetic straw biochar material by more than 100°C, so as to decompose the adsorbed fluoroquinolone antibiotics without changing the main structure of biochar.
  • the magnetic particles that are partially oxidized during use are regenerated in a high-temperature reducing atmosphere.
  • the above-mentioned fluoroquinolone antibiotics include but are not limited to at least one of ofloxacin, norfloxacin, ciprofloxacin, pefloxacin, enoxacin and the like.
  • the present invention improves the use value and economic value of straw biochar and red mud, and realizes the coordinated utilization of multiple solid wastes.
  • the straw biochar produced by this method is inexpensive and has higher performance than expensive nano zero-valent iron composite biochar. It is magnetic, which makes it convenient to recover by magnetic separation after adsorption saturation, and further regenerate by pyrolysis. It has excellent regeneration performance, which greatly improves the applicability and commercial value of straw biochar as an adsorption material.
  • Provinces such as Shandong and Henan are both major grain-producing provinces and major aluminum-producing provinces, with large straw and red mud production.
  • This method not only provides a high-value resource outlet for straw and red mud, but also reduces greenhouse gas emissions when straw is utilized compared to commonly used methods, and reduces the risk of land salinization when biomass ash is utilized.
  • the present invention can achieve homogeneous compounding of iron and carbon elements at a submicron scale by subjecting straw and red mud to ball milling, biomass ash extraction + liquid impregnation, and co-pyrolysis, thereby providing a large number of efficient adsorption sites, greatly improving the adsorption rate and adsorption amount of fluoroquinolone antibiotics by straw biochar, and at the same time giving the straw biochar magnetic properties, which is convenient for sorting and recycling.
  • the recovered adsorbent can decompose the adsorbed fluoroquinolone antibiotics by pyrolysis, and can be recycled multiple times, achieving waste treatment with waste, and improving the application value and economic value of straw biochar.
  • the used straw biochar of the present invention can be regenerated by pyrolysis after simple magnetic recovery, and the performance attenuation of the recovered product is small, and it can be reused many times, which significantly reduces the use cost and improves the product value.
  • a temperature of 300-700°C the adsorbed fluoroquinolone antibiotics are decomposed, and the adsorption performance of the straw biochar is restored. After being reused 10 times, no attenuation of the adsorption performance is observed.
  • FIG. 1 is a diagram showing the effect of red mud on the antibiotic removal rate of magnetic straw biochar material in Example 1.
  • FIG. 2 is a diagram showing the magnetic separation effect of red mud enhanced magnetic straw biochar material in Example 1.
  • FIG. 3 is a scanning electron microscope image and element distribution diagram of the red mud enhanced magnetic straw biochar material in Example 1.
  • FIG. 4 is a graph showing the antibiotic removal efficiency of the red mud-enhanced magnetic straw biochar material after 10 cycles in Example 2.
  • the straw was taken from wheat straw in Lianyungang, Jiangsu province, and the red mud was taken from the red mud yard of an alumina enterprise in Shandong.
  • the water used was ultrapure water made in the laboratory.
  • the straw was cut into sections, dried in an oven at 105°C to constant weight, crushed using a blade-type Chinese medicine grinder, and passed through a 125 ⁇ m sieve (120 mesh).
  • the red mud was dried in an oven at 105°C to constant weight, crushed using a jaw crusher, and passed through a 50-mesh sieve.
  • the straw and red mud were added to a ball mill at a ratio of 9:1, ground at 350rpm for 16h, and then taken out to form a raw material mixture A.
  • Biomass ash and water were mixed in a beaker at a ratio of 1:4, heated to 60°C, stirred for 2 hours, and then filtered for solid-liquid separation.
  • the resulting solution was biomass ash extract B.
  • the raw material mixture A and the biomass ash extract B were mixed and stirred evenly in a quartz glass boat with a glass rod at a mass ratio of 1:2, and the quartz glass boat was sent into a tube furnace, which was sealed, and nitrogen was passed at a rate of 300 ml/min to drive out the oxygen in the tube.
  • the mixture was allowed to stand for 60 minutes to allow the solid and liquid to be fully mixed.
  • the temperature was then raised to 500°C at a rate of 10°C/min and kept warm for 120 minutes. After cooling to room temperature with the furnace, the mixture was taken out to obtain the red mud enhanced magnetic straw biochar material.
  • the preparation method of magnetic biochar is as follows: 1.0 g BC and 0.15 g FeCl 3 ⁇ 6H 2 O were added to 75% ethanol, stirred for 60 min, 10 ml 10 g/L NaBH 4 solution was slowly added under nitrogen protection, and BC+Fe 0 -NP was obtained by filtration after continued stirring for 30 min.
  • the preparation method of magnetic biochar is as follows: 0.1g FeCl 3 ⁇ 6H 2 O and 0.0368g FeCl 2 ⁇ 4H 2 O are dissolved in distilled water under nitrogen protection, 1.0g BC is added, and the mixture is mechanically stirred and mixed for 30min, and ammonia water is added dropwise to adjust the pH value to between 10 and 11, and the mixture is heated to 80°C and stirred for 30min, during which nitrogen is continuously passed and ammonia water is added to maintain the pH value between 10 and 11, and then BC+Fe 3 O 4 -NP is separated by filtration; 0.1g MBC, BC, BC+Fe 0 -NP and BC+Fe 3 O 4 -NP are weighed respectively.
  • the red mud enhanced magnetic straw biochar material can be separated from the solid and liquid by a magnet for recycling, as shown in Figure 2. It can be seen that the red mud enhanced magnetic straw biochar material adsorbed with fluoroquinolone antibiotics can be well separated from the water body by the magnetism generated by a simple magnet.
  • the straw was taken from wheat straw in Nanjing, Jiangsu province, and the red mud was taken from the red mud outlet of the plate and frame filter press of an alumina enterprise in Henan province.
  • the water used was ultrapure water made in the laboratory.
  • the straw was cut into sections, dried in an oven at 105°C to constant weight, crushed using a blade-type Chinese medicine grinder, and passed through a 125 ⁇ m sieve (120 mesh).
  • the red mud was dried in an oven at 105°C to constant weight, crushed using a jaw crusher, and passed through a 50-mesh sieve.
  • the straw and red mud were added to a ball mill in a ratio of 2:1, ground at 350rpm for 5h, and then taken out to form a raw material mixture A'.
  • the mixture of sycamore branches and leaves was calcined at 900°C in a muffle furnace to a constant weight to obtain biomass ash.
  • the biomass ash was placed in a plexiglass column, and water was pumped into the column from bottom to top using a peristaltic pump for leaching by percolation.
  • the extract of the same weight as the biomass ash was collected and marked as biomass ash extract B'.
  • the raw material mixture A' and the biomass ash extract B' were mixed and stirred evenly in a quartz glass boat with a glass rod at a mass ratio of 1:0.5, and the quartz glass boat was sent into a tube furnace, which was sealed. Nitrogen was passed at a rate of 300 ml/min to drive out the oxygen in the tube, and the mixture was allowed to stand for 60 minutes to allow the solid and liquid to be fully mixed. The temperature was then raised to 800°C at a rate of 10°C/min and kept warm for 120 minutes. After cooling to room temperature with the furnace, the mixture was taken out to obtain the red mud enhanced magnetic straw biochar material.
  • the used red mud enhanced magnetic straw biochar material was separated by magnetic force and regenerated by pyrolysis at 700°C in a tubular furnace under nitrogen protection.
  • the regenerated red mud enhanced magnetic straw biochar material was further used for the adsorption of norfloxacin antibiotics.
  • the present invention provides a method and idea for the preparation and application of a magnetic straw biochar material enhanced by red mud.
  • the above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention. All components not specified in this embodiment can be implemented by existing technologies.

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  • Inorganic Chemistry (AREA)
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Abstract

本发明公开了一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用，将秸秆自然风干或烘干后粉碎；将拜耳法赤泥烘干，破碎成粉状；然后粉碎后的秸秆和粉状赤泥采用球磨混合，制备秸秆-赤泥混合粉末；将富含碱金属的生物质灰与水混合，浸提得到生物质灰提取液和脱碱的生物质灰固体残渣；将秸秆-赤泥混合粉末与生物质灰提取液混合搅拌均匀，得到糊状混合物，在保护气氛下进行共热解，共热解生成的磁性秸秆生物炭经水洗至中性，即得赤泥增强磁性秸秆生物炭材料。本发明极大地提升秸秆生物炭对典型抗生素氟喹诺酮类的吸附速率和吸附量，同时赋予秸秆生物炭磁性，利于后续分选回收。

Description

一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用 技术领域
本发明属于固体废物资源化再利用领域，具体涉及一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用。
背景技术
我国每年产生约9亿吨秸秆，除少部分用作饲料外，主要通过还田肥料化利用，几乎不产生价值。生物炭或活性炭是一种常用的吸附材料，价值较高，但普通的秸秆生物炭因为吸附能力弱，价值低。秸秆与农林废弃物部分利用作为生物质燃料进行利用产生能源，此过程中的次生废物主要是生物质灰。生物质灰呈碱性，富含磷、镁、可溶性硅等营养元素，可作为肥料利用，同时改良酸性土壤。但对于我国西部与北部广大地区的碱性土壤，直接施加生物质灰会加剧土壤盐碱化，抑制了生物质灰的综合利用。
赤泥是我国产量最大的有色金属废渣，95％的赤泥是通过拜耳法生产的，年产量约1.2亿吨。虽然拜耳法赤泥含有一定量的氧化铁，但难以分选富集，无提炼价值，综合利用率不足5％。赤泥的堆存占据了大量土地，造成了环境与安全隐患，亟需为赤泥寻找综合利用途径。山东与河南等省份既是赤泥主要产区，又是产粮大省，若秸秆和赤泥能协同利用，可以极大缓解固废处置压力。
氟喹诺酮类抗生素价格低廉、广谱抗菌、不易出现耐药性，是一类人畜通用药物。但氟喹诺酮类抗生素在水体中难以降解，大量的使用造成此类抗生素在环境中不断积累，给环境造成了较大威胁。常用的氟喹诺酮类抗生素有氧氟沙星、诺氟沙星、环丙沙星、培氟沙星、依诺沙星等。吸附是去除氟喹诺酮类抗生素的重要手段。
秸秆生物炭灰分含量高，比表面积低，吸附能力弱，经济价值低。赤泥中的铁难以通过分选富集，无冶炼价值，难以综合利用。赤泥比表面积小，对抗生素等有机污染物吸附能力极低，故使用赤泥制备的吸附材料主要面向重金属等无机污染物，有机污染物较少涉及。
CN110586038B和CN109847697B提出了在生物炭上负载纳米零价铁实现污染物高效去除的方法，但这些方法需要使用铁盐或亚铁盐作为零价铁的原料，制造成本高昂。CN107051413B和CN108543517B展示了一种用赤泥、碳源和粘结剂混合后隔氧煅烧生成磁性材料，用于富集回收废水中的重金属离子，展示了使用赤泥制作磁性吸附剂的可能性。中国发明专利公开号CN106362685A也公布了一种赤泥和生物质共热解产物去除水体砷的方法。CN113522238A介绍了一种赤泥基铁-炭复合材料及其制备方法和应用用于去除废水中的重金属，但该方法中赤泥需要用酸液处理，进行预脱碱，形成了大量酸性废水，且并未显示复合材料的吸附性能较原生物炭有提高。上述生物炭材料存在制备过程繁琐、成本高昂的缺陷，不利于秸秆、赤泥这些固废的资源化利用，同时制备得到的生物炭材料主要针对重金属。
发明内容
发明目的：本发明所要解决的技术问题是针对现有技术的不足，提供一种基于赤泥增强磁性秸秆生物炭材料的制备方法，通过赤泥、生物质灰与秸秆的协同利用，提高综合利用产品的品质与价值，实现固体废物再利用，产生经济效益。
为了实现上述目的，本发明采取的技术方案如下：
一种基于赤泥增强磁性秸秆生物炭材料的制备方法，包括如下步骤：
(1)将秸秆自然风干或烘干后粉碎；
(2)将拜耳法赤泥烘干，破碎成粉状；
(3)将步骤(1)粉碎的秸秆和步骤(2)粉状赤泥采用球磨进行混合，得到秸秆-赤泥混合粉末；
(4)将富含碱金属的生物质灰与水混合，浸提得到生物质灰提取液和脱碱的生物质灰固体残渣；
(5)将步骤(3)秸秆-赤泥混合粉末与步骤(4)得到的生物质灰提取液混合搅拌均匀，得到糊状混合物；
(6)将步骤(5)糊状混合物在保护气氛下进行共热解，热解温度为400～1000℃(优选500-850℃)，保温时间10min～5h(优选30min-3h)；共热解生成的磁性秸秆生物炭经水洗至中性，即得赤泥增强磁性秸秆生物炭材料。
具体地，步骤(1)中，秸秆经自然风干或烘干至含水率低于5wt％，粉碎至120目以下；步骤(2)中，所述的赤泥中Fe2O3含量≥30wt％，烘干至含水率低于2wt％。球磨前将赤泥和秸秆干燥，避免因残余水分产生粘罐，影响效果。
具体地，步骤(3)中，粉状赤泥按照占总混合物质量比为5％-85％与秸秆进行球磨混合，优选10％-65％；混合时间为4～72小时，优选12-24小时。在球磨的机械过程中实现两种物质颗粒的混合与嵌套。
具体地，步骤(4)中，所述富含碱金属的生物质灰选自阔叶树灰、小麦秸秆灰、稻壳灰、棉杆灰、向日葵杆灰中的任意一种或两种以上的混合；生物质灰与水按照质量比1:0.5～4混合(优选1:1～1.5)，浸提采用固液混合后过滤分离，或者使用柱式渗滤浸提；浸提后产生的生物质灰提取液，富含碱性物质，用于改性提高秸秆生物炭质量；剩下的少碱固体富含磷、镁和可溶性硅，易溶物质减少，产生的脱碱生物质灰固体残渣作为肥料利用，降低土壤盐碱化风险。
优选地，步骤(5)中，秸秆-赤泥混合粉末与生物质灰提取液按照质量比1:0.2～4进行混合，将秸秆-赤泥混合粉末与生物质灰提取液搅拌均匀，形成糊状混合物，静置0.5～2小时使固液充分反应，使生物质灰提取液中的离子和赤泥中的可溶性碱金属在水的帮助下扩散进入秸秆颗粒内部。
优选地，步骤(6)中，所述的保护气氛为氮气，氮气每分钟流量为炉膛体积的3％-30％，避免氧气进入炉内氧化产品，同时避免过高流速造成产量下降。
共热解反应过程中，碱与碳反应，促进生物炭的孔隙发育；赤泥中的氧化铁还原生产四氧化三铁和元素铁，四氧化三铁和元素铁是材料磁性的来源，赋予生物炭材料磁性。同时，热解过程中碱金属以及赤泥中的Fe、Si、Al、Na、Ti等元素与生物炭发生固相反应，形成亚微米级的均质结构，提升秸秆生物炭的吸附点位。
进一步地，上述制备方法所制备得到的赤泥增强磁性秸秆生物炭材料也在本发明的保护范围之中。
进一步地，本发明还要求保护上述赤泥增强磁性秸秆生物炭材料在作为吸附剂用于污水处理中的应用。
更进一步地，本发明要求保护上述赤泥增强磁性秸秆生物炭材料在作为吸附剂用于污水处理中去除水体中氟喹诺酮类抗生素的应用，具体包括如下步骤：
S1：将赤泥增强磁性秸秆生物炭材料与待处理污水混合均匀，充分吸附污水中的氟喹诺酮类抗生素；
S2：通过磁力将吸附有氟喹诺酮类抗生素赤泥增强磁性秸秆生物炭材料，从处理完成后的废水中分离出来；
S3：将分离出来的吸附有氟喹诺酮类抗生素赤泥增强磁性秸秆生物炭材料，在保护气氛下300-700℃热解再生，保温时间10～60min；
S4：将步骤S3热解再生的赤泥增强磁性秸秆生物炭材料重新用于吸附污水中的氟喹诺酮类抗生素。
其中，步骤S3中，热解再生的温度应低于赤泥增强磁性秸秆生物炭材料初次制备温度100℃以上，在不改变生物炭主体结构的前提下使吸附的氟喹诺酮类抗生素分解。同时，在使用过程中被部分氧化的磁性颗粒在高温还原气氛下再生。
具体地，上述含氟喹诺酮类抗生素包括但不限于氧氟沙星、诺氟沙星、环丙沙星、培氟沙星、依诺沙星等中的至少一种。
有益效果：
(1)本发明提高秸秆生物炭和赤泥的使用价值和经济价值，实现多种固体废物的协同利用。本方法产生的秸秆生物炭价格低廉，性能高于昂贵的纳米零价铁复合生物炭，具有磁性，方便在吸附饱和后通过磁选回收，并进一步通过热解再生利用，再生利用性能优异，大大提升秸秆生物炭作为吸附材料的适用性和商业价值。山东与河南等省既是粮食大省又是铝工业大省，秸秆和赤泥产量大，本方法不仅为秸秆和赤泥提供了一种高价值的资源化出路，还比常用方法减少了秸秆利用时的温室气体排放，降低了生物质灰利用时的土地盐碱化风险。
(2)本发明通过秸秆与赤泥两种固体废物经过球磨、生物质灰提取+液浸渍、共热解等处理，可以实现铁、碳元素在亚微米尺度下均质复合，提供了大量高效的吸附点位，极大地提升秸秆生物炭对氟喹诺酮类抗生素的吸附速率和吸附量，同时赋予秸秆生物炭磁性，方便分选回收。回收后的吸附剂可以通过热解方式使吸附的氟喹诺酮类抗生素分解，可以多次再生利用，实现以废治废，提升秸秆生物炭的应用价值和经济价值。
(3)本发明使用过的秸秆生物炭可通过简单磁性回收后热解再生，且回收产品性能衰减小，可多次重复使用，显著降低使用成本，提高产品价值。在300-700℃的温度下，吸附的氟喹诺酮类抗生素分解，秸秆生物炭的吸附性能恢复，重复利用10次后未见吸附性能衰减。
附图说明
下面结合附图和具体实施方式对本发明做更进一步的具体说明，本发明的上述和/或其他方面的优点将会变得更加清楚。
图1是实施例1中赤泥增强磁性秸秆生物炭材料抗生素去除率效果图。
图2是实施例1中赤泥增强磁性秸秆生物炭材料的磁性分离效果图。
图3是实施例1中赤泥增强磁性秸秆生物炭材料的扫描电子显微镜图与元素分布图。
图4是实施例2中赤泥增强磁性秸秆生物炭材料10次循环后抗生素去除率效果图。
具体实施方式
根据下述实施例，可以更好地理解本发明。
实施例1
一、制备磁性秸秆生物炭
1.原料准备：
秸秆取自江苏省连云港小麦秸秆，赤泥取自山东某氧化铝企业赤泥堆场，所用水为实验室自制超纯水。秸秆切段，在烘箱中105℃下烘干至恒重，使用刀片式中药粉碎机粉碎，过125μm筛(120目)。赤泥在烘箱中105℃下烘干至恒重，使用颚式破碎机破碎后过50目筛。将秸秆与赤泥按9:1的比例加入球磨罐中，在350rpm转速下研磨16h后取出，形成原料混合物A。
小麦秸秆在马弗炉中1000℃下烧成恒重，得到生物质灰。以生物质灰：水1:4比例在烧杯中混合，加热至60℃，搅拌混合2小时，之后过滤进行固液分离，所得溶液即为生物质灰提取液B。
2.磁性生物炭制备
将原料混合物A与生物质灰提取液B按质量比1:2在石英玻璃舟中用玻棒混合搅拌均匀，将石英玻璃舟送入管式炉中，密封管式炉，以300ml/min速率通氮气，驱赶管内氧气，静置60min，使固液充分混合。随后以10℃/min升温至500℃，保温120min。随炉冷却至室温后取出，即得赤泥增强磁性秸秆生物炭材料。
3.吸附氟喹诺酮类抗生素
作为对比，将(1)按本步骤所得的赤泥增强磁性秸秆生物炭材料(MBC)；与(2)相同热解条件下制备的小麦秸秆生物炭(BC)；以及(3)在此小麦秸秆生物炭上化学沉淀零价铁纳米颗粒得到的磁性生物炭(BC+Fe0-NP)，和(4)在此秸秆生物炭上化学沉淀四氧化三铁纳米颗粒得到的磁性生物炭(BC+Fe3O4-NP)，加入50ml浓度为20mg/L的氧氟沙星溶液中，每组试验做3个平行，在摇床中混合，定时取样监测氧氟沙星抗生素浓度的变化。结果见图1。
其中，磁性生物炭(BC+Fe0-NP)制备方法为：在75％乙醇中加入1.0g BC和0.15g FeCl3·6H2O，搅拌混合60min，在氮气保护下缓慢滴加10ml 10g/LNaBH4溶液，继续搅拌30min后过滤分离得到BC+Fe0-NP。
磁性生物炭(BC+Fe3O4-NP)制备方法为：在氮气保护的蒸馏水中溶解0.1g FeCl3·6H2O和0.0368g FeCl2·4H2O，加入1.0g BC，机械搅拌混合30min，滴加氨水调节pH值至10～11之间，加热至80℃，继续搅拌30min,期间持续通氮气并加氨水保持pH值在10～11之间，之后过滤分离得到BC+Fe3O4-NP；分别称取0.1g MBC、BC、BC+Fe0-NP和BC+Fe3O4-NP。
可以看出，直接热解得到的小麦秸秆生物炭(BC)对抗生素的去除率无法超过90％，且平衡时间较长，曲线增长缓慢；通过化学沉淀昂贵的纳米零价铁或者四氧化三铁颗粒改性的生物炭(BC+Fe0-NP和BC+Fe3O4-NP)能显著缩短平衡时间，提高处理效率，但无法提高去除率；赤泥中的氧化铁还原生产四氧化三铁和元素铁，四氧化三铁和元素铁是材料磁性的来源，赋予生物炭材料磁性。同时由附图3可见，热解过程中碱金属以及赤泥中的Fe、Si、Al、Na、Ti等元素与生物炭发生固相反应，形成亚微米级的均质结构，提升秸秆生物炭的吸附点位。本发明所得的赤泥增强磁性秸秆生物炭材料(MBC)的应用中，无论是吸附效率还是去除率均得到大幅提高，使用固废原料得到了比昂贵的纳米材料更优的功效。
4.磁性分离
实验完成后可以使用磁铁对赤泥增强磁性秸秆生物炭材料进行固液分离，以便回收利用，见附图2。可以看出，通过简易的磁铁产生的磁性，就能很好的将吸附有氟喹诺酮类抗生素赤泥增强磁性秸秆生物炭材料从水体中分离出来。
实施例2
一、制备磁性秸秆生物炭
1.原料准备：
秸秆取自江苏省南京小麦秸秆，赤泥取自河南某氧化铝企业板框压滤机赤泥出料口，所用水为实验室自制超纯水。秸秆切段，在烘箱中105℃下烘干至恒重，使用刀片式中药粉碎机粉碎，过125μm筛(120目)。赤泥在烘箱中105℃下烘干至恒重，使用颚式破碎机破碎后过50目筛。将秸秆与赤泥按2:1的比例加入球磨罐中，在350rpm转速下研磨5h后取出，形成原料混合物A’。
梧桐树枝与树叶混合物在马弗炉中900℃下烧成恒重，得到生物质灰。将生物质灰装入有机玻璃柱中，用蠕动泵，将水由下而上泵入柱中，以渗滤方式浸提，收集前段与生物质灰等重的提取液，标记为生物质灰提取液B’。
2.磁性生物炭制备
将原料混合物A’与生物质灰提取液B’按质量比1:0.5在石英玻璃舟中用玻棒混合搅拌均匀，将石英玻璃舟送入管式炉中，密封管式炉，以300ml/min速率通氮气，驱赶管内氧气，静置60min，使固液充分混合。随后以10℃/min升温至800℃，保温120min。随炉冷却至室温后取出，即得赤泥增强磁性秸秆生物炭材料。
3.吸附氟喹诺酮类抗生素
称取0.3g赤泥增强磁性秸秆生物炭材料加入50ml浓度为20mg/L的诺氟沙星抗生素溶液中，在摇床中平衡24h后，测量诺氟沙星抗生素浓度，计算去除率。
4.回收利用
吸附实验结束后，将使用过的赤泥增强磁性秸秆生物炭材料通过磁力分离，在管式炉中氮气保护下700℃热解再生。再生后的赤泥增强磁性秸秆生物炭材料继续应用于诺氟沙星抗生素的吸附。
重复3、4步骤。由附图4可见，经过10次重复使用，赤泥增强磁性秸秆生物炭材料对抗生素的去除效率未见明显降低，表明循环使用性能稳定，可显著降低使用成本。
本发明提供了一种基于赤泥增强磁性秸秆生物炭材料的制备方法与应用的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。

Claims (9)

  1. 一种基于赤泥增强磁性秸秆生物炭材料的制备方法，其特征在于，包括如下步骤：
    (1)将秸秆自然风干或烘干后粉碎；
    (2)将拜耳法赤泥烘干，破碎成粉状；
    (3)将步骤(1)粉碎的秸秆和步骤(2)粉状赤泥采用球磨进行混合，得到秸秆-赤泥混合粉末；
    (4)将富含碱金属的生物质灰与水混合，浸提得到生物质灰提取液和脱碱的生物质灰固体残渣；
    (5)将步骤(3)秸秆-赤泥混合粉末与步骤(4)得到的生物质灰提取液混合搅拌均匀，得到糊状混合物；
    (6)将步骤(5)糊状混合物在保护气氛下进行共热解，热解温度为400～1000℃，保温时间10min～5h；共热解生成的磁性秸秆生物炭经水洗至中性，即得。
  2. 根据权利要求1所述基于赤泥增强磁性秸秆生物炭材料的制备方法，其特征在于，步骤(1)中，秸秆经自然风干或烘干至含水率低于5wt％，粉碎至120目以下；步骤(2)中，所述的赤泥中Fe2O3含量≥30wt％，烘干至含水率低于2wt％。
  3. 根据权利要求1所述基于赤泥增强磁性秸秆生物炭材料的制备方法，其特征在于，步骤(3)中，粉状赤泥按照占总混合物质量比为5％-85％与秸秆进行球磨混合，混合时间为4～72小时。
  4. 根据权利要求1所述基于赤泥增强磁性秸秆生物炭材料的制备方法，其特征在于，步骤(4)中，所述富含碱金属的生物质灰选自阔叶树灰、小麦秸秆灰、稻壳灰、棉杆灰、向日葵杆灰中的任意一种或两种以上的混合；生物质灰与水按照质量比1:0.5～4混合，浸提采用固液混合后过滤分离，或者使用柱式渗滤浸提；浸提后产生的脱碱生物质灰固体残渣作为肥料利用。
  5. 根据权利要求1所述基于赤泥增强磁性秸秆生物炭材料的制备方法，其特征在于，步骤(5)中，秸秆-赤泥混合粉末与生物质灰提取液按照质量比1:0.2～4进行混合，将秸秆-赤泥混合粉末与生物质灰提取液搅拌均匀，形成糊状混合物，静置0.5～2小时使固液充分反应，使生物质灰提取液中的离子和赤泥中的可溶性碱金属在水的帮助下扩散进入秸秆颗粒内部。
  6. 权利要求1～5中任意一项制备方法所制备得到的赤泥增强磁性秸秆生物炭材料。
  7. 权利要求6所述的赤泥增强磁性秸秆生物炭材料在作为吸附剂用于污水处理中的应用。
  8. 权利要求6所述的赤泥增强磁性秸秆生物炭材料在作为吸附剂用于污水处理中去除水体中氟喹诺酮类抗生素的应用，其特征在于，包括如下步骤：
    S1：将赤泥增强磁性秸秆生物炭材料与待处理污水混合均匀，充分吸附污水中的氟喹诺酮类抗生素；
    S2：通过磁力将吸附有氟喹诺酮类抗生素赤泥增强磁性秸秆生物炭材料，从处理完成后的废水中分离出来；
    S3：将分离出来的吸附有氟喹诺酮类抗生素赤泥增强磁性秸秆生物炭材料，在保护气氛下300-700℃热解再生，保温时间10～60min；
    S4：将步骤S3热解再生的赤泥增强磁性秸秆生物炭材料重新用于吸附污水中的氟喹诺酮类抗生素。
  9. 根据权利要求9所述的应用，其特征在于，所述的氟喹诺酮类抗生素包括氧氟沙星、诺氟沙星、环丙沙星、培氟沙星、依诺沙星中的至少一种。
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