Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (05): 102-112.doi: 10.13475/j.fzxb.20230402301

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation and dynamic adsorption properties of amphoteric cellulose porous hydrogel spheres

ZHENG Kang, GONG Wenli, BAO Jie, LIU Lin()   

  1. College of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
  • Received:2023-04-18 Revised:2024-01-12 Online:2024-05-15 Published:2024-05-31

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Abstract:

Objective Cellulose porous hydrogel spheres are increasingly used as adsorption fillers by virtue of their combined properties, which have become a current research focus. However, the preparation of these spheres is currently cumbersome and they exhibit limited adsorption efficiency and single adsorption species, restricting their applications. Therefore, it is important to develop a simple and efficient biomass adsorbent with both adsorption and separation capacity for ionic dyes.

Method In this paper, amphoteric cellulose porous microsphere (ACM) was developed by a two-step chemical modification method of esterification and Schiff base reaction. The surface morphology, pore structure and mechanical properties of the hydrogel spheres were characterized and analyzed using field emission scanning electron microscopy, specific surface area and pore size distribution instrument and universal testing machine, respectively. The adsorption column device was constructed to investigate the adsorption properties of ACM.

Results The specific surface area, pore size distribution and porosity of ACM with abundant pore structure on the surface and inside were 123.97 m2/g, 0.633 cm3/g and 89.22%, respectively. The compressive strength of ACM was found to be 591.9 kPa at 30% compression deformation, and the mechanical properties were about 63% of the initial value after 40 cycles of compression. ACM showed good compressive strength as well as structural stability because the carboxylation reaction took place at a high temperature, which increased the skeletal density and strength of the hydrogel spheres. Cross-linking occurred during the two-step reaction, producing three-dimensional network structure that enhanced the mechanical properties. It was found that the dynamic adsorption efficiency of the adsorption column wase improved by reducing the initial concentration, increasing the loading height, and slowing down the feed rate. With 0.8 g hydrogel spheres it was possible to treat almost 7.5 L of dye containing wastewater. The hydrogel spheres were chemically modified in two steps to combine high porosity, high mechanical properties, and abundance of carboxyl/amino active groups. 80% separation of mixed dyes was achieved by ACM, which possesses both carboxyl and amino active groups and has different adsorption properties under different acid and base conditions.

Conclusion The influence of different device parameters on the dynamic adsorption of ACM was investigated, and it was found that the dynamic adsorption efficiency of the column could be improved by decreasing the initial concentration, increasing the loading height, and slowing down the feed rate. The final device parameters were determined as 50 mg/L inlet concentration, 12 cm filling height and 4 mL/min inlet speed. 0.8 g of hydrogel spheres could treat about 7.5 L of wastewater containing dye MeB at the optimum device parameters, demonstrating the good adsorption and separation performance of the ACM.

Key words: cellulose, amphoteric hydrogel sphere, adsorption separation, anionic and cationic dye, dynamic adsorption property, printing and dyeing wastewater, wastewater treatment

CLC Number: 

  • X703.1

Fig.1

Flow chart of preparation of ACM"

Fig.2

Schematic diagram of adsorption column device and dynamic adsorption process of ACM"

Fig.3

FT-IR spectra of CM and ACM"

Fig.4

Zeta potential of CM and ACM at different pH values"

Fig.5

FESEM images of ACM. (a) Overall morphology;(b) Surface morphology;(c) Internal pores"

Fig.6

N2 adsorption-desorption isotherm of ACM (a),pore size distribution (b) and comparison of specific surface area with other documens (c)"

Fig.7

Compressive strength-strain curve of ACM under different conditions"

Fig.8

Breakthrough curves of ACM at different initial mass concentrations"

Tab.1

Dynamic adsorption results of ACM at different initial mass concentrations"

样品 tb/min Rb/% ts/min Rs/% Qe/(mg·g-1) HMTZ/cm
C25 21 0.79 3 308 0.520 215.11 11.923
C50 42 0.81 1 870 0.467 218.71 11.744
C100 10 0.73 870 0.505 219.84 11.862

Fig.9

Breakthrough curves of ACM at different packing heights"

Tab.2

Dynamic adsorption results of ACM at different packing heights"

样品 tb/min Rb/% ts/min Rs/% Qe/(mg·g-1) HMTZ/cm
H12 42.0 0.81 1870 0.467 218.71 11.74
H10 55.0 0.81 1480 0.456 202.56 9.62
H8 6.3 0.69 1091 0.389 159.01 7.95

Fig.10

Breakthrough curves of ACM at different liquid inlet flow velocities"

Tab.3

Dynamic adsorption results of ACM at different liquid inlet flow velocities"

样品 tb/min Rb/% ts/min Rs/% Qe/(mg·g-1) HMTZ/cm
V4 42 0.81 1 870 0.467 218.71 11.74
V6 63 0.82 1 342 0.421 212.37 11.43
V8 19 0.78 896 0.329 147.75 11.74

Fig.11

Fitting graphs with Thomas model under different conditions. (a) Different initial concentrations; (b) Different filling heights; (c) Different inlet speeds"

Tab.4

Thomas model related parameters"

样品 实验数据 Thomas模型
Qe/
(mg·g-1)		 kTh/
(mL·min-1·mg-1)		 Q0/
(mg·g-1)		 R2
C25 215.11 0.031 5 218.242 0.933 9
C50 218.71 0.030 8 218.541 0.953 3
C100 219.84 0.029 1 220.010 0.974 8
H12 218.71 0.030 8 218.541 0.953 3
H10 202.56 0.035 0 197.171 0.820 7
H8 159.01 0.041 0 124.958 0.802 0
V4 218.71 0.030 8 218.541 0.953 3
V6 212.37 0.045 6 212.261 0.920 6
V8 147.75 0.060 2 115.794 0.725 5

Fig.12

Fitting graphs with Yoon-Nelson model under different conditions. (a) Different inlet concentrations; (b) Different filling heights; (c) Different inlet speeds"

Tab.5

Related parameters of Yoon-Nelson model"

样品 实验数据 Yoon-Nelson模型
t0.5/min Q0.5/mg R0.5/% kYN/min-1 τ0.5/min R2
C25 2 008 131.612 0.655 43 0.000 79 1 745.939 0.933 9
C50 721 96.624 0.670 06 0.001 54 874.162 0.953 3
C100 477 119.501 0.626 31 0.002 91 440.021 0.974 8
H12 721 96.624 0.670 06 0.001 54 874.162 0.953 3
H10 397 53.108 0.668 86 0.001 75 657.566 0.820 7
H8 184 22.368 0.607 82 0.002 05 333.639 0.802 0
V4 721 96.624 0.670 06 0.001 54 874.162 0.953 3
V6 451 87.006 0.643 06 0.002 28 566.031 0.920 6
V8 135 35.448 0.653 54 0.003 01 231.588 0.725 5

Fig.13

Fitting graphs with Adams-Bohart model under different conditions. (a) Different inlet concentrations; (b) Different heights; (c) Different inlet speeds"

Tab.6

Parameters associated with the Adams-Bohart model"

样品 kAB/(mL·min-1·mg-1) N0/(mg·L-1) R2
C25 0.008 3 72 140.0 0.909 1
C50 0.015 8 38 052.5 0.862 3
C100 0.030 4 18 983.6 0.932 2
H12 0.015 8 38 052.5 0.862 3
H10 0.019 1 29 238.5 0.692 7
H8 0.019 3 22 390.2 0.631 1
V4 0.015 8 38 052.5 0.862 3
V6 0.023 4 25 240.9 0.794 8
V8 0.028 4 16 080.7 0.572 7

Fig.14

Breakthrough curves of hydrogel spheres against mixed dyes at different pH values. (a)Acidic condition (pH=4); (b)Alkaline condition (pH=10)"

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