Preparation of cellulose nanocrystals-agarose-titanium carbide hydrogel interfacial evaporator for desalination and pulping waste liquid treatment
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摘要:
淡水资源短缺和能源危机已经严重影响到人类社会的可持续发展。因此，探寻人类及工业用水清洁脱盐技术成为研究热点。近年来利用太阳能进行水资源脱盐技术发展成为低成本生产清洁淡水的有效途径。本研究以纤维素纳米晶体(Cellulose nanocrystals)为原料，琼脂糖(Agarose)作为水凝胶自交联网络，制备纤维素纳米晶体-琼脂糖-碳化钛(MXene)(Ce-CAM)复合水凝胶界面蒸发器。采用扫描电子显微镜、傅里叶变换红外光谱仪、流变仪对Ce-CAM复合水凝胶的物理化学性能进行分析表征，并对其在海水脱盐淡化和制浆废液净化处理方面的应用进行探究。结果表明，Ce-CAM复合水凝胶在250-
2500 nm范围内的光吸收率为90%以上，在1 kW·m−2的光照强度下，其对3.5%氯化钠溶液和制浆废液的蒸发速率分别为1.44 kg·m−2·h−1、1.42 kg·m−2·h−1，且对Na+、Mg2+、K+、Ca2+四种离子去除率大于99.9%。其BOD、COD去除率分别可达到99.48%、99.53%。本研究可为基于水凝胶界面蒸发用于海水淡化和制浆废液净化处理提供了潜在的应用前景。Abstract:The shortage of fresh water resources and energy crisis have seriously affected the sustainable development of human society. Therefore, exploring sustainable water desalination technology for human and industrial use has become a research hotspot. In recent years, utilization of solar energy to achieve water desalination has become an effective way to produce clean fresh water at a low cost. Biopolymer-based hydrogels are candidates for efficient solar evaporation due to their internal porosity, structural diversity, biocompatibility and other properties. In this study, cellulose nanocrystal (CNC) was used as raw material and agarose (Agar) as hydrogel self-crosslinking network to prepare cellulose nanocrystals-agarose- titanium carbide (Ce-CAM) composite hydrogel interfacial evaporator. Scanning electron microscopy, Fourier transform infrared spectroscopy, and rheometer were used to analyze and characterize the physicochemical properties of Ce-CAM composite hydrogels, and to explore their applications in seawater desalination and desalination, and pulping waste liquid purification and treatment. The results showed that the light absorption of Ce-CAM composite hydrogel in the range of 250-
2500 nm was more than 90%, and the light absorption of Ce-CAM composite hydrogel in the range of 1 kW·m−2. Under the light intensity of 1 kW·m−2, its evaporation rate of 3.5% NaCl solution and pulping waste liquid was 1.44 kg·m−2·h−1 and 1.42 kg·m−2·h−1, respectively, and the removal rate of four ions, namely, Na+, Mg2+, K+ and Ca2+, was greater than 99.9%. Its BOD and COD removal could reach 99.48% and 99.53%, respectively. This study can provide a potential technical solution for the use of hydrogel-based interfacial evaporation for seawater desalination and pulping waste liquid purification and treatment. -
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图 1 纤维素纳米晶体-琼脂糖-碳化钛(MXene)(Ce-CAM)复合水凝胶及太阳能水蒸发器制备流程图
Figure 1. Schematic of the cellulose nanocrystals-agarose- titanium carbide (Ce-CAM) hydrogel derived solar interfacial evaporator
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图 2 扫描电镜图 (a1)，(b1)，(c1)，(d1)和(a2)，(b2)，(c2)，(d2)分别为Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶样品的孔道和孔壁截面扫描电镜图
Figure 2. Scanning electron micrographs (a1), (b1), (c1), (d1) and (a2), (b2), (c2), (d2) are scanning electron micrographs of pore channel and pore wall cross sections of Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogel samples, respectively
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图 3 Agar水凝胶, CNC-Agar水凝胶, Ce-CAM2复合水凝胶的储能模量(G')和损耗模量(G'')
Figure 3. Energy storage modulus (G') and loss modulus (G'') of Agar hydrogel, CNC-Agar hydrogel, Ce-CAM2 composite hydrogel
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图 4 CNC, Agar水凝胶, Ce-CAM2复合水凝胶的傅里叶红外变换光谱图
Figure 4. Fourier transform infrared spectra of CNC, Agar hydrogel, Ce-CAM2 composite hydrogel
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图 5 Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶的饱和水含量
Figure 5. Saturated water content of Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogels
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图 6 接触角：(a), (b), (c), (d)分别为水滴滴落在Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶的动态接触角
Figure 6. Contact angles: (a), (b), (c), (d) are the dynamic contact angles of water droplets falling on Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogels respectively
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图 7 (a). Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶的氮气吸附-解吸曲线, (b). Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶孔隙大小分布曲线
Figure 7. (a). Nitrogen adsorption-desorption curves of Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogels, (b). Pore size distribution curves of Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogels
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图 8 升温曲线：(a). 纯水, 3.5%氯化钠溶液, 制浆废液, Ce-CAM2复合水凝胶在一个太阳照射下升温曲线, (b). 漂浮在纯水中的Ce-CAM2复合水凝胶在一个太阳照射下的红外热成像图
Figure 8. Warming curves: (a). Warming curves of Ce-CAM2 composite hydrogel in pure water, 3.5% NaCl solution, pulping waste, under one sun irradiation, (b). Infrared thermography of Ce-CAM2 composite hydrogel floating in pure water under one sun irradiation
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图 9 在一个太阳照射下的红外热成像图：(a). 纯水, (b). 3.5%氯化钠溶液, (c). 制浆废液, (d). Ce-CAM2复合水凝胶
Figure 9. Infrared thermograms in a sun-illuminated: (a). Pure water, (b). 3.5% NaCl solution, (c). Pulping waste, (d). Ce-CAM2 composite hydrogel
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图 10 不同MXene量的Ce-CAM2复合水凝胶的太阳能吸收光谱
Figure 10. Solar absorption spectra of Ce-CAM2 composite hydrogels with different amounts of MXene
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图 11 海水淡化：(a). Ce-CAM2复合水凝胶在不同浓度氯化钠溶液中的蒸发速率, (b). 3.5%氯化钠溶液经过Ce-CAM2复合水凝胶蒸发前后溶液中Na+, Mg2+, K+, Ca2+四种主要离子的浓度变化
Figure 11. Desalination: (a). Evaporation rate of Ce-CAM2 composite hydrogel in different concentrations of NaCl solution, (b). Changes in the concentration of four major ions, Na+, Mg2+, K+ and Ca2+, in 3.5% NaCl solution before and after evaporation of Ce-CAM2 composite hydrogel
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图 12 废液蒸发： (a). C, 2 C, 3 C, 4 C分别为原制浆废液浓度, 原制浆废液浓度的两倍, 三倍, 四倍, (b). Ce-CAM2复合水凝胶在不同浓度制浆废液中的蒸发速率
Figure 12. Pulping waste liquid evaporation: (a). C, 2 C, 3 C, 4 C are the original concentration of pulping waste liquid, double, triple and quadruple of the original concentration of pulping waste liquid, respectively, (b). Evaporation rate of Ce-CAM2 composite hydrogel in different concentrations of pulping waste liquid.
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图 13 抗酸碱、抗盐性能：(a). Ce-CAM2复合水凝胶在1 mol·L−1 HCl和1 mol·L−1 NaOH溶液中的蒸发速率, (b). 1 mol·L−1盐酸和1 mol·L−1氢氧化钠蒸发前以及蒸发后收集蒸发液体的pH对比, (c). Ce-CAM2复合水凝胶的排盐能力
Figure 13. Acid, alkali and salt resistance: (a). Evaporation rate of Ce-CAM2 composite hydrogel in 1 mol·L−1 HCl and 1 mol·L−1 NaOH solutions, (b). Comparison of pH of the evaporated liquid collected before evaporation of 1 mol L−1 hydrochloric acid and 1 mol L−1 sodium hydroxide as well as after evaporation, (c). Salt exclusion capacity of Ce-CAM2 composite hydrogel
表 1 Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4复合水凝胶平均孔径和比表面积
Table 1 Average pore size and specific surface area of Ce-CAM1, Ce-CAM2, Ce-CAM3, Ce-CAM4 composite hydrogels
Sample Pore Diameter/nm Specific Surface Area /(m2·g−1) Ce-CAM1 2.99 0.27 Ce-CAM2 3.13 5.68 Ce-CAM3 2.92 17.02 Ce-CAM4 3.02 53.50 
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表 2 制浆废液以及制浆废液净化后的冷凝收集液的各项理化性质
Table 2 Physical and chemical properties of pulping waste liquid and condensate collection liquid after purification of pulping waste liquid
Sample pH Viscosity/
(mPa·s)Conductivity/
(mS·cm−1)Solid/
(g·g−1)Suspension/
(g·L−1)Ash/
(g·g−1)BOD/
(mg·L−1)COD/
(mg·L−1)C 5.13 3 16.80 0.04 0.004 0.011 1726.67 40021.33 C′ 4.82 1 0.17 0 0 0 8.93 187.33 Notes: C is the concentration of the original pulping waste liquid, C′ is the condensate collected after the evaporation of the pulping waste liquid, BOD: biochemical oxygen demand, COD: chemical oxygen demand.
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目的
淡水资源短缺和能源危机已经严重影响到人类社会的可持续发展。因此，探寻人类及工业用清洁脱盐水制备技术以成为研究热点。近年来利用太阳能生产脱盐水的技术发展成为低成本生产清洁淡水的有效途径。本研究以纤维素纳米晶体为原料，琼脂糖作为水凝胶自交联网络，制备纤维素纳米晶体-琼脂糖-碳化钛(Ce-CAM)复合水凝胶界面蒸发器，探索Ce-CAM复合水凝胶界面蒸发器的海水淡化以及制浆废液净化性能。
方法将一定量Agar加入去离子水配置成2%的Agar溶液，置于四个玻璃瓶内，将不同量的CNC溶液分别加入四个玻璃瓶中，使得CNC在四个玻璃瓶内的含量分别为0.5%、1%、1.5%、2%，搅拌均匀后加入0.1%的MXene溶液，搅拌均匀后超声1 h，使得MXene与溶液充分混合均匀，加入尿素、乙醇的量以Agar：尿素：乙醇的质量比为1：10：10进行添加，玻璃瓶内溶液混合均匀后将玻璃瓶置于85℃油浴中40 min，取出后将溶液倒入培养皿冷却1 h。铜柱置于液氮中充分冷却后，将在培养皿中冷却成型的Ce-CAM复合水凝胶置于底部浸泡在液氮中的铜柱顶端，以冰模板法铸造Agar水凝胶内部垂直孔结构，30 min后取出放置于冰箱内冷藏，所有样品冰模板铸造法完成后，放置于冷冻干燥机干燥48 h，取出后在去离子水中充分浸润进行测试，将CNC含量为0.5%、1%、1.5%、2%的CNC-Agar-MXene复合水凝胶分别命名为CAM、CAM、CAM、CAM，将添加尿素和乙醇的CNC含量为0.5%、1%、1.5%、2%的CNC-Agar-MXene复合水凝胶分别命名为Ce-CAM、Ce-CAM、Ce-CAM、Ce-CAM。
结果从使用扫描电子显微镜、傅里叶变换红外光谱仪、流变仪对Ce-CAM复合水凝胶的物理化学性能进行分析表征，并对其在海水脱盐淡化和制浆废液净化处理方面的应用进行探究。结果表明：①Ce-CAM复合水凝胶孔道内部表面粗糙，Ce-CAM复合水凝胶孔道结构高度互联；②Ce-CAM复合水凝胶的孔道为由下向上的垂直径向孔通道，通道间紧密互连，孔通道间含有少量的小孔，结合孔道的毛细力，使其具有优异的运输水能力；③随着CNC含量的增加，亲水基团的含量随之增加，良好的亲水性使得水珠在水凝胶表面快速消失，从侧面证明Ce-CAM复合水凝胶良好的水运输能力；④Ce-CAM复合水凝胶具有大孔结构以及较大的比表面积；⑤Ce-CAM复合水凝胶具有高效的热管理能力；⑥不同MXene含量的Ce-CAM2复合水凝胶在整个光谱吸收范围中，平均光吸收率均达到90%以上；⑦经过Ce-CAM2复合水凝胶蒸发后的蒸汽冷凝液中的四种金属离子浓度明显下降，离子去除率大于99.9%；⑧在制浆废液净化收集得到的冷凝液中，BOD、COD去除率分别为99.48%、99.53%；⑨ Ce-CAM2复合水凝胶具有快速高效的排盐能力和抗酸碱能力。
结论采用扫描电子显微镜、红外光谱仪、流变仪等对Ce-CAM复合水凝胶的性能进行分析表征，探究其在海水脱盐淡化、废水简化处理方面的性能，并进一步对其耐盐、耐酸碱性能进行了探究。得出如下
结论(1)Ce-CAM复合水凝胶不需引发剂、交联剂，分子链之间通过氢键链接即可形成水凝胶，加入的MXene作为吸光材料使其具有宽频高效的光吸收性能，其在250-2500 nm范围内的光吸收率为90%以上，在1 kW·m太阳光照下，其对3.5%氯化钠溶液和制浆废液的蒸发速率分别为1.44 kg·m·h、1.42 kg·m·h。(2)Ce-CAM复合水凝胶具有优异的耐盐、耐酸碱性能，其在3.5%、5%、10%、20%氯化钠溶液中连续运行10 h后，没有盐分积累，且在其表面撒一层氯化钠溶液后，在30 min内氯化钠完全消失，在1 mol·L的氢氧化钠和盐酸溶液中具有高效蒸发速率，这表明此复合水凝胶具有优异的耐盐和耐酸碱性能。(3)Ce-CAM复合水凝胶脱盐淡化海水的能力较强，其对Na、Mg、K、Ca等离子去除率可达到99.9%，同时Ce-CAM复合水凝胶能够净化高固含制浆废液中的大部分污染物，BOD、COD去除率分别可达到99.48%、99.53%，研究可为基于水凝胶界面蒸发用于制浆废液净化处理提供了新思路和新途径。
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