以低浓度废酸驱动中和渗析脱盐的模拟与验证

doi:10.11949/0438-1157.20230275

摘要/Abstract

摘要：

低浓度废酸的资源化长期困扰着相关涉酸工艺。基于Donnan渗析原理，提出以低浓度废酸驱动中和渗析地表水脱盐，借助模拟和实验来探索耦合工艺的可行性。首先，基于Nernst-Planck、Navier-Stokes方程和电中性条件，面向中和渗析过程数学建模，研究废酸浓度对脱盐率、脱盐速度和体系pH等脱盐效果的影响。模拟结果表明，常规低浓度废酸（pH=0.5~2）足以有效驱动中和渗析脱盐过程，且提高酸浓度也未得到明显强化。进而，以均相或异相离子交换膜构建中和渗析膜堆，开展条件实验，获得了系列与模拟结果相吻合的实验规律。实验也表明，对于高浓度废酸，异相膜较显著的同离子泄漏现象会严重劣化脱盐效率。综合研究表明，耦合新工艺有望为低浓度废酸的资源化开辟新途径。

关键词: 中和渗析, 废物处理, 离子交换膜, 脱盐, 数学模拟

Abstract:

The reclamation of low concentration waste acid has long puzzled acid-related technology. Based on the Donnan dialysis principle, a novel technology which couples the waste acid reclamation with neutralization dialysis desalination is put forward in this work. Its feasibility is demonstrated by means of model simulation and experiment validation on the basis of the practical application of surface water desalination driven by a series of waste acid with typical concentrations. Firstly, based on Nernst-Planck equation, Navier-Stokes equation and electroneutral condition, an unsteady mathematical model is established to explore the effects of acid concentration on the desalination rate, desalination speed and pH of system. The simulated results show that the relative low concentration of acid (pH=0.5—2) is strong enough to drive the neutralization dialysis process which is not strengthened remarkably after a further increase of acid concentration. Subsequently, a neutralization dialysis membrane stack is constructed by typical commercial homogeneous or heterogeneous membranes for desalination experiments and provides a series of results which agree well with model predictions. Experiments also show that for high-concentration waste acid, the more significant leakage of the same ion in the heterogeneous membrane will seriously deteriorate the desalination efficiency. The comprehensive research shows that the coupled new process is expected to open up a new way for the resource utilization of low-concentration waste acid.

Key words: neutralization dialysis, waste treatment, ion exchange membranes, desalination, mathematical modeling

中图分类号:

TQ 028.8

陈朝光, 贾玉香, 汪锰. 以低浓度废酸驱动中和渗析脱盐的模拟与验证[J]. 化工学报, 2023, 74(6): 2486-2494.

Zhaoguang CHEN, Yuxiang JIA, Meng WANG. Modeling neutralization dialysis desalination driven by low concentration waste acid and its validation[J]. CIESC Journal, 2023, 74(6): 2486-2494.

图/表 9

图1 中和渗析结构示意图

Fig.1 Schematic diagram of neutralization dialysis structure

表1 直流法测定异相商品膜电阻

Table 1 Resistance of commercial heterogeneous membrane measured by DC method

膜	$R N a / (Ω · c m 2)$	$R C l / (Ω · c m 2)$	$R H / (Ω · c m 2)$	$R O H / (Ω · c m 2)$
CEM	6.77	—	2.88	—
AEM	—	10.11	—	7.12

表1 直流法测定异相商品膜电阻

Table 1 Resistance of commercial heterogeneous membrane measured by DC method

膜	$R N a / (Ω · c m 2)$	$R C l / (Ω · c m 2)$	$R H / (Ω · c m 2)$	$R O H / (Ω · c m 2)$
CEM	6.77	—	2.88	—
AEM	—	10.11	—	7.12

表2 膜主要性能参数

Table 2 Main performance parameters of the selected membranes

膜

厚度/

$m m$

IEC/

$(m o l · k g - 1)$

WU/

$%$

$(m o l · m - 3)$

膜面积/

$c m 2$

表2 膜主要性能参数

Table 2 Main performance parameters of the selected membranes

膜

厚度/

$m m$

IEC/

$(m o l · k g - 1)$

WU/

$%$

$(m o l · m - 3)$

膜面积/

$c m 2$

CEM

0.48

2.0

4.0

100

AEM

0.48

1.8

4.5

100

表3 离子在膜和溶液中的扩散系数

Table 3 Diffusion coefficients of ions in membrane and solution

项目

$D H /$

$(c m 2 · s - 1)$

$D N a /$

$(c m 2 · s - 1)$

$D O H /$

$(c m 2 · s - 1)$

$D C l /$

$(c m 2 · s - 1)$

CEM

1.11 × 10 - 6

4.72 × 10 - 7

—

AEM

—

3.99 × 10 - 7

2.81 × 10 - 7

溶液

9.30 × 10 - 5

1.33 × 10 - 5

5.30 × 10 - 5

2.03 × 10 - 5

表3 离子在膜和溶液中的扩散系数

Table 3 Diffusion coefficients of ions in membrane and solution

项目

$D H /$

$(c m 2 · s - 1)$

$D N a /$

$(c m 2 · s - 1)$

$D O H /$

$(c m 2 · s - 1)$

$D C l /$

$(c m 2 · s - 1)$

CEM

1.11 × 10 - 6

4.72 × 10 - 7

—

AEM

—

3.99 × 10 - 7

2.81 × 10 - 7

溶液

9.30 × 10 - 5

1.33 × 10 - 5

5.30 × 10 - 5

2.03 × 10 - 5

图2 酸（碱）初始浓度对盐溶液的影响（CNaClD=0.05 mol·L-1，Q=50 L·h-1）

Fig.2 Effects of initial concentration of acid (base) on salt solution (CNaClD=0.05 mol·L-1, Q=50 L·h-1)

图3 不同酸（碱）浓度对pH的影响（CNaClD=0.05 mol·L-1，Q=50 L·h-1）

Fig.3 Effects of different acid (base) concentrations on pH (CNaClD=0.05 mol·L-1, Q=50 L·h-1)

图4 酸（碱）初始浓度的影响（均相膜，CNaClD=0.05 mol·L-1，Q=50 L·h-1）

Fig.4 Effects of initial concentration of acid (base) (homogeneous IEM, CNaClD=0.05 mol·L-1，Q=50 L·h-1)

图5 酸（碱）初始浓度的影响（异相膜，CNaClD=0.05 mol·L-1，Q=50 L·h-1）

Fig.5 Effects of initial concentration of acid (base) (heterogeneous IEM, CNaClD=0.05 mol·L-1，Q=50 L·h-1)

图6 不同体系酸（碱）初始浓度对pH的影响（CNaClD=0.05 mol·L-1，Q=50 L·h-1）

Fig.6 Effects of initial concentration of acid (base) on pH in different system (CNaClD=0.05 mol·L-1，Q=50 L·h-1)

参考文献 34

9	Muhsan M A, Ilyas S, Cheema H A, et al. Recovery of nitric acid from effluent streams using solvent extraction with TBP: a comparative study in absence and presence of metal nitrates[J]. Separation and Purification Technology, 2017, 186: 90-95.
10	Kraus K A, Nelson F, Baxter J F. Anion-exchange studies(Ⅶ^{1, 2}): Separation of sulfuric acid from metal sulfates by anion exchange[J]. Journal of the American Chemical Society, 1953, 75(11): 2768-2770.
11	Song P P, Wang M, Zhang B P, et al. Fabrication of proton permselective composite membrane for electrodialysis-based waste acid reclamation[J]. Journal of Membrane Science, 2019, 592: 117366.
12	Igawa M, Echizenya K, Hayashita T, et al. Donnan dialysis desalination[J]. Chemistry Letters, 1986, 15(2): 237-238.
13	Igawa M, Echizenya K, Hayashita T, et al. Neutralization dialysis for deionization[J]. Bulletin of the Chemical Society of Japan, 1987, 60(1): 381-383.
14	Bleha M, Tishchenko G A. Neutralization dialysis for desalination[J]. Journal of Membrane Science, 1992, 73(2/3): 305-311.
15	赵宜江, 邢卫红, 徐南平. 扩散渗析法从钛白废酸中回收硫酸[J]. 高校化学工程学报, 2002, 16(2): 217-221.
	Zhao Y J, Xing W H, Xu N P. Recovery of sulfuric acid from titanium white waste acid by diffusion dialysis[J]. Journal of Chemical Engineering of Chinese Universities, 2002, 16(2): 217-221.
16	Nikonenko V V, Kovalenko A V, Urtenov M K, et al. Desalination at overlimiting currents: state-of-the-art and perspectives[J]. Desalination, 2014, 342: 85-106.
17	Strathmann H. Electrodialysis, a mature technology with a multitude of new applications[J]. Desalination, 2010, 264(3): 268-288.
18	Kozmai A, Nikonenko V, Pismenskaya N, et al. Effect of anion exchange membrane capacity loss on pH and electric conductivity of saline solution during neutralization dialysis[J]. Journal of Membrane Science, 2020, 595: 117573.
19	Velizarov S. Transport of arsenate through anion-exchange membranes in donnan dialysis[J]. Journal of Membrane Science, 2013, 425/426: 243-250.
20	Matos C T, Velizarov S, Crespo J G, et al. Simultaneous removal of perchlorate and nitrate from drinking water using the ion exchange membrane bioreactor concept[J]. Water Research, 2006, 40(2): 231-240.
21	Chérif M, Mkacher I, Dammak L, et al. Water desalination by neutralization dialysis with ion-exchange membranes: flow rate and acid/alkali concentration effects[J]. Desalination, 2015, 361: 13-24.
22	Palatý Z, Bendová H. Neutralisation dialysis of oxalic acid in a batch cell[J]. Chemical Engineering and Processing-Process Intensification, 2020, 154: 108007.
23	Wang G Q, Tanabe H, Igawa M. Transport of glycine by neutralization dialysis[J]. Journal of Membrane Science, 1995, 106(3): 207-211.
24	Biesheuvel P M. Two-fluid model for the simultaneous flow of colloids and fluids in porous media[J]. Journal of Colloid and Interface Science, 2011, 355(2): 389-395.
25	Mareev S A, Nikonenko V V. A numerical experiment approach to modeling impedance: application to study a Warburg-type spectrum in a membrane system with diffusion coefficients depending on concentration[J]. Electrochimica Acta, 2012, 81: 268-274.
26	Nikolskii B P. Theory of the glass electrode. I.Theoretical[J]. J.Phys. Chem., 1937, 10: 495-503.
27	Galama A H, Post J W, Stuart M A C, et al. Validity of the Boltzmann equation to describe Donnan equilibrium at the membrane-solution interface[J]. Journal of Membrane Science, 2013, 442: 131-139.
28	Wang Q, Chen G Q, Kentish S E. Sorption and diffusion of organic acid ions in anion exchange membranes: acetate and lactate ions as a case study[J]. Journal of Membrane Science, 2020, 614: 118534.
29	Zabolotsky V I, Nikonenko V V. Effect of structural membrane inhomogeneity on transport properties[J]. Journal of Membrane Science, 1993, 79(2/3): 181-198.
30	Dammak L, Lteif R, Bulvestre G, et al. Determination of the diffusion coefficients of ions in cation-exchange membranes, supposed to be homogeneous, from the electrical membrane conductivity and the equilibrium quantity of absorbed electrolyte[J]. Electrochimica Acta, 2001, 47(3): 451-457.
31	Kozmai A, Chérif M, Dammak L, et al. Modelling non-stationary ion transfer in neutralization dialysis[J]. Journal of Membrane Science, 2017, 540: 60-70.
1	胡术刚, 马术文, 王之静, 等. 钛白废酸废水治理及副产石膏应用探讨[J]. 中国资源综合利用, 2003, 21(9): 2-8.
	Hu S G, Ma S W, Wang Z J, et al. Application research on titanium dioxide waste acid and acid waste water treatment and the byproduct-gypsum[J]. China Resources Comprehensive Utilization, 2003, 21(9): 2-8.
2	孙安妮, 孙根行. 废盐酸再生利用研究进展[J]. 当代化工, 2011, 40(11): 1178-1181.
	Sun A N, Sun G X. Research progress in regeneration and utilization of waste hydrochloric acid[J]. Contemporary Chemical Industry, 2011, 40(11): 1178-1181.
3	钱钧. 废酸集中处理资源化利用模式[C]//2019中国工业水处理大会暨第39届年会. 泰安, 2019.
	Qian J. Centralized treatment model of waste acid reclamation[C]//China Industrial Water Treatment Conference and the 39th Annual Meeting. Tai'an, 2019.
4	樊盛春, 李越湘. 钢铁酸洗废液的处理与综合利用[J]. 江西冶金, 2000, 20(3): 12-14
	Fan C C, Li Y X. Treatment and comprehensive utilization of pickling waste liquid of iron and steel[J]. Jiangxi Metallurgy, 2000, 20(3): 12-14.
5	Zhang Y L, Song G L, Luo T, et al. Acid-triggered polyether sulfone—polyvinyl pyrrolidone blend anion exchange membranes for the recovery of titania waste acid via diffusion dialysis[J]. Journal of Membrane Science, 2022, 662: 120980.
6	Kladnig W. New development of acid regeneration in steel pickling plants[J]. Journal of Iron and Steel Research, International, 2008, 15(4): 1-6.
7	陈文松, 宁寻安, 白晓燕. 废酸液的资源化处理技术[J]. 工业水处理, 2008, 28(3): 20-22, 80.
	Chen W S, Ning X A, Bai X Y. Treatment technologies of waste acid liquid for resource recycling[J]. Industrial Water Treatment, 2008, 28(3): 20-22, 80.
8	Song K, Meng Q Q, Shu F, et al. Recovery of high purity sulfuric acid from the waste acid in toluene nitration process by rectification[J]. Chemosphere, 2013, 90(4): 1558-1562.
32	Larchet C, Dammak L, Auclair B, et al. A simplified procedure for ion-exchange membrane characterization[J]. New Journal of Chemistry, 2004, 28(10): 1260-1267.
33	张维润. 电渗析工程学[M]. 北京: 科学出版社, 1995.
	Zhang W R. Electrodialysis Engineering[M]. Beijing: Science Press, 1995.
34	佐田俊胜. 离子交换膜: 制备, 表征, 改性和应用[M]. 汪锰, 任庆春, 译. 北京: 化学工业出版社, 2015.
	Toshikatsu S. Ion Exchange Membranes: Preparation, Characterization and Application[M]. Wang M, Ren Q C, trans. Beijing: Chemical Industry Press, 2015.

[1]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[2]	张曼铮, 肖猛, 闫沛伟, 苗政, 徐进良, 纪献兵. 危废焚烧处理耦合有机朗肯循环系统工质筛选与热力学优化[J]. 化工学报, 2023, 74(8): 3502-3512.
[3]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[4]	顾浩, 张福建, 刘珍, 周文轩, 张鹏, 张忠强. 力电耦合作用下多孔石墨烯膜时间维度的脱盐性能及机理研究[J]. 化工学报, 2023, 74(5): 2067-2074.
[5]	罗来明, 张劲, 郭志斌, 王海宁, 卢善富, 相艳. 1~5 kW高温聚合物电解质膜燃料电池堆的理论模拟与组装测试[J]. 化工学报, 2023, 74(4): 1724-1734.
[6]	刘定平, 陈爱桦, 张向阳, 何文浩, 王海. 铝灰半干法水解脱氮研究[J]. 化工学报, 2023, 74(3): 1294-1302.
[7]	闫军营, 王皝莹, 李瑞瑞, 符蓉, 蒋晨啸, 汪耀明, 徐铜文. 选择性电渗析：机遇与挑战[J]. 化工学报, 2023, 74(1): 224-236.
[8]	罗欣宜, 冯超, 刘晶, 乔瑜. 污泥不同热处理工艺产物磷的浸出回收实验研究[J]. 化工学报, 2022, 73(9): 4034-4044.
[9]	黄陆月, 刘畅, 许勇毅, 邢浩若, 王峰, 马双忱. CDI二维浓度传质模型的建立以及实验验证[J]. 化工学报, 2022, 73(7): 2933-2943.
[10]	朱嫣然, 葛亮, 李兴亚, 徐铜文. 三相结构离子交换膜的构筑及应用研究[J]. 化工学报, 2022, 73(6): 2397-2414.
[11]	郭志强, 燕可洲, 张吉元, 柳丹丹, 高阳艳, 郭彦霞. 煤矸石/粉煤灰对赤泥钠化还原焙烧反应的影响机制[J]. 化工学报, 2022, 73(5): 2194-2205.
[12]	许世佩, 王超, 李庆远, 张炳康, 许世伟, 张雪琴, 王诗颖, 丛梦晓. 氧化钙对油基钻屑热脱附产物影响的研究[J]. 化工学报, 2022, 73(4): 1724-1731.
[13]	迟子怡, 刘成伟, 张欲凌, 李学刚, 肖文德. CO氧化偶联反应器模拟与优化[J]. 化工学报, 2022, 73(11): 4974-4986.
[14]	王慧艳, 陈怡沁, 周静红, 曹约强, 周兴贵. 锂离子电池正极涂层孔隙结构优化的数值模拟[J]. 化工学报, 2022, 73(1): 376-383.
[15]	王乾浩, 赵璐, 孙付琳, 房克功. ZSM-5催化剂与低温等离子体协同转化H₂S-CO₂制合成气[J]. 化工学报, 2022, 73(1): 255-265.