Adsorption performance and mechanism of magnetic modified oyster shell powder on phosphorus in water
MENG Haoyan1,, YANG Mingfan1, LUO Guozhi1,2,3,,, TAN Hongxin1,2,3 1.Shanghai Engineering Research Center of Aquaculture, Shanghai Ocean University, Shanghai 201306, China 2.Key Laboratory of Freshwater Aquatic Genetic Resources, Ministry of Agriculture and Rural Affairs, Shanghai Ocean University, Shanghai 201306, China 3.National Demonstration Center for Experimental Fisheries Science Education, Shanghai Ocean University, Shanghai 201306, China
Abstract:In order to solve the problem of phosphorus accumulation in bio-floc culture water, the performance and and mechanism of magnetic modified oyster shell powder on phosphorus removal were studied. The results showed that the best adsorption efficiency occurred for 8 g·L?1 magnetic modified oyster shell powder at the initial TP concentration of 20.00~50.00 mg·L?1, the TP removal rate increased from (84.94±0.94)% to (87.35±1.06)%, the adsorption amount (qe) increased from (2.37±0.03) mg·g?1 to (5.45±0.22) mg·g?1. When the pH was 2.00~6.00, the TP removal rate was higher than (80.13±3.27)%, and qe was higher than (2.04±0.02) mg·g?1. ${\rm{HCO}}_3^ - $ had an obvious inhibitory effect on phosphorus adsorption by magnetic modified oyster shell powder. X-ray diffraction showed that the surface covering composition of the shell powder were Fe2(PO)5 and Fe4(PO4)2O. The adsorption process of magnetic modified oyster shell powder accorded with Freundlich model and pseudo-second kinetic model, the maximum adsorption capacity was 9.81 mg·g?1. Both physisorption and chemisorption contributed to the adsorption process, and the chemisorption played the main role. The film diffusion and intra-particle diffusion were the main speed limiting steps, ligand exchange and electrostatic interaction were the main phosphorus removal contributors. The above results can provide a reference for the actual phosphorus removal methods of aquaculture wastewater. Key words:magnetic modified oyster shell powder/ phosphorus removal/ adsorption performance/ adsorption mechanisms.
图1吸附剂添加量、初始TP浓度和pH对除磷效果的影响 Figure1.Effects of adsorbent amount, initial TP concentration and pH on phosphorus removal
表1不同牡蛎壳粉表面结构特征参数 Table1.Surface structure characteristic parameters of different OSP
样品
比表面积/(m2·g?1)
孔容/(cm3·g?1)
平均孔径/nm
天然牡蛎壳粉
1.18
0.005
16.52
载铁牡蛎壳粉
0.68
0.061
35.60
样品
比表面积/(m2·g?1)
孔容/(cm3·g?1)
平均孔径/nm
天然牡蛎壳粉
1.18
0.005
16.52
载铁牡蛎壳粉
0.68
0.061
35.60
下载: 导出CSV 表2不同温度下载铁牡蛎壳粉等温线拟合结果 Table2.Isotherm constants of magnetic modified OSP at different temperatures
温度/℃
Langmuir
Freundlich
qm/(mg·g?1)
K
R2
Kf
1/n
R2
15
24.49
0.28
0.880
0.59
0.91
0.910
25
22.81
1.11
0.821
1.09
0.80
0.973
35
9.81
6.11
0.980
1.79
0.42
0.987
温度/℃
Langmuir
Freundlich
qm/(mg·g?1)
K
R2
Kf
1/n
R2
15
24.49
0.28
0.880
0.59
0.91
0.910
25
22.81
1.11
0.821
1.09
0.80
0.973
35
9.81
6.11
0.980
1.79
0.42
0.987
下载: 导出CSV 表3不同初始TP浓度下载铁牡蛎壳粉吸附除磷的热力学参数 Table3.Thermodynamic parameters for phosphorus adsorption on magnetic modified OSP at different initial TP concentrations
C0/ (mg·L?1)
H0/ (kJ·mol?1)
S0/ (kJ·(mol·K)?1)
G0/(kJ·mol?1)
15 ℃
25 ℃
35 ℃
26.41
118.08
0.46
?10.19
?14.48
?17.85
36.95
102.18
0.40
?11.27
?14.95
?17.90
47.42
101.98
0.40
?12.13
?15.23
?18.76
61.17
53.19
0.24
?12.65
?15.93
?16.07
71.08
63.04
0.27
?13.00
?15.88
?17.08
C0/ (mg·L?1)
H0/ (kJ·mol?1)
S0/ (kJ·(mol·K)?1)
G0/(kJ·mol?1)
15 ℃
25 ℃
35 ℃
26.41
118.08
0.46
?10.19
?14.48
?17.85
36.95
102.18
0.40
?11.27
?14.95
?17.90
47.42
101.98
0.40
?12.13
?15.23
?18.76
61.17
53.19
0.24
?12.65
?15.93
?16.07
71.08
63.04
0.27
?13.00
?15.88
?17.08
下载: 导出CSV 表4载铁牡蛎壳粉吸附动力学拟合参数 Table4.Adsorption kinetic parameters of magnetic modified OSP
温度/℃
qe,exp/(mg·g?1)
准一级动力学
准二级动力学
qe,cal/(mg·g?1)
k1/(g·(min·mg)?1)
R2
qe,cal/(mg·g?1)
k2/(g·(min·mg)?1)
R2
15
4.01
4.48
0.001 7
0.832
2.25
0.001 1
0.185
25
5.55
5.29
0.002 8
0.979
6.64
0.000 6
0.988
35
6.06
5.85
0.003 3
0.988
7.19
0.000 6
1.000
温度/℃
qe,exp/(mg·g?1)
准一级动力学
准二级动力学
qe,cal/(mg·g?1)
k1/(g·(min·mg)?1)
R2
qe,cal/(mg·g?1)
k2/(g·(min·mg)?1)
R2
15
4.01
4.48
0.001 7
0.832
2.25
0.001 1
0.185
25
5.55
5.29
0.002 8
0.979
6.64
0.000 6
0.988
35
6.06
5.85
0.003 3
0.988
7.19
0.000 6
1.000
下载: 导出CSV 表5载铁牡蛎壳粉颗粒内模型拟合参数 Table5.Fitting parameters of intra-particle diffusion model of magnetic modified OSP
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1.Shanghai Engineering Research Center of Aquaculture, Shanghai Ocean University, Shanghai 201306, China 2.Key Laboratory of Freshwater Aquatic Genetic Resources, Ministry of Agriculture and Rural Affairs, Shanghai Ocean University, Shanghai 201306, China 3.National Demonstration Center for Experimental Fisheries Science Education, Shanghai Ocean University, Shanghai 201306, China Received Date: 2020-04-15 Accepted Date: 2020-07-21 Available Online: 2021-02-22 Keywords:magnetic modified oyster shell powder/ phosphorus removal/ adsorption performance/ adsorption mechanisms Abstract:In order to solve the problem of phosphorus accumulation in bio-floc culture water, the performance and and mechanism of magnetic modified oyster shell powder on phosphorus removal were studied. The results showed that the best adsorption efficiency occurred for 8 g·L?1 magnetic modified oyster shell powder at the initial TP concentration of 20.00~50.00 mg·L?1, the TP removal rate increased from (84.94±0.94)% to (87.35±1.06)%, the adsorption amount (qe) increased from (2.37±0.03) mg·g?1 to (5.45±0.22) mg·g?1. When the pH was 2.00~6.00, the TP removal rate was higher than (80.13±3.27)%, and qe was higher than (2.04±0.02) mg·g?1. ${\rm{HCO}}_3^ - $ had an obvious inhibitory effect on phosphorus adsorption by magnetic modified oyster shell powder. X-ray diffraction showed that the surface covering composition of the shell powder were Fe2(PO)5 and Fe4(PO4)2O. The adsorption process of magnetic modified oyster shell powder accorded with Freundlich model and pseudo-second kinetic model, the maximum adsorption capacity was 9.81 mg·g?1. Both physisorption and chemisorption contributed to the adsorption process, and the chemisorption played the main role. The film diffusion and intra-particle diffusion were the main speed limiting steps, ligand exchange and electrostatic interaction were the main phosphorus removal contributors. The above results can provide a reference for the actual phosphorus removal methods of aquaculture wastewater.
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