臭氧催化氧化反应器模拟与分析

doi:10.16085/j.issn.1000-6613.2018-2476

摘要/Abstract

摘要：

臭氧催化氧化法是一种高效的污水处理技术，是目前污水高级处理的主要手段之一。传统的建模方法无法研究反应器内污水浓度的时空分布和操作条件对反应器的影响，本研究利用计算流体力学（CFD），耦合多孔介质流动与传质和化学反应动力学多物理场模型，研究臭氧催化氧化过程中目标污染物浓度随时间和空间的分布情况，计算结果与实验结果有良好的一致性。进一步研究臭氧浓度和流量、循环水流量、催化剂层高度、催化剂颗粒大小等对臭氧催化氧化处理废水效率的影响，评估出最优的实验方案。结果表明，在不改变当前反应器主体结构的情况下，最优的操作条件是：臭氧浓度30～40mg/L，臭氧进口流量40～60mL/min，循环水量200～250mL/min，催化剂层填充高度600～800mm，催化剂颗粒半径大小为2mm。该研究有助于理解、设计和优化污水处理反应器。

关键词: 计算流体力学, 多物理场耦合模型, 传递过程, 臭氧催化氧化, 化学反应器

Abstract:

Catalytic ozonation is an efficient wastewater treatment method, which is one of the widely adopted advanced treatment methods. The traditional modeling method is limited to the process of sewage treatment and cannot be used to investigate the influence of operating conditions on reactors or the spatial and temporal distribution of pollutant concentration. This study develops a multi-physics model for a catalytic ozonation reactor by coupling governing equations of the free and porous media flow, mass transport, and catalytic reactions. The model is capable of revealing the temporal and spatial distributions of key process parameters (e.g., the concentrations of pollutant and dissolved ozone, fluid velocity), which are difficult to be obtained through experiments. The simulation results on treatment efficiency are in good agreement with the experimental results. By resorting to this model, the influence of different operating conditions on treatment efficiency can be systematically analyzed towards optimized operation. The results show that without changing the key structure of the reactor, the optimal operating conditions are ozone concentration of 30—40mg/L, ozone inlet flow rate of 40—60mL/min, water circulation flow rate of 200—250mL/min, catalyst layer height of 600—800mm, and catalyst radius of 2mm. This study is helpful for understanding wastewater treatment reactor and optimal design of the reactor.

Key words: computational fluid dynamics(CFD), multi-physics modeling, transport processes, ozone catalytic oxidation, chemical reactors

中图分类号:

TQ02

邹思宇,凌二锁,乐淑荣,孙胜鹏,吴张雄,陈晓东,吴铎,肖杰. 臭氧催化氧化反应器模拟与分析[J]. 化工进展, 2019, 38(9): 3969-3978.

Siyu ZOU,Ersuo LING,Shurong LE,Shengpeng SUN,Zhangxiong WU,Xiaodong CHEN,Duo WU,Jie XIAO. Numerical simulation and analysis of the catalytic ozonation reactor[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 3969-3978.

图/表 15

图1 臭氧催化氧化实验流程

图2 边界条件

表1 初始条件和边界条件

参数	数值
入口臭氧浓度c _O3/mg?L^-1	40
入口流量Q _in,1/mL?min^-1	45
循环水流量Q _in,2/mL?min^-1	160
本体溶液内初始苯酚浓度c ₀/mg?L^-1	100
催化剂内初始苯酚浓度c _{pe, 0}/mg?L^-1	100

图3 网格无关解研究

图4 反应器内流场

表2 各算例的操作条件

项目	Base case	Case1	Case2	Case3	Case4	Case5
臭氧浓度/mg·L^-1	40	20/30/40/50	40	40	40	40
臭氧流量/mL·min^-1	45	45	20/40/60/80	45	45	45
循环水流量/mL·min^-1	160	160	160	100/150/200/250/300	160	160
催化剂半径/mm	1.5	1.5	1.5	1.5	1/2/3/4/5	1.5
催化剂填充高度/m	0.67	0.67	0.67	0.67	0.67	0.2/0.4/0.6/0.8

图5 反应器内苯酚浓度随时间变化

图6 实验和模拟的苯酚降解效果比较

图7 颗粒内和本体溶液中苯酚浓度比较

图8 模拟结果与理论压降模型结果的对比

图9 不同臭氧进口浓度的影响

图10 不同臭氧进口流量的影响

图11 不同循环水流量的影响

图12 不同催化剂层高度的影响

图13 不同催化剂颗粒半径的影响

参考文献 32

1	ZAZO J , CASAS J , MOHEDANO A , et al . Catalytic wet peroxide oxidation of phenol with a Fe/active carbon catalyst[J]. Applied Catalysis B: Environmental, 2006, 65(3): 261-268.
2	PRATARN W , PORNSIRI T , THANIT S , et al . Adsorption and ozonation kinetic model for phenolic wastewater treatment[J]. Chinese Journal of Chemical Engineering, 2011,19(1): 76-82.
3	POLAT D , İ BALCI , ÖZBELGE T A . Catalytic ozonation of an industrial textile wastewater in a heterogeneous continuous reactor[J]. Journal of Environmental Chemical Engineering, 2015, 3(3): 1860-1871.
4	孙怡, 于利亮, 黄浩斌, 等 . 高级氧化技术处理难降解有机废水的研发趋势及实用化进展[J]. 化工学报, 2017, 68(5): 1743-1756.
	SUN Yi , YU Liliang , HUANG Haobin , et al . Research trend and practical development of advanced oxidation process on degradation of recalcitrant organic wastewater[J]. CIESC Journal, 2017, 68(5):1743-1756.
5	STAEHELIN J , HOIGNE J . Decomposition of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide[J]. Environmental Science & Technology, 1982,16(10): 676-681.
6	TOMIYASU H , FUKUTOMI H , GORDON G . Kinetics and mechanism of ozone decomposition in basic aqueous solution[J]. Inorganic Chemistry, 1985, 24(19): 2962-2966.
7	WOLS B A , HOFMAN J A M H , UIJTTEWAAL W S J , et al . Evaluation of different disinfection calculation methods using CFD[J]. Environmental Modelling & Software, 2010, 25(4): 573-582.
8	ZHANG J , TEJADA-MARTINEZ A E , LEI H X , et al . Indicators for technological, environmental and economic sustainability of ozone contactors[J]. Water Research, 2016, 101: 606-616.
9	ZHANG J , TEJADA-MARTÍNEZ A E , ZHANG Q , et al . Evaluating hydraulic and disinfection efficiencies of a full-scale ozone contactor using a rans-based modeling framework[J]. Water Research, 2014, 52: 155-167.
10	LI J L , ZHANG J , MIAO J , et al . Application of computational fluid dynamics (CFD) to ozone contactor optimization[J]. Water Science and Technology: Water Supply, 2006, 6(4): 9-16.
11	ZHANG J P , HUCK P M , ANDERSON W B , et al . A computational fluid dynamics based integrated disinfection design approach for improvement of full-scale ozone contactor performance[J]. Ozone: Science and Engineering, 2007, 29(6): 451-460.
12	ZHANG J , TEJADA-MARTÍNEZ A E , ZHANG Q . Developments in computational fluid dynamics-based modeling for disinfection technologies over the last two decades: a review[J]. Environmental Modelling & Software, 2014, 58: 71-85.
13	QUIÑONES-BOLAÑOS E , OCAMPO J T , RODRÍGUEZ L C . Applicability of computational fluid dynamics to simulate ozonation processes[J]. Ingenieríay Desarrollo, 2008(24): 97-116.
14	NIELD D A , BEJAN A . Convection in porous media[M]. 5 ed. Berlin: Springer, 2017.
15	ALKAM M , AL-NIMR M . Transient non-darcian forced convection flow in a pipe partially filled with a porous material[J]. International Journal of Heat and Mass Transfer, 1998, 41(2): 347-356.
16	LE BARS M , WORSTER M G . Interfacial conditions between a pure fluid and a porous medium: implications for binary alloy solidification[J]. Journal of Fluid Mechanics, 2006, 550: 149-173.
17	AMIRI A , VAFAI K . Transient analysis of incompressible flow through a packed bed[J]. International Journal of Heat and Mass Transfer, 1998, 41(24): 4259-4279.
18	XU Peng , YU Boming . Developing a new form of permeability and Kozeny-Carman constant for homogeneous porous media by means of fractal geometry[J]. Advances in Water Resources, 2008, 31(1): 74-81.
19	COSTA A . Permeability-porosity relationship: a reexamination of the kozeny-carman equation based on a fractal pore-space geometry assumption[J]. Geophysical Research Letters, 2006, 33(2): L02318.
20	MUELLER G E . Prediction of radial porosity distributions in randomly packed fixed beds of uniformly sized spheres in cylindrical containers[J]. Chemical Engineering Science, 1991, 46(2): 706-708.
21	MUELLER G E . Radial void fraction distributions in randomly packed fixed beds of uniformly sized spheres in cylindrical containers[J]. Powder Technology, 1992, 72(3): 269-275.
22	JESCHAR R . Druckverlust in mehrkornschüttungen aus kugeln[J]. Steel Research International, 1964,35(2): 91-108.
23	DE KLERK A . Voidage variation in packed beds at small column to particle diameter ratio[J]. AIChE Journal, 2003, 49(8): 2022-2029.
24	DIXON A G . Correlations for wall and particle shape effects on fixed bed bulk voidage[J]. The Canadian Journal of Chemical Engineering, 1988, 66(5): 705-708.
25	POLING B E , PRAUSNITZ J M , JOHN PAUL O C , et al . The properties of gases and liquids[M]. 5 ed. New York: McGraw-Hill, 2001.
26	SCHOTTE W . Prediction of the molar volume at the normal boiling point[J]. Chemical Engineering Journal, 1992, 48(3): 167-172.
27	LIDE D R , HAYNES W . CRC handbook of chemistry and physics 2016—2017: a ready-reference book of chemical and physical data[M]. Chemical Rubber Publishing Company, 2016.
28	JOHNSON R W . Handbook of fluid dynamics[M]. 2 ed. Boca Raton: CRC Press, 2016.
29	VAFAI K . Handbook of porous media[M]. 3 ed. Boca Raton: CRC Press, 2015.
30	MILLINGTON R , QUIRK J . Permeability of porous solids[J]. Transactions of the Faraday Society, 1961, 57: 1200-1207.
31	WAKAO N , KAGEI S . Heat and mass transfer in packed beds[M]. London: Taylor & Francis, 1982.
32	EISFELD B , SCHNITZLEIN K . The influence of confining walls on the pressure drop in packed beds[J]. Chemical Engineering Science, 2001, 56(14): 4321-4329.

[1]	王云飞, 秦蕊, 郑利军, 李焱, 李清平. 旋转填充床CFD模拟研究进展[J]. 化工进展, 2023, 42(S1): 1-9.
[2]	孙继鹏, 韩靖, 唐杨超, 闫汉博, 张杰瑶, 肖苹, 吴峰. 硫黄湿法成型过程数值模拟与操作参数优化[J]. 化工进展, 2023, 42(S1): 189-196.
[3]	罗成, 范晓勇, 朱永红, 田丰, 崔楼伟, 杜崇鹏, 王飞利, 李冬, 郑化安. 中低温煤焦油加氢反应器不同分配器中液体分布的CFD模拟[J]. 化工进展, 2023, 42(9): 4538-4549.
[4]	卜治丞, 焦波, 林海花, 孙洪源. 脉动热管计算流体力学模型与研究进展[J]. 化工进展, 2023, 42(8): 4167-4181.
[5]	邱沫凡, 蒋琳, 刘荣正, 刘兵, 唐亚平, 刘马林. 气固流化床化学反应数值模拟中颗粒尺度模型研究进展[J]. 化工进展, 2023, 42(10): 5047-5058.
[6]	马云飞, 王建兵, 贾超敏, 邢懿心, 柯述, 张先. 臭氧氧化动力学模型及反应器建模研究进展[J]. 化工进展, 2022, 41(S1): 556-570.
[7]	彭德其, 冯源, 王依然, 谭卓伟, 俞天兰, 吴淑英. 立式缩放管内液固颗粒群浓度分布与汇聚特性[J]. 化工进展, 2022, 41(9): 4662-4672.
[8]	古新, 张前欣, 王超鹏, 方运阁, 李宁, 王永庆. U形导流板换热器传热和阻力性能分析[J]. 化工进展, 2022, 41(7): 3465-3474.
[9]	刘永飞, 苏伟, 梁琪琪, 李青云, 刘幽燕, 唐爱星. 叔丁醇体系中化学酶法催化α-蒎烯环氧化[J]. 化工进展, 2022, 41(6): 3002-3009.
[10]	徐涵卓, 刘志浩, 孙宝昌, 张亮亮, 邹海魁, 罗勇, 初广文. 流体驱动旋转装备应用与数值模拟方法研究进展[J]. 化工进展, 2022, 41(6): 2806-2817.
[11]	陈龙, 李霞霞, 李伟祥, 戚锐, 邓鑫, 吴斌鑫. 聚丙烯非织造布熔喷过程的计算流体力学模拟研究进展[J]. 化工进展, 2022, 41(2): 537-553.
[12]	朱明军, 胡大鹏. 操作参数对三相卧螺离心机油水砂分离性能影响模拟及实验分析[J]. 化工进展, 2022, 41(10): 5188-5199.
[13]	王吉坤, 李阳, 陈贵锋, 刘敏, 寇丽红, 王琦, 何毅聪. 臭氧催化氧化降解煤化工高盐废水有机物的机理[J]. 化工进展, 2022, 41(1): 493-502.
[14]	王戈, 孙志伟, 谭蔚, 邱威, 朱国瑞. 异形纤维阵列过滤特性的数值模拟[J]. 化工进展, 2022, 41(1): 30-39.
[15]	王彦谦, 王远洋. 微反应器中费托合成的研究进展[J]. 化工进展, 2021, 40(S2): 185-191.