载铜活性炭的制备及其气相苯吸附性能的研究

doi:10.3969/j.issn.0253-2417.2022.03.001

摘要/Abstract

摘要：

在椰壳活性炭表面浸渍CuCl₂，经二次炭化、活化工艺制得改性活性炭，当CuCl₂质量分数为0.3%、0.4%、0.5%和0.7%时，制得的改性活性炭分别标记为AC₃、AC₄、AC₅和AC₇。通过扫描电镜(SEM)、N₂吸附-脱附、X射线衍射(XRD)和X射线光电子能谱(XPS)对改性活性炭进行表征，在常温动态吸附装置中考察改性活性炭对气相苯的吸附-脱附性能。研究结果表明：改性后活性炭表面酸性含氧官能团减少，且铜在活性炭表面及孔隙内部主要以CuO和Cu₂O形式存在，随着浸渍CuCl₂质量分数的增加活性炭比表面积降低、孔容积减小，但微孔比表面积和比例提高，其中AC₅的微孔比表面积为733.20 m²/g，微孔比例达到72.99%。改性活性炭AC₅对气相苯吸附性能最佳，对5 mg/L苯的平衡吸附量为356.40 mg/g，平衡吸附时间118.80 min，较原料活性炭(AC_raw)均提高了33.38%，吸附性能优于有机气体滤毒盒(3M-3301 CN型和3M-6001 CN型)活性炭。AC₅经5次吸附-脱附循环测试后，吸附性能仍能保留80%左右。载铜活性炭通过苯分子中π键与Cu²⁺中空d轨道发生络合作用，将活性炭对气相苯的吸附作用由物理吸附为主转化为物理-化学联合吸附，从而提高吸附性能。

关键词: 活性炭, 铜氧化物, 气相苯, 吸附, 再生

Abstract:

The modified coconut shell activated carbons were prepared by loading CuCl₂, carbonization and CO₂ activation. The Cu-loaded activated carbons were labeled as AC₃, AC₄, AC₅, and AC₇ to represent the mass fractions of cupric salt solutions 0.3%, 0.4%, 0.5% and 0.7%, respectively. The Cu-loaded activated carbons were characterized by means of N₂ adsorption isotherm, SEM, XRD and XPS. Their dynamic adsorption-desorption performance was measured by the gravimetric method. After modification, the acidic oxygenated groups on the surface of activated carbon decreased. The results showed that cupric salt existed in two forms, i.e., CuO and Cu₂O. It was found that the presence of Cu loading led to the decreasing of surface area and pore volume of modified sample, and the increasing of the surface area and proportion of micropore. AC₅ showed the largest values of the surface area(733.20 m²/g) and proportion(72.99%) of micropore. Furthermore, AC₅ had the optimal equilibrium adsorption capacity(356.40 mg/g) which increased by 33.38% compared to the raw sample, and the optimal equilibrium adsorption time(118.80 min) which increased by 33.38%. Moreover, the adsorption performance of AC₅ was better than the activated carbons in the organic gas filter cartridge(3M-3301 CN and 3M-6001 CN). After five cycles of adsorbents regeneration test, 80% of adsorption capability was still able to be reserved. The Cu-loaded activated carbons improved the adsorption performance by transforming the style from physical adsorption to physical-chemical adsorption through complexation of π-bonds in benzene with hollow d-orbitals in Cu²⁺.

Key words: activated carbon, copper oxide, gaseous benzene, adsorption, regeneration

中图分类号:

TQ35

徐州, 李伟, 刘守新. 载铜活性炭的制备及其气相苯吸附性能的研究[J]. 林产化学与工业, 2022, 42(3): 1-9.

Zhou XU, Wei LI, Shouxin LIU. Preparation of Copper Loaded Activated Carbon and Its Adsorption Performance of Gaseous Benzene[J]. Chemistry and Industry of Forest Products, 2022, 42(3): 1-9.

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样品 sample	C/%	O/%	Cu/%
AC_raw	90.62	9.38	0
AC₃	90.92	8.61	0.47
AC₄	91.24	8.14	0.62
AC₅	92.57	6.57	0.86
AC₇	93.02	6.06	0.92

样品 sample	比表面积/(m²·g^-1) S_BET	微孔比表面积/(m²·g^-1) S_micro	微孔比例/% R_micro	总孔容/(cm³·g^-1) V_total	平均孔径/nm d_average
AC_raw	1385.58	530.98	38.90	0.78	2.24
AC₃	1298.49	682.97	52.60	0.71	2.17
AC₄	1215.18	724.58	59.63	0.66	2.18
AC₅	1145.66	733.20	72.99	0.62	2.16
AC₇	1073.94	622.35	57.95	0.58	2.17

样品 sample	苯吸附质量/g mass of benzene	平衡吸附量/(mg·g^-1) equilibrium adsorption capacity	平衡吸附时间/min equilibrium adsorption time
AC_raw	13.36	267.20	89.07
AC₃	13.58	315.15	94.55
AC₄	13.59	316.56	94.97
AC₅	17.82	356.40	118.80
AC₇	14.75	346.49	103.95
AC₁	15.68	313.60	104.47
AC₂	16.93	338.60	112.00

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