New polymeric membrane nanofiltration for succinate recovery: a comparative study

Bio-based succinic acid recovery from fermentation broth has remained a challenge in the separation industry due the presence of by-products with similar physicochemical properties. In this work, the selective separation of succinate from succinate model solutions and the actual fermentation broth were investigated using newly fabricated polyimide P84 (PI) nanofiltration (NF) membrane and compared with three types of commercial pressure filtration membranes namely NF1, NF2 and NF270. Results show that PI membrane demonstrated comparable inorganic salt rejections performance as the commercial NF membranes of 86% and 99% for NaCl and Na₂SO₄, respectively. However PI shows much lower surface roughness, beneficial in reducing the fouling effect. PI also demonstrated equivalent performance for succinate permeation flux and retention at high concentration as the commercial membranes. PI exhibited high succinate retention (95%) in actual fermentation broth, equivalent to the commercial membranes (92–99%) and also higher selectivity factor (SF) < 0.14 compared to the NF1 membrane, SF < 0.19. Thus the PI membrane could give better succinate recovery against other carboxylates in the fermentation broth than the commercial membranes.     

Coupling of nanofiltration with microfiltration and membrane bioreactor for textile effluent reclamation

This work investigates the application of a microfiltration–membrane bioreactor–nanofiltration hybrid process for textile effluent reclamation. The indigo blue dye was efficiently retained by the microfiltration membrane (100%), which allows its recovery from the concentrate stream. The membrane bioreactor resulted in chemical oxygen demand (COD) and ammonia removal of 73% and 100%, respectively. Nanofiltration technology was successfully applied to polish textile effluent. The principal cause of flux decline was determined to be concentration polarization. The nanofiltration permeate meets the quality requirements for all processes within the textile industry, while the nanofiltration concentrate can be used for less demanding purposes.     

Preparation of a polyimide nanofiltration membrane for lubricant solvent recovery

Polyimide (PI) membrane has been proven to be an efficient approach for solvent recovery. However, the inherent fragility of the PI membrane limits the range of separation conditions and process economics. In this study, copolyimides were synthesized from 3,3′,4,4′‐benzophenone–tetracarboxylic dianhydride (BTDA) and 4,4′‐biamino‐3,3′‐dimethyldiphenyl–methane (DMMDA) by chemical imidization in a two‐step procedure. Then, a PI nanofiltration (NF) membrane was prepared through a phase‐inversion process for solvent recovery from lube oil filtrates. The results indicated that the immersion of the PI (BTDA–DMMDA) NF membrane in a 1,6‐diaminohexane/ethanol crosslinking agent solution carried on the chemical crosslinking modification, which could effectively improve the solvent resistance of the NF membrane. Moreover, the addition of inorganic salt in the polymer solution further enhanced the solvent resistance and pressure resistance of the membrane, which was favorable for the solvent recovery. The lubricant rejection was above 93%, and the solvent flux was about 30 L m^?2 h^?1 with the NF membrane prepared in optimum conditions, and this membrane showed great potential for future development in the application of solvent recovery from lube oil filtrates. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40338.     

硝基T酸萃余硫酸溶液纳滤膜法净化技术

H酸的中间体硝基T酸生产中产生大量废酸,通过叔胺类萃取剂N₂₃₅处理该废酸,再采用纳滤膜脱除萃余液中残留萃取剂及可溶性萘系磺化物。适宜的纳滤前处理萃取条件：在萃取油相中不添加正辛醇;N₂₃₅体积分数为33%,W/O（水油比）为2：1。经过二级萃取后,COD_Cr去除率为79%。二级萃余液采用纳滤膜浓缩至1/6体积,平均通量可达9.9~20.9 L·m^-2·h^-1,纳滤后可回收27%浓度的硫酸,COD_Cr总去除率为94%~97%,总色度去除率99%。大幅降低污染物排放量。     

铜冶炼烟气制酸低温位热回收产汽量探讨

介绍了铜冶炼烟气制酸含空气干燥及低温位热回收的干吸工序串酸的典型流程、串酸水平衡和SO₃平衡的物料衡算方法,分析了干燥塔入口烟气温度、不同浓度硫酸产量比例、串至二吸塔的硫酸温度等因素对低温位热回收系统产汽量的影响。在烟气条件一定的情况下,低温位热回收系统的产汽量主要跟补水量及串至二吸塔的硫酸温度有关。补水量与进干燥塔的烟气、空气的含水量与不同浓度硫酸产量比例有关,产w(H₂SO₄)93%硫酸越多,产汽量越多,但当超过低温位热回收系统保持喷淋密度及硫酸浓度恒定的最大补水量时,产汽量保持不变。     

A fundamental study on recovery of copper with a cation exchange membrane: Part 2 — Transfer rate of copper and hydrogen ion through a cation exchange membrane

Transfer rates of copper and hydrogen ion through a cation exchange membrane were measured experimentally for the systems of Cu/H-SO₄ and Cu/H-NO₃. Transfer rates of anions in the membrane were also measured, and they were negligible compared to those of the cations. Cupric ion and hydrogen ion transfer in a ratio of 1:2 and in opposite directions. The self-diffusion coefficient of cupric ion in the membrane is obtained from the transfer rate of copper in high concentrations of sulfuric or nitric acid solutions using the equilibria data obtained in our previous work. The coefficient of the hydrogen ion is similarly obtained.     

Separation of acetic acid from dilute aqueous solution by nanofiltration membrane

NF membranes have been prepared from α, β, γ‐cyclodextrin (CD) composite with polysulfone and characterized by pore size, thickness, pure water permeability, contact angle measurement and membrane morphology study. The permeation performances of the prepared membranes have been tested for separation of acetic acid from dilute aqueous solution. Effect of concentration, pressure, flow rate on flux and rejection have been calculated and interpreted. Different permeation models have been tested for experimental values and validated by comparing the values with the experimental data. It has observed that in β‐CD membranes 99% recovery of acetic acid from aqueous solution has been obtained and found to be the best membrane for separation of acetic acid from dilute solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40537.     

丙烯酸接枝聚酰胺/聚醚酰亚胺复合纳滤膜的制备

为了提高复合纳滤膜的抗污染性能,采用紫外光照接枝法将丙烯酸接枝到聚酰胺/聚醚酰亚胺(PA/PEI)复合纳滤膜的皮层上,通过引入羧基基团来增加膜表面的亲水性。考察了丙烯酸单体质量分数、辐照时间对表面接枝率和膜分离性能的影响,并对优选的膜进行了抗污染性能测试。结果表明:丙烯酸质量分数与紫外辐照时间对膜分离性能的影响规律相同,膜通量随质量分数的增加与辐照时间的延长呈现先增加后减小的趋势,而截留率则保持基本不变,当丙烯酸质量分数2%,辐照时间2 min时,膜的通量达到13.12 L/(m2·h),较接枝前的11.94 L/(m2·h)略高;在含有1 g/L牛血清蛋白(BSA)的溶液中,接枝后的膜通量下降明显低于接枝前的膜。研究表明丙烯酸接枝可以有效改善膜表面亲水性,从而有利于提高膜的抗污染性能。     

中空纤维纳滤膜与反渗透膜的研究

根据界面聚合反应成膜原理,以哌嗪(PIP)或间苯二胺(m-PD)水溶液为水相,均苯三甲酰氯(TMC)正己烷溶液为有机相,以聚砜中空纤维超滤膜为基膜,制备了一系列聚酰胺/聚砜纳滤或反渗透复合膜.研究了水相浓度、有机相浓度、界面聚合时间和温度等条件对复合膜性能的影响.结果表明:中空纤维纳滤复合膜在0.4 MPa、室温条件下,对2 g/L MgSO_4水溶液的通量可达36.64 L/(m~2·h),截留率为97.2%;中空纤维反渗透膜在0.7 MPa、室温条件下,对0.5 g/L的NaCl水溶液通量可达12.2 L/(m~2·h),截留率96.5%.     

A study of bitumen recovery by gravity drainage using low temperature soluble gas injection

A gravity drainage concept has been proposed and tested for in-situ recovery of bitumen by mobilization with soluble gases at ambient reservoir temperature conditions. Experiments were done using carbon dioxide and ethane gases at ～ 20°C to recover Athabasca bitumen from a scaled reservoir model. Thermal gravity drainage theory has been modified for the mass transfer case. The measured drainage rates were higher than those predicted by the model using molecular diffusivity data but fit the model better using an increased effective diffusivity. Lateral dispersion theory does not predict the high measured effective diffusivities. A preliminary economic evaluation of field production indicates potential application to recovery of Lloydminster heavy oil.     

Deformed reverse osmosis membrane and low pressure operation

The phenomena of hysteresis described elsewhere in cellulose acetate RO membranes are discussed, in order to show that the pressure normally required by the desalting process produces two effects: one deforming the membrane and the other maintaining the flux through the deformed membrane. This paper shows that the use of independently deformed membranes can permit a lower operating pressure while maintaining the rejection factor and flux in the effluent water.     

Effect of pH on the rejection of inorganic salts and organic compound using nanofiltration membrane

Nanofiltration (NF) has recently received increased attention as a possible tertiary treatment process providing high rejection of solutes and high water flux rate. In this research, solute separation experiments using NF membranes were made with inorganic salts including heavy metal and organic compounds in different pH levels. The rejection of inorganics from feed solution was found to be dependent on the electric charge of membrane as well as the ionic radius and valence of ion. The divalent cation appeared to reduce the potential of negatively charged membrane to lower the rejection of ion. The results of organic compounds showed that the rejection could be estimated from the pKa value and molecular weight of organics, and the pH of the feed solution.     

A study on selective flotation in low and high pyritic copper sulphide ores

The effect of chemical reagent configurations was investigated on two different copper sulphide ore types, including high and low pyritic feeds. Three different combinations of collectors as isopropyl-n-ethyl thionocarbamate (C-4132), mixture of mercaptobenzothiazole and butyl sodium dithiphosphate (Flomin 7240) and sodium isopropyl xanthate (Z11) were used in flotation experiments. Solely using C-4132 was selected as the best pattern for both feed types with regard to achieving the highest copper grade and the lowest iron recovery. However, the selectivity index (SI) results showed that the combination of Z11+F7240 provides the highest selectivity of chalcopyrite against pyrite in either low or high pyritic ores.     

利用纳滤膜分离精制饱和卤水的研究

针对饱和卤水直接制碱过程需要去除硫酸根、钙离子、镁离子（SO₄^2-、Ca²⁺、Mg²⁺）等杂质离子的问题,探索了利用纳滤膜分离精制饱和卤水新工艺。通过考察NF270、DL2540、ESNA1 3种类型纳滤膜的透过通量和离子截留率,确定了选用DL2540为实验用膜;分析了DL2540纳滤膜对离子的截留性能和对盐田饱和卤水的分离性能及其对饱和卤水精制的效果。结果表明,增加同离子浓度、降低压力有利于不同价态阳离子、阴离子间的分离,DL2540纳滤膜对盐田饱和卤水中SO₄^2-、Ca²⁺、Mg²⁺截留率分别达到95%以上、30%~50%、30%~70%,对Na⁺、Cl^-截留率均低于15%,进一步证明DL2540纳滤膜具有较好的稳定性和二价离子截留效果,在饱和卤水精制上展示出较好的应用前景。     

炼化污水抗污染反渗透膜回用处理中试研究

采用氧化混凝-复合过滤-反渗透组合工艺处理大庆炼化公司外排污水，考察了预处理系统的操作参数和抗污染反渗透膜组件性能的变化规律，为工程设计提供了基本参数。结果表明，预处理出水水质主要受过滤速度和絮凝剂加药量的影响，而膜污染是影响反渗透系统运行的主要因素。系统出水水质符合工业用水软化除盐设计规范。     

Effects of operating conditions on membrane charge property and nanofiltration

The effects of the operating pressure, cross flow velocity, feed concentration, and temperature on the streaming and Zeta potential of the membranes were studied. The permeate flux and the retention rate under different nanofiltration operating conditions were also investigated. The results show that the higher pressure, feed concentration, temperature, and lower cross flow velocity lead to the higher absolute value of streaming and Zeta potential. The permeate flux of the nanofiltration decreases with the feed concentration and increases with not only the pressure but also the cross flow velocity and temperature. The higher the pressure and the cross flow velocity, the higher the retention rate. The lower feed concentration and higher temperature leads to lower retention rate. The effects of the operating conditions on the permeate flux and the retention rate were explained by the variation of the membrane charge property.     

Pervaporation membrane reactor study for the esterification of acetic acid and isobutanol using polydimethylsiloxane membrane

In this study, isobutyl acetate, a valuable solvent in cosmetics, aroma and paint industries, is produced by pervaporation–esterification equilibrium reaction in a batch pervaporation membrane reactor (PVMR) using homogeneous (sulphuric acid) and heterogeneous (Dowex 50W-X8) catalysts. The effects of catalyst loading, catalyst type, reaction time, membrane thickness, temperature and initial molar ratio of reactants were investigated. A cross-linked polydimethylsiloxane (PDMS) membrane selective to esters was prepared and used in PVMR. Batch reactions were carried out also in a simple batch reactor (SBR) without pervaporation under the same conditions to compare the conversions for the reactions with and without pervaporation. In conclusion, PVMR experiments showed that the PDMS membrane can be used to remove the isobutyl acetate formed selectively with acceptable conversions and pervaporation fluxes.     

Effect of coating and surface modification on water and organic solvent nanofiltration using ceramic hollow fiber membrane

Nanofiltration ceramic hollow fiber membranes were developed to simplify the manufacturing process and improve water and organic solvent permeation performance. The alumina hollow fiber support was prepared by a phase-inversion/sintering method, and a γ-Al₂O₃ sol was coated thereon as a selective layer. Polyvinyl alcohol and ethanol were used as the drying control chemical additive in the coating solution, so that a coating layer could be formed without defects in only one coating step. The coating layer thickness could be adjusted to 0.6–2 μm depending on the coating drawing speed. A sintering temperature of 350 °C was selected to provide both reasonable water permeability (6.91 LMH/bar) and rejection (a molecular weight cutoff of 1000 Da or less) and to form a stable γ-Al₂O₃ phase. In the case of a membrane that was surface-modified with (3-chloropropyl)-trimethoxysilane, the permeability of toluene and hexane was 2.3 and 4.3 LMH/bar, respectively. The newly developed ceramic membrane showed excellent permeability and separation properties, as well as potential effectiveness for organic solvent nanofiltration applications.     

Preparation and separation properties of polyamide nanofiltration membrane

Utilizing an interfacial polymerization technique for the preparation of a polymeric composite nanofiltration membrane, both high permeation flux of water and high salt rejection can be achieved. Synthesis conditions, such as concentration of monomer, reaction time, and swelling agent, significantly affected the separation performance of composite membranes. The composite polyamide membrane had a permeation rate of ～2–5 gallon/ft²/day (gfd) and a salt rejection rate of ～94–99% when 2000 ppm aqueous salt solution was fed at 200 psi and 25°C. Also, a higher performance nanofiltration membrane could be prepared by suitably swelling the support matrix in the period of polymerization. The results of various feed concentrations showed that permeate flux decreased with increasing salt concentration in the feed solution. This result may be due to concentration polarization on the surface of polyamide membranes. The separation performance of polyamide membranes showed an almost independent relationship with operation pressure until it was up to 200 psi. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1112–1118, 2002