双极膜电渗析技术在工业高含盐废水中的应用

双极膜电渗析（BMED）作为新型膜分离技术,可将盐转变为相应的酸和碱,围绕BMED技术在工业高含盐废水领域的应用已逐渐成为热点,但在实际应用中还存在一些亟需解决的难点。本文主要介绍了近年来BMED技术在处理工业高含盐废水领域的研究现状,提出和探讨了限制BMED技术在该领域大规模工业化应用的3个关键性问题,即与酸碱浓度和纯度有关的技术问题、与过程成本有关的技术经济性问题以及与投资成本有关的经济性问题。针对这3个问题,指出BMED技术未来发展方向应致力于降低双极膜成本,减弱或消除离子交换膜同离子泄漏及水迁移过程。对于现阶段而言,将制备的酸碱回用于系统内部,是解决酸碱品质较低而未能商品化的主要途径,同时该过程可节省酸碱外购费用,弥补BMED技术投资成本过高问题。     

Asymmetric bipolar membrane electrodialysis for acid and base production

Bipolar membrane electrodialysis (BMED) is a promising technique for upgrading traditional manufacturing procedures and achieving a circular economy. However, the industrial applications of BMED technology have been restricted by the large consumption of expensive bipolar membranes and the unmatching behavior between water splitting and ion migration. Herein, we proposed a novel asymmetric bipolar membrane electrodialysis (ABMED) to regulate the water splitting in the bipolar membrane and orientational ion migration in the electrodialysis (ED). It was found that the ABMED exhibited comparable performances to BMED for acid/base production when the area of the bipolar membrane was reduced to 50% of the monopolar membrane. The total process cost of ABMED was 0.78 $/kg NaOH, which is 21% lower than the BMED process. The asymmetric membrane design was capable to boost the water splitting in the bipolar membrane and to eliminate the concentration polarization in the ED process.     

双极膜电渗析法麦草畏生产废水的资源化利用研究

采用双极膜电渗析（bipolar membrane electrodialysis,BMED）将麦草畏生产废水中的NaCl转化为HCl和NaOH回用于农药生产,实现农药废水的资源化利用。首先进行了BMED法处理单组分NaCl溶液体系的110 min间歇运行实验来探索最优操作条件,结果表明,当NaCl初始浓度为160 g/L,电流密度为70 mA/cm²,初始酸碱室浓度为0.075 mol/L时,产物HCl、NaOH的浓度能分别达到1.98 mol/L和 2.06 mol/L,且此时的电流效率较高,达到42.74%。然后考虑实际废水的COD指标主要是甲醇造成的,所以用含不同浓度甲醇的NaCl溶液模拟实际农药废水,实验结束后在酸、碱隔室中检测到少量的甲醇,表明其在BMED运行过程中存在一定程度的渗透,但未对膜堆性能造成明显影响。最后用BMED处理经过预处理后含有机物的麦草畏生产废水,发现在操作时间内膜堆性能与处理高浓度单组分NaCl溶液情况类似,证实BMED法处理麦草畏生产废水并实现资源化利用的可行性。     

双极膜电渗析技术的研究进展

双极膜电渗析技术(BMED)是利用直流电场作用下双极膜界面层内发生水解离生成H+和OH-这一电化学特性,通过将双极膜与阴、阳离子交换膜适当组合,可实现不同的特种分离功能。与传统工艺相比,BMED具有高效节能、环境友好、操作便捷等突出技术优势。本文介绍了3种不同的BMED工作模型以及BMED在有机酸生产、水除盐、蛋白分离、超纯水制备等领域的最新研究进展,对BMED技术的进一步研究与发展进行了展望。     

Bipolar membrane electrodialysis for cleaner production of N-methylated glycine derivative amino acids

In this study, cleaner production of N-methylglycine (NMG), N,N-dimethylglycine (DMG), and N,N,N-trimethylglycine (TMG) with similar structures but different methylate groups was performed using bipolar membrane electrodialysis (BMED). The effects of the feed mass concentration and current density on the separation performance were intensively analysed in terms of the molecular size, molecular structure, ion concentration, and interaction between amino acids and membranes. The results indicated that the optimal recovery performance was achieved at a current density of 200 A/m² and feed mass concentration of 6%. Under the optimal conditions, the energy consumption and current efficiencies were 2.3 kWh/kg and 78% for NMG, 2.49 kWh/kg and 69.5% for DMG, and 3.52 kWh/kg and 39.6% for TMG, respectively. It was speculated a competition for water splitting occurs between the bipolar membranes and anion exchange membranes when BMED is used for the separation and purification of large-sized bioproducts.     

Membrane fouling caused by amino acid and calcium during bipolar membrane electrodialysis

BACKGROUND: Bipolar membrane electrodialysis (BMED) has been widely applied in the recovery/production of organic acids and in the treatment of wastewater containing ammonium sulfate, sodium nitrate, sodium acetate and ammonium nitrate. However, membrane fouling is still one of the major problems in the electrodialysis process. Since calcium and amino acid are present naturally in fermentation wastewater, this study was carried out to determine the effects of calcium and amino acid on membrane fouling when simulated fermentation wastewater containing ammonium sulfate was treated by BMED. RESULTS: Calcium formed a scale on the cation exchange membrane (CEM) surface in contact with the base cell, but this had no significant adverse effect on the BMED performance. Amino acid, however, caused CEM fouling of the inner membrane, which hampered the BMED process. The coexistence of calcium and amino acid aggravated the membrane fouling, as observed morphologically on the CEM surface on the base cell side. Elemental mapping analysis showed that the membrane foulant was composed of calcium hydroxide and amino acid. CONCLUSION: The CEM fouling caused by calcium and that due to amino acid, which were distributed differently on the membrane, had different effects on the BMED performance. The coexistence of amino acid and calcium deteriorated the CEM fouling during BMED. Copyright © 2008 Society of Chemical Industry     

双极膜电渗析法制备酸碱的研究

在直流电场的作用下，双极膜水解离生成H^ ，OH^-，能将盐转化为相应的酸和碱，本文对此工艺及操作方式进行探讨，研究该过程中，电压电流变化，酸碱浓度关系以及盐室溶液浓度，通电量对双极膜电渗析制备酸碱的影响。     

高含盐采油污水特性研究

研究了盐质量浓度为5×104～2×105mg/L的高含盐采油污水的油水乳化、腐蚀、结垢特性.结果表明,溶解盐的含量和离子价态、水质结垢趋势等因素影响油水乳化情况;温度、盐含量、溶解氧浓度对采油污水腐蚀性有影响;由于伴生可溶性盐垢,高含盐采油污水结垢情况比理论推导情况严重.     

Recovery of alpha-ketoglutaric acid from model fermentation broth using electrodialysis with bipolar membrane

ABSTRACT

A bipolar (BP) membrane electrodialysis (EDBM) was used to recover the alpha-ketoglutaric acid (AKG) from the model broth. A two-chamber EDBM membrane stack consisting of an anion exchange membrane and a BP membrane was used. The effect of the initial composition, applied current density, and pH of diluate on the efficiency of EDBM processes was investigated. The obtained results showed that the used membrane stack configuration allows complete separation of AKG from glucose and ethanol and simultaneous conversion of AKG salts to the acidic form. The scale-up of the EDBM process for model fermentation broth was also carried out.     

双极膜电渗析处理生物质水解液的过程性能研究

在由双极膜和阴离子交换膜组成的两室双极膜电渗析装置中,研究了生物质水解液糖、酸分离和酸回收的过程性能。考察了不同膜对、进料浓度、电流密度、处理室循环流量及操作温度等因素对于处理水解液过程中的电流效率和平均功耗的影响。结果表明,由BP-1双极膜与A501SB阴离子交换膜组成的膜对的性能最佳;过程的电流效率随进料液酸浓度的增大而下降,过高酸浓度的水解液进料对电渗析分离过程不利;较高操作电流密度条件下电流效率高,利于降低功耗,本装置的处理室适宜循环流量为30.0 mL/m in;操作温度的升高,对提高电流效率作用不明显,但利于降低平均功耗,本实验装置的合适操作温度为35℃。     

双极膜电渗析法制备1,5-戊二胺

1,5-戊二胺(C5H14N2)是生物法制备尼龙材料的重要原料,具有广泛应用前景。利用双极膜电渗析产碱技术可将盐溶液中的1,5-戊二胺盐转换为1,5-戊二胺,实现生物发酵液中1,5-戊二胺的无害化提取过程。本工作用1,5-戊二胺硫酸盐模拟生物发酵液的主要成分,探究了不同电流模式、电流密度、盐室初始浓度及杂质离子对1,5-戊二胺制备过程指标产生的影响,分析了双极膜在长时间运行后膜表面的损伤和污染情况。结果表明,料液中的硫酸根离子可以有效地被分离,在电流为3.6 A的恒流模式下,1,5-戊二胺回收率可达到97.5%以上;在电压为29 V的恒压模式下,1,5-戊二胺回收率可达到90%以上。高至3.45 kWh/kg双极膜在反复使用35次左右后,其阳离子交换层表面出现损伤的迹象,阴离子交换层表面黏附微量固体污染物。     

Application of response surface methodology to optimize the operation process for regeneration of acid and base using bipolar membrane electrodialysis

BACKGROUND: Bipolar membrane electrodialysis (BMED) has been widely used for desalination, concentration, separation, and purification in many fields. The purpose of this study is to optimize the operation conditions using response surface methodology (RSM) for the regeneration of sulfuric acid and ammonia from ammonium sulfate solution by BMED coupled with ammonia in situ stripping. RESULTS: A three‐factor central composite design of RSM was used to analyze the effect of operation conditions (current density, flow rate, initial acid concentration) on average current efficiency (ACE) and establish the optimal operation conditions. The ACE was 76.7 ± 2.2% under optimal operation conditions (current density 23.8 mA cm^?2, flow rate 27.3 L h^?1, initial acid concentration 0.09 mol L^?1). CONCLUSION: A suitable regression model for predicting ACE within the ranges of variables used was developed based on experimental results. The operation conditions were optimized by RSM and the ACE obtained under the optimal operation conditions was in good agreement with the value predicted by the regression model (78%), which proved the validity of the model. Copyright © 2007 Society of Chemical Industry     

离子膜电解法处理环氧丙烷氯醇化尾气碱洗废水

介绍了离子膜电解法处理环氧丙烷氯醇化尾气碱洗废水的实验研究.在不添加任何化学物质的前提下,其COD去除率可达到78%,同时可回收废水中的碱,迅速降低废水pH,碱回收率可达到73.55%,可为后续生化单元起到良好的预处理作用.     

Design and study of a novel ammonia-based CO2 capture process with bipolar membrane electrodialysis

Aqueous ammonia is a promising absorbent in the field of post combustion CO₂ capture. However, the high volatilization of NH₃ results in a high energy requirement, as well as solid precipitation during the CO₂ regeneration process. A novel process was designed to reduce energy consumption and solve the problem. The bipolar membrane electrodialysis (EDBM) unit and CO₂ regeneration reactor were taken as the regeneration part. In the novel process, the bubble in the EDBM unit would be eliminated, and the regeneration of CO₂ and aqueous ammonia would be operated separately, which significantly reduced energy consumption and avoided the risk of precipitation during regeneration. According to the simulation and calculation results, the CO₂ regeneration energy consumption of the novel process using H₂SO₄ for CO₂ regeneration is 39.0% lower than that of the conventional ammonia-based process, which shows good energy saving potential. Moreover, the novel process will be more competitive as membrane technology develops.     

Characterization of cation‐exchange membrane fouling during bipolar membrane electrodialysis of monosodium glutamate isoelectric supernatant

BACKGROUND: A novel procedure that involved regeneration and recycling of ammonia and sulfuric acid from monosodium glutamate isoelectric supernatant with bipolar membrane electrodialysis (BMED) was proposed. As the performance of the membranes deteriorated during the batch runs, fouling of the cation‐exchange membrane (CEM) in contact with the base cell was studied. RESULTS: During ten consecutive batches of BMED, some operating parameters deteriorated gradually. Using scanning electron microscopy observations, fouling deposits were found on the CEM surface on the base cell side. Using Fourier transform infrared spectroscopy and reversed‐phase high‐performance liquid chromatography (RP‐HPLC), the organic fouling fraction of the CEM foulants was found to contain eight amino acids. Using X‐ray energy‐dispersive analysis, the mineral fouling fraction was shown to be mainly O and Ca elements, and a little Mg. Using X‐ray diffraction, the inorganic foulant was identified as CaCO₃, mainly in the form of calcite and a little aragonite. CONCLUSION: The CEM was subject to membrane fouling consisting of an organic fouling fraction and a mineral fraction. The organic fraction occurred as ions with some positive charges from the isoelectric supernatant and probably existed in the form of amino acids or their peptides. The mineral fraction was mainly CaCO₃ calcite and aragonite, and probably a little amorphous Ca and Mg hydroxides. Copyright © 2011 Society of Chemical Industry     

双极膜电渗析法连续制备聚合硫酸铁

研究了双极膜电渗析法连续制备聚合硫酸铁（PFS）的工艺。主要考察了电流密度、原料补充液中硫酸亚铁和硫酸的摩尔比以及原料补充液流速对产品PFS各性能指标（盐基度、全铁含量、pH、密度等）和过程能耗的影响。研究结果表明：电流密度从10mA/cm²增加到20mA/cm²时,盐基度从8.59%显著增加到11.32%,去浊率从84.31%逐渐增加到95.34%,但当电流密度大于20mA/cm² 时,盐基度和去浊率稍有下降,过程能耗最高可达4.26kW·h/kg H₂SO₄,酸液罐酸浓度最高可达0.45mol/L;原料补充液中硫酸亚铁和硫酸的摩尔比从2.01增加到4.08时,盐基度从8.69%增加到11.38%,去浊率从94.96%逐渐增加到95.88%,能耗在3.05~3.15kW·h/kg H₂SO₄ 范围内变化,酸液罐酸浓度约为0.38mol/L;原料补充液流速从1mL/min增加到3mL/min时,盐基度从11.52%下降到6.75%,去浊率从95.92%逐渐降低到75.61%,同时,能耗从3.09kW·h/kg H₂SO₄下降到2.77kW·h/kg H₂SO₄。     

电渗析处理印刷线路板废水的研究

用电渗析技术研究了从印刷线路板废水中精制回收Cu2+的效能。试验结果表明,电渗析能有效富集线路板废水中的Cu2+。当电压为15 V,进水Cu2+、CODCr的质量浓度分别为257、507 mg/L时,Cu2+的富集倍数为2.29,淡室出水的Cu2+质量浓度为0.9 mg/L,Cu2+的去除率达99%,对CODCr的去除率达到43%。但电渗析连续运行结果表明,离子交换膜发生膜污染,产生浓差极化,影响Cu2+的富集,使用的膜还有待改进。     

二氧化碳在双极膜电渗析系统中溶解吸收过程的研究

在二氧化碳捕集、利用和封存（CCUS）技术中,海水固碳技术绿色环保、安全可靠,具有很好的发展前景。其中,双极膜电渗析法海水固碳技术的关键之处在于二氧化碳在系统中的溶解吸收。考察了结晶器中添加晶种、通气体系成分、模拟烟道气流量、双极膜电渗析装置的电流密度对海水固碳过程中二氧化碳溶解吸收效果的影响,结果表明：系统外加晶种、模拟烟道气作为通气体系时更有利于二氧化碳在双极膜电渗析系统中的溶解吸收,促进碳酸钙生成。在上述基础上,随着模拟烟道气流量的增加,二氧化碳的比吸收速率降低,二氧化碳在溶液中大部分转化成碳酸氢根,碳酸根和碳酸钙的生成速率则会降低;随着电渗析装置电流密度的提高,碳酸氢根、碳酸根和碳酸钙的生成速率均会随之提高。该研究为酸性气体在双极膜电渗析系统中溶解吸收和矿化利用提供了指导。     

电渗析法处理丙烯腈废水的研究

为了去除丙烯腈废水中的硫酸铵,采用电渗析法对丙烯腈废水进行脱盐处理。脱盐率随流量的升高而降低,随电压的升高而升高,但达到一定值后,脱盐率基本不随电压的变化而变化。流量升高,能耗降低;电压越高,能耗越高。在电压为10V、流量为50L/h的条件下,具有较好的电渗析效果,能耗在16.81kJ/g左右,温度提高有利于电渗析过程的进行。实验结果表明,该法切实可行。     

Ammonium nitrate wastewater treatment by coupled membrane electrolysis and electrodialysis

A process coupling membrane electrolysis and electrodialysis is implemented to treat ammonium nitrate wastewater. Membrane electrolysis produces ammonia and nitric acid while electrodialysis reconcentrates the depleted salt solution. Ammonia is removed continuously by in situ stripping; thus allowing gas production with a constant current efficiency (about 70%). Nitric acid up to 8 mol L^–1 is obtained. The current efficiency of acid production depends on nitric acid concentration. When this concentration varies from 1 to 8 mol L^–1 the average current efficiency is about 58%. Electrodialysis produces a rejected stream containing less than 3 × 10^–3 mol L^–1 of ammonium nitrate.