亚硫酸铵微界面强化氧化特性研究

doi:10.11949/0438-1157.20200803

摘要/Abstract

摘要：

以亚硫酸铵水溶液的空气氧化为研究对象，考察了微界面强化对该体系传质与氧化过程的影响。在同一实验平台和操作工况下，对微界面强化与传统鼓泡塔氧化过程的传质和反应性能进行了实验研究。利用高速摄像与压差测量技术，分别对反应过程的空气气泡分布与气含率变化进行了测定。结果表明，相较于传统鼓泡塔空气氧化反应器，微界面强化氧化反应器以微界面体系取代了传统毫-厘米级宏界面，在不同盐离子浓度与氧化气量工况下均表现出了良好的强化效能。在微界面体系强化下，亚硫酸铵氧化过程气含率大幅提升，相界面积增加十余倍，反应速率平均提升56.8%，实验结论为微界面强化反应器的多相反应体系工业应用提供了一定的数据支撑。

关键词: 相界面积, 气液传质, 过程强化, 气泡尺寸分布, 亚硫酸铵氧化

Abstract:

The process intensification of interfacial area and reaction conditions in multi-phase systems are important issues in industrially scaled reactors. In order to investigate the intensifying effect of micro-interface system on gas-liquid mass transfer and reaction rate, the ammonium sulfite oxidation was selected as the research object. A systematic air forced oxidation experiment was carried out through the micro-interface intensification reactor (MIR) and the traditional bubble column reactor (BCR) under the same experiment platform and operating conditions. The bubble size distribution and overall gas holdup were measured by high-speed camera technology and differential pressure measurement, respectively. The experimental results showed that MIR obtained higher gas holdup because of the micro-interface structure, the interfacial area was increased by more than 10 times, the reaction rate increased by 56.8% averagely compared with BCR. The experimental conclusions provide certain data support for the industrial application of the multiphase reaction system of the micro-interface intensification reactor.

Key words: interfacial area, gas-liquid mass transfer, process intensification, bubble size distribution, ammonium sulfite oxidation

中图分类号:

TQ 021.4

杨国强,曾伟,罗华勋,杨高东,张志炳. 亚硫酸铵微界面强化氧化特性研究[J]. 化工学报, 2020, 71(11): 4918-4926.

Guoqiang YANG,Wei ZENG,Huaxun LUO,Gaodong YANG,Zhibing ZHANG. Study on the characteristics of micro-interface intensified oxidation of ammonium sulfite[J]. CIESC Journal, 2020, 71(11): 4918-4926.

图/表 14

图1 实验装置示意图

Fig.1 Schematic diagram of experimental apparatus

表1 反应液的主要物性

Table 1 Physical properties of solution

亚硫酸铵

浓度/(mol/L)

密度ρ_l/

(kg/m³)

表面张力σ_l/

(N/m)

动力黏度μ_l/

(Pa·s)

图2 MIR与BCR的反应实拍对比（0.13 mol/L，100 L/h）

Fig.2 Experimental photos of MIR and BCR（0.13 mol/L，100 L/h）

图3 MIR与BCR的高速相机微观照片对比（0.13 mol/L，100 L/h）

Fig.3 Pictures taken by high speed camera of MIR and BCR（0.13 mol/L，100 L/h）

表2 不同亚硫酸铵浓度下气泡d32

Table 2 Sauter mean diameters under different ammonium sulfite concentrations

亚硫酸铵浓度/ (mol/L)	d₃₂/μm		效果对比（MIR∶BCR）
亚硫酸铵浓度/ (mol/L)	MIR	BCR	效果对比（MIR∶BCR）
0.06	1726.63	5241.79	32.94%
0.10	1334.73	4997.27	26.71%
0.13	703.28	4134.18	17.01%

图4 MIR与BCR气泡粒径分布对比 (Qg=200 L/h)

Fig.4 Comparison of bubble size distribution (BSD) between MIR and BCR (Qg=200 L/h)

图5 不同亚硫酸铵浓度下气含率对比

Fig.5 Comparison of gas holdup between MIR and BCR under different ammonium sulfite concentrations

图6 不同亚硫酸铵浓度下相界面积对比

Fig.6 Comparison of interfacial area between MIR and BCR under different ammonium sulfite concentrations

表3 不同空气进料量下气泡d32

Table 3 Sauter mean diameters under different gas flowrates

空气进料量/ (L/h)	d₃₂/μm		效果对比（MIR∶BCR）
空气进料量/ (L/h)	MIR	BCR	效果对比（MIR∶BCR）
40	592.84	3402.77	17.42%
100	636.67	3851.50	16.53%
200	703.28	4134.18	17.01%
300	1108.31	5555.37	19.95%

图7 MIR与BCR气泡粒径分布对比 (Qg=40 L/h)

Fig.7 Comparison of bubble size distribution (BSD) between MIR and BCR (Qg=40 L/h)

图8 不同空气进料量下气含率对比

Fig.8 Comparison of gas holdup between MIR and BCR under different gas flowrates

图9 不同空气进料量下相界面积对比

Fig.9 Comparison of interfacial area between MIR and BCR under different gas flowrates

图10 不同起始亚硫酸铵浓度下亚硫酸根离子浓度随时间的变化

Fig.10 Comparison of reaction rate between MIR and BCR under different ammonium sulfite concentrations

图11 不同通气量下亚硫酸根离子浓度随时间的变化

Fig.11 Comparison of reaction rate between MIR and BCR under different gas flowrates

参考文献 32

1	Stacy C J, Melick C A, Cairncross R A. Esterification of free fatty acids to fatty acid alkyl esters in a bubble column reactor for use as biodiesel[J]. Fuel Processing Technology, 2014, 124(8): 70-77.
2	Farmer T C, McFarland E W, Doherty M F. Membrane bubble column reactor model for the production of hydrogen by methane pyrolysis[J]. International Journal of Hydrogen Energy, 2019, 4(29): 14721-14731.
3	Adhami M, Jamshidi N, Zarghami R, et al. Characterization of hydrodynamics of bubble columns by recurrence quantification analysis[J]. Chaos, Solitons & Fractals, 2018, 111: 213-226.
4	Wei B S, Jie Y, Guang L, et al. Modelling of breakage rate and bubble size distribution in bubble columns accounting for bubble shape variations[J]. Chemical Engineering Science, 2018, 187: 391-405.
5	Shu S L, Vidal D, Bertrand F, et al. Multiscale multiphase phenomena in bubble column reactors: a review[J]. Renewable Energy, 2019, 141: 613-631.
6	Joshi J B, Vitankar V S, Kulkarni A A, et al. Coherent flow structures in bubble column reactors[J]. Chemical Engineering Science, 2002, 57(16): 3157-3183.
7	García-Abuín A, Gómez-Díaz D, Losada M, et al. Bubble column gas-liquid interfacial area in a polymer+surfactant+water system[J]. Chemical Engineering Science, 2012, 75: 334-341.
8	Patel S, Daly J, Bukur D. Holdup and interfacial area measurements using dynamic gas disengagement[J]. AIChE Journal, 1989, 35: 931-942.
9	张志炳, 田洪舟, 张锋, 等. 多相反应体系的微界面强化简述[J]. 化工学报, 2018, 69(1): 44-49.
	Zhang Z B, Tian H Z, Zhang F, et al. Overview of microinterface intensification in multiphase reaction systems[J]. CIESC Journal, 2018, 69(1): 44-49.
10	张志炳, 田洪舟, 王丹亮, 等. 气液反应体系相界面传质强化研究[J]. 化学工程, 2016, 44(3): 1-8.
	Zhang Z B, Tian H Z, Wang D L, et al. Intensification of interfacial mass transfer in gas-liquid reaction systems [J]. Chemical Engineering (China), 2016, 44(3): 1-8.
11	Levenspiel O. Chemical Reaction Engineering [M]. 3rd ed. New York: John Wiley & Sons Inc., 1999.
12	Wen J, Sun Q, Sun Z, et al. An improved image processing technique for determination of volume and surface area of rising bubble[J]. International Journal of Multiphase Flow, 2018, 104: 294-306.
13	Zaruba A, Krepper E, Prasser H M, et al. Measurement of bubble velocity profiles and turbulent diffusion coefficients of the gaseous phase in rectangular bubble column using image processing[J]. Experimental Thermal and Fluid Science, 2005, 29(7): 851-860.
14	Zhou J, Li W, Xiao W. Kinetics of heterogeneous oxidation of concentrated ammonium sulfite[J]. Chemical Engineering Science, 2000, 55(23): 5637-5641.
15	Wang L, Wu S, Liu S, et al. Cobalt impregnated porous catalyst promoting ammonium sulfate recovery in an ammonia-based desulfurization process[J]. Chemical Engineering Journal, 2018, 331: 416-424.
16	Guo S, Wang J, Chen X, et al. Kinetics and reaction mechanism of catalytic oxidation of ammonium sulfite[J]. Asian Journal of Chemistry, 2014, 26(1): 69-74.
17	Mishra G C, Srivastava R D. Kinetics of heterogeneous oxidation of ammonium sulphite[J]. Journal of Applied Chemistry & Biotechnology, 1976, 26(1): 401-405.
18	Craig V S, Ninham B W, Pashley R M. The effect of electrolytes on bubble coalescence in water[J]. Journal of Physical Chemistry, 1993, 97(39): 10192-10197.
19	Deschenes L A, Barrett J, Muller L J, et al. Inhibition of bubble coalescence in aqueous solutions (1): Electrolytes[J]. Journal of Physical Chemistry B, 1998, 102(26): 5115-5119.
20	Besagni G, Inzoli F. The effect of electrolyte concentration on counter-current gas-liquid bubble column fluid dynamics: gas holdup, flow regime transition and bubble size distributions[J]. Chemical Engineering Research and Design, 2017, 118: 170-193.
21	Marrucci G, Nicodemo L. Coalescence of gas bubbles in aqueous solutions of inorganic electrolytes[J]. Chemical Engineering Science, 1967, 22(9): 1257-1265.
22	Lessard R R, Zieminski S A. Bubble coalescence and gas transfer in aqueous electrolytic solutions[J]. Industrial & Engineering Chemistry Fundamentals, 1971, 10(2): 260-269.
23	胡华, 朱德权, 刘永民, 等. 电解质对溶液中气泡大小的影响[J]. 清华大学学报(自然科学版), 1995, (3): 106-110.
	Hu H, Zhu D Q, Liu Y M, et al. Effect of electrolyte on bubble size in solution[J]. Journal of Tsinghua University (Sci. & Tech.), 1995, (3): 106-110.
24	Akita K, Yoshida F. Bubble size, interfacial area, and liquid-phase mass transfer coefficient in bubble columns[J]. Industrial & Engineering Chemistry Process Design and Development, 1974, 13(1): 84-91.
25	Camarasa E, Vial C, Poncin S, et al. Influence of coalescence behaviour of the liquid and of gas sparging on hydrodynamics and bubble characteristics in a bubble column[J]. Chemical Engineering and Processing: Process Intensification, 1999, 38(4): 329-344.
26	Basha O M, Morsi B I. Novel approach and correlation for bubble size distribution in a slurry bubble column reactor operating in the churn-turbulent flow regime[J]. Industrial & Engineering Chemistry Research, 2018, 57(16): 5705-5716.
27	Lehr F, Millies M, Mewes D. Bubble-size distributions and flow fields in bubble columns[J]. AIChE Journal, 2002, 48(11): 2426-2443.
28	Kazakis N, Mouza A A, Paras S V. Experimental study of bubble formation at metal porous spargers: effect of liquid properties and sparger characteristics on the initial bubble size distribution[J]. Chemical Engineering Journal, 2008, 137(2): 265-281.
29	Ramezani M, Mostoufi N, Mehrnia M. Improved modeling of bubble column reactors by considering the bubble size distribution[J]. Industrial & Engineering Chemistry Research, 2012, 51: 5705-5714.
30	Levenspiel O. Chemical reaction engineering[J]. Industrial & Engineering Chemistry Research, 1999, 38(11): 4140-4143.
31	Cho J S, Wakao N. Determination of liquid-side and gas-side volumetric mass transfer coefficients in a bubble column[J]. Journal of Chemical Engineering of Japan, 1988, 21(6): 576-581.
32	Wilkinson P M, Haringa H, Dierendonck L. Mass transfer and bubble size in a bubble column under pressure[J]. Chemical Engineering Science, 1994, 49(9): 1417-1427.

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