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中国生物工程杂志

China Biotechnology
China Biotechnology
China Biotechnology  2022, Vol. 42 Issue (10): 21-30    DOI: 10.13523/j.cb.2206011
    
Study on the Performance of Oxidative Diesel Desulfurization Catalyzed by Bioenzyme/γ-Al2O3 Spheres
Shuang JIN,Yun-song YANG,Jin-hua LIANG,Xiao-rui YANG,Xiao-tong LI,Jian-liang ZHU*()
College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, China
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Abstract  

The bioenzymes were loaded on the γ-Al2O3 spherical carrier by adsorption method, and the bioenzymes/γ-Al2O3 and the carrier were characterized by scanning electron microscopy (SEM), specific surface area analysis (BET), Fourier infrared spectroscopy (FT-IR) and circular dichroism (CD). The results showed that the bioenzymes were adsorbed on the carriers. The prepared bioenzyme/γ-Al2O3 catalyzed oxidative desulfurization of real diesel fuel, and the effects of reaction temperature, reaction flow rate and enzyme solution concentration on the desulfurization effect of real diesel fuel were investigated, and qualitative and quantitative analyses of the desulfurization effect were performed; further response surface design optimization of the desulfurization process conditions was carried out to find out the optimal reaction conditions. The experimental results showed that the optimum desulfurization rate of 93.16% was derived from the reaction temperature of 49℃, reaction flow rate of 1.0 mL/min and enzyme solution concentration of 15.5% (enzyme loading of 28.13 g). Finally, the performance of the immobilized enzyme was investigated for repeated use, and the activity of the catalyst did not decrease significantly after seven uses, indicating that the immobilized enzyme is effective in catalyzing oxidative diesel desulfurization and has potential application value.

Key words： Diesel      Immobilized enzymes      Oxidation desulfurization      Responsive surface design     
Received: 10 June 2022      Published: 04 November 2022
ZTFLH:  Q819  
Corresponding Authors: Jian-liang ZHU     E-mail: jlzhu@njtech.edu.cn
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Shuang JIN
Yun-song YANG
Jin-hua LIANG
Xiao-rui YANG
Xiao-tong LI
Jian-liang ZHU
Cite this article:

Shuang JIN,Yun-song YANG,Jin-hua LIANG,Xiao-rui YANG,Xiao-tong LI,Jian-liang ZHU. Study on the Performance of Oxidative Diesel Desulfurization Catalyzed by Bioenzyme/γ-Al2O3 Spheres. China Biotechnology, 2022, 42(10): 21-30.

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https://manu60.magtech.com.cn/biotech/10.13523/j.cb.2206011     OR     https://manu60.magtech.com.cn/biotech/Y2022/V42/I10/21

噻吩类化合物类型 结构
噻吩
二苯并噻吩
苯并噻吩
4,6-二甲基二苯并噻吩
Table 1 Main thiophene substances in diesel fuel
Fig.1 Schematic diagram of reactor unit
Fig.2 FT-IR spectra of enzyme catalysts before and after reaction
Fig.3 SEM images before and after immobilization of the enzyme on the carrier (a) Blank carrier (b) Immobilized enzyme post-vector
Fig.4 N2 adsorption and desorption isotherms before and after enzyme loading
Fig.5 BJH aperture distribution before and after loading
Fig.6 Enzyme protein CD analysis map
Fig.7 Effect of reaction temperature on desulfurization rate of real diesel
Fig.8 Effect of reaction flow rate on desulfurization of real diesel
浸泡液浓度/% 酶载量/g
10 23.79
15 27.86
20 32.36
25 36.32
30 40.28
Table 2 Different enzyme solution immersion carrier enzyme load
Fig.9 Effect of enzyme solution concentration on desulfurization of real diesel oil
Fig.10 Sulfate concentration standard curve
编号 反应温度
/℃		 反应流速
/(mL/min)		 酶溶液浓度
/%		 脱硫率
/%
1 50 1.20 10 77.47
2 60 0.80 15 48.76
3 50 1.00 15 92.43
4 40 1.20 15 65.88
5 50 1.00 15 91.78
6 40 0.80 15 64.15
7 60 1.00 20 51.56
8 40 1.00 20 61.48
9 50 0.80 20 80.03
10 50 1.20 20 81.75
11 40 1.00 10 58.95
12 60 1.00 10 45.99
13 60 1.20 15 50.18
14 50 1.00 15 90.86
15 50 1.00 15 92.86
16 50 1.00 15 91.05
17 50 0.80 10 79.51
Table 3 Response surface experimental design and results
来源 平方和 自由度 均方 F值 P值
模型 4 684.53 9 520.50 255.53 <0.000 1
A 364.10 1 364.10 178.74 <0.000 1
B 1.00 1 1.00 0.49 0.505 9
C 20.80 1 20.80 10.21 0.015 2
AB 0.024 1 0.024 0.012 0.916 6
AC 2.31 1 2.31 1.13 0.322 2
BC 3.53 1 3.53 1.74 0.229 2
A2 3 757.77 1 3 757.77 1 844.78 <0.000 1
B2 92.19 1 92.19 45.26 0.000 3
C2 232.24 1 232.24 114.01 <0.000 1
残差 14.26 7 2.04
失拟误差 11.29 3 3.76 5.07 0.075 3
纯误差 2.97 4 0.74
总和 4 698.78 16
标准偏差=1.43 R2=0.9970
均值=72.04 校正后R2=9931
变异系数=1.98 预测R2=0.9606
误差平方和=185.31 信噪比=42.407
Table 4 Response surface experimental data analysis
Fig.11 Horizontal three-dimensional curved surface diagram of the influence of various factors on desulfurization rate (a) Response surface of reaction temperature and reaction flow rate on desulfurization rate (b) Response surface of reaction temperature and enzyme solution concentration on desulfurization rate (c) Response surface of reaction flow rate and enzyme solution concentration on desulfurization rate
Fig.12 Performance test of real diesel desulfurization catalyst
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