高浓度Na+//NO3-， SO42--H2O溶液的膜蒸馏结晶耦合过程调控

doi:10.11949/0438-1157.20220177

化工学报 ›› 2022, Vol. 73 ›› Issue (7): 3078-3089.DOI: 10.11949/0438-1157.20220177

高浓度Na⁺//NO $3 -$ ， SO $4 2 -$ -H₂O溶液的膜蒸馏结晶耦合过程调控

孙国鑫¹(),苟萌萱¹,周诚²,常佩²,贺高红¹,姜晓滨¹()

^1.大连理工大学化工学院，精细化工国家重点实验室，辽宁省石化行业高效节能分离技术工程实验室，辽宁大连 116024
^2.西安近代化学研究所，陕西西安 710065

收稿日期:2022-02-10 修回日期:2022-03-21 出版日期:2022-07-05 发布日期:2022-08-01
通讯作者: 姜晓滨
作者简介:孙国鑫（1996—），男，硕士，guoxinsun@dlut.edu.cn
基金资助:
国家自然科学基金项目(21978037);国家重点研发计划项目(2021YFC2901300)

Membrane distillation crystallization coupling process for the treatment of high concentration Na⁺//NO $3 -$ , SO $4 2 -$ -H₂O solution

Guoxin SUN¹(),Mengxuan GOU¹,Cheng ZHOU²,Pei CHANG²,Gaohong HE¹,Xiaobin JIANG¹()

^1.State Key Laboratory of Fine Chemicals, Engineering Laboratory for Petrochemical Energy-efficient Separation Technology of Liaoning Province, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^2.Xi’an Modern Chemistry Research Institute, Xi’an 710065, Shaanxi, China

Received:2022-02-10 Revised:2022-03-21 Online:2022-07-05 Published:2022-08-01
Contact: Xiaobin JIANG

摘要/Abstract

摘要：

煤化工、含能材料等工业领域产生的富含硝酸盐、硫酸盐的高浓废水排放量巨大、环境危害严重。高浓度复合盐水低能耗处理的同时实现高品质结晶过程调控，已经成为一个重要的研究方向。针对典型的高浓度Na⁺//NO $3 -$ ， SO $4 2 -$ -H₂O溶液体系，提出利用膜蒸馏结晶耦合技术处理，通过微孔膜界面调控目标盐分的成核能垒，有效控制了典型蒸发结晶过程中多元盐离子扩散差异、爆发成核，避免了形成空心、高杂质离子包藏的晶体，提升了结晶纯度和分离效率；同时，提出在膜蒸馏的优势分离区间内蒸发溶剂，然后再通过减压蒸发结晶的优化设计思路，降低了膜表面结垢和膜孔润湿风险，进一步提升了整个过程能量效率，提高了膜可重复利用率。研究为开发高浓度复合无机盐水处理技术提供了新思路。

关键词: 膜蒸馏, 减压蒸发, 结晶, 过程耦合, 盐水处理

Abstract:

The high-concentration wastewater rich in nitrates and sulfates produced in industrial fields such as coal chemical industry and energetic materials has a huge amount of discharge and serious environmental damage. It is an important research direction to realize the regulation of high-quality crystallization process while treating high-concentration composite brine with low energy consumption. Aiming at the typical high-concentration Na⁺//NO $3 -$ , SO $4 2 -$ -H₂O solution system, this paper proposes a membrane distillation and crystallization coupling method to treat this kind of high-concentration composite inorganic brine. The nucleation energy barrier of the target salt is effectively regulated at the microporous membrane interface, which effectively controls the diffusion difference and explosive nucleation of multi-salt ions in the typical evaporative crystallization process. In addition, the formation of hollow and high-impurity ion crystals can be avoided, and the crystal purity and separation performance is improved. The design strategy of evaporating for concentrating the solvent in the advantageous range of membrane distillation, and then evaporating for crystallization under vacuum vaporization, is proposed to reduce the risk of membrane surface scaling and membrane pore wetting. In addition, this strategy further improves the energy efficiency of the entire separation process. The above research provides a new idea for the technology development of high-concentration inorganic brine treatment.

Key words: membrane distillation, vacuum evaporation, crystallization, process coupling, brine treatment

中图分类号:

TQ 028.8

孙国鑫, 苟萌萱, 周诚, 常佩, 贺高红, 姜晓滨. 高浓度Na⁺//NO $3 -$ ， SO $4 2 -$ -H₂O溶液的膜蒸馏结晶耦合过程调控[J]. 化工学报, 2022, 73(7): 3078-3089.

Guoxin SUN, Mengxuan GOU, Cheng ZHOU, Pei CHANG, Gaohong HE, Xiaobin JIANG. Membrane distillation crystallization coupling process for the treatment of high concentration Na⁺//NO $3 -$ , SO $4 2 -$ -H₂O solution[J]. CIESC Journal, 2022, 73(7): 3078-3089.

图/表 25

图1 复合盐水处理技术框架图

Fig.1 Framework of brine treatment technology

表1 实验药品与试剂

Table 1 Drugs and reagents used in the experiment

名称	规格	厂家
硝酸钠	分析纯	天津市大茂化学试剂厂
无水硫酸钠	分析纯	天津市科密欧化学试剂有限公司
超纯水	离子含量<0.1 μg/L	莱特莱德环境工程有限公司

表2 中空纤维膜材料的结构参数

Table 2 Membrane structure parameters of hollow fiber membrane

膜材料	外径/μm	内径/μm	纯水接触角/（°）	体积空隙率
PTFE	2110±50	1200±35	120±2	0.53±0.01

表3 实验中使用的仪器

Table 3 Apparatus used during the experiment

名称	规格	厂家
中空纤维膜组件	内径20 mm，高150 mm，装填密度454.0、340.5、227.0 m²/m³	自制
电子天平	Adventurer AR	奥豪斯仪器有限公司
蠕动泵	BT100-2J	保定兰格恒流泵有限公司
隔膜真空泵	N820	优莱博技术有限公司
真空控制器	NVC-3000	东京理化器械株式会社
恒温水浴	CF41	优莱博技术有限公司
玻璃夹套反应釜	500 ml	优莱博技术有限公司

图2 减压蒸发结晶装置示意图① 天平数据记录计算机;②天平;③结晶釜;④加热水浴;⑤冷却水浴;⑥热电偶;⑦真空控制器;⑧真空泵

Fig.2 Schematic diagram of the experimental device for vacuum evaporative crystallization

图3 真空膜蒸馏结晶装置示意图① 加热水浴;②冷却水浴;③天平;④天平数据记录计算机;⑤结晶釜;⑥真空泵;⑦真空控制器;⑧膜组件;⑨蠕动泵;⑩热电偶

Fig.3 Schematic diagram of the experimental device for vacuum membrane distillation crystallization

图4 Na+//NO3-, SO42--H2O 三元体系相图

Fig.4 Phase diagram of the ternary system Na+//NO3-, SO42--H2O

图5 353.15 K 三元体系Na+//NO3-, SO42--H2O相图

Fig.5 Phase diagram of the ternary system Na+//NO3-, SO42--H2O at 353.15 K

表4 353.15 K 三元体系Na+//NO3-， SO42--H2O 稳定相图数据

Table 4 Stable phase diagram data of the ternary system Na+//NO3-，SO42--H2O at 353.15 K

点	w(NaNO₃)/%	w(Na₂SO₄)/%
固相Q	57.143	42.857
液相E	57.804	1.790
液相M	18.182	13.636
液相N	20.122	15.096

表5 313.15 K 三元体系Na+//NO3-， SO42--H2O 稳定相图数据

Table 5 Stable phase diagram data of the ternary system Na+//NO3-， SO42--H2O at 313.15 K

点	w(NaNO₃)/%	w(Na₂SO₄)/%
液相P₃	48.970	2.480
液相E₁	57.804	1.790

图6 313.15 K 三元体系Na+//NO3-, SO42--H2O 相图

Fig.6 Phase diagram of the ternary system Na+//NO3-, SO42--H2O at 313.15 K

图7 减压蒸发结晶产品扫描电镜图

Fig.7 SEM images of vacuum evaporation crystallization product

图8 经典（第1~3步）和新提出的反向晶体生长路线（第4~10步）的示意图

Fig.8 Schematic of classic (steps 1—3) and newly proposed reversed crystal growth routes (steps 4—10)

图9 不同膜组件装填密度下蒸发量随时间变化趋势

Fig.9 Change of evaporation with time under different membrane module package density

图10 不同膜组件装填密度下渗透通量随时间变化趋势

Fig.10 Change of permeate flux with time under different membrane module package density

图11 膜蒸馏结晶产品光学显微镜图

Fig.11 Optical microscope images of membrane distillation crystallization products

图12 膜蒸馏结晶产品扫描电镜图

Fig.12 SEM images of membrane distillation crystallization products

图13 膜蒸馏结晶产品表面元素分析

Fig.13 Elemental mapping of membrane distillation crystallization products surface

图14 不同膜组件装填密度下得到的样品与标准样品XRD谱图

Fig.14 XRD patterns of samples and standard samples obtained under different membrane package density

表6 膜蒸馏结晶产品纯度

Table 6 Purity of membrane distillation crystallization products

编号	纯度/% (质量分数)
1^#	97.900
2^#	96.380
3^#	95.960
4^#	96.160
5^#	95.630
6^#	98.700
7^#	96.660
平均值	96.770

图15 膜蒸馏过程的典型膜通量（a）和阶段性变化原理示意图（b）

Fig.15 Schematic diagram of typical membrane flux (a) and step-by-step change principle of membrane distillation process (b)

图16 MDC-VEC耦合过程蒸发量变化趋势

Fig.16 Evaporation of MDC-VEC coupling process

图17 MDC-VEC耦合过程膜通量（蒸发强度）变化趋势对比

Fig.17 Permeation flux (evaporation rate) of MDC-VEC coupling process

图18 MDC-VEC耦合过程产品晶体表面元素分布

Fig.18 Elemental mapping of MDC-VEC coupling process products surface

表7 MDC-VEC耦合过程晶体收率、总蒸发量及纯度

Table 7 Crystal yield， total evaporation and purity during MDC-VEC coupling process

实验编号	晶体收率/%	总蒸发量/ml	纯度/% (质量分数)
1^#	76.310	214.21	96.060
2^#	79.340	220.23	94.110
3^#	78.890	221.45	94.860
4^#	78.320	218.54	93.760
平均值	78.220	218.61	94.700

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高浓度Na⁺//NO $3 -$ ， SO $4 2 -$ -H₂O溶液的膜蒸馏结晶耦合过程调控

Membrane distillation crystallization coupling process for the treatment of high concentration Na⁺//NO $3 -$ , SO $4 2 -$ -H₂O solution

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