WO2023122998A1 - 一种矿化铁碳复合材料及其制备方法与应用 - Google Patents

一种矿化铁碳复合材料及其制备方法与应用 Download PDF

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WO2023122998A1
WO2023122998A1 PCT/CN2021/142217 CN2021142217W WO2023122998A1 WO 2023122998 A1 WO2023122998 A1 WO 2023122998A1 CN 2021142217 W CN2021142217 W CN 2021142217W WO 2023122998 A1 WO2023122998 A1 WO 2023122998A1
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iron
composite material
carbon composite
preparation
cross
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PCT/CN2021/142217
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English (en)
French (fr)
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王祺
王勇
刘亚茹
李嘉晨
郭丽莉
熊静
薛晋美
李书鹏
瞿婷
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北京建工环境修复股份有限公司
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Publication of WO2023122998A1 publication Critical patent/WO2023122998A1/zh

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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction

Definitions

  • the invention relates to the field of microbial technology applications, in particular to an iron-carbon composite material and its preparation method and application.
  • Zero-valent iron has lively chemical properties and strong reducing ability.
  • a large number of studies have shown that zero-valent iron can not only degrade chlorinated organic compounds in water, but also reduce and remove heavy metals, azo dyes, nitroaromatics, nitrates, and high chlorine. This greatly promotes the application of zero-valent iron in environmental pollution control. Due to its low cost, it is often used as a filler or injectant in permeable reactive walls and in-situ injection techniques.
  • hydroxides are gradually deposited on the surface of the iron, blocking the internal iron powder from participating in the reaction, weakening the oxidation-reduction reaction, and reducing the ability to treat pollutants.
  • the iron-carbon composite material is formed by solidifying and combining carbon and zero-valent iron. It is used as a micro-electrolytic filler, which can effectively prevent the accumulation of deposits on the surface of iron powder, thereby treating pollutants more efficiently.
  • carbon and iron can be combined to form stable micro-electrolytic materials through cross-linking and sintering.
  • the cross-linking curing combination refers to the use of cross-linking curing agents to bond and cure iron and carbon together.
  • patent application CN111377497A uses sodium alginate and calcium chloride as cross-linking curing agents to combine iron, carbon and medical stone to form materials to remove phosphorus particles from water.
  • Patent application CN110330082A uses sodium alginate and calcium chloride as cross-linking curing agents to combine iron and carbon to form materials, and as a catalyst to catalyze sodium persulfate to treat ibuprofen pollution.
  • the simple cross-linking curing method requires a large amount of curing agent, and the obtained iron-carbon material has low strength, which cannot meet the requirements of high mechanical strength operation of in-situ injection or permeable reaction wall technology, and in the water environment where microorganisms exist may disintegrate quickly, losing structural character.
  • Sintering solidification solves the strength problem of the material.
  • the sintering process requires the material to be processed at a high temperature of hundreds of degrees Celsius for several hours, which consumes a lot of energy, and also makes the surface of the material harden at high temperature, the original slow-release channels are closed, and some iron powder and carbon powder, etc.
  • the active material is locked inside the cured material, unable to react with the outside world, and the utilization rate of the material is low.
  • the object of the present invention is to provide an iron-carbon composite material with high compressive strength and good sewage treatment effect, as well as its preparation method and application.
  • the invention provides a kind of preparation method of iron-carbon composite material, comprises the following steps:
  • Cross-linking and curing step using alkaline earth metal salt and cross-linking agent to carry out cross-linking and curing of iron powder and carbon powder;
  • Mineralization treatment step Soak the cross-linked and solidified iron-carbon composite material in the mineralization bacteria liquid for 5-15 minutes, and then dry it.
  • the soaking time is 5-10min.
  • the mineralizing bacteria are selected from one or more of Myxococcus xanthus, sulfate-reducing bacteria, denitrifying bacteria, and Bacillus pasteurianus.
  • the sulfate-reducing bacteria are selected from one or more of Desulfovibrio vulgaris, Desulfovibrio and Desulfobacillus.
  • the denitrifying bacteria are selected from one or more of Thiobacillus denitrificans, Pseudomonas and Alcaligenes.
  • the Pseudomonas genus includes one or more of Pseudomonas aeruginosa, Pseudomonas fluorescens, Pseudomonas mallei and Pseudomonas pseudomallei.
  • the genus of Alcaligenes includes one or more of Alcaligenes pseudoalcaligenes, Alcaligenes denitrificans and Alcaligenes aromatica.
  • the absorbance (OD 600 ) at 600 nm of the mineralizing bacteria liquid is 1-5; preferably 1-3.
  • the preparation method of the mineralizing bacteria liquid includes the following steps: mixing the mineralizing bacteria powder, ammonium sulfate, urea and water, and culturing.
  • the culture temperature is 25°C-37°C, and the culture time is 24-72h.
  • the mass ratio of mineralizing bacteria powder, ammonium sulfate, urea and water is: (20-30): (15-20): (10-15): (800-1200).
  • a step of adjusting the pH is also included; preferably, the pH is adjusted to 6.5-9.5.
  • the step of dispersing the iron-carbon composite material and leaching the bacterial solution is also included.
  • the dispersing adopts a screen with a pore size of 2.0-4.0mm, and vibrates horizontally for 30-60s to disperse the bonded iron-carbon composite material.
  • the bacterial liquid is drained using a screen with a particle size of 0.5-3.0mm, and the sieve is shaken horizontally for 30-60s to drain excess bacterial liquid.
  • the drying temperature is 40-60° C.
  • the drying time is 3-5 hours.
  • the carbon powder is selected from one or both of activated carbon and graphite.
  • the alkaline earth metal salt is selected from one or more of calcium chloride, calcium nitrate, zinc chloride, and zinc nitrate.
  • the crosslinking agent is sodium alginate.
  • the step of cross-linking and curing includes: mixing iron powder, carbon powder, cross-linking agent with water, adding them to alkaline earth metal salt solution and standing still, separating solid and liquid, and drying to obtain cross-linked and cured iron-carbon composite material.
  • the mass ratio of the iron powder, carbon powder, and crosslinking agent is (40-80):(10-30):(3-6).
  • the particle size of the carbon powder is 200-400 mesh.
  • the iron powder is pickled iron powder; preferably, the preparation method of the pickled iron powder includes: soaking the iron powder in 0.05-0.5mol/L acid solution for at least 3 minutes, separating solid from liquid, washing to neutral.
  • the particle size of the iron powder is 200-400 mesh.
  • the acid solution is selected from one or more of hydrochloric acid solution, sulfuric acid solution, and nitric acid solution.
  • the water temperature is 50-70°C.
  • the mass ratio of the total mass of the acidified iron powder, carbon powder and crosslinking agent to water is (3-5):20.
  • the mass percent concentration of the alkaline earth metal salt solution is 2-6%.
  • the rate of adding to the alkaline earth metal salt solution is 5-15 mL/min.
  • the standing time is 30-90 minutes.
  • the drying temperature is 40-60° C.
  • the drying time is 6-10 hours.
  • the obtained cross-linked and solidified iron-carbon composite material has a particle size of 1.2-3mm.
  • the present invention further provides the iron-carbon composite material prepared by the above preparation method.
  • the grain size of the iron-carbon composite material is 1.5-3.5 mm.
  • the invention also provides the application of the iron-carbon composite material prepared by the above preparation method in sewage treatment.
  • the preparation method of a kind of iron-carbon composite material provided by the present invention comprises the following steps: cross-linking solidification step: adopt alkaline earth metal salt and cross-linking agent to carry out cross-linking solidification to iron powder and charcoal powder; Mineralization treatment step: put The cross-linked and solidified iron-carbon composite material is soaked in the mineralizing bacteria liquid for 5-15 minutes, and then dried.
  • Mineralizing bacteria use alkaline earth metal ions to form alkaline earth metal carbonates on the surface of the iron-carbon composite material, and the alkaline earth metal carbonates are interconnected and wrapped on the surface of the pellets, finally forming a coating structure, which greatly enhances the strength of the iron-carbon composite material; at the same time Control the time of immersion in the mineralizing bacteria solution to 5-15 minutes to ensure that the mineralizing bacteria only convert some alkaline earth metal ions on the surface of the iron-carbon composite material, and will not convert too much alkaline earth metal ions inside, so the iron-carbon composite material The slow-release structure of the internal iron-carbon composite material can still be maintained, and the formation of a dense alkaline earth metal carbonate film can be avoided to affect the function of the active ingredients inside the iron-carbon composite material, thereby obtaining an iron-carbon composite with high compressive strength and good slow-release performance. Material.
  • control iron-carbon composite material soaking time in bacterial liquid is 5-10min, makes the alkaline earth metal carbonate film that mineralization bacteria forms on the surface of iron-carbon composite material The structure is more reasonable, which is more conducive to the reduction of the effective components inside the iron-carbon composite material.
  • the mineralizing bacteria are selected from one or more of Myxococcus flavum, sulfate-reducing bacteria, denitrifying bacteria, and Bacillus pasteurianus.
  • the above mineralizing bacteria can form an alkaline earth metal carbonate film on the surface of the iron-carbon composite material more quickly and improve the compressive strength of the iron-carbon composite material;
  • the carbon powder is selected from one or both of activated carbon and graphite, and can be combined with iron powder to form a micro-electrolytic structure;
  • the alkaline earth metal salt is selected from one or more of calcium chloride, calcium nitrate, zinc chloride, and zinc nitrate, and can bond iron powder and carbon powder together with a cross-linking agent into a
  • it provides a material basis for mineralizing bacteria to produce mineralization.
  • a kind of preparation method of iron-carbon composite material provided by the present invention when the OD 600 of mineralization bacterial liquid is 1-5, helps to control mineralization rate, and the structure that forms alkaline earth metal carbonate film is comparatively suitable, on the one hand Improve the strength of the iron-carbon composite material, on the one hand, avoid the alkaline earth metal carbonate film forming a dense film to wrap the iron-carbon composite material and lose the reducing effect of sewage treatment.
  • the preparation method of the iron-carbon composite material provided by the present invention by controlling the mass ratio of iron powder, charcoal powder, cross-linking agent to be (40-80): (10-30): (3-6), improve iron-carbon Redox reaction efficiency of composite materials.
  • the preparation method of the iron-carbon composite material provided by the present invention adopts pickling iron powder as a raw material, removes the oxide film on the surface of the iron powder through pickling treatment, and improves the reducing activity of the iron powder.
  • the preparation method of an iron-carbon composite material provided by the present invention carbon-iron is combined into a micro-electrolytic structure, which accelerates the electron exchange in the reaction system, promotes the oxidation of iron and the reduction of pollutants, and has a stronger ability to treat pollutants ,higher efficiency.
  • the iron powder is separated by carbon powder, which makes it difficult to agglomerate, the deposition sites of hydroxide are dispersed, and the reactivity lasts longer.
  • the main component of the iron-carbon composite material provided by the invention is alginate, which decomposes organic matter through mineralization bacteria, Under the condition of alkaline earth metal ions, alkaline earth metal carbonates are formed on the surface of carbon-iron, and the mechanical strength is significantly increased. It will not easily disintegrate during the process of mixing agents and building walls with iron-carbon composite materials.
  • the coated alkaline earth metal carbonates It is a porous structure that will not hinder the function of the internal iron-carbon material.
  • Fig. 1 is the appearance picture of the iron-carbon composite material after cross-linking and curing in the preparation method of Example 1 of the present invention
  • Fig. 2 is the appearance picture of the iron-carbon composite material treated with the mineralizing bacteria solution prepared by the preparation method of Example 1 of the present invention
  • Fig. 3 is the relationship figure between soaking different times in the mineralizing bacteria liquid and the particle size of the iron-carbon composite material in Experimental Example 3;
  • Fig. 4 is the relationship diagram between the reduction rate of Cr and soaking time after the iron-carbon composite material soaked in the mineralizing bacteria liquid for different times in Experimental Example 3 treated the sewage containing Cr for 1 h;
  • Fig. 5 is the iron-carbon composite material immersed in the mineralizing bacteria liquid for different time in Experimental Example 3, after treating the sewage containing Cr 6+ for 3 days, the relationship diagram of Cr 6+ reduction rate and soaking time;
  • Fig. 6 is a graph showing the relationship between immersion in the mineralizing bacteria solution for different times and the compressive strength of the iron-carbon composite material in Experimental Example 3.
  • the used Bacillus pasteurianum preservation number ATCC 11859, was purchased from the American Type Culture Collection.
  • the standard substance of 1000 ⁇ g/mL hexavalent chromium solution was purchased from Shangcheng Beina Chuanglian Biotechnology Co., Ltd., product number BWZ6851-2016.
  • reduced iron powder was purchased from Nangong Zhongzhou Alloy Material Co., Ltd. ultra-fine high-purity iron powder; biological activated carbon powder was purchased from Henan Songshan Science and Technology Co., Ltd. powdery activated carbon, materials include peach shell, coconut shell, apricot shell and walnut shells; sodium alginate powder was purchased from Guangzhou Changyu Chemical Co., Ltd., model HG80; graphite powder was purchased from Qingdao Dongkai Graphite Co., Ltd. 1000 mesh graphite powder.
  • a method for preparing an iron-carbon composite material comprising the steps of:
  • Bacterial solution preparation Weigh 20g of Bacillus pasteurian bacteria powder, 20g of ammonium sulfate, and 10g of urea to mix, add 1L of water, adjust the pH value to 7.54, place it at 25°C for 72 hours of fermentation, and obtain the OD600 of the bacterial solution to be 4.7;
  • Dispersion and bacterial liquid leaching place the iron-carbon composite material in a layered vibrating sieve and shake horizontally for 60s; the upper hole diameter is 3.0mm to realize the dispersion of the iron-carbon composite material; the lower layer hole diameter is 1.5mm to drain the excess bacterial liquid;
  • the iron-carbon composite material was dried in a vacuum oven at 50°C for 4 hours, and 25 grains were randomly selected.
  • the measured particle diameters were all within the range of 1.9-3.5mm, and the average particle diameter was 2.6mm.
  • a method for preparing an iron-carbon composite material comprising the steps of:
  • Bacterial solution preparation Weigh 25g of Myxococcus xanthus bacteria powder, 20g of ammonium sulfate, and 12g of urea, mix them, add 1L of water, adjust the pH value to 6.55, and ferment at 28°C for 36 hours to obtain a bacterial solution with an OD 600 of 3.2;
  • Dispersion and bacterial liquid leaching place the iron-carbon composite material in a layered vibrating sieve and shake it horizontally for 30s; the upper layer has an aperture of 2.0 mm to realize the dispersion of the iron-carbon composite material; the lower layer has an aperture of 0.5 mm to drain the excess bacterial liquid;
  • the iron-carbon composite material was dried in a vacuum oven at 60°C for 3 hours, and 25 grains were randomly selected.
  • the particle diameters measured by a vernier caliper were all in the range of 1.5-3.3mm, with an average particle diameter of 2.19mm.
  • a method for preparing an iron-carbon composite material comprising the steps of:
  • Bacterial solution preparation Weigh 30g of Bacillus pasteurian bacteria powder, 15g of ammonium sulfate, and 15g of urea, mix them, add 1L of water, adjust the pH to 9.0, and ferment at 37°C for 24 hours to obtain a bacterial solution with an OD 600 of 1.5;
  • Dispersion and bacterial liquid leaching place the iron-carbon composite material in a layered vibrating sieve and shake it horizontally for 45s; the upper hole diameter is 4.0mm to realize the dispersion of the iron-carbon composite material; the lower layer hole diameter is 3.0mm to drain the excess bacterial liquid;
  • the iron-carbon composite material is dried in a vacuum oven at 40°C for 5 hours, and 25 grains are randomly selected.
  • the particle diameters measured by a vernier caliper are all in the range of 1.7-3.3mm, and the average particle diameter is 2.47mm.
  • This embodiment provides a method for preparing an iron-carbon composite material. Compared with Example 1, the difference lies in step (3) mineralization treatment, immersing the iron-carbon composite material after cross-linking and solidification into the bacterial solution for 15 minutes, and the rest of the steps and parameter conditions are the same.
  • This comparative example provides a method for preparing an iron-carbon composite material. Compared with Example 1, the only difference is that the mineralization step of mineralizing bacteria is omitted, and the other steps and parameter conditions are the same.
  • This comparative example provides a method for preparing an iron-carbon composite material. Compared with Example 1, the difference lies in step (3) mineralization treatment, immersing the iron-carbon composite material after cross-linking and curing in the bacterial solution for 1 min, and the rest of the steps and parameter conditions are the same.
  • This comparative example provides a method for preparing an iron-carbon composite material. Compared with Example 1, the difference lies in step (3) mineralization treatment, the iron-carbon composite material after cross-linking and solidification is immersed in the bacterial solution for 30 minutes, and the remaining steps and parameter conditions are the same.
  • This comparative example provides a method for preparing an iron-carbon composite material. Compared with Example 1, the difference lies in that step (2) adopts sintering and solidification to prepare the iron-carbon composite material, and the rest of the steps and parameters are the same.
  • the sintering and curing steps are as follows:
  • Grind biological activated carbon to 200 mesh to obtain activated carbon powder take 375g of dry pickling iron powder, 100g of activated carbon powder, 135g of water, 75g of Xiong brand heat stabilizer 340RF, a total of 685g of mixed powder, mix and pass through a disc granulator Granulation; then heated to 200°C for sintering for 30 minutes under anaerobic conditions, and cooled to room temperature in a vacuum-dried environment.
  • the iron-carbon composite material prepared by Examples 1-4 and Comparative Example 1-2 is tested for compressive strength, and is measured according to GB/T 10516-2012 "Measurement of Average Crush Resistance of Nitrophosphate Fertilizer Granules";
  • the present invention forms an alkaline earth metal carbonate protective film on the surface of the iron-carbon composite material through the mineralization technology of mineralizing bacteria, which significantly improves the compressive strength of the iron-carbon composite material and can meet the requirements of in-situ injection or infiltration.
  • the mineralization treatment step of mineralizing bacteria was omitted
  • the mineralization treatment time of mineralizing bacteria was 1 min.
  • the compressive strength of the iron-carbon composite material was low, and disintegration occurred after 3 days of use, and it was impossible to Continuously playing the role of treating sewage further proves that mineralization treatment can improve the strength of iron-carbon composite materials, make them maintain their original shape, and prolong their service life.
  • Cr 6+ reduction rate (% ) (Cr 6+ concentration in sewage before treatment-Cr 6+ concentration in sewage after treatment)/Cr 6+ concentration in sewage before treatment.
  • the preparation method of the 30mg/L Cr 6+ solution is: take 3mL of 1000 ⁇ g/mL hexavalent chromium solution standard substance, add water and dilute to 100mL to obtain.
  • the mineralization time of Examples 1-4 of the present invention is 5-15 minutes, and the obtained iron-carbon composite material can effectively treat Cr 6+ in sewage.
  • the mineralization time of Comparative Example 3 was 30 minutes, and the coating time was too long, resulting in a relatively dense alkaline earth metal carbonate film formed on the surface of the iron-carbon composite material, which could not be in contact with sewage for sewage restoration. Therefore, the restoration efficiency for hexavalent chromium was remarkable decrease;
  • comparative example 4 uses sintering and solidification to prepare iron-carbon composite materials, and then uses the same method for mineralization treatment, but because sintering and solidification closes the slow-release channels inside the iron-carbon composite material, the effect of sewage treatment is poor.
  • the iron-carbon composite material after cross-linking and solidification was prepared, and it was divided into 7 groups, wherein one group was not mineralized by mineralizing bacteria (denoted as 0min), and the remaining 6 groups were treated by mineralizing bacteria mineralization , respectively soaked in the mineralizing bacteria liquid for 5, 10, 15, 30, 60, and 120 min, and the parameters and conditions of the remaining steps were all the same as in Example 1.
  • one group was not mineralized by mineralizing bacteria (denoted as 0min)
  • the remaining 6 groups were treated by mineralizing bacteria mineralization , respectively soaked in the mineralizing bacteria liquid for 5, 10, 15, 30, 60, and 120 min, and the parameters and conditions of the remaining steps were all the same as in Example 1.
  • test methods for compressive strength and Cr 6+ reduction ability are the same as those in Experimental Example 1 and Experimental Example 2, and the particle size adopts Vernier caliper measurement, randomly select 5 from each group, measure their diameter respectively, take the average value, the results are shown in Table 3 and Figure 3-6.
  • the particle size of the iron-carbon composite material is due to the mineralization of the mineralizing bacteria to form a calcium carbonate film on the surface of the iron-carbon composite material, and the growth process of the calcium carbonate film can be simplified into three stages: In the contact period before 5 minutes, the microorganisms have just come into contact with the calcium ions on the surface of the slow-release material. Due to the lack of crystal nuclei and supporting framework, the synthesis of calcium carbonate film is relatively slow.
  • the stable period of more than 60 minutes because the calcium carbonate formed in the early stage gradually forms a covering on the surface of the particles, which prevents external microorganisms from continuing to react with the calcium ions released inside the particles, and then cannot continue to form calcium carbonate to wrap on the surface of the particles, so the particle size tends to be Stable and unchanged.
  • the generated calcium carbonate will not seal the surface of the pellets, and the reduction effect of the material can be retained; on the other hand, it can also improve to a certain extent
  • the compressive strength of the iron-carbon composite material prevents the material from breaking during use.

Abstract

本发明属于微生物技术应用领域，具体提供一种铁碳复合材料及其制备方法与应用，包括以下步骤：交联固化步骤：采用碱土金属盐和交联剂对铁粉和生物活性炭进行交联固化；矿化处理步骤：将交联固化后的铁碳复合材料浸泡于矿化菌菌液中5-15min，干燥即得。矿化菌利用碱土金属离子在铁碳复合材料表面形成碱土金属碳酸盐结构，大大增强铁碳复合材料的强度，同时控制在矿化菌菌液中浸泡的时间，避免致密金属碳酸盐膜的形成而影响铁碳复合材料内部有效成分发挥作用。

Description

一种矿化铁碳复合材料及其制备方法与应用 技术领域
本发明涉及微生物技术应用领域，具体涉及一种铁碳复合材料及其制备方法与应用。
背景技术
零价铁化学性质活泼，具有较强的还原能力，大量研究表明零价铁不但可以降解水体中的氯代有机物，还能还原去除重金属、偶氮染料、硝基芳香族以及硝酸盐、高氯酸盐、除草剂等多种污染物，这极大推动了零价铁在环境污染治理方面的应用。由于其价钱低廉，常用作渗透式反应墙和原位注入技术中的填料或注入剂。但随着零价铁的反应，氢氧化物逐渐沉积在铁的表面，阻隔内部铁粉参加反应，氧化还原反应减弱，对污染物的处理能力降低。
铁碳复合材料是由碳与零价铁固化组合后形成，其作为微电解填料使用，可有效防止沉积物在铁粉表面富集，从而更高效的处理污染物。目前，可通过交联固化与烧结固化两种方式结合碳与铁形成稳定的微电解材料。交联固化组合是指使用交联固化剂将铁碳粘连并固化组合在一起，例如：专利申请CN111377497A使用海藻酸钠、氯化钙作为交联固化剂将铁、碳与麦饭石固化组合形成材料，去除水中磷颗粒。专利申请CN110330082A使用海藻酸钠、氯化钙作为交联固化剂将铁、碳固化组合形成材料，作为催化剂催化过硫酸钠处理布洛芬污染。但是单纯的交联固化方式，固化剂使用量大，得到的铁碳材料强度较低，无法满足原位注入或渗透式反应墙技术的高机械强度操作的要求，并且在有微生物存在的水环境中可能会很快崩解，失去结构特征。
烧结固化解决了材料的强度问题。但是，烧结过程需要将材料在上百摄氏度的高温中处理若干小时，能耗极高，而且还会使材料在高温中表面硬化，原有的缓释孔道被封闭，部分铁粉与炭粉等活性材料被锁在固化材料内部，无法与外界反应，材料利用率低。
因此，寻求一种抗压强度高且处理污水效果好的铁碳复合材料是当前铁碳催化剂产品推广利用中亟需解决的技术问题。
发明内容
因此，本发明的目的在于提供一种抗压强度高且处理污水效果好的铁碳复合材料及其制备方法与应用。
为此，本发明提供一种铁碳复合材料的制备方法，包括以下步骤：
交联固化步骤：采用碱土金属盐和交联剂对铁粉和炭粉进行交联固化；
矿化处理步骤：将交联固化后的铁碳复合材料浸泡于矿化菌菌液中5-15min，干燥即得。
优选的，所述浸泡时间为5-10min。
优选的，所述矿化菌选自黄色粘球菌、硫酸盐还原菌、反硝化细菌、巴氏芽孢杆菌中的一种或多种。
优选的，所述硫酸盐还原菌选自普通脱硫弧菌、脱硫螺菌、脱硫芽孢弧菌中的一种或多种。
优选的，所述反硝化细菌选自脱氮硫杆菌、假单胞菌属、产碱杆菌属中的一种或多种。
优选的，所述假单胞菌属包括铜绿假单胞菌、荧光假单胞菌、鼻疽假单胞菌、类鼻疽假单胞菌中的一种或多种。
优选的，所述产碱杆菌属包括类产碱杆菌、去硝产碱杆菌和芳香产碱杆菌中的一种或多种。
优选的，所述矿化菌菌液在600nm处的吸光度(OD 600)为1-5；优选为1-3。
优选的，所述矿化菌菌液的制备方法，包括以下步骤：将矿化菌菌粉、硫酸铵、尿素和水混合，进行培养。
优选的，所述培养温度为25℃-37℃，培养时间为24-72h。
优选的，矿化菌菌粉、硫酸铵、尿素和水的质量比为：(20-30)：(15-20)：(10-15)：(800-1200)。
优选的，矿化菌菌粉与硫酸铵、尿素和水混合后还包括调节pH的步骤；优选调节pH为6.5-9.5。
优选的，所述干燥步骤前还包括对铁碳复合材料的分散和菌液沥除的步骤。
优选的，所述分散采用孔径为2.0-4.0mm的筛网，水平震荡30-60s，将粘接的铁碳复合材料分散。
优选的，所述菌液沥除采用粒径为0.5-3.0mm的筛网，水平震荡30-60s，沥除多余菌液。
优选的，所述干燥温度40-60℃，干燥时间为3-5h。
优选的，所述炭粉选自活性炭、石墨中的一种或两种。
优选的，碱土金属盐选自氯化钙、硝酸钙、氯化锌、硝酸锌中的一种或多种。
优选的，所述交联剂为海藻酸钠。
优选的，所述交联固化步骤包括：将铁粉、炭粉、交联剂与水混合后，加至碱土金属盐溶液中静置，固液分离，干燥，得交联固化后的铁碳复合材料。
优选的，所述铁粉、炭粉、交联剂的质量比为(40-80)：(10-30)：(3-6)。
优选的，所述炭粉粒径为200-400目。
优选的，所述铁粉为酸洗铁粉；优选的，所述酸洗铁粉的制备方法包括：将铁粉浸泡于0.05-0.5mol/L酸溶液中至少3min后，固液分离，洗涤至中性。
优选的，所述铁粉粒径为200-400目。
优选的，所述酸溶液选自盐酸溶液、硫酸溶液、硝酸溶液中的一种或多种。
优选的，所述交联固化步骤中，水温度为50-70℃。
优选的，所述酸化铁粉、炭粉和交联剂的总质量与水的质量比为(3-5)：20。
优选的，所述碱土金属盐溶液的质量百分浓度为2-6％。
优选的，交联固化步骤中，加至碱土金属盐溶液中的速度为5-15mL/min。
优选的，交联固化步骤中，静置时间为30-90min。
优选的，交联固化步骤中，干燥温度40-60℃，干燥时间6-10h。
优选的，得到的交联固化后的铁碳复合材料粒径为1.2-3mm。
本发明进一步提供上述制备方法制备得到的铁碳复合材料。
优选的，所述铁碳复合材料的粒径为1.5-3.5mm。
本发明还提供上述制备方法制备得到的铁碳复合材料在处理污水中的应用。
本发明技术方案，具有如下优点：
1.本发明提供的一种铁碳复合材料的制备方法，包括以下步骤：交联固化步骤：采用碱土金属盐和交联剂对铁粉和炭粉进行交联固化；矿化处理步骤：将交联固化后的铁碳复合材料浸泡于矿化菌菌液中5-15min，干燥即得。矿化菌利用碱土金属离子在铁碳复合材料表面形成碱土金属碳酸盐，碱土金属碳酸盐相互联结，包裹在小球表面，最终形成包膜结构，大大增强铁碳复合材料的强度；同时控制在矿化菌菌液中浸泡的时间为5-15min，保证矿化菌只将铁碳复合材料表面部分碱土金属离子转化，而不会过多转化内部的碱土金属离子，因此铁碳复合材料依然可以维持内部铁碳复合材料的缓释结构，避免致密碱土金属碳酸盐膜的形成而影响铁碳复合材料内部有效成分发挥作用，从而得到抗压强度高且缓释性能好的铁碳复合材料。
2.本发明提供的一种铁碳复合材料的制备方法，控制铁碳复合材料在菌液中浸泡时间为5-10min，使得矿化菌在铁碳复合材料表面形成的碱土金属碳酸盐膜结构更为合理，更利于铁碳复合材料内部有效成分发挥还原作用。
3.本发明提供的一种铁碳复合材料的制备方法，矿化菌选自黄色粘球菌、硫酸盐还原菌、反硝化细菌、巴氏芽孢杆菌中的一种或多种。以上矿化菌能够更迅速地在铁碳复合材料表面形成碱土金属碳酸盐膜，提高铁碳复合材料的抗压强度；炭粉选自活性炭、石墨中的一种或两种，可与铁粉形成微电解结构；所述含碱土金属盐选自氯化钙、硝酸钙、氯化锌、硝酸锌中的一种或多种，可与交联剂共同将铁粉和炭粉粘接为一体，同时为矿化菌产生矿化作用提供物质基础。
4.本发明提供的一种铁碳复合材料的制备方法，矿化菌液的OD 600为1-5时，有利于控制矿化速度，形成碱土金属碳酸盐膜的结构较为合适，一方面提高铁碳复合材料的强度，一方面避免碱土金属碳酸盐膜形成致密膜包裹铁碳复合材料而失去处理污水的还原作用。
5.本发明提供的铁碳复合材料的制备方法，通过控制铁粉、炭粉、交联剂的质量比为(40-80)：(10-30)：(3-6)，提高铁碳复合材料的氧化还原反应效率。
6.本发明提供的铁碳复合材料的制备方法，采用酸洗铁粉作为原料，通过酸洗处理将铁粉表面的氧化膜去除，提高铁粉的还原活性。
7.本发明提供的一种铁碳复合材料的制备方法，炭-铁组合成为微电解结构，加速反应体系内电子交换，促进铁的氧化和污染物的还原，对污染物的处理能力更强，效率更高。同时铁粉被炭粉间隔，不易团聚，氢氧化物的沉积点位被分散，反应活性保持时间更久，本发明提供的铁碳复合材料主要成分是海藻酸盐，通过矿化菌分解有机物，在碱土金属离子条件下使炭-铁表面形成碱土金属碳酸盐，机械强度显著增加，在药剂混合、铁碳复合材料建墙的过程中不会轻易崩解，同时包裹的碱土金属碳酸盐为多孔结构，不会阻碍内部铁碳材料发挥作用。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例1的制备方法中交联固化后的铁碳复合材料的外观图片；
图2是本发明实施例1的制备方法制备得到的经过矿化菌菌液处理的铁碳复合材料的外观图片；
图3是实验例3中在矿化菌菌液中浸泡不同时间与铁碳复合材料粒径的关系图；
图4是实验例3中在矿化菌菌液中浸泡不同时间的铁碳复合材料处理1h含Cr 6+的污水后，Cr 6+还原率与浸泡时间的关系图；
图5是实验例3中在矿化菌菌液中浸泡不同时间的铁碳复合材料，处理3天含Cr 6+的污水后，Cr 6+还原率与浸泡时间的关系图；
图6是实验例3中在矿化菌菌液中浸泡不同时间与铁碳复合材料抗压强度的关系图。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
本发明以下实施例中，所用巴氏芽孢杆菌保藏号：ATCC 11859，购自美国典型培养物保藏中心。所用黄色粘球菌，保藏号：ATCC 25232，购自美国典型培养物保藏中心。
本发明实验例中，1000μg/mL六价铬溶液标准物质购自商城北纳创联生物科技有限公司，产品编号BWZ6851-2016。
本发明以下实施例中，还原铁粉购自南宫市中州合金材料有限公司的超细高纯铁粉；生物活性炭粉购自河南嵩山科技有限公司的粉状活性炭，材质包括桃壳、椰壳、杏壳和核桃壳；海藻酸钠粉购自广州昌彧化工有限公司，型号HG80；石墨粉购自青岛东凯石墨有限公司1000目石墨粉。
实施例1
一种铁碳复合材料的制备方法，包括以下步骤：
(1)酸洗铁粉制备：将500g还原铁粉研磨至200目，置于1000mL 0.1mol/L盐酸中，搅拌5min后，减压过滤，去离子水洗涤至滤液pH值为7.2，真空烘箱中50℃干燥2h，并保存于无氧环境中；
(2)交联固化：将生物活性炭研磨至200目，得到活性炭粉；取干燥的酸洗铁粉375g、活性炭粉100g、海藻酸钠粉25g，配制总计500g的混合粉末，搅拌中加入2kg 60℃水中，持续搅拌10min，整体悬浮液均匀无颗粒团聚，且具有一定粘稠度，得悬浮液；在搅拌条件下，将悬浮液通过内径0.5mm的软管，以10mL/min的泵速泵入质量百分浓度3％的CaCl 2溶液中，静置60min后，使用孔径1mm的筛子使铁碳复合材料分散，置于真空干燥箱中，50℃烘8h，得交联固化后铁碳复合材料，无氧保存，随机取其中25粒，用游标卡尺测得粒径均在1.2-3mm范围内，平均粒径为1.84mm。
(3)矿化菌矿化：
菌液配制：称取巴氏芽孢杆菌菌粉20g、硫酸铵20g、尿素10g混合，加水1L，调节pH值为7.54，置于25℃条件下发酵培养72h，得到菌液OD 600为4.7；
矿化处理：将步骤(2)得到的交联固化后铁碳复合材料，置于孔径1mm的筛网中，浸泡于菌液中10min后取出；
分散和菌液沥除：将铁碳复合材料置于层级振荡筛中，水平震荡60s；上层孔径3.0mm，实现铁碳复合材料的分散；下层孔径1.5mm，将多余的菌液沥除；
干燥：矿化后铁碳复合材料置于真空烘干箱中50℃烘4h，随机取其中25粒，测得粒径均在1.9-3.5mm范围内，平均粒径为2.6mm。
实施例2
一种铁碳复合材料的制备方法，包括以下步骤：
(1)酸洗铁粉制备：将500g还原铁粉研磨至400目，置于1000mL 0.05mol/L硫酸中，搅拌4min后，减压过滤，去离子水洗涤至滤液pH值为7.3，真空烘箱中50℃干燥2h，并保存于无氧环境中；
(2)交联固化：将石墨研磨至400目，得到石墨粉；取干燥的酸洗铁粉400g、石墨粉50g、海藻酸钠粉15g，配制总计465g的混合粉末，搅拌中加入1.86kg 70℃水中，持续搅拌10min，整体悬浮液均匀无颗粒团聚，且具有一定粘稠度，得悬浮液；在搅拌条件下，将悬浮液通过内径0.5mm的软管，以5mL/min的泵速泵入质量百分浓度为2％的ZnCl 2溶液中，静置30min后，使用孔径1mm的筛子使铁碳复合材料分散，置于真空干燥箱中，40℃烘10h，得交联固化后铁碳复合材料，无氧保存，随机取其中25粒，用游标卡尺测得粒径均在1.2-3mm范围内，平均粒径为1.82mm。
(3)矿化菌矿化：
菌液配制：称取黄色粘球菌菌粉25g，硫酸铵20g，尿素12g，混合，加水1L，调节pH值为6.55，28℃条件下发酵培养36h，得到菌液OD 600为3.2；
矿化处理：将步骤(2)得到的交联固化后铁碳复合材料，置于孔径1mm的筛网中，浸泡于菌液中5min后取出；
分散和菌液沥除：将铁碳复合材料置于层级振荡筛中，水平震荡30s；上层孔径2.0mm，实现铁碳复合材料的分散；下层孔径0.5mm，将多余的菌液沥除；
干燥：矿化后铁碳复合材料置于真空烘干箱中60℃烘3h，随机取其中25粒，用游标卡尺测得粒径均在1.5-3.3mm范围内，平均粒径2.19mm。
实施例3
一种铁碳复合材料的制备方法，包括以下步骤：
(1)酸洗铁粉制备：将500g还原铁粉研磨至300目，置于1000mL 0.5mol/L磷酸中，搅拌3min后，减压过滤，去离子水洗涤至滤液pH值为7.1，真空烘箱中50℃干燥3h，并保存于无氧环境中；
(2)交联固化：将生物活性炭研磨至300目，得到活性炭粉；取干燥的酸洗铁粉200g、活性炭粉150g、海藻酸钠粉30g，配制总计380g的混合粉末，搅拌中加入2.53kg 50℃水中，持续搅拌15min，整体悬浮液均匀无颗粒团聚，且具有一定粘稠度，得悬浮液；在搅拌条件下，将悬浮液通过内径0.5mm的软管，以15mL/min的泵速泵入质量百分浓度6％的CaCl 2溶液中，静置90min后，使用孔径1mm的筛子使铁碳复合材料分散，置于真空干燥箱中，60℃烘6h，得交联固化后铁碳复合材料，无氧保存，随机取其中25粒，用游标卡尺测得粒径均在1.2-3mm范围内，平均粒径为1.80mm。
(3)矿化菌矿化：
菌液配制：称取巴氏芽孢杆菌菌粉30g，硫酸铵15g，尿素15g，混合，加水1L，调节pH＝9.0，37℃条件下发酵培养24h，得到菌液OD 600为1.5；
矿化处理：将步骤(2)得到的交联固化后铁碳复合材料，置于孔径1mm的筛网中，浸没入菌液中7min后取出；
分散和菌液沥除：将铁碳复合材料置于层级振荡筛中，水平震荡45s；上层孔径4.0mm，实现铁碳复 合材料的分散；下层孔径3.0mm，将多余的菌液沥除；
干燥：矿化后铁碳复合材料置于真空烘干箱中40℃烘5h，随机取其中25粒，用游标卡尺测得粒径均在1.7-3.3mm范围内，平均粒径2.47mm。
实施例4
本实施例提供一种铁碳复合材料的制备方法，其与实施例1相比，区别在于步骤(3)矿化处理，将交联固化后铁碳复合材料浸没入菌液中15min，其余步骤和参数条件均相同。
对比例1
本对比例提供一种铁碳复合材料的制备方法，其与实施例1相比，区别仅在于省略矿化菌矿化步骤，其余步骤和参数条件均相同。
对比例2
本对比例提供一种铁碳复合材料的制备方法，其与实施例1相比，区别在于步骤(3)矿化处理，将交联固化后铁碳复合材料浸没入菌液中1min，其余步骤和参数条件均相同。
对比例3
本对比例提供一种铁碳复合材料的制备方法，其与实施例1相比，区别在于步骤(3)矿化处理，将交联固化后铁碳复合材料浸没入菌液中30min，其余步骤和参数条件均相同。
对比例4
本对比例提供一种铁碳复合材料的制备方法，其与实施例1相比，区别在于步骤(2)采用烧结固化的方式制备铁碳复合材料，其余步骤和参数均相同。烧结固化步骤具体如下：
将生物活性炭研磨至200目，得到活性炭粉；取干燥的酸洗铁粉375g、活性炭粉100g、水135g、熊牌热稳定剂340RF 75g，总计685g的混合粉末，混合后通过圆盘造粒机造粒；然后在绝氧条件下加热至200℃烧结30min，于真空干燥的环境中冷却至室温。
实验例1
将实施例1-4和对比例1-2制备得到的铁碳复合材料进行抗压强度测试，按照GB/T 10516-2012《硝酸磷肥颗粒平均抗压碎力的测定》进行测定；
同时，分别称取10g上述铁碳复合材料置于100mL 30mg/L的Cr 6+溶液中3天后，观察铁碳复合材料的形状，结果见表1。
表1不同铁碳复合材料的抗压强度和使用后形状
Figure PCTCN2021142217-appb-000001
Figure PCTCN2021142217-appb-000002
由上表数据可知，本发明通过矿化菌矿化技术，在铁碳复合材料表面形成碱土金属碳酸盐保护膜，使铁碳复合材料的抗压强度明显提升，能够满足原位注入或渗透式反应墙技术的机械强度要求；并且在使用3天后，仍然能够保持原有的形状，无崩解或破碎现象，铁碳复合材料可继续发挥处理污水的作用。对比例1省略了矿化菌矿化处理步骤，对比例2的矿化菌矿化处理时间为1min，铁碳复合材料抗压强度均较低，并且在使用3天后都出现崩解现象，无法持续发挥处理污水的作用，进一步证明了矿化处理能提高铁碳复合材料的强度，使其维持原有的形状，使用寿命得以延长。
实验例2
考察实施例1-4，对比例3-4制备得到的铁碳复合材料处理污水的能力，具体方法为：分别称取10g铁碳复合材料，置于锥形瓶中，加入100mL 30mg/L Cr 6+溶液，将锥形瓶置于振荡机中，110rpm振荡1h，取样按照GB/T 7467-1987《水质六价铬的测定二苯碳酰二肼分光光度法》测定Cr 6+的浓度；再静置，分别于12h、24h、48h、72h取样，测定Cr 6+的浓度，计算Cr 6+还原率，结果见表2。
Cr 6+还原率(％)＝(处理前污水中Cr 6+的浓度-处理后污水中Cr 6+的浓度)/处理前污水中Cr 6+的浓度。
其中，30mg/L Cr 6+溶液的制备方法为：取3mL 1000μg/mL六价铬溶液标准物质，加水定容至100mL得到。
表2不同铁碳复合材料还原Cr 6+能力
Figure PCTCN2021142217-appb-000003
Figure PCTCN2021142217-appb-000004
由上表数据可知，本发明实施例1-4的矿化时间为5-15min，得到的铁碳复合材料能够有效处理污水中的Cr 6+。对比例3的矿化时间为30min，包膜时间过长导致在铁碳复合材料表面形成的碱土金属碳酸盐膜较为致密，无法与污水接触进行污水修复，因此，对六价铬修复效率显著下降；对比例4采用烧结固化的方式制备铁碳复合材料，然后采用相同的方式进行矿化处理，但是由于烧结固化将铁碳复合材料内部的缓释孔道封闭，因此处理污水的效果较差。
实验例3
按照实施例1的制备方法制备交联固化后的铁碳复合材料，将其分成7组，其中一组不进行矿化菌矿化(记为0min)，其余6组进行矿化菌矿化处理，分别于矿化菌菌液中浸泡5、10、15、30、60、120min，其余步骤参数条件均与实施例1相同。考察不同矿化时间对铁碳复合材料粒径、Cr 6+还原能力以及抗压强度的影响，其中抗压强度以及Cr 6+还原能力的测试方法同实验例1和实验例2，粒径采用游标卡尺测量，从各组中随机选取5个，分别测定其直粒径，取平均值，结果见表3及图3-6。
表3不同浸泡时间对铁碳复合材料性能的影响
Figure PCTCN2021142217-appb-000005
上表数据可以看出，关于铁碳复合材料的粒径，是由于矿化菌的矿化作用在铁碳复合材料表面形成碳酸钙膜，而碳酸钙膜生长的过程可以简化为三个阶段：5min之前的接触期，此阶段微生物刚与缓释材料表面的钙离子接触，由于缺少晶核和支撑骨架，碳酸钙膜合成相对较慢。5-60min的快速生长期，经过前5min的接触，微生物在缓释材料表面多点位少量合成了碳酸钙，而后续微生物以5min以前合成的碳酸钙为晶核和骨架，开始大量合成碳酸钙，并逐渐联结，形成完整的碳酸钙包膜。60min以上的稳定期，由于前期形成的碳酸钙逐渐在颗粒表面形成覆盖，阻隔了外部的微生物继续反应颗粒内部释放的钙离子，进而无法再继续形成碳酸钙包裹在颗粒表面，因此粒径趋于稳定不变。
对于1h时Cr 6+还原率，在矿化初期形成的碳酸钙包膜虽然对粒径的影响较大，但是并非是致密的碳酸钙结构，因此铁碳复合材料内部的还原材料仍可以释放出来。但是15min后碳酸钙的生成则是同时提升粒径和碳酸钙膜的致密度，因此内部的还原铁碳复合材料越来越难以释放，还原作用逐渐减弱。
处理Cr 6+3天后，浸没少于15min的处理在静置过程中仍有进一步的还原效果，长于15min的处理则几乎不会再进一步还原Cr 6+。说明长时间浸没生产的碳酸钙是致密的，阻碍了内部还原材料的释放。
对于抗压强度，可以比较清晰的看出矿化膜致密程度的变化。在5min之前生成的矿化膜强度并不高，而在10-60min之间，矿化膜迅速生长且愈发致密，导致材料抗压强度显著增加，硬度显著提升。
综上所述，将浸没时间控制在5-15min，尤其是5-10min，一方面生成的碳酸钙并不会封闭小球表面，可保留材料的还原效果；另一方面也可一定程度上提升铁碳复合材料抗压强度，防止材料在使用过程中破碎。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种铁碳复合材料的制备方法，其特征在于，包括以下步骤：
    交联固化步骤：采用碱土金属盐和交联剂对铁粉和炭粉进行交联固化；
    矿化处理步骤：将交联固化后的铁碳复合材料浸泡于矿化菌菌液中5-15min，干燥即得。
  2. 根据权利要求1所述的制备方法，其特征在于，所述浸泡时间为5-10min。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述矿化菌选自黄色粘球菌、硫酸盐还原菌、反硝化细菌、巴氏芽孢杆菌中的一种或多种；
    和/或，所述炭粉选自活性炭、石墨中的一种或两种；
    和/或，碱土金属盐选自氯化钙、硝酸钙、氯化锌、硝酸锌中的一种或多种；
    和/或，所述交联剂为海藻酸钠。
  4. 根据权利要求1-3任一项所述的制备方法，其特征在于，所述矿化菌菌液OD 600为1-5；优选为1-3。
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，所述交联固化步骤包括：将铁粉、炭粉、交联剂与水混合后，加至碱土金属盐溶液中静置，固液分离，干燥，得交联固化后的铁碳复合材料。
  6. 根据权利要求1-5任一项所述的制备方法，其特征在于，所述铁粉、炭粉、交联剂的质量比为(40-80)：(10-30)：(3-6)。
  7. 根据权利要求1-6任一项所述的制备方法，其特征在于，所述铁粉为酸洗铁粉，优选地，所述酸洗铁粉的制备方法包括：将铁粉浸泡于0.05-0.5mol/L酸溶液中至少3min后，固液分离，洗涤至中性。
  8. 根据权利要求5-7任一项所述的制备方法，其特征在于，所述碱土金属盐溶液的质量百分浓度为2-6％。
  9. 一种权利要求1-8任一所述的制备方法制得的铁碳复合材料。
  10. 权利要求1-8任一项所述制备方法制备得到的铁碳复合材料在处理污水中的应用。
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