WO2024007797A1 - 一种用于吸附镉的富硒改性生物炭的制备方法 - Google Patents

一种用于吸附镉的富硒改性生物炭的制备方法 Download PDF

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WO2024007797A1
WO2024007797A1 PCT/CN2023/098524 CN2023098524W WO2024007797A1 WO 2024007797 A1 WO2024007797 A1 WO 2024007797A1 CN 2023098524 W CN2023098524 W CN 2023098524W WO 2024007797 A1 WO2024007797 A1 WO 2024007797A1
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selenium
biochar
rich
hydrochloric acid
modified biochar
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单德鑫
高宗玉
李俊
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Chongqing University of Arts and Sciences
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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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • B01J2220/48—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
    • C02F2101/10—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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to the technical field of heavy metal wastewater treatment, and in particular to a preparation method of selenium-rich modified biochar for adsorbing cadmium.
  • Biochar has the characteristics of high carbon content, good stability, rich surface functional groups, and developed pores, with high specific surface area and cation exchange capacity. Biochar can be used as an adsorbent to absorb heavy metals and organic pollution in water and soil. things. Due to different preparation raw materials, pyrolysis technology and pyrolysis conditions, biochar has different physical and chemical properties such as pore structure, density, specific surface area, pH, cation exchange capacity, and oxygen-containing functional groups. These differences in physical and chemical properties have a negative impact on heavy metals. The ion adsorption properties are also different.
  • the object of the present invention is to provide a method for preparing selenium-rich modified biochar for adsorbing cadmium.
  • the prepared selenium-rich modified biochar can effectively fix heavy metal cadmium through multiple effects and significantly improve the removal efficiency of Cd 2+ in wastewater.
  • a method for preparing selenium-rich modified biochar for adsorbing cadmium which is characterized in that: the selenium-rich rice husk is immersed in a hydrochloric acid solution of CaCl 2 for 20-24 hours, and then carbonized after drying.
  • the carbonization temperature is 300-300 700°C
  • carbonization time is 0.5-1.5h.
  • the above-mentioned carbonization temperature is 600-700°C, and the carbonization time is 1 hour.
  • drying temperature is 100-105°C
  • drying time is 10-12 hours.
  • selenium-rich rice husk is pretreated by spraying rice husk or straw with a selenium-rich chelated water and fertilizer solution; the main component of selenium in the selenium-rich chelated water and fertilizer solution is sodium selenite, with a concentration of 20-30g/L .
  • the above-mentioned impregnation is to heat the selenium-rich rice husk in a CaCl2 hydrochloric acid solution to 80-100°C for 1-2 hours, and then soak it at room temperature for 22-16 hours.
  • the hydrochloric acid has a certain reducing property, and it reacts with sodium selenite to a certain extent, so that the content of selenium in the biochar can be significantly increased during the pyrolysis process. Effectiveness, in the subsequent adsorption process of Cd 2+ , it has a certain complexing effect and has a good promotion effect on the adsorption of Cd 2+ .
  • the generated CaCO 3 effectively deposits Cd 2+ on the surface of biochar through physical precipitation.
  • hydrochloric acid more acidic functional groups are generated after pyrolysis, which directly complexes with Cd 2+ , and the acidic functional group reacts with CaCO 3 to form calcium salt, which generates ion exchange with Cd 2+ , and the removal efficiency of Cd 2+ is synergistically improved through multiple adsorption removal methods.
  • a method for preparing selenium-rich modified biochar for adsorbing cadmium is characterized by following the following steps:
  • Pretreatment Agricultural and forestry straw or rice husk is used as raw material. Crush the straw to 3-5cm. After washing, air-dry and crush it through a 20-60 mesh sieve. Spray selenium-rich chelated water fertilizer on its surface, and then place it in a CaCl 2 In hydrochloric acid solution, keep it at 80-100°C for 1-2h, then let it stand at room temperature for 12-16h, and finally dry it at 100-105°C for 10-12h;
  • the selenium-rich biochar prepared by the present invention has a specific surface area of 31.79m 2 /g.
  • the selenium element in the biochar plays a special role in promoting the adsorption of Cd 2+ and cooperates with other multiple mechanisms to improve the treatment of heavy metal Cd 2 in wastewater. + adsorption performance, the adsorption capacity of Cd 2+ with a concentration of 100mg/L is 51.7mg/g.
  • Figure 1 Scanning electron microscope image of rice straw selenium-rich biochar prepared in Example 1 of the present invention after adsorption of Cd 2+ .
  • Figure 2 Infrared spectrum of rice straw selenium-rich biochar prepared in Example 1 of the present invention.
  • Figure 3 Comparison of adsorption capacity of rice straw selenium-rich biochar prepared in Example 1 of the present invention.
  • Figure 4 The adsorption capacity of rice straw selenium-rich biochar prepared in Example 1 of the present invention for different concentrations of Cd 2+ .
  • Figure 5 Cd 2+ adsorption capacity of rice husk selenium-rich biochar prepared with different activators.
  • a method for preparing selenium-rich modified biochar for adsorbing cadmium as follows:
  • Pretreatment Agricultural and forestry straw or rice husk is used as raw material. Crush the straw to 3-5cm. After washing, air-dry and crush it through a 40-mesh sieve. Spray selenium-rich chelated water fertilizer on its surface, and then place it in a CaCl 2 hydrochloric acid solution. medium, keep it at 90°C for 1.5h, then let it stand at room temperature for 14h, and finally dry it at 105°C for 12h;
  • the main component containing selenium in the above-mentioned selenium-rich chelated water fertilizer is sodium selenite, with a concentration of 20g/L.
  • Example 1 What is different from Example 1 is that the straw sprayed with selenium-rich chelated water fertilizer in this program uses CaCl 2 water-soluble fertilizer. The solution was left to soak at room temperature for 20 h, and the remaining steps were consistent with Example 1.
  • Example 1 What is different from Example 1 is that the straw raw material in the present invention is not sprayed with selenium-rich chelated water fertilizer, and is directly placed in a hydrochloric acid solution of CaCl 2 after washing. The remaining steps are consistent with Example 1.
  • the modified biochar prepared by this method is not sprayed with selenium-rich chelated water and fertilizer, there is no more metal ions to react with hydrochloric acid, which causes hydrochloric acid to seriously etch the straw at high temperatures, resulting in the collapse of some pores in the straw and the specific surface area. In Example 1, it dropped seriously, to only 17.64m 2 /L.
  • the equilibrium adsorption capacities of the selenium-rich modified biochar prepared in Example 1 were measured to be 48.1 mg/g and 51.7 mg/g. , 55.4mg/g, 47.8mg/g and 59.2mg/g.
  • Comparative Example 1 is rich in selenium, but it is not modified with CaCl 2 hydrochloric acid solution. After high temperature treatment, the selenium in the straw failed to promote the adsorption and removal of Cd 2+ , and its acidic functional groups were not increased. The complexation of functional groups reduces the Cd 2+ removal efficiency, and the ion exchange between the acidic functional groups and CaCO 3 to form calcium salts and Cd 2+ will also decrease. This makes the overall removal efficiency of Cd 2+ poor.
  • a method for preparing selenium-rich modified biochar for adsorbing cadmium which is characterized by following the following steps:
  • Pretreatment Use rice straw as raw material, crush the rice straw to 3-5cm, wash, air-dry and grind through a 20-mesh sieve, spray selenium-rich chelated water fertilizer on its surface, and then place it in a CaCl 2 hydrochloric acid solution , keep it at 100°C for 1h, then let it stand at room temperature for 12h, and finally dry it at 105°C for 10h;
  • the main component containing selenium in the above-mentioned selenium-rich chelated water fertilizer is sodium selenite, with a concentration of 30g/L.
  • the rice straw selenium-rich modified biochar prepared in this example has a Cd 2+ adsorption capacity of 48.9 mg/g in wastewater with a Cd 2+ concentration of 100 mg/L.
  • a method for preparing selenium-rich modified biochar for adsorbing cadmium as follows:
  • Pretreatment Use rice husk as raw material, wash it, air-dry and grind it through a 60-mesh sieve, spray selenium-rich chelated water fertilizer on its surface, then place it in a CaCl2 hydrochloric acid solution, keep it at 80°C for 2 hours, and then Leave at room temperature for 16 hours, and finally dry at 100°C for 12 hours;
  • the main component containing selenium in the above-mentioned selenium-rich chelated water fertilizer is sodium selenite, with a concentration of 25g/L.
  • the selenium-rich modified biochar prepared in this example has a Cd 2+ adsorption capacity of 32.6 mg/g in wastewater with a Cd 2+ concentration of 100 mg/L.
  • the prepared selenium-rich rice husk modified biochar has a small improvement in the adsorption capacity of Cd 2+ , while in the absence of selenium-rich rice husk modified biochar In the rice husk solution, after adding hydrochloric acid and CaCl 2 for collaborative treatment, the adsorption performance decreased slightly.

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

一种用于吸附镉的富硒改性生物炭的制备方法，将富硒的稻壳在CaCl2的盐酸溶液中浸渍20-24h，烘干后进行碳化，碳化温度为300-700℃，碳化时间为0.5-1.5h。本发明制备富硒生物炭具有31.79m2/g的比表面积，通过改性后，生物炭中的硒元素发挥促进吸附Cd2+的特殊作用，协同其他多重机制提高对废水中的重金属Cd2+的吸附性能，对浓度为100mg/L的Cd2+吸附量为51.7mg/g。

Description

一种用于吸附镉的富硒改性生物炭的制备方法 技术领域
本发明涉及重金属废水处理技术领域，具体涉及一种用于吸附镉的富硒改性生物炭的制备方法。
背景技术
当前镉污染废水的处理方法有以下几种：沉淀法、离子交换法、膜分离法和吸附法。生物炭由于其具有含碳量高、稳定性好、表面官能团丰富等特性，且孔隙发达，具有较高的比表面积和阳离子交换量，可充当吸附剂用来吸附水体和土壤中重金属和有机污染物。生物炭由于制备原料、热解技术及热解条件不同，决定其具备的孔隙结构、密度、比表面积、pH、阳离子交换量、含氧官能团等理化性质均不同，而这些理化性质的不同对于重金属离子吸附性能也不同。
发明内容
本发明目的在于提供一种用于吸附镉的富硒改性生物炭的制备方法。制备的富硒改性生物炭可通过多重作用，有效固定重金属镉，显著提高废水中Cd2+的去除效率。
本发明目的通过如下技术方案实现：
一种用于吸附镉的富硒改性生物炭的制备方法，其特征在于：将富硒的稻壳在CaCl2的盐酸溶液中浸渍20-24h，烘干后进行碳化，碳化温度为300-700℃，碳化时间为0.5-1.5h。
优选的，上述碳化的温度为600-700℃，碳化时间为1h。
进一步，上述烘干的温度是100-105℃，烘干时间为10-12h。
进一步，上述CaCl2的盐酸溶液是将CaCl2加入盐酸溶液中，调节溶液pH为2-4，CaCl2浓度为0.5-1.5mol/L。
进一步，上述富硒稻壳是将稻壳或秸秆喷施富硒螯合水肥溶液进行预处理；富硒螯合水肥溶液中含硒主要组分是亚硒酸钠，浓度为20-30g/L。
进一步，上述浸渍是将富硒稻壳在CaCl2的盐酸溶液中加热至80-100℃保温1-2h，然后常温浸泡22-16h。
现有技术中，硒对镉的络合排毒作用主要作用于生物体内，通过亚硒酸盐在生物体内进过一系列反应后，与体内蛋白质的巯基结合，进而络合Cd2+形成硒镉复合物，从而达到吸附镉的作用。但是在生物体外直接对于Cd2+的络合未见报道。且通常农林秸秆等原料富硒通常是通过喷洒亚硒酸盐来富硒，在高温热解时，会发生分解或流失，最后制备的生物炭中硒含量较少，且保留的硒大多无效，对Cd2+的吸附并不明显。
在制备过程中发现，采用CaCl2的盐酸溶液浸泡处理后，盐酸具有一定的还原性，其与亚硒酸钠发生一定的反应，使得热解过程中能显著提高硒在生物炭中的含量以及有效性，在后续Cd2+的吸附过程中，具有一定的络合作用，对于Cd2+的吸附存在较好的促进作用。
此外，通过氯化钙改性，生成的CaCO3通过物理沉淀的方式有效沉积Cd2+于生物炭表面，通过盐酸作用，在热解后生成更多酸性官能团，直接与Cd2+形成络合，且酸性官能团与CaCO3反应生成钙盐，与Cd2+产生离子交换，通过多重吸附去除手段协同提高了Cd2+的去除效率。
最具体的，一种用于吸附镉的富硒改性生物炭的制备方法，其特征在于，按如下步骤进行：
(1)预处理：农林秸秆或稻壳作为原料，将秸秆粉碎至3-5cm，洗涤后风干粉碎过20-60目筛，在其表面喷施富硒螯合水肥，然后置于CaCl2的盐酸溶液中，在80-100℃下保温1-2h，然后常温静置12-16h，最后在100-105℃下烘干10-12h；
(2)碳化：将预处理后的原料在缺氧环境中，于300-700℃下碳化0.5-1.5h，得生物炭；
(3)清洗：将炭化结束后的生物炭清洗至中性，然后在105℃下烘干后磨碎过100目筛，得富硒改性生物炭。
本发明技术效果如下：
本发明制备富硒生物炭具有31.79m2/g的比表面积，通过改性后，生物炭中的硒元素发挥促进吸附Cd2+的特殊作用，协同其他多重机制提高对废水中的重金属Cd2+的吸附性能，对浓度为100mg/L的Cd2+吸附量为51.7mg/g。
附图说明
图1：本发明实施例1制备的稻秆富硒生物炭吸附Cd2+后的扫描电镜图。
图2：本发明实施例1制备的稻秆富硒生物炭的红外光谱图。
图3：本发明实施例1制备的稻秆富硒生物炭的吸附量对比图。
图4：本发明实施例1制备的稻秆富硒生物炭对于不同浓度Cd2+的吸附量。
图5：采用不同活化剂制备的稻壳富硒生物炭对Cd2+的吸附量。
具体实施方式
实施例1
一种用于吸附镉的富硒改性生物炭的制备方法，按如下步骤进行：
(1)预处理：农林秸秆或稻壳作为原料，将秸秆粉碎至3-5cm，洗涤后风干粉碎过40目筛，在其表面喷施富硒螯合水肥，然后置于CaCl2的盐酸溶液中，在90℃下保温1.5h，然后常温静置14h，最后105℃下烘干12h；
(2)碳化：将预处理后的原料在缺氧环境中，于700℃下碳化0.5h，得生物炭；
(3)清洗：将炭化结束后的生物炭清洗至中性，然后在105℃下烘干后磨碎过100目筛，得富硒改性生物炭。
上述富硒螯合水肥中含硒主要组分是亚硒酸钠，浓度为20g/L。
本实施例制备的富硒改性生物炭的扫描电镜图如图1(b)所示，表面粗糙，孔径丰富，其比表面积为31.79m2/g。
对比例1：
与实施例1不同的是，本方案中喷施了富硒螯合水肥的秸秆采用CaCl2水溶 液常温静置浸泡处理20h，其余步骤与实施例1保持一致。
本方案制备的改性生物炭的扫描电镜图如图1(a)所示，明显看出其制备的改性生物炭表面的孔径结构没有本发明制备的富硒改性生物炭孔径丰富，其比表面积为20.23m2/g。
对比例2：
与实施例1不同的是，本发明中秸秆原料不进行喷施富硒螯合水肥，洗涤后直接置于CaCl2的盐酸溶液中，其余步骤与实施例1保持一致。
本方案制备的改性生物炭由于没有喷洒富硒螯合水肥，没有较多的金属离子与盐酸反应，使得盐酸在高温时对秸秆产生严重刻蚀，导致秸秆中部分孔径坍塌，比表面积较实施例1反而下降严重，仅仅为17.64m2/L。
将浓度为100mg/L的Cd2+废水pH调节为5，按照每100mL废水中加入0.2g生物炭，分别加入实施例1、对比例1和对比例2制备的生物炭，在150rpm下振荡2h，然后过0.45μm的水系滤膜，用火焰原子吸收分光光度法测定废水中Cd2+浓度，根据吸附前后Cd2+浓度变化计算出平衡吸附量，如图3所示，实施例1、对比例1和对比例2制备的生物炭对于Cd2+的吸附量为51.7mg/g、41.4mg/g和40.1mg/g。通过调节废水中Cd2+的浓度为80、100、120、180、200mg/L，测得实施例1制备的富硒改性生物炭对应的平衡吸附量为48.1mg/g、51.7mg/g、55.4mg/g、47.8mg/g和59.2mg/g。
通过Boehm滴定法测定生物炭表面官能团，测试结果如表1所示。
表1：
由于制备的生物炭中羧基羟基等官能团的增加，使得这些官能团与Cd2+形成络合，从而提高对Cd2+的去除效率：
-COOH+Cd2++H2O→COOCd2++H3O+
-OH+Cd2++H2O→-OCd2++H3O+
对比例1中富硒，但是没有采用CaCl2的盐酸溶液进行改性处理，经过高温处理后，秸秆中硒没能发挥出促进对Cd2+的吸附去除作用，且其酸性官能团没有得到增加，官能团的络合去除Cd2+效率降低，且酸性官能团与CaCO3生成钙盐与Cd2+的离子交换作用也会降低。使其对于Cd2+的整体去除效率较差。而对比例2中由于没有喷洒富硒螯合水肥，没有较多的金属离子与盐酸反应，使得盐酸在高温时对秸秆产生严重刻蚀，导致秸秆中部分孔径坍塌，比表面积反而下降，各官能团失去位点导致增加受到一定的抑制。
实施例2
一种用于吸附镉的富硒改性生物炭的制备方法，其特征在于，按如下步骤进行：
(1)预处理：以水稻秸秆作为原料，将水稻秸秆粉碎至3-5cm，洗涤后风干粉碎过20目筛，在其表面喷施富硒螯合水肥，然后置于CaCl2的盐酸溶液中，在100℃下保温1h，然后常温静置12h，最后在105℃下烘干10h；
(2)碳化：将预处理后的原料在缺氧环境中，于600℃下碳化0.5h，得生物炭；
(3)清洗：将炭化结束后的生物炭清洗至中性，然后在105℃下烘干后磨碎过100目筛，得富硒改性生物炭。
上述富硒螯合水肥中含硒主要组分是亚硒酸钠，浓度为30g/L。
本实施例制备的稻秆富硒改性生物炭在Cd2+浓度为100mg/L的废水中，对Cd2+吸附量为48.9mg/g。
实施例3
一种用于吸附镉的富硒改性生物炭的制备方法，按如下步骤进行：
(1)预处理：以稻壳作为原料，洗涤后风干粉碎过60目筛，在其表面喷施富硒螯合水肥，然后置于CaCl2的盐酸溶液中，在80℃下保温2h，然后常温静置16h，最后在100℃下烘干12h；
(2)碳化：将预处理后的原料在缺氧环境中，于300℃下碳化1.5h，得生物炭；
(3)清洗：将炭化结束后的生物炭清洗至中性，然后在105℃下烘干后磨碎过100目筛，得富硒改性生物炭。
上述富硒螯合水肥中含硒主要组分是亚硒酸钠，浓度为25g/L。
本实施例制备的富硒改性生物炭在Cd2+浓度为100mg/L的废水中，对Cd2+吸附量为32.6mg/g。
在制备过程中，我们尝试采用KOH、NaOH、ZnCl2、BaCl2等常见的活化剂代替CaCl2的盐酸溶液对富硒稻壳进行处理，制备的稻壳生物炭对于Cd2+浓度为100mg/L的废水中Cd2+的吸附性能如图5所示，各种活化剂处理后的富硒秸秆制备的生物炭对于Cd2+的吸附性能波动不大，但较未加活化剂的富硒秸秆有显著提高；其中在BaCl2中加入盐酸后，按照本发明方法进行热处理，制备出的富硒稻壳改性生物炭对于Cd2+的吸附能力有少量的提高，而在没有富硒的稻壳方案中，加入盐酸与CaCl2协同处理后，吸附性能有细微下降。

Claims (2)

  1. 一种用于吸附镉的富硒改性生物炭的制备方法，其特征在于，按如下步骤进行：
    (1)预处理：以农林秸秆作为原料，将秸秆粉碎至3-5cm，洗涤后风干粉碎过20-60目筛，在其表面喷施富硒螯合水肥，然后置于CaCl2的盐酸溶液中，在80-100℃下保温1-2h，然后常温静置12-16h，最后在100-105℃下烘干10-12h；
    (2)碳化：将预处理后的原料在缺氧环境中，于600-700℃下碳化0.5h，得生物炭；
    (3)清洗：将碳化结束后的生物炭清洗至中性，然后在105℃下烘干后磨碎过100目筛，得富硒改性生物炭。
  2. 如权利要求1所述的一种用于吸附镉的富硒改性生物炭的制备方法，其特征在于：所述CaCl2的盐酸溶液是将CaCl2加入盐酸溶液中，调节溶液pH为2-4，CaCl2浓度为0.5-1.5mol/L。
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