Membrane distillation crystallization coupling process for the treatment of high concentration Na+//NO3-, SO42--H2O solution

doi:10.11949/0438-1157.20220177

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 25

Fig.1 Framework of brine treatment technology

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

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

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

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

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

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

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

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

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

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

Fig.7 SEM images of vacuum evaporation crystallization product

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

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

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

Fig.11 Optical microscope images of membrane distillation crystallization products

Fig.12 SEM images of membrane distillation crystallization products

Fig.13 Elemental mapping of membrane distillation crystallization products surface

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

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

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

Fig.16 Evaporation of MDC-VEC coupling process

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

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

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

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

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