Research progress of high-efficiency membrane distillation crystallization process

doi:10.11949/0438-1157.20200542

Abstract

Abstract:

The global shortage of water resources and environmental pollution has made the demands for industrial wastewater treatment, seawater desalination, and comprehensive utilization of high-value solutes increasingly urgent. Membrane distillation crystallization process cannot only make full use of low-quality heat sources, achieve high-purity water-solvent separation, but also achieve salt crystallization preparation, which is of great significance for achieving zero liquid discharge and synergistic efficiency in the separation process. At the same time, membrane distillation crystallization process can also be coupled with multi-stage flash evaporation, multi-effect distillation, nanofiltration, forward infiltration, reverse osmosis and other processes to further improve the overall separation efficiency. In addition, it also has a positive impact on regulating the external morphology of the crystal, preparing crystal products with relatively concentrated crystal size distribution and good flowability. Based on this, this article has discussed several aspects of membrane distillation crystallization principles, process control mechanisms and innovative process applications, and looking forward to the key issues and development trends of membrane distillation crystallization technology in the fields of efficient separation and precise control of the crystallization process.

Key words: membrane distillation, crystallization, separation process, water treatment, process coupling

摘要：

全球性的水资源短缺及环境污染问题，使得工业废水处理、海水淡化、高价值溶质综合利用的需求日益迫切。膜蒸馏结晶过程可以充分利用低品质热源，实现高纯度水溶剂分离、盐分结晶制备，对于实现分离过程零排放和协同增效有重要意义。同时，膜蒸馏结晶也可以与多级闪蒸，多效精馏、纳滤、正向渗透、反渗透等过程进行耦合，进一步提高整体分离效率。此外，该过程对于调控晶体外部形貌，制备晶体尺寸分布集中、流动性好的晶体产品也有积极作用。基于此，针对膜蒸馏结晶原理、过程调控机制以及创新过程应用几个方面开展论述，总结了膜蒸馏结晶技术在高效分离、结晶过程精准控制等领域的关键问题和发展趋势。

关键词: 膜蒸馏, 结晶, 分离过程, 水处理, 过程耦合

CLC Number:

TQ 026.5

Xiaobin JIANG, Guoxin SUN, Gaohong HE. Research progress of high-efficiency membrane distillation crystallization process[J]. CIESC Journal, 2020, 71(9): 3905-3918.

姜晓滨, 孙国鑫, 贺高红. 高效膜蒸馏结晶过程的研究进展[J]. 化工学报, 2020, 71(9): 3905-3918.

Figures/Tables 14

Fig.1 SEM images of typical hollow fiber membrane structures used for membrane crystallization[24]

Fig.2 SEM image of C-D35-2 film prepared on the surface of hollow yttrium-stabilized zirconia (YSZ) tube (a); FIB-SEM image of the square in Fig.2(a)（The clear interface between carbon and YSZ is clearly visible. You can also see the nanopores on the carbon side. The pore size near the carbon fiber-ceramic interface is considered to be the smallest, which is determined to be about 31 nm by gas penetration） (b); HRTEM image of typical single carbon nanofibers in C-D35-2 film (The arrow points to the “slubby” structure inside the carbon fiber, which divides the internal space into multiple compartments) (c)[31]

Fig.3 Comparison of nucleation work W of KNO3 in membrane distillation crystallization of different membrane materials and porosities at T = 70℃ (343.15 K) and S = 1.01[32]

Fig.4 Schematic diagram of solution heterogeneous nucleation, growth and detachment on the membrane surface during MDC[33]

Fig.5 Membrane distillation unit: direct contact membrane distillation (DCMD), osmotic membrane distillation (OMD), sweep gas membrane distillation (SGMD), air gap membrane distillation (AGMD) and vacuum membrane distillation (VMD)[34]

Fig.6 Permeation flux in SMDC at various feed temperatures[42]

Fig.7 Morphology of LiCl crystals obtained by film crystallization: orthogonal polymorph (a), cubic polymorph (b); distribution of cubic and orthogonal structures at various feed temperatures and flow rates[(c)—(e)][47]

Fig.8 Under natural cooling and cooling rate of 0.1 K/min, CSD (bar graph) of different crystallization time of membrane distillation coupled cooling crystallization (KNO3) (a), optical microscope image of the crystal [magnification 100 times (b), magnification 40 times (c)]; under membrane assisted crystallization and cooling rate of 0.2 K/min, CSD of different crystallization time of membrane distillation coupled cooling crystallization (KNO3) (d), optical microscope image of the crystal [magnification 100 (e), magnification 40 times (f)]; under rapid cooling crystallization and cooling rate of 0.33 K/min, CSD of different crystallization time of membrane distillation coupled cooling crystallization (KNO3) (g),the optical microscope image of the crystal [magnification 100 times (h), magnified 40 times (i)] （The dot line in the figure: the kinetic simulation results obtained by the MATLAB programming to establish the particle number balance equation; Ni/Ntotal: the percentage of the number of crystals of different sizes; the number marked at the peak: C.V.; lˉ: the average crystal size）[32]

Fig.9 Crystal particle size distribution and microscope photo (inset，×200) in rapid cooling model [49]

Fig.10 Basic process of membrane distillation crystallization of high-salt wastewater[42]

Fig.11 Simultaneous recovery and crystallization control of EG and organic saline wastewater in MDC: experimental device (a); permeation flux, EG and NaCl rejection rate under repeated experiments (b); comparison of the properties of crystal particles obtained by MDC and vacuum evaporation crystallization (VEC) (c)[58]

Fig.12 SEM images of different CaCO3 crystals generated by hydrogel composite membrane[11]

Fig.13 Schematic diagram of HCMs membrane crystallization process(a); schematic diagram of membrane module unit decomposition(b); multi-channel continuous experiment platform(c); crystal nucleation regulation and highly selective growth mechanism and experimental results of PEGDA-NIPAM HCMs(d) [69]

Fig.14 Important progress and further directions of membrane distillation crystallization research

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