Article(id=1236276112188297450, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1236276104999268557, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.04.028, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1745942400000, receivedDateStr=2025-04-30, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772680794045, onlineDateStr=2026-03-05, pubDate=1753977600000, pubDateStr=2025-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772680794045, onlineIssueDateStr=2026-03-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772680794045, creator=13701087609, updateTime=1772680794045, updator=13701087609, issue=Issue{id=1236276104999268557, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='4', pageStart='1', pageEnd='200', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1772680792331, creator=13701087609, updateTime=1772681498687, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236279067746562719, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1236276104999268557, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236279067746562720, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1236276104999268557, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=153, endPage=157, ext={EN=ArticleExt(id=1236276112502870273, articleId=1236276112188297450, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Experimental Study and Application of Membrane Distillation Technology in Treating High-Salinity Wastewater, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

An experiment was carried out on treating high-salinity wastewater by air gap membrane distillation (AGMD). Effects of different operating conditions on the performance of AGMD were investigated, and membrane fouling and its control measures were also analyzed. It is shown that the permeation flux increases with the increase of temperature and flow rate of feed, and decreases with the increase of cooling water temperature and salt concentration. The salt rejection rate can maintain above 99.8% with the salinity less than 60 g/L, and still exceed 90% with salinity within the range of 60-100 g/L. It is concluded that AGMD technology can be adopted to treat high salinity wastewater.

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采用气隙式膜蒸馏(AGMD)对高盐废水进行处理,考察了不同操作条件对AGMD性能的影响,分析了膜污染情况及控制措施。结果表明,渗透通量随着进料温度和进料流量升高而升高,随着冷却水温度和盐浓度升高而降低。实验操作条件下,盐浓度小于60 g/L时,盐截留率可保持在99.8%以上;盐浓度60~100 g/L时,盐截留率仍可达到90%以上。AGMD技术可应用于高盐废水处理。

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孙伟(1973—),男,河北邯郸人,教授,主要研究方向为复杂矿产资源综合利用、有色选冶固废资源化。E-mail:
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陈博明(1981—),男,湖南长沙人,博士,高级工程师,主要研究方向为环境规划管理与环境工程。E-mail:

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陈博明(1981—),男,湖南长沙人,博士,高级工程师,主要研究方向为环境规划管理与环境工程。E-mail:

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articleId=1236276112188297450, language=EN, label=Fig.6, caption=SEM images and contact angles of new membrane and polluted membrane, figureFileSmall=K/biI3MPhTyx05vPeIaqQA==, figureFileBig=U1caNujpCp7Ja2ofVdBjCQ==, tableContent=null), ArticleFig(id=1236348224278156241, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1236276112188297450, language=CN, label=图6, caption=新膜及污染膜SEM图像和接触角

(a)新膜;(b)污染膜

, figureFileSmall=K/biI3MPhTyx05vPeIaqQA==, figureFileBig=U1caNujpCp7Ja2ofVdBjCQ==, tableContent=null), ArticleFig(id=1236348224374625249, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1236276112188297450, language=EN, label=Table 1, caption=

Chemical composition in new membrane and polluted membrane

, figureFileSmall=null, figureFileBig=null, tableContent=
膜种类FCONNaClS
新膜73.3026.070.570.030.0300
污染膜66.5126.331.650.771.391.821.53
), ArticleFig(id=1236348224492065774, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1236276112188297450, language=CN, label=表1, caption=

新膜与污染膜中各元素含量(质量分数)

, figureFileSmall=null, figureFileBig=null, tableContent=
膜种类FCONNaClS
新膜73.3026.070.570.030.0300
污染膜66.5126.331.650.771.391.821.53
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膜蒸馏技术处理高盐废水的试验研究与应用
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陈博明 1, 2 , 孙伟 2
矿冶工程杂志 | 冶金 2025,45(4): 153-157
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矿冶工程杂志 | 冶金 2025, 45(4): 153-157
膜蒸馏技术处理高盐废水的试验研究与应用
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陈博明1, 2 , 孙伟2
作者信息
  • 1.湖南省生态环境事务中心,湖南 长沙 410014
  • 2.中南大学 资源加工与生物工程学院,湖南 长沙 410083
  • 陈博明(1981—),男,湖南长沙人,博士,高级工程师,主要研究方向为环境规划管理与环境工程。E-mail:

通讯作者:

孙伟(1973—),男,河北邯郸人,教授,主要研究方向为复杂矿产资源综合利用、有色选冶固废资源化。E-mail:
Experimental Study and Application of Membrane Distillation Technology in Treating High-Salinity Wastewater
Boming CHEN1, 2 , Wei SUN2
Affiliations
  • 1.Hunan Ecological and Environmental Affairs Center, Changsha 410014, Hunan, China
  • 2.School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, Hunan, China
出版时间: 2025-08-01 doi: 10.3969/j.issn.0253-6099.2025.04.028
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采用气隙式膜蒸馏(AGMD)对高盐废水进行处理,考察了不同操作条件对AGMD性能的影响,分析了膜污染情况及控制措施。结果表明,渗透通量随着进料温度和进料流量升高而升高,随着冷却水温度和盐浓度升高而降低。实验操作条件下,盐浓度小于60 g/L时,盐截留率可保持在99.8%以上;盐浓度60~100 g/L时,盐截留率仍可达到90%以上。AGMD技术可应用于高盐废水处理。

废水处理  /  膜蒸馏  /  气隙式膜蒸馏  /  高盐废水  /  膜分离  /  膜污染

An experiment was carried out on treating high-salinity wastewater by air gap membrane distillation (AGMD). Effects of different operating conditions on the performance of AGMD were investigated, and membrane fouling and its control measures were also analyzed. It is shown that the permeation flux increases with the increase of temperature and flow rate of feed, and decreases with the increase of cooling water temperature and salt concentration. The salt rejection rate can maintain above 99.8% with the salinity less than 60 g/L, and still exceed 90% with salinity within the range of 60-100 g/L. It is concluded that AGMD technology can be adopted to treat high salinity wastewater.

wastewater treatment  /  membrane distillation  /  air gap membrane distillation  /  high-salinity wastewater  /  membrane separation  /  membrane fouling
陈博明, 孙伟. 膜蒸馏技术处理高盐废水的试验研究与应用. 矿冶工程杂志, 2025 , 45 (4) : 153 -157 . DOI: 10.3969/j.issn.0253-6099.2025.04.028
Boming CHEN, Wei SUN. Experimental Study and Application of Membrane Distillation Technology in Treating High-Salinity Wastewater[J]. Mining and Metallurgical Engineering, 2025 , 45 (4) : 153 -157 . DOI: 10.3969/j.issn.0253-6099.2025.04.028
高盐废水是指含有机物和至少3.5%(质量分数)总溶解性固体物的废水[1]。高盐废水成分复杂,主要来源于农药、医药、染料、焦化、冶金、新材料、化纤等行业,通常含有大量Cl、SO42-、Na+、Ca2+、Mg2+等可溶性无机盐离子以及含量不等的重金属离子[2]。我国高盐废水产生量约占总废水量的5%,每年仍以2%的速率增长[3]。因此,高盐废水处理在污水处理中有重要地位,是废水处理研究的重点和难点。
目前,常见的高盐废水处理方法主要包括蒸发法、电解法、膜分离法、焚烧法和生物法等[4-7]。膜蒸馏技术作为新型膜分离技术,处理高盐废水优势显著[8],其操作温度低(40~80 ℃),较蒸发法等高温操作技术能耗大幅降低,对盐度适应性强,能处理盐浓度达数十甚至上百克每升的废水,无反渗透技术受盐浓度限制的问题。该技术还能利用太阳能、工业废热等低品位热能[9],降低运行成本,节能潜力良好。基于以上优势,膜蒸馏技术在高盐废水处理领域应用潜力巨大,有望成为解决高盐废水处理难题的有效方案。
膜蒸馏技术根据渗透侧的不同,可分为直接接触式膜蒸馏(DCMD)、气隙式膜蒸馏(AGMD)、吹扫气膜蒸馏(SGMD)、真空膜蒸馏(VMD)[10-12]
本文以AGMD膜组件为基础,研究不同操作条件对膜蒸馏性能的影响规律,分析膜蒸馏过程中的膜污染情况及其对膜性能的影响,探讨减轻膜污染的有效措施,为该技术的实际应用提供科学依据和优化方案。
选用聚四氟乙烯(PTFE)膜材料进行试验。聚四氟乙烯具有优异的化学稳定性和疏水性,能有效抵抗高盐废水中各种化学物质的侵蚀,保证膜在高盐环境下的稳定性。该膜材料孔径0.2 μm,孔隙率75%。选择聚四氟乙烯膜材料的依据主要有以下3点:①化学稳定性高,使其能适应高盐废水的复杂化学环境,不易被腐蚀和降解;②具有良好的疏水性,能有效阻止液体水通过膜孔,确保膜蒸馏过程正常进行;③具有合适的孔径和孔隙率,能在传质和截留之间取得较好的平衡,满足试验对膜性能的要求。
高盐废水水样一部分来源于某化工企业的实际排放废水,该废水经过初步预处理,去除了较大颗粒的悬浮物和杂质。水样的主要成分包括氯化钠、硫酸钠等盐分,以及少量的有机物和重金属离子。其中,氯化钠浓度50 g/L,硫酸钠浓度30 g/L,有机物含量(以化学需氧量COD计)200 mg/L,重金属离子铜、锌、铅质量浓度分别为10、8、5 mg/L。
另一部分高盐废水通过人工配制作为模拟废水。模拟废水的成分根据实际高盐废水的主要成分和浓度进行配制,以确保试验条件与实际情况相近。模拟废水中氯化钠、硫酸钠等盐分的浓度范围与实际废水相似,并添加了适量的有机物和微量元素,可以更准确地模拟实际高盐废水的水质。
有机膦酸盐类阻垢剂,用于防止高盐废水中的盐分在膜表面和设备管道内结垢,避免影响膜蒸馏的效果和设备的正常运行。
试验装置主要由AGMD膜组件、热料液循环系统、冷却水循环系统等部分组成,试验装置示意图见图1。膜组件采用平板式结构,膜面积0.05 m2,能够提供足够的传质面积。热料液循环系统由蠕动泵和管道组成,蠕动泵可以精确控制料液流量,使料液在膜组件中均匀流动。冷凝系统采用蛇形冷凝管,通过循环冷却水将透过膜的水蒸气冷凝成液态水,确保冷凝效果。
首先,将配制好的模拟高盐废水加入料液储槽中,启动料液循环系统,使料液在管道中循环流动,排除管道中的空气。然后,启动温度控制系统,将料液加热至设定温度。当料液温度稳定后,启动冷凝系统,调节相关参数至设定值。待系统运行稳定后,开始采集样品,每隔一定时间采集一次产水和料液样品,分别测量其盐分含量。同时,记录系统的运行参数,如温度、流量等。试验结束后,将料液排出,对装置进行清洗和维护。
运行过程中,监测指标及监测方法如下:通过温度传感器测量温度,精度±0.1 ℃;通过压力传感器测量压力,精度±0.5 kPa;通过流量计测量流量,精度±1%。
采用离子色谱法检测进料液及产水中Cl、SO42-、Na+等离子浓度。具体操作步骤为:将样品适当稀释后,注入离子色谱仪中,通过分离柱分离不同离子,然后通过检测器检测离子信号,根据标准曲线计算离子浓度,从而得到样品的盐分含量。
渗透通量为单位时间内通过单位膜面积的冷凝水质量,计算公式为:
式中:J为膜蒸馏过程的渗透通量,kg/(m2·h);W为通过膜的冷凝水质量,kg;S为膜组件的有效膜面积,m2t为测量时间,h。
用盐截留率表示膜蒸馏过程中对盐分的阻隔效果,计算公式为:
式中:R为盐截留率,%;ρ1为进料液中盐分的质量浓度,mg/L;ρ2为膜蒸馏产水中盐分的质量浓度,mg/L。
利用扫描电子显微镜(SEM)表征膜的微观结构变化。在试验前后,分别取一小块膜样品,进行预处理(如镀金等),然后放入SEM中观察膜表面和断面的形态结构,如膜孔的大小、形状、分布情况等。通过对比试验前后膜的微观结构,可以了解膜在高盐废水处理过程中的变化,如膜孔是否堵塞、膜表面是否有污染物附着等。
能谱分析(EDS)可快速确定膜污染层中主要元素的种类和相对含量,可初步判断污染物的类型,如有机污染或无机污染。
通过接触角测量仪研究膜表面亲疏水性变化。将水滴在膜表面,测量水滴与膜表面的接触角,接触角越大,表明膜表面的疏水性越强。通过对比试验前后膜表面接触角,可以了解膜在高盐废水处理过程中疏水性的变化,从而评估膜污染情况。
进料流速2 L/min、冷却水流量1 L/min、盐浓度40 g/L、冷却水温度20 ℃条件下,探究了进料温度对AGMD过程膜性能的影响,结果如图2所示。进料温度从45 ℃升高到70 ℃时,渗透通量从2.74 kg/(m2·h)增至14.68 kg/(m2·h)。进料温度升高时,AGMD过程渗透通量随之增加,这是因为水蒸气分压与温度的关系符合Antoine方程,即水蒸气分压随着温度升高呈指数增加。进料温度升高时,水蒸气分压的增大使膜两侧的水蒸气压差显著增大,进而增大了AGMD传质过程的驱动力,最终表现为渗透通量的增加[13]。此外,升高进料温度也会使进料液黏度下降。不改变其他条件的情况下,进料液黏度下降,流体雷诺数增大,流体湍动程度增大,可以削弱温差极化和浓差极化的影响,最终表现为渗透通量增加。此外,AGMD过程24 h内的盐截留率一直保持在99.8%以上,对进料液中的非挥发性组分表现出良好的截留效果。70 ℃时盐截留率略有下降,可能是高温改变膜结构或促进溶质挥发所致。选择进料温度65 ℃。
进料温度65 ℃,其他条件不变,进料流速对AGMD过程膜性能的影响如图3所示。结果表明,进料流速从0.5 L/min提升至2.5 L/min时,渗透通量从6.64 kg/(m2·h)增至11.78 kg/(m2·h)。进料流速升高时,AGMD过程的渗透通量随之增加,这是因为增加进料流速可提高进料通道中的湍流水平,雷诺数增加,进料边界层的传热系数增加,温度极化层厚度减小,边界层减薄,传质作用增强[14]。AGMD过程24 h内的盐截留率一直维持在99.8%以上,变化较小,主要是因为流速对膜两侧蒸气压差影响小。但进料流速过高会导致膜表面的湍流增强,虽然可以减少边界层厚度,但同时也会增加膜表面的剪切力,可能导致膜孔堵塞或膜表面损伤,反而降低传质效率,且能耗增加。综合考虑,选择进料流速2.0 L/min。
进料流量2.0 L/min,其他条件不变,冷却水温度对AGMD过程膜性能的影响如图4所示。冷却水温度从10 ℃升高到30 ℃,渗透通量从11.31 kg/(m2·h)降到9.61 kg/(m2·h)。随着冷却水温度升高,膜两侧的跨膜温差降低,传质驱动力减小,导致渗透通量减小[15]。与进料温度对渗透通量的影响相比,冷却水温度对渗透通量的影响较小。实际应用中,进料温度较高时,建议使用温度更接近室温的冷却水,从而将其维持在室温以下。AGMD过程24 h内的盐截留率一直保持在99.8%以上,对进料液中的非挥发性组分表现出良好的截留效果。
冷却水温度20 ℃,其他条件不变,盐浓度对AGMD过程膜性能的影响如图5所示。结果表明,渗透通量随着盐浓度上升而下降,盐浓度20 g/L时渗透通量为11.01 kg/(m2·h),盐浓度100 g/L时渗透通量降至8.60 kg/(m2·h)。随着盐浓度增加,浓差极化效应不断增加,跨膜水蒸气压差减小,热力学驱动力下降,导致渗透通量逐渐降低[16]。盐截留率在低盐浓度时稳定在97.5%以上,在高盐浓度时略有下降,如盐浓度80 g/L时盐截留率降至95.84%,盐浓度100 g/L时盐截留率进一步降至93.23%。但与其他膜分离技术相比,如反渗透技术中的高盐浓度严重影响系统的稳定性(盐浓度上限为75 g/L)[17],AGMD过程盐浓度对渗透通量的影响不太显著,高盐浓度下,盐截留率仍可保持在90%以上。
采用扫描电镜对新膜和运行48 h后的污染膜随机表面进行表征,并测定膜材料接触角,结果见图6。由图6可见:新膜为丝状网络结构,该结构可以成为无定形污染物的黏附介质;持续运行48 h后,膜表面有一层污染物附着,部分膜孔堵塞。新膜的原始接触角为146.0°,持续运行48 h后接触角降为135.5°。一般来说,膜污染会导致膜表面疏水性下降,接触角减小。
新膜与污染膜中各元素的EDS分析结果见表1。由表1可知,污染物主要为钠、氯、硫等盐分元素,还有少量碳、氮、氧,可能来自有机物吸附。
对比发现,新膜渗透通量保持在10 kg/(m2·h)左右,盐截留率99%以上;污染膜渗透通量降至7 kg/(m2·h)左右,盐截留率约90%。主要是膜孔堵塞增大了传质阻力导致渗透通量降低,膜表面性质改变使截留能力下降。
文献[18]认为,采用膜表面改性的方法可以提高膜的疏水性能,降低污染物与膜表面之间的相互作用力,从而提高多孔膜抗污染性能。其次,可优化操作条件,如提高进料温度、进料流速,维持高通量,有效防止膜表面杂质的积累,从而减轻膜污染。添加少量阻垢剂可有效降低结晶速率,实现良好的阻垢效果。另一方面,可采用清洗的方式恢复污染膜的性能。膜蒸馏工作压力低,膜污染可逆性高,一般可通过纯水清洗恢复通量,污染严重时可采用酸洗或碱洗[19]
1)对AGMD影响最显著的操作条件为进料温度,其次为进料流量;渗透通量随着进料温度和进料流量升高而升高,随着冷却水温度和盐浓度升高而降低。
2)在24 h运行时间内,盐浓度小于60 g/L时,在实验操作条件下盐截留率均保持在99.8%以上;盐浓度60~100 g/L时,盐截留率仍保持在90%以上。
3)扫描电镜、接触角测量及能谱分析结果均表明,膜污染后渗透通量及盐截留率均有一定程度降低。
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doi: 10.3969/j.issn.0253-6099.2025.04.028
  • 接收时间:2025-04-30
  • 首发时间:2026-03-05
  • 出版时间:2025-08-01
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  • 收稿日期:2025-04-30
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    1.湖南省生态环境事务中心,湖南 长沙 410014
    2.中南大学 资源加工与生物工程学院,湖南 长沙 410083

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孙伟(1973—),男,河北邯郸人,教授,主要研究方向为复杂矿产资源综合利用、有色选冶固废资源化。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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