WO2021017455A1 - 一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用 - Google Patents

一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用 Download PDF

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WO2021017455A1
WO2021017455A1 PCT/CN2020/075929 CN2020075929W WO2021017455A1 WO 2021017455 A1 WO2021017455 A1 WO 2021017455A1 CN 2020075929 W CN2020075929 W CN 2020075929W WO 2021017455 A1 WO2021017455 A1 WO 2021017455A1
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composite material
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cyanobacteria
modified cyanobacteria
biochar composite
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严群
王赫
王寒
赵辉
张勇
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Jiangnan University
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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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a modified cyanobacteria biochar composite material, a preparation method thereof, and application in the treatment of electroplating wastewater, belonging to the technical field of biochar composite material preparation.
  • Electroplating is an indispensable link in the production process of durable metal materials. Through electroplating treatment, the aesthetics and performance of the material can be greatly improved.
  • the domestic and foreign electroplating industry accounted for about 37% of the total market share of the metal surface treatment industry.
  • nearly one billion cubic meters of electroplating wastewater is generated every year.
  • Electroplating wastewater contains heavy metals such as copper, chromium, nickel, zinc and various organic pollutants.
  • Zinc-nickel alloy can give metal materials excellent mechanical strength and anti-corrosion ability. Therefore, zinc-nickel alloy is one of the most important plating species in the electroplating industry.
  • organic reagents such as complexing agents, antistatic agents, co-solvents and brighteners are used in the zinc-nickel alloy electroplating process to improve the quality of electroplating, which makes the metal ions in the zinc-nickel alloy electroplating wastewater in a complex state.
  • Ordinary chemical precipitation cannot remove the metal ions in the complex state, which greatly increases the difficulty of treating zinc-nickel alloy electroplating wastewater. If the zinc-nickel alloy electroplating wastewater is directly discharged without advanced treatment, the heavy metal ions in the zinc-nickel alloy electroplating wastewater will be enriched through the food chain network, thus endangering the safety of the ecosystem and human health.
  • the methods used to treat electroplating wastewater include adsorption, precipitation, flocculation, flotation, ion exchange, and membrane treatment.
  • adsorption and precipitation are often the first choice due to lower cost input and higher treatment efficiency.
  • some electroplating wastewater containing complexing agents cannot be treated by simple adsorption or precipitation.
  • transition metal If the transition metal is loaded on the adsorbent material, in the presence of hydrogen peroxide, the transition metal will catalyze the hydrogen peroxide to produce hydroxyl radicals ( ⁇ OH), resulting in advanced oxidation (AOP); through advanced oxidation, complexing agents and other organic pollution The substance will be degraded, releasing the complexed metal, turning the complexed metal into ionic metal, which is beneficial to the removal of heavy metals.
  • Biochar is a material with high carbon content formed by the thermal cracking of biomass under anaerobic or anoxic conditions.
  • Biochar generally has a high specific surface area and abundant oxygen-containing functional groups. Therefore, biochar has a strong adsorption capacity and is widely used in soil restoration. Due to the strong adsorption capacity of biochar, it can be used as a matrix to load other materials to obtain biochar composite materials, which can be used to treat wastewater.
  • the patent (CN108455603A) discloses a biochar rich in mesopores and a preparation method thereof. Wood chips, bamboo powder, walnut shells or straws are carbonized under an inert gas atmosphere to obtain biochar rich in mesopores. However, the biochar obtained by this method has a specific surface area of 569 m 2 /g and a pore volume of 0.194 cm 3 /g.
  • the patent (201810177711.4) discloses a method for preparing a biochar-based negative composite material.
  • the orange peel powder and urea solution are mixed, stirred, freeze-dried, and then mixed with rectorite powder and calcined to obtain the stability of the biochar composite material.
  • the adsorption capacity is large.
  • the composite material only has adsorption capacity, not catalytic capacity.
  • cyanobacteria are widely distributed all over the world.
  • the point source pollution of industrial sewage and the non-point source pollution of agricultural fertilizers in modern times made the concentration of nitrogen and phosphorus in the water body high, which led to the rapid growth of freshwater algae and the formation of blooms.
  • the large-scale outbreak of cyanobacteria will destroy the ecological environment of local water bodies and threaten the drinking water safety of residents in the basin.
  • the annual fishing volume of blue algae in the Taihu Lake Basin alone reached 1.86 million tons. It is not difficult to see that the resource utilization of cyanobacteria is imminent.
  • the patent discloses a method for producing hydrogen by anaerobic fermentation of blooming cyanobacteria. This method is to pack the salvaged and collected cyanobacteria in a closed container to induce hydrogen production, thereby obtaining clean energy.
  • the anaerobic reaction will produce odor and anaerobic sludge. Therefore, a cleaner method for resource utilization of cyanobacteria remains to be developed.
  • the invention provides a method for preparing a modified cyanobacteria biochar composite material.
  • the obtained biochar composite material has a large specific surface area, strong adsorption capacity and good stability, and the obtained biochar composite material has both adsorption capacity and catalytic capacity. , Can produce the synergistic effect of adsorption and Fenton-like oxidation in the presence of hydrogen peroxide.
  • the preparation method of the modified cyanobacteria biochar composite material includes the following steps:
  • step (3) Grind the sample after pyrolysis treatment in step (2), and screen it with a sieve of 80-100 mesh, and then wash the sample that has passed through the sieve with acid and water until the pH of the wastewater produced by washing is medium Properties, drying samples;
  • step (3) Dry and roast the sample after drying in step (3) after soaking in iron-containing solution, adjusting alkali and depositing;
  • step (4) Wash the sample calcined in step (4) with water and filter, collect the filtered solid and dry the solid to obtain a modified cyanobacteria biochar composite material.
  • the cyanobacteria described in step (1) are all taken from Taihu Lake, China.
  • the drying temperature in step (1) is 80-120°C, and the drying time is 12-24 hours.
  • the activator in step (1) is one of potassium hydroxide, zinc chloride, and potassium hydrogen phosphate, and the mass ratio of the cyanobacteria and the activator is (0.5-1) :1.
  • the inert gas in step (2) is nitrogen, and the flow rate of the inert gas is 60-100 sccm.
  • the thermal cracking in step (2) is divided into two stages, wherein the thermal cracking temperature of the first stage is 200-400°C, and the thermal cracking time is 60-90 min; the second stage The thermal cracking temperature is 600-800°C, and the thermal cracking time is 60-120min.
  • the acid in step (3) is dilute hydrochloric acid, the concentration of dilute hydrochloric acid is 0.1-1 mol/L; the drying temperature is 80-120°C, and the drying time is 12-24h.
  • the iron-containing solution in step (4) is a ferric chloride solution or a ferric nitrate solution, and the quality of iron in the solution is the same as that of the sample (charcoal) after drying in step (3).
  • the mass ratio of) is (0.05-0.2):1;
  • the reagent used for adjusting alkali is aqueous ammonia solution, the concentration of the aqueous ammonia solution is 10-20wt%;
  • the roasting device is a muffle furnace, the roasting temperature is 200-400°C, and the roasting time is 2 -4h.
  • the drying in step (5) is vacuum drying, the drying temperature is 60-85°C, and the drying time is 12-24h.
  • the invention also provides a method for using the prepared modified cyanobacteria biochar composite material to treat electroplating wastewater.
  • the modified cyanobacteria biochar composite material is added to the electroplating wastewater, and after adsorption equilibrium, hydrogen peroxide is added to perform Fenton-like oxidation reaction After the reaction is completed, alkali precipitation is added, and the supernatant is effluent.
  • the modified cyanobacteria biochar composite material is reused after desorption and cleaning.
  • the pH value of the electroplating wastewater is adjusted to 2-8.
  • the dosage of the modified cyanobacteria biochar composite material is 0.5-5 g/L wastewater.
  • the adsorption equilibrium time is 20 minutes.
  • the addition amount of hydrogen peroxide is 5-30 mmol, and the Fenton reaction time is 60 min.
  • the modified cyanobacteria biochar composite material can be recycled and reused at least 4 times.
  • the invention uses waste biomass cyanobacteria as a raw material, and performs staged pyrolysis under the condition of adding an activator, so that the pyrolyzed biochar has a huge specific surface area. This approach improves the adsorption capacity of cyanobacteria biochar.
  • Cyanobacteria are rich in organic matter and high in carbon content. After pyrolysis treatment, cyanobacteria have less biochar ash. In addition, cyanobacteria have a relatively small molecular weight, and the particle size of biochar after pyrolysis is much smaller than that of biochar such as straw.
  • a modified cyanobacteria biochar composite material can be obtained, which not only has excellent adsorption capacity, but also has catalytic capacity. In the presence of hydrogen peroxide, it can also catalyze the Fenton-like reaction, and iron oxide can catalyze the hydrogen peroxide to produce hydroxyl radicals, thereby achieving the degradation of organic pollutants. Therefore, the modified cyanobacteria biochar composite material can efficiently remove heavy metals in electroplating wastewater containing complexing agent through adsorption and Fenton-like reaction, and can be reused.
  • Figure 1 is a scanning electron microscope (SEM) image of the modified cyanobacteria biochar obtained in Example 1.
  • Example 2 is a scanning electron microscope (SEM) image of the modified cyanobacteria biochar composite material obtained in Example 2.
  • Example 3 is an X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) graphs of the modified cyanobacteria biochar and modified cyanobacteria biochar composite material in Example 3.
  • XPS X-ray photoelectron spectroscopy
  • XRD X-ray diffraction
  • Figure 4 shows how the nickel ion concentration in the treated wastewater changes over time when the modified cyanobacteria biochar composite material is recycled.
  • Figure 5 shows how the nickel ion content in the electroplating wastewater changes over time when different biochar composite materials are used to treat electroplating wastewater;
  • ⁇ Unactivated cyanobacteria biochar, that is, step (1) is omitted on the basis of Example 1.
  • Cyanobacteria biochar obtained after the step of mixing with potassium hydroxide;
  • ⁇ straw biochar composite material, that is, the straw biochar composite material prepared in Comparative Example 1;
  • Modified cyanobacteria biochar namely the modified cyanobacteria biochar prepared in Example 1;
  • Modified cyanobacteria biochar composite material that is, the modified cyanobacteria biochar composite material prepared in Example 2;
  • ⁇ iron oxide powder, that is, the same amount of iron as in Example 2.
  • Detection method of nickel content in wastewater Flame atomic absorption spectrometry is used to detect the concentration of metal ions in wastewater.
  • the water sample is filtered through a 0.45 ⁇ m water-based filter membrane for testing.
  • the instrument used is a flame atomic absorption spectrometer (AAF-7000F).
  • the standard curve has been set to accurately obtain the concentration of metal ions in the water sample.
  • a method for preparing modified cyanobacteria biochar includes the following steps:
  • the mixed sample is thermally cracked.
  • the thermal cracking process is divided into two stages. First, the temperature is raised to 400°C at 5°C/min, and the thermal cracking is performed at 400°C for 90 minutes. Then, heat up to 800°C at a rate of 10°C/min, and keep it at 800°C for 2h;
  • Figure 1 is a scanning electron microscope (SEM) image of the modified cyanobacteria biochar obtained in Example 1.
  • SEM scanning electron microscope
  • Table 1 The specific surface area and pore volume of the modified cyanobacteria biochar material prepared in Example 1 are shown in Table 1.
  • the modified cyanobacteria biochar has a rich pore structure and a large specific surface area, so it improves the adsorption capacity and is also conducive to compounding with other materials.
  • a preparation method of modified cyanobacteria biochar composite material includes the following steps:
  • the mixed sample is thermally cracked.
  • the thermal cracking process is divided into two stages. Firstly, the temperature is raised to 400°C at 5°C/min, and the thermal cracking is performed at 400°C for 90 minutes. , Then heat up to 800°C at a rate of 10°C/min, and keep it at 800°C for 2h;
  • FIG. 1 The specific surface area and pore volume of the biochar composite material prepared in Example 2 are shown in Table 1.
  • Figure 2 is a scanning electron microscope (SEM) image of the modified cyanobacteria biochar composite material obtained in Example 2. It can be seen from the figure that the surface of the composite material has become relatively rough.
  • FIG. 3 both X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) have iron oxide peaks, and the above results together indicate that iron oxide has been successfully combined with cyanobacteria biochar.
  • XPS X-ray photoelectron spectroscopy
  • XRD X-ray diffraction
  • the materials prepared in the foregoing Examples 1 and 2 are used to treat zinc-nickel alloy electroplating wastewater.
  • the parameters of electroplating wastewater are shown in Table 2.
  • the specific treatment process is as follows: First, adjust the initial pH value of the electroplating wastewater to 6, then add 0.5g of modified cyanobacteria biochar or modified cyanobacteria biochar composite material, wait for 20 minutes to reach adsorption equilibrium, add 30mmol of hydrogen peroxide to Fenton-like Oxidation reaction. After the reaction (about 60min), sodium hydroxide is added for precipitation, the supernatant is collected and filtered with a 0.45 ⁇ m filter, the concentration of nickel ions in the filtrate is measured by flame atomic absorption method, and the cyanobacteria biochar composite material is modified Reuse after desorption and cleaning.
  • the calculation formula of the nickel removal rate is shown in the following formula (1).
  • Figure 5 shows the effect of electroplating wastewater treatment.
  • Modified cyanobacteria biochar shows excellent adsorption capacity. According to formula (1), it can absorb 69.8% of nickel, but it cannot completely remove the nickel in electroplating wastewater; it is compounded with iron oxide
  • the modified cyanobacteria biochar composite material prepared later can efficiently remove heavy metals in water through the synergy of adsorption and Fenton-like reaction. The removal rate calculated according to formula (1) reaches 99.1%.
  • iron oxide powder is taken to treat the electroplating wastewater.
  • the treatment conditions are as follows: adjust the pH of the zinc-nickel alloy wastewater to about 3, then add iron oxide powder for adsorption for 20 minutes, then add hydrogen peroxide, and after 60 minutes of reaction, add sodium hydroxide for precipitation. After precipitation, take the supernatant and pass through a 0.45 ⁇ m filter membrane After filtering, the metal ion concentration was measured by flame atomic absorption method. The amount of iron oxide is the same as the iron content of the biochar composite material in Example 2. The treatment result is shown in Figure 5. According to formula (1), the removal rate of nickel by iron oxide in the adsorption stage is 8.23%, and after the Fenton-like reaction, the removal rate of nickel is 74.01%.
  • the modified cyanobacteria biochar composite material is collected, first washed with alkali solution (0.1mol/L sodium hydroxide solution), then washed with deionized water until the pH is neutral, and finally placed Dry in an oven for 12 hours.
  • alkali solution 0.1mol/L sodium hydroxide solution
  • deionized water until the pH is neutral
  • deionized water until the pH is neutral
  • Dry in an oven for 12 hours followed the same method as above to treat zinc-nickel alloy electroplating wastewater again.
  • Figure 4 shows the recycling diagram of the modified cyanobacteria biochar composite material. After 4 cycles of recycling, the nickel removal rate can still reach 93.7%, indicating that the composite material has good stability.
  • the raw material is soaked in the ferric nitrate solution for 8 hours.
  • the mass ratio of iron in the ferric nitrate solution to the biochar in the sample is 0.2:1.
  • stir While adding 10% aqueous ammonia solution dropwise to the solution until pH 9, continue to stir for 2h, dry the mixed solution first, and then roast it in a muffle furnace at 200°C for 2h; wash the roasted sample with water , Filtration, and place the solid part in a vacuum drying oven at 60°C for 24 hours to obtain a straw biochar composite material.
  • the parameters of electroplating wastewater are shown in Table 2. Adjust the pH value of electroplating wastewater to 6, then add 0.5g of straw biochar composite material, wait for 20min to reach adsorption equilibrium, add 30mmol of hydrogen peroxide to perform Fenton-like oxidation reaction, after the reaction is over (About 60min), sodium hydroxide was added for precipitation, the supernatant was collected and filtered with a 0.45 ⁇ m filter, and the concentration of nickel ions in the filtrate was measured by flame atomic absorption method.
  • the calculation formula of the nickel removal rate is shown in the following formula (1).
  • the treatment result is shown in Fig. 5. In the adsorption stage, the nickel removal rate calculated according to formula (1) is 23.99%. After the Fenton-like reaction, the nickel removal rate calculated according to formula (1) is 47.92%.
  • Example 2 On the basis of Example 2, the mass ratio of iron to carbon in step (4) was adjusted to 0.05:1, 0.1:1 and 0.2:1, respectively, to prepare different modified cyanobacteria composite materials. These modified cyanobacteria composite materials were used to treat the same zinc-nickel alloy electroplating wastewater using the process in Example 3. The treatment effect is shown in Table 3. After the adsorption coupling Fenton-like reaction is completed, the nickel removal rate calculated according to formula (1) is 86.28%, 90.61% and 99.14%, respectively. It can be seen that the removal rate of nickel is different for different iron loads, and the iron load with an appropriate concentration can efficiently remove nickel in wastewater.
  • Iron to carbon ratio Nickel removal rate (%) 0.05:1 86.28 0.1:1 90.61 0.2:1 99.14

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Abstract

一种改性蓝藻生物炭复合材料的制备方法，包括以下步骤：(1)将蓝藻烘干、研磨，并利用80～100目筛子进行筛选，收集通过筛孔的蓝藻并与活化剂混合，得到混合后的样品；(2)在惰性气氛下，对混合后的样品进行热裂解处理；(3)将热裂解处理后的样品进行研磨，并用80～100目的筛子筛选，然后，分别用酸、水洗涤通过了筛孔的样品，直至洗涤产生的废水的pH呈中性，烘干样品；(4)将烘干后的样品在含铁溶液中浸泡、调碱沉积之后烘干、焙烧；(5)焙烧后的样品用水洗，并过滤，收集过滤得到的固体并干燥该固体得到改性蓝藻生物炭复合材料。还公开了改性蓝藻生物炭复合材料及其处理电镀废水的方法。

Description

一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用 技术领域
本发明涉及一种改性蓝藻生物炭复合材料及其制备方法以及在处理电镀废水中的应用，属于生物炭复合材料制备技术领域。
背景技术
近年来，航空航天、汽车以及珠宝首饰等产业迅速发展，因此，人们对耐用型金属材料及相关工艺的需求也不断增长。电镀是耐用型金属材料生产过程中不可或缺的一个环节，通过电镀处理，能够大幅度提高材料的美观度及性能。2015年，国内外电镀产业占金属表面处理行业总市场份额的37％左右。与此相应地，每年会产生近十亿立方米的电镀废水。电镀废水中含有铜、铬、镍、锌等重金属以及各类有机污染物。锌镍合金能够赋予金属材料优异的机械强度及防腐能力，因此，锌镍合金是电镀行业中最主要的镀种之一。同时，锌镍合金电镀过程中会使用络合剂、抗静电剂、助溶剂和光亮剂等有机试剂以提高电镀的品质，这就使得锌镍合金电镀废水中的金属离子为络合态。普通的化学沉淀无法将络合态的金属离子去除，这就极大地提高了锌镍合金电镀废水的处理难度。如果，锌镍合金电镀废水不经深度处理，就直接排放，那么，锌镍合金电镀废水中的重金属离子将通过食物链网进行富集，从而危害生态系统安全以及人类健康。
目前，用来处理电镀废水的方法有吸附、沉淀、絮凝、浮选、离子交换和膜处理等，其中，吸附和沉淀由于较低的成本投入和较高的处理效率，往往成为首选方案。但是，某些含有络合剂的电镀废水不能通过单纯的吸附或者沉淀来处理。如果，将过渡金属负载到吸附材料上，在双氧水存在的条件下，过渡金属会催化双氧水产生羟基自由基(·OH)，从而发生高级氧化(AOP)；通过高级氧化，络合剂等有机污染物将会被降解，释放出络合态金属，使络合态金属变为离子态金属，从而有利于重金属的去除。
生物炭是生物质在厌氧或缺氧的条件下热裂解形成的一种含碳量高的材料。生物炭一般具有高的比表面积和丰富的含氧官能团，因此，生物炭的吸附能力较强，从而被广泛应用于修复土壤。由于生物炭具体吸附能力较强的特性，因此，可以作为基质来负载其他材料以便得到生物炭复合材料，生物炭复合材料可用于处理废水。
专利(CN108455603A)公开了一种富含介孔生物炭及其制备方法，将木屑、竹粉、核桃壳或者秸秆在惰性气体氛围下炭化，得到富含介孔的生物炭。但是，该方法得到的生物炭比表面积为569m 2/g，孔容积为0.194cm 3/g。
专利(201810177711.4)公开了一种生物炭基负复合材料的制备方法，将橘子皮粉末和尿素溶液混合搅拌、冻干，然后与累托石粉末粉末混合煅烧，制得的生物炭复合材料稳定性好，吸附容量大。但是，该复合材料仅具有吸附能力，而不具备催化能力。
蓝藻作为一种淡水藻类，在世界各地均广泛分布。近代工业污水的点源污染以及农业肥料的面源污染，使得水体的氮磷浓度偏高，从而导致淡水藻类的疯长，形成水华。蓝藻的大面积爆发将会破坏当地水体的生态环境，威胁流域内居民的饮用水安全。例如，在中国，2018年仅太湖流域全年打捞蓝藻的量就达到186万吨。不难看出，蓝藻资源化利用迫在眉睫。目前，人们处理蓝藻的方式以打捞为主。对于打捞上来的蓝藻，缺少资源化利用的方式，大多是厌氧发酵。专利(CN102618585A)公开了一种利用水华蓝藻厌氧发酵产氢的方法，这种方法是将打捞和收集的蓝藻装于密闭容器中进行诱导产氢，从而得到清洁能源。但是，厌氧反应会产生臭气以及厌氧污泥等问题。所以，一种更加清洁地将蓝藻资源化利用的方法有待开发。
发明内容
本发明提供了一种改性蓝藻生物炭复合材料的制备方法，所得生物炭复合材料的比表面积大、吸附能力强、稳定性好，所得生物炭复合材料在具有吸附能力的同时还具有催化能力，能在双氧水存在的条件下，产生吸附和类芬顿氧化的协同作用。
所述改性蓝藻生物炭复合材料的制备方法，包括以下步骤：
(1)将蓝藻烘干、研磨，并利用80～100目筛子进行筛选，收集通过筛孔的蓝藻并与活化剂混合，得到混合后的样品；
(2)在惰性气氛下，对步骤(1)中得到的混合后的样品进行热裂解处理；
(3)将步骤(2)中热裂解处理后的样品进行研磨，并用80～100目的筛子筛选，然后，分别用酸、水洗涤通过了筛孔的样品，直至洗涤产生的废水的pH呈中性，烘干样品；
(4)将步骤(3)中烘干后的样品在含铁溶液中浸泡、调碱沉积之后烘干、焙烧；
(5)将步骤(4)中焙烧后的样品用水洗，并过滤，收集过滤得到的固体并干燥该固体得到改性蓝藻生物炭复合材料。
在本发明的一种实施方式中，步骤(1)中所述的蓝藻均取自中国的太湖。
在本发明的一种实施方式中，步骤(1)中烘干温度为80～120℃，烘干时间为12～24h。
在本发明的一种实施方式中，步骤(1)中所述活化剂为氢氧化钾、氯化锌、磷酸氢钾其中的一种，蓝藻与活化剂混合的质量比为(0.5-1):1。
在本发明的一种实施方式中，步骤(2)中所述惰性气体为氮气，惰性气体流速为60～100sccm。
在本发明的一种实施方式中，步骤(2)中所述热裂解分为两个阶段，其中，第一阶段热裂解温度为200～400℃，热裂解时间为60～90min；第二阶段热裂解温度为600～800℃，热裂解时间为60～120min。
在本发明的一种实施方式中，步骤(3)中所述酸为稀盐酸，稀盐酸的浓度为0.1～1mol/L；烘干温度为80～120℃，烘干时间为12～24h。
在本发明的一种实施方式中，步骤(4)中所述的含铁溶液为氯化铁溶液或硝酸铁溶液，溶液中的铁的质量与步骤(3)中烘干后的样品(炭)的质量比为(0.05-0.2)：1；调碱所用试剂为氨水溶液，氨水溶液的浓度为10～20wt％；焙烧装置为马弗炉，焙烧温度为200～400℃，焙烧时间为2-4h。
在本发明的一种实施方式中，步骤(5)中所述干燥为真空干燥，干燥温度为60～85℃，干燥时间为12～24h。
本发明还提供了应用所制备的改性蓝藻生物炭复合材料用来处理电镀废水的方法，向电镀废水中加入改性蓝藻生物炭复合材料，待吸附平衡后，加入双氧水进行类芬顿氧化反应，反应结束后，加碱沉淀，上清液即出水，改性蓝藻生物炭复合材料经脱附和清洗后进行回用。
在本发明的一种实施方式中，向电镀废水中加入改性蓝藻生物炭复合材料之前，先将电镀废水的pH值调整为2～8。
在本发明的一种实施方式中，改性蓝藻生物炭复合材料的投加量为0.5～5g/L废水。
在本发明的一种实施方式中，吸附平衡时间为20min。
在本发明的一种实施方式中，双氧水添加量为5～30mmol，芬顿反应时间为60min。
在本发明的一种实施方式中，改性蓝藻生物炭复合材料至少可以回收反复利用4次。
本发明以废弃的生物质蓝藻为原料，在添加活化剂的条件下进行分阶段热裂解，使热解后的生物炭具有巨大的比表面积。这种做法提高了蓝藻生物炭的吸附能力。
蓝藻富含有机物、含碳量高，蓝藻经过热裂解处理后生物炭灰分较少。并且，蓝藻具有相对较小的分子量，热裂解后的生物炭粒度远小于秸秆等生物炭。
蓝藻生物炭负载氧化铁后，可以得到改性蓝藻生物炭复合材料，该复合材料在具有优异的吸附能力的同时，还具有催化能力。在双氧水存在时，还能催化发生类芬顿反应，氧化铁会催化双氧水产生羟基自由基，从而实现有机污染物的降解。因此，改性蓝藻生物炭复合材料能够通过吸附和类芬顿反应高效去除含有络合剂电镀废水中的重金属，并且可以重复利用。
附图说明
图1为实施例1得到的改性蓝藻生物炭的扫描电镜(SEM)图。
图2为实施例2得到的改性蓝藻生物炭复合材料的扫描电镜(SEM)图。
图3为实施例3中改性蓝藻生物炭与改性蓝藻生物炭复合材料的X射线光电子能谱(XPS)和X射线衍射(XRD)图。
图4为循环利用改性蓝藻生物炭复合材料时，被处理的废水中的镍离子浓度随时间变化的情况。
图5为采用不同生物炭复合材料处理电镀废水时，电镀废水中的镍离子含量随时间变化的情况；●：未活化蓝藻生物炭，即在实施例1的基础上省略了步骤(1)中与氢氧化钾混合的步骤后所得到的蓝藻生物炭；▲：秸秆生物炭复合材料，即对比例1中制备的秸秆生物炭复合材料；
Figure PCTCN2020075929-appb-000001
改性蓝藻生物炭，即实施例1制备的改性蓝藻生物炭；
Figure PCTCN2020075929-appb-000002
改性蓝藻生物炭复合材料，即实施例2制备得到的改性蓝藻生物炭复合材料；■：氧化铁粉末，即与实施例2中铁用量相同。
具体实施方式
废水中镍含量的检测方法：废水中金属离子浓度检测采用火焰原子吸收光度法，将水样通过0.45μm水系滤膜过滤后进行测试，所用仪器为火焰原子吸收光谱仪(AAF-7000F)，仪器根据已设置好的标准曲线精确得出水样中金属离子浓度。
实施例1 没有负载铁的改性蓝藻生物炭的制备
一种改性蓝藻生物炭的制备方法，包括以下步骤：
(1)将太湖蓝藻置于105℃烘箱中烘干24h，烘干后研磨并过80目筛，然后取过筛后的样品与氢氧化钾混合，样品与氢氧化钾的质量比为1:1；
(2)在气体流速为80sscm的氮气保护下，将混合后的样品进行热裂解，热裂解过程分为两段式，首先以5℃/min升温至400℃，在400℃下热裂解90min，然后，再以10℃/min的速率升温至800℃，在800℃下保温2h；
(3)将热裂解后的样品置于研钵中研磨后过100目筛，然后在1mol/L的盐酸中酸洗、水洗至中性，并置于烘箱中，于105℃烘干样品，得到改性蓝藻生物炭。
图1为实施例1得到的改性蓝藻生物炭的扫描电镜(SEM)图。本实施例1所制备的改性蓝藻生物炭材料的比表面积及孔容积如表1所示。改性蓝藻生物炭具有丰富的孔道结构，比表面积大，因此提高了吸附能力，也有利于与其他材料进行复合。
实施例2 负载铁的改性蓝藻生物炭复合材料的制备
一种改性蓝藻生物炭复合材料的制备方法，包括以下步骤：
(1)将太湖蓝藻置于105℃烘箱中烘干24h，烘干后研磨并过80目筛。然后取过筛后 的样品与氢氧化钾混合，样品与氢氧化钾的质量比为1:1；
(2)在气体流速为80sscm的氮气保护下，将混合后的样品热裂解，热裂解过程分为两段式，首先以5℃/min升温至400℃，在400℃下热裂解90min，然后，再以10℃/min的速率升温至800℃，在800℃下保温2h；
(3)将热裂解后的样品置于研钵中研磨后过100目筛，然后在1mol/L的盐酸中酸洗、水洗至pH＝7，并置于烘箱中，于105℃烘干样品；
(4)将烘干后的样品在硝酸铁溶液中浸泡8h，硝酸铁溶液中铁与样品中生物炭的质量比为0.2:1，浸泡结束后，在连续搅拌的条件下向溶液中逐滴滴加质量浓度为10％的氨水溶液直至溶液的pH＝9，继续搅拌2h，将混合溶液先烘干，再置于200℃马弗炉中焙烧2h；
(5)将焙烧后的样品水洗、过滤，并将固形物部分置于60℃真空干燥箱中干燥24h，得到改性蓝藻生物炭复合材料。
本实施例2制备的生物炭复合材料的比表面积及孔容积如表1所示。图2为实施例2得到的改性蓝藻生物炭复合材料扫描电镜(SEM)图，从图中可以看出复合材料表面变得相对粗糙。进一步地，如图3所示，X射线光电子能谱(XPS)以及X射线衍射(XRD)均出现铁的氧化物的峰，以上结果共同表明氧化铁已成功与蓝藻生物炭复合。
实施例3 电镀废水的处理实例
将上述实施例1、实施例2制得的材料，用于处理锌镍合金电镀废水。电镀废水的参数如表2所示。
具体处理过程为：首先，将电镀废水的初始pH值调节至6，然后加入改性蓝藻生物炭或改性蓝藻生物炭复合材料0.5g，待20min达到吸附平衡后，加入双氧水30mmol进行类芬顿氧化反应，反应结束后(约60min)，加氢氧化钠进行沉淀，收集上清液并利用0.45μm滤头过滤，用火焰原子吸收法测定滤液中的镍离子浓度，改性蓝藻生物炭复合材料经脱附和清洗后进行回用。镍去除率的计算公式如下式(1)所示。
Figure PCTCN2020075929-appb-000003
式中：η-------------镍去除率(％)
C 0-------------未经处理时，电镀废水中的镍的初始浓度(mg/L)
C t-------------经处理后镍的浓度(mg/L)
图5为电镀废水处理效果图，改性蓝藻生物炭表现出优异的吸附能力，根据公式(1)计算得到能够吸附69.8％的镍，但是并不能完全去除电镀废水中的镍；与氧化铁复合后制得的 改性蓝藻生物炭复合材料，通过吸附和类芬顿反应的协同作用，能够高效地去除水中重金属，根据公式(1)计算得到去除率达到了99.1％。
另外，取氧化铁粉末处理上述电镀废水。处理条件如下：将锌镍合金废水pH调至3左右，然后加入氧化铁粉末吸附20min，然后加入双氧水，反应60min后加入氢氧化钠进行沉淀，沉淀结束后取上清液，经0.45μm滤膜过滤后，用火焰原子吸收法测量金属离子浓度。氧化铁用量与实施例2中生物炭复合材料含铁量相同。处理结果如图5所示，根据公式(1)计算得，氧化铁在吸附阶段对镍的去除率为8.23％，类芬顿反应后，镍的去除率为74.01％。
可见，单独的蓝藻生物炭吸附或者单独的氧化铁催化双氧水发生的类芬顿反应均不能够深度处理锌镍合金电镀废水，而改性蓝藻生物炭复合材料通过将吸附和类芬顿耦合，能够高效处理锌镍合金电镀废水。
锌镍合金电镀废水处理结束后，收集改性蓝藻生物炭复合材料，先用碱溶液(0.1mol/L的氢氧化钠溶液)清洗，然后用去离子水清洗至pH为中性，最后置于烘箱中干燥12h。按照与上文同样的方法，再次处理锌镍合金电镀废水。图4为改性蓝藻生物炭复合材料回用图，经4次循环利用后，对镍的去除率仍能达到93.7％，说明该复合材料有较好的稳定性。
表1：实施例制备样品比表面积及孔容积
样品 比表面积(m 2/g) 总孔容积(cm 3/g) 平均孔径(nm)
未改性蓝藻生物炭 17.9 0.0235 4.281
改性蓝藻生物炭 1657.8 0.9559 2.306
改性蓝藻生物炭复合材料 1256.5 0.5662 2.137
对比例 569 0.399 2.81
表2：电镀废水各项指标
指标 pH COD(mg/L) Ni(mg/L) 电导率(ms/S)
实测值 11.78 524.16 2.818 1.32
对比例1
以南京智融联科技有限公司生产的玉米秸秆生物炭为原料，将原料在硝酸铁溶液中浸泡8h，硝酸铁溶液中铁与样品中生物炭的质量比为0.2:1，浸泡结束后，边搅拌边向溶液中逐滴滴加质量浓度为10％的氨水溶液直至pH＝9，继续搅拌2h，将混合溶液先烘干，再置于200℃马弗炉中焙烧2h；将焙烧后的样品水洗、过滤，将固形物部分置于60℃真空干燥箱中干燥24h，得到秸秆生物炭复合材料。
电镀废水的参数如表2所示，将电镀废水的pH值调节至6，然后加入秸秆生物炭复合材 料0.5g，待20min达到吸附平衡后，加入双氧水30mmol进行类芬顿氧化反应，反应结束后(约60min)，加氢氧化钠进行沉淀，收集上清液并利用0.45μm滤头过滤，用火焰原子吸收法测定滤液中的镍离子浓度。镍去除率的计算公式如下式(1)所示。处理结果如图5所示，在吸附阶段，根据公式(1)计算得到镍的去除率为23.99％，类芬顿反应后，根据公式(1)计算得出镍的去除率为47.92％。
对比例2
在实施例2的基础上，将步骤(4)中铁炭质量比分别调整为0.05:1、0.1:1和0.2:1，制备得到不同的改性蓝藻复合材料。将这些改性蓝藻复合材料采用实施例3中的工艺处理同样的锌镍合金电镀废水。处理效果如表3所示，吸附耦合类芬顿反应结束后，根据公式(1)计算得到镍的去除率分别为86.28％、90.61％和99.14％。可见，不同的铁负载对镍的去除率不同，适宜浓度的铁负载能够高效去除废水中的镍。
表3：不同铁炭比制备的复合材料对镍的去除率
铁炭比 镍去除率(％)
0.05:1 86.28
0.1:1 90.61
0.2:1 99.14

Claims (10)

  1. 一种制备改性蓝藻生物炭复合材料的方法，其特征在于，包括以下步骤：
    (1)将蓝藻烘干、研磨，并利用80～100目筛子进行筛选，收集通过筛孔的蓝藻并与活化剂混合，得到混合后的样品；
    (2)在惰性气氛下，对步骤(1)中得到的混合后的样品进行热裂解处理；
    (3)将步骤(2)中热裂解处理后的样品进行研磨，并用80～100目的筛子筛选，然后，分别用酸、水洗涤通过了筛孔的样品，直至洗涤产生的废水的pH呈中性，烘干样品；
    (4)将步骤(3)中烘干后的样品在含铁溶液中浸泡、调碱沉积之后烘干、焙烧；
    (5)将步骤(4)中焙烧后的样品用水洗，并过滤，收集过滤得到的固体并干燥该固体得到改性蓝藻生物炭复合材料。
  2. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(1)中烘干温度为80～120℃，烘干时间为12～24h。
  3. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(1)中所述活化剂为氢氧化钾、氯化锌、磷酸氢钾其中的一种，蓝藻与活化剂混合的质量比为(0.5-1):1。
  4. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(2)中所述惰性气体为氮气，惰性气体流速为60～100sccm。
  5. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(2)中所述热裂解分为两个阶段，其中，第一阶段热裂解温度为200～400℃，热裂解时间为60～90min；第二阶段热裂解温度为600～800℃，热裂解时间为60～120min。
  6. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(3)中所述酸为稀盐酸，稀盐酸的浓度为0.1～1mol/L；烘干温度为80～120℃，烘干时间为12～24h。
  7. 根据权利要求1所述的一种改性蓝藻生物炭复合材料的制备方法，其特征在于，步骤(4)中所述的含铁溶液为氯化铁溶液或硝酸铁溶液，溶液中的铁的质量与步骤(3)中烘干后的样品(炭)的质量比为(0.05-0.2)：1；调碱所用试剂为氨水溶液，氨水溶液的浓度为10～20wt％；焙烧装置为马弗炉，焙烧温度为200～400℃，焙烧时间为2-4h。
  8. 一种改性蓝藻生物炭复合材料，其特征在于，是负载了铁的蓝藻生物炭。
  9. 根据权利要求1～7任一所述方法制备得到改性蓝藻生物炭复合材料。
  10. 应用权利要求8或9所述改性蓝藻生物炭复合材料处理电镀废水的方法，其特征在于，向电镀废水中加入权利要求8或9所述改性蓝藻生物炭复合材料，待吸附平衡后，加入双氧水进行类芬顿氧化反应。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN116673001A (zh) * 2023-05-04 2023-09-01 江南大学 一种基于硅酸钠改性的蓝藻生物炭及其在修复土壤Cd污染和降低温室气体排放中的应用
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110272085B (zh) * 2019-07-30 2023-02-24 江南大学 一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用
CN110787771A (zh) * 2019-10-25 2020-02-14 天津大学 一种改性蓝藻生物炭及其制备方法及应用
CN111003711A (zh) * 2019-12-04 2020-04-14 武汉热解无限能源科技有限公司 一种绿色制备高含碳多孔生物炭材料的方法
CN111450810B (zh) * 2020-04-07 2022-05-27 武夷学院 一种改进材料孔隙结构的方法
CN111659398A (zh) * 2020-06-05 2020-09-15 南京师范大学 一种蓝藻基碳镍复合催化剂的制备方法
CN111704191A (zh) * 2020-06-28 2020-09-25 南通大学 具有高效吸附核黄素的蓝藻生物炭材料的制备方法与应用
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CN112121764A (zh) * 2020-09-22 2020-12-25 拉萨波玛拉生物科技有限公司 酸碱预处理强化的青稞秸秆基水热炭的制备方法
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CN115739014A (zh) * 2022-07-29 2023-03-07 镇江市和云工业废水处置有限公司 一种电镀废水处理剂及其制备方法和应用
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CN115770604B (zh) * 2022-11-15 2024-07-30 江南大学 一种利用太湖蓝藻制备的Fe-N@C催化剂及其制备方法和应用
CN115849614A (zh) * 2022-12-10 2023-03-28 漳州市东龙电子科技有限公司 一种电镀前废水处理工艺
CN116532083A (zh) * 2023-04-23 2023-08-04 江苏鸿祺生物科技有限公司 一种改性生物炭基co2高效选择性吸附材料及其制备方法
CN116272873A (zh) * 2023-04-24 2023-06-23 武汉大学 一种改性累托石/秸秆/污泥复合生物炭材料的制备及应用
CN117720180A (zh) * 2023-12-05 2024-03-19 江苏中林环工生态环境科技有限公司 负载型蓝藻生物炭制备方法及负载型蓝藻生物炭流动电极

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298327A (zh) * 2008-01-24 2008-11-05 云南大学 蓝藻水华活性炭及其制备方法
CN101891188A (zh) * 2010-03-22 2010-11-24 中国科学院等离子体物理研究所 一种利用蓝藻藻渣制备纳米活性碳球的方法
WO2013126477A1 (en) * 2012-02-22 2013-08-29 University Of Florida Research Foundation, Inc. Biochar/metal composites, methods of making biochar/metal composites, and methods of removing contaminants from water
CN104138743A (zh) * 2014-07-23 2014-11-12 河海大学 一种藻基磁性活性炭材料的制备方法及应用
WO2014194363A1 (en) * 2013-06-05 2014-12-11 James Cook University Algal biomass biosorbent and methods for use
CN109894115A (zh) * 2017-12-11 2019-06-18 中国科学院大连化学物理研究所 一种用于类芬顿处理的改性活性炭催化剂的制备方法
CN109957408A (zh) * 2017-12-25 2019-07-02 苏州市农业科学院 一种利用蓝藻制成生物炭的方法
CN110272085A (zh) * 2019-07-30 2019-09-24 江南大学 一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0028814D0 (en) * 2000-11-25 2001-01-10 Univ Belfast Improvements relating to biosorbtion
WO2011111052A1 (en) * 2010-03-12 2011-09-15 Ben-Gurion University Of The Negev Research And Development Authority Process for the preparation of heterogeneous fenton catalytic filter
CN102019169B (zh) * 2010-12-06 2012-07-04 浙江商达环保有限公司 一种有机硅废水处理中活性炭的再生方法
CN102335628B (zh) * 2011-07-21 2013-04-10 南京大学 一种负载型纳米双金属复合催化剂及其制备方法
CN102744055A (zh) * 2012-07-20 2012-10-24 武汉大学 活性炭负载氧化锌催化剂及其在降解有机污染物中应用
KR101473923B1 (ko) * 2014-06-25 2014-12-17 경희대학교 산학협력단 β-이산화망간 나노입자와 탄소나노튜브의 융합 수처리제와 그의 제조방법, 그를 이용한 수처리 장치 및 지하수 현장처리 장치
CN105709755B (zh) * 2016-03-22 2019-02-05 浙江清华长三角研究院 一种生物炭催化剂、铁碳催化剂及其应用
CN106007056B (zh) * 2016-06-02 2019-06-04 哈尔滨工业大学 一种同步去除电镀废水中微量重金属的装置及方法
JP6010718B1 (ja) * 2016-07-01 2016-10-19 株式会社ダイセル 鉄化合物担持酸化チタン光触媒
CN106495377B (zh) * 2016-11-16 2019-05-10 安徽工程大学 一种络合镍废水的处理方法
KR101862989B1 (ko) * 2017-04-28 2018-05-30 울산대학교 산학협력단 이산화티타늄이 분산된 활성 탄소 섬유를 포함하는 광촉매 및 이를 이용한 수처리 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101298327A (zh) * 2008-01-24 2008-11-05 云南大学 蓝藻水华活性炭及其制备方法
CN101891188A (zh) * 2010-03-22 2010-11-24 中国科学院等离子体物理研究所 一种利用蓝藻藻渣制备纳米活性碳球的方法
WO2013126477A1 (en) * 2012-02-22 2013-08-29 University Of Florida Research Foundation, Inc. Biochar/metal composites, methods of making biochar/metal composites, and methods of removing contaminants from water
WO2014194363A1 (en) * 2013-06-05 2014-12-11 James Cook University Algal biomass biosorbent and methods for use
CN104138743A (zh) * 2014-07-23 2014-11-12 河海大学 一种藻基磁性活性炭材料的制备方法及应用
CN109894115A (zh) * 2017-12-11 2019-06-18 中国科学院大连化学物理研究所 一种用于类芬顿处理的改性活性炭催化剂的制备方法
CN109957408A (zh) * 2017-12-25 2019-07-02 苏州市农业科学院 一种利用蓝藻制成生物炭的方法
CN110272085A (zh) * 2019-07-30 2019-09-24 江南大学 一种改性蓝藻生物炭复合材料及在处理电镀废水中的应用

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114105290A (zh) * 2021-11-24 2022-03-01 江苏泰源环保科技股份有限公司 一种改性蓝藻生物炭负载纳米零价铁材料的制备方法及其应用
CN114105290B (zh) * 2021-11-24 2023-11-17 江苏泰源环保科技股份有限公司 一种改性蓝藻生物炭负载纳米零价铁材料的制备方法及其应用
CN114405473A (zh) * 2022-02-17 2022-04-29 广东石油化工学院 一种氢氧化钙改性稻草秸秆生物炭的制备方法及其应用
CN115722251A (zh) * 2022-12-14 2023-03-03 昆明理工大学 异原子掺杂藻基生物炭负载纳米零价金属催化剂的制备方法及应用
CN115722251B (zh) * 2022-12-14 2024-01-30 昆明理工大学 异原子掺杂藻基生物炭负载纳米零价金属催化剂的制备方法及应用
CN116673001A (zh) * 2023-05-04 2023-09-01 江南大学 一种基于硅酸钠改性的蓝藻生物炭及其在修复土壤Cd污染和降低温室气体排放中的应用
CN118724335A (zh) * 2024-06-25 2024-10-01 湖南汽车工程职业学院 一种从锂电池工业废水中富集、回收镍的处理工艺

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