高浓度含盐草甘膦溶液的纳滤分离实验研究

doi:10.11949/0438-1157.20190014

摘要/Abstract

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。

关键词: 纳滤, 分离, 氯化钠, 草甘膦, 废水

Abstract:

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.

Key words: nanofiltration, separation, sodium chloride, glyphosate, waste water

中图分类号:

TQ 028

唐元晖, 扈阳, 燕至琴, 李春玉. 高浓度含盐草甘膦溶液的纳滤分离实验研究[J]. 化工学报, 2019, 70(7): 2574-2583.

Yuanhui TANG, Yang HU, Zhiqin YAN, Chunyu LI. Experimental study on nanofiltration separation of high concentrated saline glyphosate solution[J]. CIESC Journal, 2019, 70(7): 2574-2583.

图/表 12

图1 草甘膦结构式

Fig.1 Structure of glyphosate

图2 纳滤透过实验装置

Fig.2 Schematic diagram for cross-flow NF equipment adopted in experiments

表1 实验中采用的原料液组成

Table1 Concentrations of feed solution

原料液编号	原料液组成/(g/L)
原料液编号	草甘膦	NaCl
1		60
2		80
3		100
4	1
5	4
6	7
7	1	100
8	4	100
9	7	100

图3 纳滤膜的纯水通量随操作压力变化关系

Fig.3 Relationship between pure water flux of nanofiltration membrane and operating pressure

图4 DK膜对NaCl溶液的体积透过通量和截留率

Fig.4 Relationship between volume permeate flux and rejection rate of DK membrane on NaCl solution with operating pressure and concentration

图5 DK膜对草甘膦溶液的体积透过通量和截留率

Fig.5 Volumetric flux and rejection of DK membrane to glyphosate solution as a function of operating pressure and concentration

图6 DK膜对不同溶质的真实截留率随通量变化关系及S-K拟合曲线

Fig.6 Relationship between true rejection rate of DK membranes on different solute with flux and S-K fitting

表2 DK膜对实验体系的透过实验中膜特征参数和

Table 2 Fitting calculation results of membrane characteristic parameters and structural parameters of DK membrane on experimental system

溶质	浓度/(g/L)	σ	P×10⁶/(m/s)
NaCl	60	0.151	3.07
	80	0.121	3.36
	100	0.119	3.89
草甘膦	1	0.971	0.271
	4	0.973	0.202
	7	0.985	0.198

表3 不同操作条件下的浓差极化程度表征

Table 3 Characterization of concentration polarization degree under different operating conditions

操作压力/MPa	草甘膦浓度/(g/L)			NaCl浓度/(g/L)
操作压力/MPa	1	4	7	60	80	100
0.6	0.048	0.046	0.044	0.0025	0.0015	0.00079
0.9	0.067	0.065	0.064	0.0039	0.0027	0.0017
1.2	0.094	0.091	0.087	0.0059	0.0042	0.0025
1.5	0.11	0.12	0.11	0.0079	0.0050	0.0034

图7 DK膜对草甘膦与NaCl混合溶液的体积透过通量和截留率随操作压力和浓度的变化关系

Fig.7 Volumetric flux of DK membrane on glyphosate and NaCl mixed solution and interception rate as a function of operating pressure and concentration

图8 预浓缩-连续恒容渗滤过程中料液中草甘膦和NaCl浓度比随浓缩倍数（V0/ Vf）与渗滤过程中水消耗量（Vw/ V0’）的变化关系

Fig.8 Relationship between concentration ratio of glyphosate and NaCl in feed solution during preconcentration-continuous constant volume percolation with concentration factor (V0/Vf ) and water consumption during percolation process (Vw/V0)

表4 整个浓缩-渗滤过程中的水消耗量、料液及透过液的体积和浓度变化

Table 4 Variations of water consumption, volume and concentration of feed and permeate during whole concentration-infiltration process

渗滤过程	水消耗量	料液			透过液
渗滤过程	水消耗量	体积	c(草甘膦)/(g/L)	c(NaCl)/(g/L)	体积	c(草甘膦)/(g/L)	c(NaCl)/(g/L)
初始	—	V₀	1.00	100.0	—	—	—
预浓缩后	0	1/10 V₀	8.51	125.92	9/10 V₀	0.17	97.12
连续恒容渗滤后	1/5 V₀	1/10 V₀	7.43	20.81	11/10 V₀	0.24	89.02

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