硅藻土基复合填料制备及滴滤塔去除二甲苯的性能

doi:10.16085/j.issn.1000-6613.2022-1655

摘要/Abstract

摘要：

以硅藻土（DE）为骨架，聚乙烯醇（PVA）、海藻酸钠（SA）为固定化材料，采用微生物固定化技术制备出一种包含高效降解菌和具有营养缓释功能的复合填料。探究了装填复合填料生物滴滤塔（BTF）净化二甲苯的性能。复合填料比表面积为4.53m²/g，具有良好的持水能力，且复合填料的重复使用性较好，连续处理8批污染物后，去除效率保持在95%以上。负载复合填料的BTF经过11d运行，出口浓度低于GB 16297—1996中规定的排放限值[ρ(二甲苯)=70mg/m³]，结果表明此时BTF完成启动；进气浓度为1200mg/m³，空床停留时间（EBRT）分别为53s、38s、28s时，去除效率为98%、86%、78%；在EBRT为28s，进气浓度为700mg/m³、250mg/m³时，去除效率分别为91%、99%；在9天内外界不提供养分时，去除效率无明显下降。系统停运2天和7天，分别可在运行9.5h和1天内恢复原来的净化性能。实验结果表明复合填料具有较好理化性质，对二甲苯去除性能好，抗冲击负荷及停滞能力强，可为其应用提供一定参考价值。

关键词: 固定化, 填料, 结构表征, 生物反应器, 硅藻土

Abstract:

Composite fillers containing efficient xylene-degrading bacteria with nutrient slow-release function were prepared by microbial immobilization technique, using diatomaceous earth (DE) as the backbone, and polyvinyl alcohol (PVA) and sodium alginate (SA) as immobilization materials. A biotrickling filter (BTF) was loaded with the composite fillers and the xylene purification performance was investigated. The specific surface area of the composite filler was 4.53m²/g, which had good water-holding capacity,and the composite filler showed good reusability with the removal efficiency maintaining above 95% after continuous treatment of 8 batches of pollutants. After 11 d of operation, the outlet concentration of the BTF loaded with composite filler was below the emission limit [ρ(xylene)=70mg/m³] specified in GB 16297—1996, which indicated that the start-up of the BTF was completed at this time. When the inlet concentration was 1200 mg/m³ and the empty bed residence time (EBRT) was 53s, 38s and 28s, the removal efficiency was 98%、86% and 78%, respectively. When the EBRT was 28s and the inlet concentration was 700mg/m³and 250mg/m³, the removal efficiency was 91% and 99%, respectively. When no additional nutrients were provided for 9d, the removal efficiency did not decrease significantly. When the system was stagnated for 2d and 7d, the performance could be restored within 9.5h and 1d of operation, respectively. The results showed that the composite fillers had better physicochemical properties, good removal performance for xylene, and strong resistance to shock loading and stagnation, which can provide some reference value for its application.

Key words: immobilization, fillers, structural characterization, bioreactors, diatomaceous earth

中图分类号:

X701

鲁少杰, 刘佳, 冀芊竹, 李萍, 韩月阳, 陶敏, 梁文俊. 硅藻土基复合填料制备及滴滤塔去除二甲苯的性能[J]. 化工进展, 2023, 42(7): 3884-3892.

LU Shaojie, LIU Jia, JI Qianzhu, LI Ping, HAN Yueyang, TAO Min, LIANG Wenjun. Preparation of diatomaceous earth-based composite filler and its xylene removal performance by a biotrickling filter[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3884-3892.

图/表 15

图1 复合填料的合成过程

图2 生物滴滤工艺流程图1—进气泵；2—转子流量计；3—二甲苯挥发瓶；4—混气瓶；5—取气口；6—取样口；7—潜水泵；8—储液槽；9—上液管；10—液体缓冲槽；11—电磁阀；12—喷头

表1 生物滴滤塔运行条件

阶段	时间 /天	空床停留时间（EBRT）/s	二甲苯质量浓度 /mg·m^-3	循环液
Ⅰ	1~41	53	1200	营养液
Ⅱ	42~50	53	1200	营养液
	51~57	停滞
	58~64	53	1200
	65~75	38	1200
	76~84	28	1200
Ⅲ	85~91	28	700	营养液
	92~93	停滞
	94~109	28	700
	110~123	28	250
Ⅳ	124~132	28	250	去离子水

图3 复合填料、硅藻土及陶粒失水率随时间变化图

图4 合成原材和样品的红外光谱

图5 凝胶球可能的形成机理

图6 合成原材和样品的XRD图谱

图7 填料使用次数对于去除效率的影响

图8 不同运行阶段生物滴滤塔对二甲苯的去除效率

图9 不同EBRT条件下进气负荷对体积去除负荷的影响

图10 冲击负荷对去除效率的影响

图11 短期停滞后生物滴滤塔重启性能

表2 生物过滤塔和生物滴滤塔停滞后重启性能

反应器	污染物	填料	停滞方式	停运时间/d	恢复时间
生物过滤塔^[36]	二甲苯	木炭	完全停滞	10	4d
生物过滤塔^[37]	甲苯	聚氨酯泡沫	完全停滞	10	10d
生物过滤塔^[38]	甲烷	石料	持续提供不含VOCs的潮湿空气	30	15d
生物过滤塔^[13]	氯苯	凝胶胶囊	完全停滞	6 20	3d 8d
生物滴滤塔^[39]	硫化氢	聚氨酯泡沫	完全停滞	2 5	32h 12d
生物滴滤塔	二甲苯	本实验填料	完全停滞	2 7	9.5h 1d

图12 单位填料蛋白含量随运行时间变化

图13 生物滴滤塔压降随运行时间变化图

参考文献 41

1	LING Z H, GUO Hai. Contribution of VOC sources to photochemical ozone formation and its control policy implication in Hong Kong[J]. Environmental Science & Policy, 2014, 38: 180-191.
2	赵诗琳, 孟范平, 林雨霏, 等. 二甲苯吸附剂及其在泄漏事故水域的适用性评述[J]. 化工进展, 2019, 38(6): 2813-2824.
	ZHAO Shilin, MENG Fanping, LIN Yufei, et al. Sorbents for seprating xylene and their applicability in waters after the accidental spills: A review[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2813-2824.
3	ZHANG Yun, LIU Jia, DENG Wei, et al. Research on pressure drop solution and pilot-scale application of bio-trickling filter for the treatment of butan-2-yl ethanoate[J]. Process Biochemistry, 2019, 79:118-126.
4	杜佳辉, 刘佳, 杨菊平，等. 生物法联合工艺治理VOCs的研究进展[J]. 化工进展, 2021, 40(5):2802-2812.
	DU Jiahui, LIU Jia, YANG Juping, et al. Recent advances in biological combined technology for VOCs treatment[J]. Chemical Industry and Engineering Progress, 2021, 40(5):2802-2812.
5	Eldon RENE R, MURTHY D V S, SWAMINATHAN T. Performance evaluation of a compost biofilter treating toluene vapours[J]. Process Biochemistry, 2005, 40(8):2771-2779.
6	AMIN Mohammad Mehdi, RAHIMI Amir, BINA Bijan, et al. Performance evaluation of a scoria-compost biofilter treating xylene vapors[J]. Journal of Environmental Health Science and Engineering, 2014, 12(1):140.
7	LEE Sanghun, LI Congna, HEBER Albert J, et al. Biofiltration of a mixture of ethylene, ammonia, n-butanol, and acetone gases[J]. Bioresource Technology, 2013, 127: 366-377.
8	Manuel CÁCERES, DORADO Antonio D, GENTINA Juan C, et al. Oxidation of methane in biotrickling filters inoculated with methanotrophic bacteria[J]. Environmental Science and Pollution Research, 2017, 24(33): 25702-25712.
9	李海玲, 陈丽华, 肖朝虎, 等. 微生物固定化载体材料的研究进展[J]. 现代化工, 2020, 40(8): 58-61, 66.
	LI Hailing, CHEN Lihua, XIAO Chaohu, et al. Research progress in microorganisms immobilized carrier materials[J]. Modern Chemical Industry, 2020, 40(8): 58-61, 66.
10	KUMAR Munna, GIRI Balendu Shekher, KIM Ki Hyun, et al. Performance of a biofilter with compost and activated carbon based packing material for gas-phase toluene removal under extremely high loading rates[J]. Bioresource Technology, 2019, 285:121317.
11	CHENG Zhuowei, FENG Ke, XU Danhua, et al. An innovative nutritional slow-release packing material with functional microorganisms for biofiltration: Characterization and performance evaluation[J]. Journal of Hazardous Materials, 2019, 366:16-26.
12	FENG Rongfang, ZHAO Gang, YANG Yonggang, et al. Enhanced biological removal of intermittent VOCs and deciphering the roles of sodium alginate and polyvinyl alcohol in biofilm formation[J]. PLoS One, 2019, 14(5): e0217401.
13	YANG Nanyang, WANG Can, HAN Mengfei. Gel-encapsulated microorganisms used as a strategy to rapidly recover biofilters after starvation interruption[J]. Journal of Environmental Management, 2020, 261:110237.
14	季文标, 陈雪松, 陈水荣, 等. 固定化生物滴滤塔处理模拟喷漆废气的中试研究[J]. 浙江冶金, 2009(2): 21-23.
	JI Wenbiao, CHEN Xuesong, CHEN Shuirong, et al. Pilot study on the treatment of simulated paint spraying exhaust gas by immobilized biological trickling filter tower[J]. Journal of Zhejiang Metallurgy, 2009(2): 21-23.
15	ERDEM Emin, Gülay ÇÖLGEÇEN, DONAT Ramazan. The removal of textile dyes by diatomite earth[J]. Journal of Colloid and Interface Science, 2005, 282(2): 314-319.
16	白云峰, 孟欣, 秦杰, 等. 我国硅藻土产业发展前景及对策建议[J]. 居业, 2018, 10(9): 2-3.
	BAI Yunfeng, MENG Xin, QIN Jie, et al. Prospects for the development of diatomaceous earth industry in China and suggestions for countermeasures[J]. Create Living, 2018, 10(9): 2-3.
17	XIE Fazhi, WU Fengchang, LIU Guijian, et al. Removal of phosphate from eutrophic lakes through adsorption by in situ formation of magnesium hydroxide from diatomite[J]. Environmental Science & Technology, 2014, 48(1): 582-590.
18	杨勤桃, 农接亮, 解庆林, 等. 改性硅藻土在污水处理中的应用研究进展[J].化工新型材料, 2022, 50(1): 298-302.
	YANG Qintao, NONG Jieliang, XIE Qinglin, et al. Research progress on application of modified diatomite in wastewater treatment [J]. New Chemical Materials, 2022, 50(1): 298-302.
19	冯荣芳. 生物滴滤池对非稳态VOCs废气的净化性能与生物膜特性研究[D]. 广州: 华南理工大学, 2019.
	FENG Rongfang. Purification performance of biotrickling filters on unsteady state VOCs-containing waste gases and properties of biofilm[D]. Guangzhou: South China University of Technology, 2019.
20	朱仁成, 张雅丽, 徐淑敏, 等. 废气生物净化用填料的研究进展[J]. 环境科学与技术, 2015, 38(7): 146-151, 181.
	ZHU Rencheng, ZHANG Yali, XU Shumin, et al. Review in biological filters for the waste gas purification[J]. Environmental Science & Technology, 2015, 38(7): 146-151, 181.
21	杨亮, 李韦霖, 宋鑫钥, 等. 基于聚乙烯醇复合膜的改性研究进展[J]. 印染助剂, 2022, 39(11): 5-11.
	YANG Liang, LI Weilin, SONG Xinyue, et al. Research progress on modification of polyvinyl alcohol compositive film[J]. Textile Auxiliaries, 2022, 39(11): 5-11.
22	聂发辉, 吴道, 黄慧倩. 海藻酸钠复合材料吸附污染物研究进展[J]. 化工新型材料, 2022, 50(6): 307-312.
	Fahui NEI, WU Dao, HUANG Huiqian. Research progress on sodium alginate composites adsorption[J]. New Chemical Materials, 2022, 50(6): 307-312.
23	徐梦洁, 张秀梅, 胡银春, 等.双交联聚乙烯醇/海藻酸钠水凝胶的制备与表征[J]. 高分子材料科学与工程, 2020, 36(4): 55-60, 66.
	XU Mengjie, ZHANG Xiumei, HU Yinchun, et al. Preparation and characterization of double crosslinked polyvinyl alcohol/sodium alginate hydrogels[J]. Polymer Materials Science & Engineering, 2020, 36(4): 55-60, 66.
24	王宏丽, 陈风雷, 胡雪梅. 纳米羟基磷灰石/海藻酸钠/聚乙烯醇多孔支架材料的制备与表征[J]. 西南大学学报(自然科学版), 2013, 35(1): 160-164.
	WANG Hongli, CHEN Fenglei, HU Xuemei. Preparation and characterization of a nano-hydoxyapatite/sodium alginate-polyvinyl alcohol composite scaffold[J]. Journal of Southwest University (Natural Science Edition), 2013, 35(1): 160-164.
25	张敏. 化学交联海藻酸盐—明胶水凝胶的研究[D]. 天津: 天津大学, 2006.
	ZHANG Min. Study on covalently cross-linked alginate-gelatin hydrogels[D]. Tianjin: Tianjin University, 2006.
26	TENG Shaoxiang, WANG Shuguang, GONG Wenxin, et al. Removal of fluoride by hydrous manganese oxide-coated alumina: Performance and mechanism[J]. Journal of Hazardous Materials, 2009, 168(2/3): 1004-1011.
27	蒋瑶珮, 杨涛, 费国霞，等. 医用聚乙烯醇/海藻酸钠/氧化石墨烯水凝胶的制备及性能[J]. 高分子材料科学与工程, 2018, 34(7): 150-155.
	JIANG Yaopei, YANG Tao, FEI Guoxia, et al. Synthesis and properties of graphene oxide/sodium alginate/polyvinyl alcohol hydrogel [J]. Polymer Materials Science & Engineering, 2018, 34(7): 150-155.
28	JORIO Hasnaa, BIBEAU Louise, VIEL Guy, et al. Effects of gas flow rate and inlet concentration on xylene vapors biofiltration performance[J]. Chemical Engineering Journal, 2000, 76(3): 209-221.
29	ELMRINI Hicham, BREDIN Nathalie, SHAREEFDEEN Zarook, et al. Biofiltration of xylene emissions: Bioreactor response to variations in the pollutant inlet concentration and gas flow rate[J]. Chemical Engineering Journal, 2004, 100(1/2/3): 149-158.
30	Anil MATHUR K, SUNDARAMURTHY J, BALOMAJUMDER C. Kinetics of the removal of mono-chlorobenzene vapour from waste gases using a trickle bed air biofilter[J]. Journal of Hazardous Materials, 2006, 137(3): 1560-1568.
31	SARAVANAN V, RAJAMOHAN N. Treatment of xylene polluted air using press mud-based biofilter[J]. Journal of Hazardous Materials, 2009, 162(2/3): 981-988.
32	YANG Nanyang, WANG Can, HAN Mengfei, et al. Performance improvement of a biofilter by using gel-encapsulated microorganisms assembled in a 3D mesh material[J]. Chemosphere, 2020, 251: 126618.
33	MOUSSAVI Gholamreza, BAHADORI Mohammad Bagher, FARZADKIA Mehdi, et al. Performance evaluation of a thermophilic biofilter for the removal of MTBE from waste air stream: Effects of inlet concentration and EBRT[J]. Biochemical Engineering Journal, 2009, 45(2): 152-156.
34	ROMERO HERNANDEZ A C, RODRÍGUEZ SUSA M S, ANDRÈS Y, et al. Steady- and transient-state H₂S biofiltration using expanded schist as packing material[J]. New Biotechnology, 2013, 30(2): 210-218.
35	KIM Jung Hoon, RENE Eldon R, PARK Hung Suck. Biological oxidation of hydrogen sulfide under steady and transient state conditions in an immobilized cell biofilter[J]. Bioresource Technology, 2008, 99(3): 583-588.
36	SINGH Kiran, GIRI B S, SAHI Amrita, et al. Biofiltration of xylene using wood charcoal as the biofilter media under transient and high loading conditions[J]. Bioresource Technology, 2017, 242: 351-358.
37	SINGH R S, RAI B N, UPADHYAY S N. Removal of toluene vapour from air stream using a biofilter packed with polyurethane foam[J]. Process Safety and Environmental Protection, 2010, 88(5): 366-371.
38	FERDOWSI Milad, VEILLETTE Marc, RAMIREZ Antonio Avalos, et al. Performance evaluation of a methane biofilter under steady state, transient state and starvation conditions[J]. Water Air & Soil Pollution, 2016, 227(6): 168.
39	NAMINI M T, ABDEHAGH Niloufar, HEYDARIAN Seyed Mohammad, et al. Hydrogen sulfide removal performance of a bio-trickling filter employing Thiobacillus thiparus immobilized on polyurethane foam under various starvation regimes[J]. Biotechnology and Bioprocess Engineering, 2012, 17(6): 1278-1283.
40	HASSAN Ashraf ALY, SORIAL George A. Removal of benzene under acidic conditions in a controlled Trickle Bed Air Biofilter[J]. Journal of Hazardous Materials, 2010, 184(1/2/3): 345-349.
41	聂阳, 朱仁成, 李顺义, 等. 微包埋恶臭假单胞菌复合填料制备及性能评价[J]. 环境工程学报, 2019, 13(3): 678-684.
	NIE Yang, ZHU Rencheng, LI Shunyi, et al. Preparation and performance evaluation of a composite filler micro-embedded with the Pseudomonas putida [J]. Chinese Journal of Environmental Engineering, 2019, 13(3): 678-684.

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