Research Progress on the Application of Functionalized Celluloses in Mineral Flotation
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摘要:
传统燃料油副产物及化学合成类浮选药剂会对环境造成潜在污染，而纤维素基浮选药剂凭借来源广、成本低、可降解及易功能化等优势，成为矿物分选绿色药剂的现实选择之一。详细归纳了纤维素基抑制剂和捕收剂的种类、作用机理、应用矿物类型及发展趋势。纤维素基抑制剂（如羧甲基纤维素CMC、羟乙基纤维素等）通过表面羟基与矿物形成氢键降低矿物表面电位，羧基与矿物表面Mg2+/Ca2+反应增强矿物亲水性，常被用作白云石、方解石、蛇纹石等钙镁硅酸盐矿物的浮选抑制剂，具有环境友好、成本低廉等优势。纤维素基捕收剂（如胺烷基、硅烷化改性纳米纤维素等）通过静电作用提高矿物表面疏水性，促进颗粒−气泡黏附，实现矿物浮选，兼具环保性和高效性。未来，结合工艺创新与结构设计，开发低成本、高效能的纤维素基药剂，对于推动绿色浮选药剂的发展，降低化学合成类浮选药剂耗量、减少对环境的潜在危害具有重要的实践意义。
Abstract:Traditional fuel oil by−products and chemically synthesized flotation reagents pose significant environmental pollution risks. In contrast, cellulose−based flotation reagents are considered a promising environment friendly alternative for mineral flotation, offering advantages such as widespread availability, low cost, biodegradability, and functionality. This paper provides a comprehensive review of the types, mechanisms, applications, and development trends of cellulose−based depressants and collectors. Cellulose−based depressants, such as carboxymethyl cellulose (CMC) and hydroxyethyl cellulose, have been used to inhibit the flotation of calcium−magnesium silicate minerals, including dolomite, calcite, and serpentine. These depressants function by forming hydrogen bonds through the reaction of their −OH groups with mineral surfaces, thereby reducing the surface potential of the minerals. Furthermore, the Mg2+/Ca2+ ions on the mineral surfaces interact with the −COOH groups of the cellulose molecules, enhancing the hydrophilicity of the mineral surfaces. Cellulose−based collectors, such as amino−alkyl or silanized modified nanocellulose, enhance the hydrophobicity of the mineral surface via electrostatic interactions, thereby promoting particle−bubble adhesion and improving mineral flotation efficiency. These collectors offer the dual advantages of environmental sustainability and high performance. In the future, the integration of process innovation with structural design will be crucial to the development of low−cost and high−efficiency cellulose−based reagents. This development has significant practical implications for advancing green flotation reagents, minimizing the reliance on chemically synthesized flotation reagents, and mitigating potential environmental damage.
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Key words:
- flotation /
- cellulose /
- depressant /
- collector /
- carboxymethyl cellulose
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表 1 纤维素抑制剂研究进展
Table 1. Research progress of cellulose inhibitors
抑制剂 矿石类型 作用效果 估算价格
/(元·kg−1)羧甲基纤维素CMC 辉石 降低矿物表面的接触角，在矿物表面形成亲水膜[23] 低分子量
(<100 000Da):
4.6~6.3
中等分子量
(100000 ~
500 000Da): 9~11.5
高分子量
(>500 000Da): 18~25闪矿石 含炭铅锌硫矿石 改善铅锌硫的优先浮选[24] 铜钼 抑钼浮铜[25-26] 石膏 与石膏表面的Ca2+反应生成了亲水性的羧甲基纤维素钙盐，使石膏保持分散亲水状态[27] 氢氧化锌 CMC对Zn(OH)2沉淀产生高分子桥联作用使Zn(OH)2絮凝到适合浮选的粒级 蛇纹石、黄铁矿 （1）通过调整表面电性而起到分散作用，减少蛇纹石与黄铁矿的异向凝聚；（2）改变蛇纹石的表面电性，使蛇纹石与黄铁矿之间相互作用能从吸引变为排斥，分散二者的
人工混合矿[28]滑石 通过羟基和羧基与硫化矿表面作用[29] 石墨 煤浮选过程中脉石的抑制剂[36] 磁铁矿 抑制磁铁矿的上浮[35] 高岭石和石英 降低分选过程中的细泥夹带[37] 蛇纹石 抑制蛇纹石上浮,实现蛇纹石和硼镁石的分选[38] 磷灰石和白云石 实现白云石与磷灰石的高效分离[39] 甲基纤维素 滑石 温度较低时，矿物表面亲水性增强，抑制滑石浮选[30] 55~60 滑石和黄铜矿 低用量的甲基纤维素可以抑制滑石浮选，但对黄铜矿的浮选抑制作用很弱，可以实现二者的分离[34] 羟乙基纤维素 铜硫 铜硫分离中黄铁矿的抑制剂，较好地实现铜、硫分离[31] 30~40 CMC、十二烷基苯磺酸、羧甲基纤维素和羟乙基纤维素 方解石萤石 对方解石抑制作用强于萤石，抑制效果顺序为：CMC>十二烷基苯磺酸－羧甲基纤维素>羟乙基纤维素[32] —— 木浆半纤维 高黏土铜钼
混合矿提高铜的浮选回收率，降低钼的浮选回收率[33] 15~20 注：有工业应用是工业价格，没有工业应用的是按照制备方法所用试剂价格估算。 
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胺烷基纳米纤维素 简称 接触角/ (°) 甲基胺化纤维素 MAC 78.2±2.77 乙基胺化纤维素 EAC 64.0±3.40 正丙基胺化纤维素 PRAC 85.5±4.47 正丁基胺化纤维素 BAC 88.5±3.37 正戊基胺化纤维素 PEAC 101.6±2.16 正己基胺化纤维素 HAC 109.2±2.64
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表 3 纤维素捕收剂研究进展
Table 3. Research progress of cellulose collectors
捕收剂 矿石类型 浮选效果 原料 功能化药剂 估算价格/(元·kg−1) 改性纤维素纳米纤（NFC）−(两亲型)胺烷基纤维素 石英 两亲型纳米纤维素可以用作石英的捕收剂，其捕收性能和石英的商用捕收剂相当[40] 纤维素纸浆 高碘酸钠、氯化锂、已丁胺盐酸盐、正丁胺盐酸盐、叔丁胺盐酸盐 60~80 改性纤维素纳米纤（NFC）−
（亲水型）二羧酸纳米纤维素赤铁矿 亲水型纳米纤维素对赤铁矿的抑制作用较强[40] 纤维素纸浆 高硼酸盐、偏碘酸钠、亚氯酸钠、醋酸 20~25 胺烷基纤维素 氧化铝和石英混合矿 烷基链足够长的胺烷基纳米纤维素可以有效地实现氧化铝和石英混合矿的浮选分离[41−42] 纤维素纸浆 高碘酸钠、氯化锂、伯胺开链胺盐酸盐
（甲基胺盐酸盐、乙基胺盐酸盐、正丙基胺盐酸盐、正戍基胺盐酸盐、正丁基胺盐酸盐、正己胺盐酸盐）70~80 胺烷基类纤维素纳米晶 石英 己基胺纤维素纳米晶对石英的可浮性最好[43]；甲基胺纤维素纳米晶更多的是充当矿物抑制剂；胺烷基纤维素表面烷基的链长越长，越有利于矿物的
浮选硬木纸浆 甲胺盐酸盐、丁胺盐酸盐、己胺盐酸盐 45~50 纳米纤维素使用条件是在偏碱性条件，在此条件下，由于矿物表面电荷的减少，纤维素在矿物表面会沿着矿物表面
吸附[16]氯化锂、2−吡啶硼烷、高碘酸钠、甲胺盐酸盐、正丁胺盐酸盐、正己胺盐酸盐、2−吡啶硼烷 80~90 硅烷化纤维素 石英 硅烷化后纤维素的接触角可以达到135°，功能化的同时还影响了纤维素的表面电位，使得纤维素捕收石英的效果下降[44] 商业CNC材料 氨基丙基三乙氧基硅烷、正丙基三乙氧基硅烷、己基三乙氧基硅烷和三乙氧基正辛基硅烷 65~72 丁胺基纤维素、己胺基纤维素 石英、赤铁矿 己胺纤维素纳米晶存在时石英颗粒−气泡的附着发生在几十微米距离级别内，纤维素作用的石英浮选回收率可以达到90%以上[45,49] 硬木纸浆 氯化锂、高碘酸钠、2−吡啶硼烷、正丁胺盐酸盐、正己胺
盐酸盐65~80 N−烷基甲壳素纤维素 孔雀石 可以作为孔雀石的一种潜在捕收剂[50] 甲壳素粉 己醛、辛醛、葵醛、吡啶硼烷络合物 60~70 丁基胺化纤维素纳米晶 混合硫化矿（黄铜矿、闪锌矿和毒砂的混合矿）的浮选 较多地作用于黄铜矿表面，而与闪锌矿、毒砂作用的极少，经一次浮选可将黄铜矿富集五倍，回收率达到60%以上[51] 牛皮桦木浆 高碘酸钠、氯化锂、2−吡啶硼烷、醛基胺盐酸盐 80~95 黄铜矿 在中性条件下，使用丁基胺纤维素作为捕收剂时，黄铜矿的浮选回收率较高 纤维素纳米晶 单一和混合二氧化硅和二氧化钛矿物 二氧化硅和二氧化钛矿物分离的合适pH范围在2～3之间，在此条件下，二氧化硅与二氧化钛矿物具有相反的电荷[52] 针叶木浆 无水葡萄糖、辛醇 15~25 注：有工业应用是工业价格，没有工业应用的是按照制备方法所用试剂价格估算。
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