胶原基衍生炭在水处理领域的研究进展

doi:10.16085/j.issn.1000-6613.2022-0271

摘要/Abstract

摘要：

胶原基衍生炭具有原料来源广泛、成本低廉、孔结构可调、导电性能优异、缺陷密度高和多原子掺杂等优点，在水处理领域展现出巨大的发展潜力。本文回顾了胶原基衍生炭在国内外的研究现状；对目前常用的前体材料，包括虾壳、鱼鳞、蟹壳、牡蛎壳、动物骨骼和动物皮等进行归纳总结；并就不同的活化与改性工艺，包括碳酸钙或羟基磷灰石自活化法、羟基磷灰石（或碳酸钙）和KOH协同活化法、钾化合物辅助法等，对调控孔隙结构和表面官能团等方面的影响进行了分析比较；重点探讨了其在吸附与催化氧化等水处理领域中的应用。最后，针对水处理过程中存在的问题，提出了相应的对策措施并展望了发展趋势，以期为胶原基衍生炭在实际废水处理中的应用提供理论依据。

关键词: 胶原, 生物炭, 吸附, 催化

Abstract:

Collagen-derived carbon has many advantages, such as wide source of raw materials, low cost, adjustable porous structure, excellent conductivity, high defect density and rich heteroatom doping. The research status of collagen-derived carbon at home and abroad is reviewed in this paper. The commonly used precursor materials, such as shrimp shell, fish scale, crab shell, oyster shell, animal skeleton and animal skin, are summarized. And then, the effects of different activation and modification methods, including calcium carbonate/hydroxylapatite self-activation, synergy activation of hydroxylapatite/calcium carbonate and KOH, potassium compound-assistant synthesis, on pore structure and chemical functional groups of collagen-derived carbon are analysed and compared. Additionally, the application of collagen-derived carbon in water treatment, involving adsorption and catalysis, is emphatically analysed. Finally, in view of the problems in the water treatment process, the corresponding countermeasures and the development trend are prospected, which could provide the theoretical basis for the application of collagen-derived carbon in practical wastewater treatment.

Key words: collagen, biochar, adsorption, catalysis

中图分类号:

陈一萍, 黄耀裔, 郑朝洪. 胶原基衍生炭在水处理领域的研究进展[J]. 化工进展, 2022, 41(12): 6606-6614.

CHEN Yiping, HUANG Yaoyi, ZHENG Chaohong. Research progress of collagen-derived carbon in water treatment[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6606-6614.

图/表 9

参考文献 44

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活化方法	优点	缺点	参考文献
自活化法
碳酸钙自活化	无须额外的模板或活化剂，活化成本低廉，无腐蚀性，操作简便	只能保留前体本身所固有的结构形态，对孔隙结构等的调控存在一定的局限性	[3]
羟基磷灰石自活化	无须额外的模板或活化剂，活化成本低廉，无腐蚀性，操作简便	只能保留前体本身所固有的结构形态，对孔隙结构等的调控存在一定的局限性	[15]
羟基磷灰石（或碳酸钙）和KOH协同活化法	短时间内可刻蚀出大量的孔，碳表面含氧官能团更多	KOH的用量较大，具有腐蚀性，对设备的要求较为苛刻，且高温热解过程中易造成杂原子的损失，后续加工时也易造成二次污染	[17,19]
钾化合物辅助法	低温热解即可实现孔隙结构的调控，造孔效果好，减少化学试剂和能源的使用量，减少设备腐蚀	操作复杂，所需的设备比较多	[20-21]

活化方法	优点	缺点	参考文献
自活化法
碳酸钙自活化	无须额外的模板或活化剂，活化成本低廉，无腐蚀性，操作简便	只能保留前体本身所固有的结构形态，对孔隙结构等的调控存在一定的局限性	[3]
羟基磷灰石自活化	无须额外的模板或活化剂，活化成本低廉，无腐蚀性，操作简便	只能保留前体本身所固有的结构形态，对孔隙结构等的调控存在一定的局限性	[15]
羟基磷灰石（或碳酸钙）和KOH协同活化法	短时间内可刻蚀出大量的孔，碳表面含氧官能团更多	KOH的用量较大，具有腐蚀性，对设备的要求较为苛刻，且高温热解过程中易造成杂原子的损失，后续加工时也易造成二次污染	[17,19]
钾化合物辅助法	低温热解即可实现孔隙结构的调控，造孔效果好，减少化学试剂和能源的使用量，减少设备腐蚀	操作复杂，所需的设备比较多	[20-21]

胶原基生物炭	制备工艺	生物炭特性	吸附效果	参考文献
硅锰双金属氧化物改性虾壳衍生炭	预处理：室温，NaOH，24h；化学涂层：0.2mol/L Na₂SiO₃和0.05mol/L MnSO₄，12h；热解条件：800℃，5℃/min，2h，N₂氛围	S_BET=13.81m²/g；V_total=0.0655cm³/g；平均孔径为18.98nm	对Cu²⁺的最大吸附容量为141.76mg/g	[16]
虾壳衍生水热炭	预处理：2.5mol/L NaOH，90℃，4h和50%NaOH，130℃，4h；水热反应条件：180℃，12h；后处理：1.5mol/L HCl，室温，1.5h	S_BET=12.65m²/g；	对甲基橙的最大吸附容量为755.08mg/g	[23]
小龙虾壳生物炭	热解条件：700℃，15℃/min，N₂氛围，2h	S_BET=21.75m²/g；V_total=0.13cm³/g；平均孔径为23.06nm	对Pb²⁺的最大吸附容量为1166.44mg/g	[24]
鳌虾壳衍生炭	热解条件：600℃，N₂氛围，2h	S_BET=63.79m²/g；	对Pb²⁺的最大吸附容量为190.7mg/g	[25]
ZnCl₂改性小龙虾壳生物炭	热解条件：600℃，N₂氛围，2h；后处理：2mol/LZnCl₂溶液，24h	S_BET=236.93m²/g；V_total=0.23cm³/g；平均孔径为39.17nm	对三氯乙酸的最大吸附容量为17.8mg/g	[26]
小龙虾壳生物炭	热解条件：800℃，N₂氛围，2h		对磷的最大吸附容量为70.9mg/g	[27]
氮掺杂石墨烯修饰磁性虾壳生物炭	热解条件：以Fe²⁺和Fe³⁺为磁性前驱物，800℃，10℃/min，N₂氛围；后处理：结合氮掺杂石墨烯水凝胶，80℃，2h	S_BET=398.05m²/g；V_total=6.6cm³/g；	对Cr⁶⁺的最大吸附容量为350.42mg/g	[28]
氮掺杂多级孔虾壳衍生炭	热解条件：400℃，5℃/min，2h，N₂氛围；活化条件：KOH，850℃，5℃/min，1h，N₂氛围	S_BET=3171m²/g；V_total=1.934cm³/g；平均孔径为2.44nm	对磺胺二甲基嘧啶和氯霉素的最大吸附容量分别为699.3mg/g和742.4mg/g	[29]
KOH活化虾壳衍生炭材料	热解条件：800℃，10℃/min，3h，N₂氛围；活化条件：KOH，800℃，1h，N₂氛围	S_BET=3160m²/g；V_total=2.382cm³/g；平均孔径为1.35nm	Cu²⁺、Cr⁶⁺和Cd²⁺共存时，金属离子总吸附量为560mg/g	[30]
虾壳与玉米秸秆共混衍生炭	热解条件：800℃，5℃/min，2h，N₂氛围	S_BET=57.87m²/g；V_total=0.068cm³/g；平均孔径为6.89nm	对Cu²⁺的最大吸附量为79.77mg/g	[14]
厚壳贻贝衍生炭	热解条件：800℃，4h，N₂氛围	S_BET=4.363m²/g；V_total=0.09cm³/g；孔径为412.95nm	对氟化物的最大吸附容量为82.93mg/g	[31]
蟹壳衍生炭	热解条件：800℃，10℃/min，2h，N₂氛围		对金霉素的最大吸附容量为1432.3mg/g	[32]
蟹壳衍生炭	热解条件：900℃，10℃/min，2h，N₂氛围	S_BET=81.57m²/g；V_total=0.0861mL/g；平均孔径为4.22nm	对孔雀石绿和刚果红的最大吸附容量分别为12502mg/g和20317mg/g	[33]
蟹壳衍生炭	热解条件：800℃，10℃/min，2h，N₂氛围	S_BET=81.57m²/g；V_total=0.0861mL/g	对磷的吸附量达到80mg/g	[34]
蟹壳活性炭	脱盐条件：1mol/L HCl，6h；热解条件：500℃，10℃/min，1.5h，N₂氛围；活化条件：KOH，800℃，1h	S_BET=2197m²/g；V_total=1.192cm³/g；平均孔径为2.17nm	对酸性大红的最大吸附容量为1667mg/g	[35]
磁性蟹壳衍生炭	热解条件：500℃，8℃/min，1h，N₂氛围；后处理：在碱性介质中化学共沉淀法，［Fe³⁺］∶［Fe²⁺］摩尔比为2∶1	S_BET=74.53m²/g；V_total=0.298cm³/g；平均孔径为3.94nm	对As³⁺和Pb²⁺的最大吸附容量分别为15.8mg/g和62.4mg/g	[36]
蟹壳衍生炭	热解条件：700℃，10℃/min，2h，N₂氛围；活化条件：KOH，800℃，1h	S_BET=2441m²/g；V_total=1.682cm³/g；孔径为1.937nm	对柴油的最大吸附容量为57.74mg/g	[37]
牡蛎壳生物炭	热解条件：900℃，2h	S_BET=4.85m²/g；平均孔径为11.06nm	对Cd²⁺和Pb²⁺的最大吸附容量分别为153.8mg/g和923.3mg/g	[7]
棉花/聚酯废料与牡蛎壳复合碳材料	热解条件：900℃，1~2h；后处理：10% HCl，12h	S_BET=645.05m²/g；V_total=0.38cm³/g；平均孔径为0.64nm	对四环素的最大吸附容量为496.66mg/g	[38]
鱼骨炭	热解条件：900℃，10℃/min，2h，N₂氛围；后处理：用0.1mol/L HCl和0.1mol/L NaOH先后润洗	S_BET=124m²/g；V_total=0.214cm³/g；平均孔径为7.4nm	对四环素的最大吸附容量为141.70mg/g	[39]
牛骨衍生炭	热解条件：450℃，2h，N₂氛围；改性方法：4% Fe₂(SO₄)₃浸泡0.5h；8% Al₂(SO₄)₃浸泡1h	S_BET=91.3m²/g；V_total=0.3cm³/g；平均孔径为26.2nm	对水中氟的最大吸附容量为45.455mg/g	[40]
牛骨衍生炭	预处理：300r/min研磨12h，离心；热解条件：600℃，2h，N₂氛围	S_BET=313.09m²/g；V_total=0.4538cm³/g；平均孔径为6.46nm	对Cd²⁺、Cu²⁺和Pb²⁺的吸附容量分别为165.77mg/g、287.58mg/g和558.88mg/g	[41]
鱼鳞衍生炭	预氧化条件：350℃，2h，O₂氛围；热解与活化条件：与KOH混合，850℃，2.5h，10℃/min，N₂氛围	S_BET=3370m²/g；V_total=1.91cm³/g；平均孔径为1.49nm	对水中环丙沙星的最大吸附容量为1013.96mg/g	[5]

胶原基生物炭	制备工艺	生物炭特性	吸附效果	参考文献
硅锰双金属氧化物改性虾壳衍生炭	预处理：室温，NaOH，24h；化学涂层：0.2mol/L Na₂SiO₃和0.05mol/L MnSO₄，12h；热解条件：800℃，5℃/min，2h，N₂氛围	S_BET=13.81m²/g；V_total=0.0655cm³/g；平均孔径为18.98nm	对Cu²⁺的最大吸附容量为141.76mg/g	[16]
虾壳衍生水热炭	预处理：2.5mol/L NaOH，90℃，4h和50%NaOH，130℃，4h；水热反应条件：180℃，12h；后处理：1.5mol/L HCl，室温，1.5h	S_BET=12.65m²/g；	对甲基橙的最大吸附容量为755.08mg/g	[23]
小龙虾壳生物炭	热解条件：700℃，15℃/min，N₂氛围，2h	S_BET=21.75m²/g；V_total=0.13cm³/g；平均孔径为23.06nm	对Pb²⁺的最大吸附容量为1166.44mg/g	[24]
鳌虾壳衍生炭	热解条件：600℃，N₂氛围，2h	S_BET=63.79m²/g；	对Pb²⁺的最大吸附容量为190.7mg/g	[25]
ZnCl₂改性小龙虾壳生物炭	热解条件：600℃，N₂氛围，2h；后处理：2mol/LZnCl₂溶液，24h	S_BET=236.93m²/g；V_total=0.23cm³/g；平均孔径为39.17nm	对三氯乙酸的最大吸附容量为17.8mg/g	[26]
小龙虾壳生物炭	热解条件：800℃，N₂氛围，2h		对磷的最大吸附容量为70.9mg/g	[27]
氮掺杂石墨烯修饰磁性虾壳生物炭	热解条件：以Fe²⁺和Fe³⁺为磁性前驱物，800℃，10℃/min，N₂氛围；后处理：结合氮掺杂石墨烯水凝胶，80℃，2h	S_BET=398.05m²/g；V_total=6.6cm³/g；	对Cr⁶⁺的最大吸附容量为350.42mg/g	[28]
氮掺杂多级孔虾壳衍生炭	热解条件：400℃，5℃/min，2h，N₂氛围；活化条件：KOH，850℃，5℃/min，1h，N₂氛围	S_BET=3171m²/g；V_total=1.934cm³/g；平均孔径为2.44nm	对磺胺二甲基嘧啶和氯霉素的最大吸附容量分别为699.3mg/g和742.4mg/g	[29]
KOH活化虾壳衍生炭材料	热解条件：800℃，10℃/min，3h，N₂氛围；活化条件：KOH，800℃，1h，N₂氛围	S_BET=3160m²/g；V_total=2.382cm³/g；平均孔径为1.35nm	Cu²⁺、Cr⁶⁺和Cd²⁺共存时，金属离子总吸附量为560mg/g	[30]
虾壳与玉米秸秆共混衍生炭	热解条件：800℃，5℃/min，2h，N₂氛围	S_BET=57.87m²/g；V_total=0.068cm³/g；平均孔径为6.89nm	对Cu²⁺的最大吸附量为79.77mg/g	[14]
厚壳贻贝衍生炭	热解条件：800℃，4h，N₂氛围	S_BET=4.363m²/g；V_total=0.09cm³/g；孔径为412.95nm	对氟化物的最大吸附容量为82.93mg/g	[31]
蟹壳衍生炭	热解条件：800℃，10℃/min，2h，N₂氛围		对金霉素的最大吸附容量为1432.3mg/g	[32]
蟹壳衍生炭	热解条件：900℃，10℃/min，2h，N₂氛围	S_BET=81.57m²/g；V_total=0.0861mL/g；平均孔径为4.22nm	对孔雀石绿和刚果红的最大吸附容量分别为12502mg/g和20317mg/g	[33]
蟹壳衍生炭	热解条件：800℃，10℃/min，2h，N₂氛围	S_BET=81.57m²/g；V_total=0.0861mL/g	对磷的吸附量达到80mg/g	[34]
蟹壳活性炭	脱盐条件：1mol/L HCl，6h；热解条件：500℃，10℃/min，1.5h，N₂氛围；活化条件：KOH，800℃，1h	S_BET=2197m²/g；V_total=1.192cm³/g；平均孔径为2.17nm	对酸性大红的最大吸附容量为1667mg/g	[35]
磁性蟹壳衍生炭	热解条件：500℃，8℃/min，1h，N₂氛围；后处理：在碱性介质中化学共沉淀法，［Fe³⁺］∶［Fe²⁺］摩尔比为2∶1	S_BET=74.53m²/g；V_total=0.298cm³/g；平均孔径为3.94nm	对As³⁺和Pb²⁺的最大吸附容量分别为15.8mg/g和62.4mg/g	[36]
蟹壳衍生炭	热解条件：700℃，10℃/min，2h，N₂氛围；活化条件：KOH，800℃，1h	S_BET=2441m²/g；V_total=1.682cm³/g；孔径为1.937nm	对柴油的最大吸附容量为57.74mg/g	[37]
牡蛎壳生物炭	热解条件：900℃，2h	S_BET=4.85m²/g；平均孔径为11.06nm	对Cd²⁺和Pb²⁺的最大吸附容量分别为153.8mg/g和923.3mg/g	[7]
棉花/聚酯废料与牡蛎壳复合碳材料	热解条件：900℃，1~2h；后处理：10% HCl，12h	S_BET=645.05m²/g；V_total=0.38cm³/g；平均孔径为0.64nm	对四环素的最大吸附容量为496.66mg/g	[38]
鱼骨炭	热解条件：900℃，10℃/min，2h，N₂氛围；后处理：用0.1mol/L HCl和0.1mol/L NaOH先后润洗	S_BET=124m²/g；V_total=0.214cm³/g；平均孔径为7.4nm	对四环素的最大吸附容量为141.70mg/g	[39]
牛骨衍生炭	热解条件：450℃，2h，N₂氛围；改性方法：4% Fe₂(SO₄)₃浸泡0.5h；8% Al₂(SO₄)₃浸泡1h	S_BET=91.3m²/g；V_total=0.3cm³/g；平均孔径为26.2nm	对水中氟的最大吸附容量为45.455mg/g	[40]
牛骨衍生炭	预处理：300r/min研磨12h，离心；热解条件：600℃，2h，N₂氛围	S_BET=313.09m²/g；V_total=0.4538cm³/g；平均孔径为6.46nm	对Cd²⁺、Cu²⁺和Pb²⁺的吸附容量分别为165.77mg/g、287.58mg/g和558.88mg/g	[41]
鱼鳞衍生炭	预氧化条件：350℃，2h，O₂氛围；热解与活化条件：与KOH混合，850℃，2.5h，10℃/min，N₂氛围	S_BET=3370m²/g；V_total=1.91cm³/g；平均孔径为1.49nm	对水中环丙沙星的最大吸附容量为1013.96mg/g	[5]

胶原基生物炭	制备工艺	生物炭特性	降解效果	参考文献
多级孔虾壳衍生炭	热解条件：800℃，5℃/min，2h，N₂氛围；后处理：室温，HCl，24h	S_BET=594m²/g；V_total=0.93mL/g；平均孔径为3.1nm	当[2,4-二氯苯酚]=100mg/L，[pH]=5.82，[虾壳衍生炭]=0.2mg/L时，60min后吸附率达到40%左右；加入[过硫酸根]=0.5g/L后，70min内去除率达到98%	[42]
鱼骨衍生炭	热解条件：800℃，5℃/min，2h，N₂氛围	S_BET=758.44m²/g	当[苯酚]=20mg/L；［过硫酸根]=1.0g/L；[鱼骨衍生炭]=0.1mg/L时，60min后苯酚的去除率接近100%	[43]
多级孔猪骨衍生炭	预炭化条件：450℃，N₂氛围；热解条件：900℃，5℃/min，2h，N₂氛围；后处理：6mol/L HCl，12h	S_BET=1024.3m²/g	当[2,4-二氯苯酚]=0.2g/L，[pH]=5.15，[猪骨炭]=0.2g/L时，预吸附60min后加入[过硫酸盐]=2g/L进行催化降解，180min后去除率接近100%	[44]