高浓度含盐草甘膦溶液的纳滤分离实验研究
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摘要
为了考察纳滤技术分离含高浓度单价盐的草甘膦溶液的可行性,采用商业化Desal-DK纳滤膜对含有高浓度NaCl的草甘膦溶液开展了分离实验研究和模拟计算。首先研究了物料浓度、跨膜压差等因素对NaCl和草甘膦的单组分溶液的体积通量及截留率的影响,并通过拟合SK(Spiegler-Kedem)方程计算得到了膜的特征参数;其次探究了Desal-DK纳滤膜对高浓度NaCl和不同浓度草甘膦混合溶液的分离效果,实验结果说明Desal-DK纳滤膜对NaCl呈现较高的透过性,而对草甘膦则呈现较高的截留性,从而能够有效实现草甘膦和NaCl的分离;最后通过对含有100 g/L NaCl和1 g/L草甘膦的混合溶液进行预浓缩-连续恒容渗滤过程的模拟计算,得到了较高浓度的草甘膦溶液和相对较纯的NaCl溶液,证明通过纳滤渗滤过程实现含草甘膦浓盐水的资源化利用是可行的。
To investigate the feasibility of nanofiltration technology to separate glyphosate solution containing high concentration of monovalent salt, a commercial Desal-DK nanofiltration membrane was used to carry out separation experiments and simulation calculations of glyphosate solution containing high concentration of NaCl. Firstly,effects of feed compositions and transmembrane pressures on the flux and the solute retention for single solutions were investigated by the NF filtration experiments. Membrane parameters were obtained by fitting the experimental results to the SK(Spiegler-Kedem) equations. The results showed that the Desal-DK NF membrane had a low rejection to NaCl and a high rejection to glyphosate for the single solutions. For the high-concentrated binary component solutions, volumetric fluxes of the mixed solution is significantly reduced compared to the single solutions, while the NF membrane presented higher retention rate(more than 90%) to glyphosate and a lower rejection(less than 10%) to NaCl. Finally the selective separation of NaCl and glyphosate by NF diafiltration was simulated for the binary solution containing 1 g/L glyphosate and 100 g/L NaCl. After pre-concentration and diafiltration, a highly concentrated solution of glyphosate(7.43 g/L) and a relatively pure solution of NaCl(89.02 g/L) were obtained. This work demonstrated that DK NF membrane is a practical way for the separation of glyphosate and NaCl in the industry.
To investigate the feasibility of nanofiltration technology to separate glyphosate solution containing high concentration of monovalent salt, a commercial Desal-DK nanofiltration membrane was used to carry out separation experiments and simulation calculations of glyphosate solution containing high concentration of NaCl. Firstly,effects of feed compositions and transmembrane pressures on the flux and the solute retention for single solutions were investigated by the NF filtration experiments. Membrane parameters were obtained by fitting the experimental results to the SK(Spiegler-Kedem) equations. The results showed that the Desal-DK NF membrane had a low rejection to NaCl and a high rejection to glyphosate for the single solutions. For the high-concentrated binary component solutions, volumetric fluxes of the mixed solution is significantly reduced compared to the single solutions, while the NF membrane presented higher retention rate(more than 90%) to glyphosate and a lower rejection(less than 10%) to NaCl. Finally the selective separation of NaCl and glyphosate by NF diafiltration was simulated for the binary solution containing 1 g/L glyphosate and 100 g/L NaCl. After pre-concentration and diafiltration, a highly concentrated solution of glyphosate(7.43 g/L) and a relatively pure solution of NaCl(89.02 g/L) were obtained. This work demonstrated that DK NF membrane is a practical way for the separation of glyphosate and NaCl in the industry.
引文
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[27]Yuan J,Duan J M,Saint C P.Removal of glyphosate and aminomethylphosphonic acid from synthetic water by nanofiltration[J].Environmental Technology,2018,39(11):1384-1392.
[28]徐演初,吴礼光,沈江南,等.一种集成膜分离浓缩草甘膦母液方法:1775786B[P].2011.Xu Y C,Wu L G,Shen J N,et al.A method for separating and separating glyphosate mother liquor by integrated membrane:1775786B[P].2011.
[29]Shen J N,Huang J,Ruan H M,et al.Techno-economic analysis of resource recovery of glyphosate liquor by membrane technology[J].Desalination,2014,342(S1):118-125.
[30]Shen J N,Huang J,Liu L F,et al.The use of BMED for glyphosate recovery from glyphosate neutralization liquor in view of zero discharge[J].Journal of Hazardous Materials,2013,260(18):660-667.
[31]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.草甘膦原药:GB/T 12686-2017[S].北京:中国标准出版社,2017.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Glyphosate technical:GB/T 12686-2017[S].Beijing:Standards Press of China,2017.
[32]Spiegler K S,Kedem O.Thermodynamics of hyperfiltration(reverse osmosis):criteria for efficient membranes[J].Desalination1966,1(S1):311-326.
[33]Schock G,Miquel A.Mass transfer and pressure loss in spiral wound modules[J].Desalination,1987,64(S1):339-352.
[34]Hilal N,Al-zoubi H,Mohammad A W,et al.Nanofiltration of highly concentrated salt solutions up to seawater salinity[J].Desalination,2005,184(1/2/3):315-326.
[35]燕至琴.高浓一二价盐溶液的纳滤膜分离性能研究[D].北京:清华大学,2016.Yan Z Q.Research on separation performance of mono and divalent salt solution with high concentration by nanofiltration membrane[D].Beijing:Tsinghua University,2016.
[2]Mohammad A W,Teow Y H,Ang W L,et al.Nanofiltration membranes review:recent advances and future prospects[J].Desalination,2015,356(S1):226-254.
[3]Esmia C F,Schrivea L,Barrea Y,et al.Using nanofiltration in a"zero-rejection"process:the removal of Ni2+and Co2+from salty wastewater[J].Desalination and Water Treatment,2013,51(1/2/3):476-484.
[4]Perez-Gonzalez A,Ibanez R,Gomez P,et al.Nanofiltration separation of polyvalent and monovalent anions in desalination brines[J].Journal of Membrane Science,2015,473:16-27.
[5]Bennani C F,M'hiri O.Comparative study of the removal of heavy metals by two nanofiltration membranes[J].Desalination and Water Treatment,2015,53(4):1024-1030.
[6]Wang X L,Zhang C H,Ouyang P.The possibility of separating saccharides from a NaCl solution by using nanofiltration in diafiltration mode[J].Journal of Membrane Science,2002,204(1/2):271-281.
[7]Zhao H F,Hua X,Yang R J,et al.Diafiltration process on xylooligosaccharides syrup using nanofiltration and its modeling[J].International Journal of Food Science and Technology,2012,47(1):32-39.
[8]Mikulaseka P,Cuhorka J.Desalination and concentration of liquid dyes by nanofiltration[J].Desalination and Water Treatment,2015,55(10):2711-2720.
[9]He Y,Li G,Wang H,et al.Diafiltration and water recovery of Reactive Brilliant Blue KN-R solution by two-stage membrane separation process[J].Chemical Engineering and Processing,2010,49(5):476-483.
[10]Tu C H,Fang Y Y,Zhu J,et al.Free energies of the ion equilibrium partition of KCl into nanofiltration membranes based on applied electrical potential and rejection[J].Langmuir,2011,27(16):10274-10281.
[11]Tu C H,Wang H L,Wang X L.Study on transmembrane electrical potential of nanofiltration membranes in KCl and MgCl2solutions[J].Langmuir,2010,26(22):17656-17664.
[12]Tu C H,Wu L,Wang D X,et al.Prediction of separation performance of NF membranes for mixed electrolytes solution[J].Desalination,2010,260(1/2/3):218-224.
[13]Wang D X,Su M,Yu Z Y,et al.Separation performance of a nanofiltration membrane influenced by species and concentration of ions[J].Desalination,2005,175(2):219-225.
[14]Su M,Wang D X,Wang X L,et al.Rejection of ions by NFmembranes for binary electrolyte solutions of NaCl,NaNO3,CaCl2and Ca(NO3)2[J].Desalination,2006,191(1/2/3):303-308.
[15]Murthy Z V P,Chaudhari L B.Rejection behavior of nickel ions from synthetic wastewater containing Na2SO4,NiSO4,MgCl2and CaCl2salts by nanofiltration and characterization of the membrane[J].Desalination,2009,247(1/2/3):610-622.
[16]Wu L,Song L,Wang X L,et al.Experimental study on separation performance of nanofiltration membranes for bicarbonate salts solution[J].Desalination,2009,236(1/2/3):299-305.
[17]Tanninen J,Manttari M,Nystrom M.Effect of salt mixture concentration on fractionation with NF membranes[J].Journal of Membrane Science,2006,283(1/2):57-64.
[18]Al-Zoubi H,Omar W.Rejection of salt mixtures from high saline by nanofiltration membranes[J].Korean Journal of Chemical Engineering,2009,26(3):799-805.
[19]Silva V,Geraldes V,Brites Alves A M,et al.Multi-ionic nanofiltration of highly concentrated salt mixtures in the seawater range[J].Desalination,2011,277(1/2/3):29-39.
[20]Hilal N,Kochkodan V,Al Abdulgader H,et al.A combined ion exchange-nanofiltration process for water desalination(Ⅱ):Membrane selection[J].Desalination,2015,363(S1):51-57.
[21]Yaroshchuk A E.Non-steric mechanisms of nanofiltration:superposition of Donnan and dielectric exclusion[J].Separation and Purification Technology,2001,22/22/23(S1):143-158.
[22]吴哲峰.草甘膦生产线上副产固体盐精制的研究[D].浙江:浙江理工大学,2015.Wu Z F.Study on the purification of the buproduct salt from the glyphosate production process[D].Zhejiang:Zhejiang Sci-tech University,2015.
[23]Xie M,Liu Z Y,Xu Y H,Removal of glyphosate in neutralization liquor from the glycine-dimethylphosphit process by nanofiltration[J].Journal of Hazardous Materials,2010,181(1/2/3):975-980.
[24]谢明,刘志英,赵贤广,等.草甘膦模拟废水的纳滤分离过程研究[J].环境工程学报,2010,4(7):1483-1487.Xie M,Liu Z Y,Zhao X G,et al.Nanofiltration separation process of model glyphosate wastewater[J].Chinese Journal of Environmental Engineering,2010,4(7):1483-1487.
[25]黄华,李雪梅,潘成,等.SPEEK涂层纳滤膜处理草甘膦废水[J].环境工程学报,2012,6(8):2489-2494.Huang H,Li X M,Pan C,et al.Treatment of glyphosate containing wastewater using SPEEK coated nanofiltration membranes[J].Chinese Journal of Environmental Engineering,2012,6(8):2489-2494.
[26]Song J F,Li X M,Albeto F,et al.Composite hollow fiber nanofiltration membranes for recovery of glyphosate from saline wastewater[J].Water Research,2013,47(6):2065-2074.
[27]Yuan J,Duan J M,Saint C P.Removal of glyphosate and aminomethylphosphonic acid from synthetic water by nanofiltration[J].Environmental Technology,2018,39(11):1384-1392.
[28]徐演初,吴礼光,沈江南,等.一种集成膜分离浓缩草甘膦母液方法:1775786B[P].2011.Xu Y C,Wu L G,Shen J N,et al.A method for separating and separating glyphosate mother liquor by integrated membrane:1775786B[P].2011.
[29]Shen J N,Huang J,Ruan H M,et al.Techno-economic analysis of resource recovery of glyphosate liquor by membrane technology[J].Desalination,2014,342(S1):118-125.
[30]Shen J N,Huang J,Liu L F,et al.The use of BMED for glyphosate recovery from glyphosate neutralization liquor in view of zero discharge[J].Journal of Hazardous Materials,2013,260(18):660-667.
[31]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.草甘膦原药:GB/T 12686-2017[S].北京:中国标准出版社,2017.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China,Standardization Administration of the People's Republic of China.Glyphosate technical:GB/T 12686-2017[S].Beijing:Standards Press of China,2017.
[32]Spiegler K S,Kedem O.Thermodynamics of hyperfiltration(reverse osmosis):criteria for efficient membranes[J].Desalination1966,1(S1):311-326.
[33]Schock G,Miquel A.Mass transfer and pressure loss in spiral wound modules[J].Desalination,1987,64(S1):339-352.
[34]Hilal N,Al-zoubi H,Mohammad A W,et al.Nanofiltration of highly concentrated salt solutions up to seawater salinity[J].Desalination,2005,184(1/2/3):315-326.
[35]燕至琴.高浓一二价盐溶液的纳滤膜分离性能研究[D].北京:清华大学,2016.Yan Z Q.Research on separation performance of mono and divalent salt solution with high concentration by nanofiltration membrane[D].Beijing:Tsinghua University,2016.