UIO-66-NH2doped organosilicon high salinity wastewater treatment membrane and a preparation method thereof

Patent metadata

Field	Value
Publication number	US-11596906-B2
Application number	US-202117165966-A
Country	US
Kind code	B2
Filing date	Feb 3, 2021
Priority date	Feb 25, 2020
Publication date	Mar 7, 2023
Grant date	Mar 7, 2023

Abstract

The invention belongs to the technical field of composite membrane, and in particular discloses a UIO-66-NH2 doped organosilicon high salinity wastewater treatment membrane and a preparation method thereof. The membrane is formed into UIO-66-NH2/organosilicon hybrid membrane on the prefabricated ceramic support surface through the dip-coating method by doping the UIO-66-NH2 metal-organic framework material into the organosilicon polymeric sol. The UIO-66-NH2/organosilicon hybrid membrane prepared by the present invention exhibits high water permeability (up to 1.6×10−10 m3/(m2 s Pa) and high salt retention (NaCl retention rate is more than 99.9. %) in the application of pervaporation desalination, and maintains stable membrane structure in the treatment process of TDS>5 wt % high salinity wastewater.

First claim

What is claimed is:

1. A method of preparing a UiO-66-NH 2 doped organosilicon high salinity wastewater treatment membrane, the method comprising steps of:
(1) hydrolyzing and polymerizing a silicon source precursor and a hydrochloric acid catalyst with water in ethanol solution to obtain an organosilicon polymeric sol;
(2) adding UiO-66-NH 2 crystal into the organosilicon polymeric sol by ultrasonic mixing and uniform dispersion to prepare a UiO-66-NH 2 /organosilicon hybrid sol;
(3) dip-coating the UiO-66-NH 2 /organosilicon hybrid sol on a ceramic support of a silica-zirconia nanometer transition layer; and
(4) flash-burning the dip-coated UiO-66-NH 2 /organosilicon hybrid sol in air to obtain the UiO-66-NH 2 doped organosilicon high salinity wastewater treatment membrane.

2. The method of claim 1 , wherein the silicon source precursor according to the step (1) is 1,2-Bis(triethoxysilyl)ethylene, abbreviated as BTESEthy.

3. The method of claim 1 ,
wherein the silicon source precursor, the water and the hydrochloric acid catalyst according to the step (1) are having a molar ratio of 1:60:0.2;
wherein a hydrolytic-polymeric reaction temperature according to the step (1) is 40 DEG C; and
wherein a hydrolytic-polymeric reaction time according to the step (1) is 2 h.

4. The method of claim 1 ,
wherein the step (2) comprises is:
dissolving ZrCl 4 and 2-amino-1,4-benzenedicarboxylic acid in N,N-dimethylformamide (DMF) resulting in a first mixture and subjecting the first mixture to ultrasonic agitation for 10 min;
adding acetic acid to the first mixture resulting in a second mixture and subjecting the second mixture to ultrasonic agitation for 10 min;
putting the second mixture into a preheated 130 DEG C oven for 24 h resulting in a product UiO-66-NH 2 ;
washing the product UiO-66-NH 2 with N,N-dimethylformamide and methanol; and
drying the washed product UiO-66-NH 2 overnight at 100 DEG C to obtain the UiO-66-NH 2 crystal;

wherein molar ratio of ZrCl 4 , BDC-NH 2 , HAC and DMF is 1:1:50:500.

5. The method of claim 1 , wherein weight ratio (UB-n) of UiO-66-NH 2 and organosilicon in the hybrid sol according to the step (2) is 0.2-1.

6. The method of claim 1 , wherein the ultrasonic mixing duration according to the step (2) is 30 min.

7. The method of claim 1 , wherein the ceramic support according to the step (3) is a α-Al 2 O 3 ceramic membrane.

8. The method of claim 1 , wherein the step (3) comprises:
soaking the ceramic support of the silica-zirconia nanometer transition layer in a silica-zirconia sol for 10-60 s;
drying the soaked ceramic support at room temperature for 5-10 min; and
calcining the dried ceramic support in air for 15-30 min at a temperature of 500-600 DEG C under air atmosphere; and
repeating the calcination 2-3 times.

9. The method of claim 1 ,
wherein the flash-burning temperature according to the step (3) is 250 DEG C; and
the flash-burning time according to the step (3) is 20 min.

Assignees

• Univ Changzhou

Inventors

• Xu Rong
• Liu Qian
• Zhu Chunhui
• Zhong Jing
• Ren Xiuxiu
• Shen Min
• Zhang Yihan

Classifications

• B01D69/108

  Inorganic support material · CPC title

• B01D71/70 Primary

  Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only · CPC title

• B01D69/148

  Organic/inorganic mixed matrix membranes · CPC title

• B01D67/0079

  Manufacture of membranes comprising organic and inorganic components · CPC title

• B01D67/0006

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title