Synthesis and methyl blue adsorption performance of oil shale ash-based zeolites

doi:10.16085/j.issn.1000-6613.2024-0813

Abstract

Abstract:

The structure-function relationship between the type and structure of the oil shale ash-based zeolite and its ability to adsorb dyes is unclear. NaP1, NaX and NaA zeolites were prepared from Beipiao oil shale ash (BPA) and used to adsorb methylene blue (MB). The effects of zeolite dosage, initial MB concentration, pH, adsorption temperature and time on the MB adsorption performance were investigated, and the adsorption mechanism was revealed. The structure-function relationship between the type of zeolite and its ability to adsorb MB was explored. The results showed that the specific surface area and pore structure of the zeolite have great effects on its adsorption capacity. Under the optimal adsorption conditions, the MB removal percentages by NaP1, NaX and NaA zeolites are 99.7%, 94.5% and 96.5%, respectively. The synthesized zeolites have excellent recyclability. The adsorption processes conform to the pseudo-second-order kinetic and the Langmuir isothermal adsorption models. The adsorption thermodynamics results show that the MB adsorption on the NaP1 zeolite is a spontaneous endothermic process of increased entropy while that on the NaX and NaA zeolites is a spontaneous exothermic process of decreased entropy. The study of adsorption mechanism showed that electrostatic attraction, hydrogen bond and pore diffusion are the main driving forces during the MB adsorption on the zeolites. This work can provide valuable practical and theoretical reference for the efficient utilization of oil shale ash and low-cost treatment of dyeing wastewater by adsorption method.

Key words: oil shale ash, zeolite, methylene blue, adsorption mechanism, structure-function relationship

摘要：

针对油页岩灰基分子筛的类型和结构与其吸附染料分子能力间构效关系不明确的问题，以北票油页岩灰（BPA）为原料制备了NaP1、NaX和NaA三种不同类型的分子筛，并将其用于吸附亚甲基蓝（MB），考察了分子筛用量、MB初始浓度、pH、吸附温度和时间对吸附的影响规律，阐明了分子筛吸附MB过程的吸附机理，明确了不同类型分子筛与其吸附MB能力之间的构效关系。结果表明，分子筛的比表面积和孔结构对其吸附能力影响较大，在最优化吸附条件下，NaP1、NaX和NaA型分子筛对MB的去除率分别为99.7%、94.5%和96.5%，且均具有良好的可再生重复利用性能。吸附过程符合拟二级动力学和Langmuir等温吸附模型。NaP1型分子筛对MB的吸附是自发的、吸热的熵增过程；NaX和NaA型分子筛对MB的吸附是自发的、放热的熵减过程。吸附机理研究表明，静电引力、氢键和孔扩散是分子筛吸附MB过程的主要推动力。可为油页岩灰的资源化利用以及低成本吸附法处理印染废水提供有价值的实践和理论借鉴。

关键词: 油页岩灰, 分子筛, 亚甲基蓝, 吸附机理, 构效关系

CLC Number:

TQ09

SHI Lei, WANG Qian, ZHAO Xiaosheng, LIU Hongchen, CHE Yuanjun, DUAN Yu, LI Qing. Synthesis and methyl blue adsorption performance of oil shale ash-based zeolites[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 650-661.

石磊, 王倩, 赵晓胜, 刘宏臣, 车远军, 段玉, 李庆. 油页岩灰基分子筛的制备及对亚甲基蓝的吸附[J]. 化工进展, 2024, 43(S1): 650-661.

Figures/Tables 20

References 37

1	任南琪, 周显娇, 郭婉茜, 等. 染料废水处理技术研究进展[J]. 化工学报, 2013, 64(1): 84-94.
	REN Nanqi, ZHOU Xianjiao, GUO Wanqian, et al. A review on treatment methods of dye wastewater[J]. CIESC Journal, 2013, 64(1): 84-94.
2	DUTA Anca, VISA Maria. Simultaneous removal of two industrial dyes by adsorption and photocatalysis on a fly-ash-TiO₂ composite[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2015, 306: 21-30.
3	HADDAD Mohammadine EL, SLIMANI Rachid, MAMOUNI Rachid, et al. Removal of two textile dyes from aqueous solutions onto calcined bones[J]. Journal of the Association of Arab Universities for Basic and Applied Sciences, 2013, 14(1): 51-59.
4	CAO Jiashun, LIN Junxiong, FANG Fang, et al. A new absorbent by modifying walnut shell for the removal of anionic dye: Kinetic and thermodynamic studies[J]. Bioresource Technology, 2014, 163: 199-205.
5	DOYLE Aidan M, ALISMAEEL Ziad T, ALBAYATI Talib M, et al. High purity FAU-type zeolite catalysts from shale rock for biodiesel production[J]. Fuel, 2017, 199: 394-402.
6	LI Hui, ZHENG Feng, WANG Jing, et al. Facile preparation of zeolite-activated carbon composite from coal gangue with enhanced adsorption performance[J]. Chemical Engineering Journal, 2020, 390: 124513.
7	Piotr ROŻEK, Magdalena KRÓL, Włodzimierz MOZGAWA. Geopolymer-zeolite composites: A review[J]. Journal of Cleaner Production, 2019, 230: 557-579.
8	WANG Qian, HOU Yucui, WU Weize, et al. A deep insight into the structural characteristics of Yilan oil shale kerogen through selective oxidation[J]. Carbon Resources Conversion, 2019, 2(3): 182-190.
9	WANG Qian, HOU Yucui, WU Weize, et al. The relationship between the humic degree of oil shale kerogens and their structural characteristics[J]. Fuel, 2017, 209: 35-42.
10	张立栋, 刘洪鹏, 贾春霞, 等. 我国油页岩综合利用相关研究进展[J]. 化工进展, 2012, 31(11): 2359-2363.
	ZHANG Lidong, LIU Hongpeng, JIA Chunxia, et al. Research progress of comprehensive utilization of oil shale in China[J]. Chemical Industry and Engineering Progress, 2012, 31(11): 2359-2363.
11	WANG Sha, JIANG Xiumin, HAN Xiangxin, et al. Investigation of Chinese oil shale resources comprehensive utilization performance[J]. Energy, 2012, 42(1): 224-232.
12	QIAN Yu, YANG Qingchun, ZHANG Jun, et al. Development of an integrated oil shale refinery process with coal gasification for hydrogen production[J]. Industrial & Engineering Chemistry Research, 2014, 53(51): 19970-19978.
13	SHAWABKEH Reyad, Adnan AL-HARAHSHEH, HAMI Malik, et al. Conversion of oil shale ash into zeolite for cadmium and lead removal from wastewater[J]. Fuel, 2004, 83(7/8): 981-985.
14	Phuong Lan TRAN-NGUYEN, Kim-Phung LY, THANH Luong Huynh Vu, et al. Facile synthesis of zeolite NaX using rice husk ash without pretreatment[J]. Journal of the Taiwan Institute of Chemical Engineers, 2021, 123: 338-345.
15	YU Xiaohua, Hailiang LYU, ZHOU Guowei, et al. Absorption of methyl orange by modified fly zeolites[J]. Advanced Materials Research, 2012, 476/477/478: 1365-1369.
16	赵晓胜, 周自成, 王倩, 等. 油页岩灰基NaX型沸石的合成及表征[J]. 煤炭与化工, 2022, 45(7): 145-149, 160.
	ZHAO Xiaosheng, ZHOU Zicheng, WANG Qian, et al. Synthesis and characterization of NaX zeolite based on the oil shale ash[J]. Coal and Chemical Industry, 2022, 45(7): 145-149, 160.
17	BAI Shuxia, ZHOU Lingmei, CHANG Zhibing, et al. Synthesis of Na-X zeolite from Longkou oil shale ash by alkaline fusion hydrothermal method[J]. Carbon Resources Conversion, 2018, 1(3): 245-250.
18	李燕, 周思奇, 李翔. 油页岩废渣水热合成4A分子筛[J]. 山东化工, 2017, 46(17): 40-41.
	LI Yan, ZHOU Siqi, LI Xiang. Hydrothermal synthesis of 4A molecular sieve from oil shale waste[J]. Shandong Chemical Industry, 2017, 46(17): 40-41.
19	BAO Weiwei, LIU Lu, ZOU Haifeng, et al. Removal of Cu²⁺ from aqueous solutions using Na-A zeolite from oil shale ash[J]. Chinese Journal of Chemical Engineering, 2013, 21(9): 974-982.
20	赵雯, 李函霏, 吴畏. 油页岩灰渣合成P型沸石及对Co²⁺吸附性研究[J]. 硅酸盐通报, 2021, 40(5): 1720-1727.
	ZHAO Wen, LI Hanfei, WU Wei. Synthesis of P-type zeolite from oil shale ash and its adsorption to Co²⁺ [J]. Bulletin of the Chinese Ceramic Society, 2021, 40(5): 1720-1727.
21	SHI Lei, WANG Qian, ZHAO Xiaosheng, et al. The methyl blue adsorption performance and mechanism of NaX zeolite synthesized from Huadian oil shale ash[J]. Journal of the Taiwan Institute of Chemical Engineers, 2023, 147: 104904.
22	SAPAWE N, JALIL AA, TRIWAHYONO S, et al. Cost-effective microwave rapid synthesis of zeolite NaA for removal of methylene blue[J]. Chemical Engineering Journal, 2013, 229: 388-398.
23	SUPELANO G I, GÓMEZ CUASPUD J A, MORENO-ALDANA L C, et al. Synthesis of magnetic zeolites from recycled fly ash for adsorption of methylene blue[J]. Fuel, 2020, 263: 116800.
24	CHENG Yong, XU Longjun, LIU Chenglun. NaP1 zeolite synthesized via effective extraction of Si and Al from red mud for methylene blue adsorption[J]. Advanced Powder Technology, 2021, 32(10): 3904-3914.
25	ZHOU Qi, JIANG Xuguang, QIU Qili, et al. Synthesis of high-quality NaP1 zeolite from municipal solid waste incineration fly ash by microwave-assisted hydrothermal method and its adsorption capacity[J]. Science of the Total Environment, 2023, 855: 158741.
26	DU Tao, LIU Liying, XIAO Penny, et al. Preparation of zeolite NaA for CO₂ capture from nickel laterite residue[J]. International Journal of Minerals, Metallurgy, and Materials, 2014, 21(8): 820-825.
27	HOR Kar Yan, CHEE Jasmine Mun Cheng, CHONG Mengnan, et al. Evaluation of physicochemical methods in enhancing the adsorption performance of natural zeolite as low-cost adsorbent of methylene blue dye from wastewater[J]. Journal of Cleaner Production, 2016, 118: 197-209.
28	SIMSEK Gulsah, IMAMOGLU Mustafa. Investigation of equilibrium, kinetic and thermodynamic of methylene blue adsorption onto dehydrated hazelnut husk carbon[J]. Desalination and Water Treatment, 2015, 54(6): 1747-1753.
29	BAO Weiwei, ZOU Haifeng, GAN Shucai, et al. Adsorption of heavy metal ions from aqueous solutions by zeolite based on oil shale ash: Kinetic and equilibrium studies[J]. Chemical Research in Chinese Universities, 2013, 29(1): 126-131.
30	MIYAH Youssef, BENJELLOUN Mohammed, LAHRICHI Anissa, et al. Highly-efficient treated oil shale ash adsorbent for toxic dyes removal: Kinetics, isotherms, regeneration, cost analysis and optimization by experimental design[J]. Journal of Environmental Chemical Engineering, 2021, 9(6): 106694.
31	程绿竹, 王宗乾, 王邓峰, 等. 高中空生物质活性碳纤维制备及其对亚甲基蓝的吸附性能[J]. 纺织学报, 2021, 42(2): 129-134.
	CHENG Lüzhu, WANG Zongqian, WANG Dengfeng, et al. Preparation of highly hollow biomass-based activated carbon fiber and its adsorption property to methylene blue[J]. Journal of Textile Research, 2021, 42(2): 129-134.
32	CHENG Yong, XU Longjun, JIANG Zao, et al. Feasible low-cost conversion of red mud into magnetically separated and recycled hybrid SrFe₁₂O₁₉@NaP1 zeolite as a novel wastewater adsorbent[J]. Chemical Engineering Journal, 2021, 417: 128090.
33	DAI Chengyi, ZHANG Menghan, GUO Xinwen, et al. Mesoporous composite Ni-C-N/SA for selective adsorption of methylene blue from water[J]. Chemical Engineering Journal, 2021, 407: 127181.
34	LIU Yi, YAN Chunjie, ZHANG Zuhua, et al. A comparative study on fly ash, geopolymer and faujasite block for Pb removal from aqueous solution[J]. Fuel, 2016, 185: 181-189.
35	CHEN Dan, HU Xin, SHI Lu, et al. Synthesis and characterization of zeolite X from lithium slag[J]. Applied Clay Science, 2012, 59: 148-151.
36	AHMED Kedir Ebrahim, KUO Dong-Hau, KEBEDE Worku Lakew. In-situ synthesis and characterizations of Bi₂(O,S)₃/Zn(O,S) composites for visible light hexavalent chromium reduction[J]. Advanced Powder Technology, 2019, 30(8): 1664-1671.
37	全姗姗, 朱玉婵, 任占海, 等. 改性MCM-41分子筛对阴离子偶氮染料的吸附作用机理[J]. 化工进展, 2016, 35(1): 320-326.
	QUAN Shanshan, ZHU Yuchan, REN Zhanhai, et al. Adsorption performance of anionic azo dye by the modified MCM-41 mesoporous molecular sieve[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 320-326.

分子筛	灰碱比	熔融	灰水比	老化	沉降	水热	干燥
NaP1	ABPA∶NaOH=1∶1.5	650℃；2h	1∶10	60℃；2h	—	120℃；10h	60℃；10h
NaX	BPA∶NaOH=1∶2	600℃；1h	1∶6	室温；3h	—	80℃；12h	110℃；5h
NaA	BPA∶NaOH∶Al₂O₃=1∶0.8∶0.3669	700℃；2h	1∶10	室温；3h	12h	100℃；24h	105℃；10h

分子筛	灰碱比	熔融	灰水比	老化	沉降	水热	干燥
NaP1	ABPA∶NaOH=1∶1.5	650℃；2h	1∶10	60℃；2h	—	120℃；10h	60℃；10h
NaX	BPA∶NaOH=1∶2	600℃；1h	1∶6	室温；3h	—	80℃；12h	110℃；5h
NaA	BPA∶NaOH∶Al₂O₃=1∶0.8∶0.3669	700℃；2h	1∶10	室温；3h	12h	100℃；24h	105℃；10h

样品	SiO₂	Al₂O₃	CaO	Fe₂O₃	K₂O	MgO	SO₃	其他
BPA	60.08	14.38	9.13	5.08	3.66	3.22	2.09	2.35
ABPA	75.76	11.39	1.94	3.11	4.40	1.79	0.10	1.49

样品	SiO₂	Al₂O₃	CaO	Fe₂O₃	K₂O	MgO	SO₃	其他
BPA	60.08	14.38	9.13	5.08	3.66	3.22	2.09	2.35
ABPA	75.76	11.39	1.94	3.11	4.40	1.79	0.10	1.49

分子筛	模型	参数	数值
分子筛	模型	参数	25℃	35℃	45℃	55℃	65℃
NaP1	实验值拟一级动力学	q_e,exp/mg·g^-1	43.51	45.13	45.17	45.21	45.61
		q_e,cal/mg·g^-1	42.26	23.94	10.43	3.68	1.46
		k₁/min^-1	0.070	0.047	0.039	0.022	0.023
		R²	0.9778	0.8938	0.7699	0.2270	0.0463
	拟二级动力学	q_e,cal/mg·g^-1	46.51	47.62	46.21	46.02	46.00
		k₂/g·mg^-1·min^-1	0.003	0.003	0.008	0.019	0.049
		R²	0.9981	0.9994	0.9997	0.9996	0.9999
	内扩散动力学	C₁/mg·g^-1	19.45	21.48	29.33	35.06	40.45
		k_p/mg·g^-1·min^-1/2	2.5212	2.4930	1.7203	1.1736	0.6013
		R²	0.8503	0.7861	0.5078	0.3960	0.4552
NaX	实验值拟一级动力学	q_e,exp/mg·g^-1	47.76	47.59	47.35	45.76	44.65
		q_e,cal/mg·g^-1	11.71	9.22	9.33	4.72	8.30
		k₁/min^-1	0.025	0.039	0.023	0.023	0.018
		R²	0.8922	0.6879	0.6586	0.8418	0.6734
	拟二级动力学	q_e,cal/mg·g^-1	48.47	48.47	47.82	45.93	44.82
		k₂/g·mg^-1·min^-1	0.006	0.009	0.008	0.020	0.008
		R²	0.9992	0.9996	0.9994	0.9999	0.9984
	内扩散动力学	C₁/mg·g^-1	33.72	34.76	33.84	38.93	33.38
		k_p/mg·g^-1·min^-1/2	1.3788	1.3598	1.3632	0.6989	1.0673
		R²	0.8682	0.6934	0.6867	0.6749	0.8305
NaA	实验值拟一级动力学	q_e,exp/mg·g^-1	24.55	24.75	24.90	25.82	25.82
		q_e,cal/mg·g^-1	5.70	6.31	10.11	5.17	6.58
		k₁/min^-1	0.029	0.054	0.075	0.016	0.028
		R²	0.8848	0.9250	0.8714	0.7841	0.9527
	拟二级动力学	q_e,cal/mg·g^-1	24.94	25.18	25.29	25.89	26.32
		k₂/g·mg^-1·min^-1	0.015	0.021	0.022	0.012	0.012
		R²	0.9997	0.9999	0.9999	0.9971	0.9991
	内扩散动力学	C₁/mg·g^-1	17.71	19.00	20.23	19.13	18.86
		k_p/mg·g^-1·min^-1/2	0.6911	0.6112	0.4837	0.6074	0.6797
		R²	0.8292	0.7336	0.8755	0.8296	0.9406