氨基硫脲/季铵木质素对铂的吸附

张恒; 张保平; 肖煜坤; 王尹

doi:10.13801/j.cnki.fhclxb.20211018.004

氨基硫脲/季铵木质素对铂的吸附

doi: 10.13801/j.cnki.fhclxb.20211018.004

张恒^{1, 2},
张保平^{1, 2, ,},
肖煜坤^{1, 2},
王尹^{1, 2}

1.
武汉科技大学　省部共建耐火材料与冶金国家重点实验室，武汉 430081
2.
武汉科技大学　钢铁冶金及资源利用省部共建教育部重点实验室，武汉 430081

基金项目: 国家自然科学基金 (U1960108)

详细信息

通讯作者:
张保平，博士，副教授，硕士生导师，研究方向为木质素复合材料的应用　E-mail: zhangbaoping@wust.edu.cn

中图分类号: TF833
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出版历程
- 收稿日期: 2021-08-24
- 修回日期: 2021-09-28
- 录用日期: 2021-10-10
- 网络出版日期: 2021-10-18
- 刊出日期: 2022-08-22

Adsorption of platinum by thiosemicarbazide/quaternary ammonium lignin

ZHANG Heng^{1, 2},
ZHANG Baoping^{1, 2
, ,},
XIAO Yukun^{1, 2},
WANG Yin^{1, 2}

1.
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
2.
Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, China

摘要

摘要: 木质素及其衍生物因具有经济高效和无污染等特点，在有价金属提取和有毒金属离子去除等领域具有广阔的应用前景。本研究采用氨基硫脲/季铵木质素吸附铂，通过FTIR分析揭示了吸附过程的机制，考察了盐酸浓度、Pt(IV)初始浓度、吸附时间和吸附剂用量对吸附效果的影响。结果表明，改性木质素中含有大量的酚羟基、胺基和季铵官能团，PtCl₆²⁻被氨基硫脲/季铵木质素中的酚羟基还原成PtCl₄²⁻后与胺基发生配合反应和氯离子发生离子交换反应，在盐酸浓度为0.5 mol·L⁻¹、Pt(IV)初始浓度为1 170 mg·L⁻¹和吸附时间为120 min的条件下，1 g·L⁻¹氨基硫脲/季铵木质素对Pt(IV)的饱和吸附容量为267.80 mg·g⁻¹，7 g·L⁻¹时的最大吸附率为88.50%。吸附过程遵循Freundlich模型和准二级动力学模型，表明吸附过程为单分子层非均质的化学吸附。
- 氨基硫脲 /
- 季铵木质素 /
- 铂 /
- 吸附机制 /
- 吸附行为
Abstract: Lignin and its derivatives have broad application prospects in the fields of extraction of valuable metals and removal of toxic metal ions because of the characteristics of economical, efficient and friendly. Platinum was adsorbed by thiosemicarbazide/quaternary ammonium lignin in this study. The mechanism of adsorption was revealed by FTIR and the influence factors such as initial concentration of Pt(IV), hydrochloric acid concentration, adsorption time and adsorbent dosage on adsorption were optimized. The results show that the modified lignin contains a large number of phenolic hydroxyl, amino and quaternary ammonium functional groups. PtCl₆²⁻ is reduced to PtCl₄²⁻ by phenolic hydroxyl and then reacts with amino group by coordination reaction and chloride by ion exchange reaction. Using the optimum conditions, which include hydrochloric acid of 0.5 mol·L⁻¹, Pt(IV) of 1 170 mg·L⁻¹, adsorption time of 120 min and thiosemicarbazide/quaternary ammonium lignin addition of 1 g·L⁻¹, the maximum adsorption capacity is 267.80 mg·g⁻¹. Under the same conditions besides 7 g·L⁻¹ thiosemicarbazide/quaternary ammonium lignin, the maximum adsorption ratio is 88.50%. The adsorption process can be simulated by Freundlich model and quasi-second-order kinetic model, which indicates that adsorption is chemisorptions of monolayer heterogeneous.
- thiosemicarbazide /
- quaternary ammonium lignin /
- platinum /
- adsorption mechanism /
- adsorption behavior

HTML全文

图 1 氨基硫脲木质素合成过程

Figure 1. Synthesis of thiosemicarbazide lignin

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图 2 氨基硫脲/季铵木质素合成过程

Figure 2. Synthesis of thiosemicarbazide/quaternary ammonium lignin

DMF—Dimethyl formamide

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图 3 稻草木质素与氨基硫脲/季铵木质素FTIR图谱

Figure 3. FTIR spectra of rice straw lignin and thiosemicarbazide/ quaternary ammonium lignin

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图 4 稻草木质素 (a) 与氨基硫脲/季铵木质素 (b) 的SEM图像

Figure 4. SEM images of rice straw lignin (a) and thiosemicarbazide/ quaternary ammonium lignin (b)

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图 5 Pt(IV)初始浓度对氨基硫脲/季铵木质素吸附容量的影响

Figure 5. Effect of Pt(IV) initial concentration on the adsorption capacity of thiosemicarbazide/quaternary ammonium lignin

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图 6 氨基硫脲/季铵木质素吸附PtCl₆²⁻的吸附等温线

Figure 6. Adsorption isotherm of PtCl₆²⁻ adsorbed by thiosemicarbazide/quaternary ammonium lignin

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图 7 吸附时间对氨基硫脲/季铵木质素吸附容量的影响

Figure 7. Effect of adsorption time on the adsorption capacity of thiosemicarbazide/quaternary ammonium lignin

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图 8 氨基硫脲/季铵木质素对PtCl₆²⁻吸附的动力学拟合曲线

Figure 8. Kinetic fitting curves of PtCl₆²⁻ adsorption by thiosemicarbazide/quaternary ammonium lignin

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图 9 盐酸浓度对氨基硫脲/季铵木质素吸附容量的影响

Figure 9. Effect of the concentration of hydrochloric acid on adsorption capacity of thiosemicarbazide/quaternary ammonium lignin

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图 10 吸附剂用量对氨基硫脲/季铵木质素吸附效果的影响

Figure 10. Effect of the adsorbent dosage on the adsorption of thiosemicarbazide/quaternary ammonium lignin

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图 11 解吸次数对解吸率的影响

Figure 11. Effect of desorption times on desorption ratio

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图 12 氨基硫脲/季铵木质素吸附前和吸附后的红外图谱

Figure 12. FTIR spectra of thiosemicarbazide/quaternary ammonium lignin before and after adsorption

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图 13 氨基硫脲/季铵木质素对PtCl₆²⁻的吸附机制

Figure 13. Adsorption mechanism of PtCl₆²⁻ by thiosemicarbazide/quaternary ammonium lignin

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表 1 不同种类吸附剂对Pt(IV)的吸附容量

Table 1. Adsorption capacities of different kinds of adsorbents for Pt(IV)

Adsorbents	Adsorption capacities/(mg·g⁻¹)	Ref.
Magnetic cellulose functionalized with thiol and amine	40.48	[28]
Macrocyclic polyphenol resin	44.85	[20]
Silicon dioxide and copolymer of 4-vinylpyridine and 2-hydroxyethylmethacrylate	188.00	[22]
Ion recognition rice straw lignin	218.75	[29]
Thiosemicarbazide/quaternary ammonium lignin	267.80	This work

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表 2 氨基硫脲/季铵木质素对PtCl₆²⁻的等温吸附模型参数

Table 2. Parameters of adsorption isotherm models for the adsorption of PtCl₆²⁻ by thiosemicarbazide/quaternary ammonium lignin

Adsorption isotherm models	Parameters
Langmuir	q_m/(mg·g⁻¹)	K_L/(L·mg⁻¹)	R²
Langmuir	270.40	0.00859	0.894
Freundlich	1/n	K_F/(L·mg⁻¹)	R²
Freundlich	0.45	12.034	0.978
Temkin	RTb⁻¹	K_T	R²
Temkin	76.86	0.0307	0.949
Notes: q_m—Maximum adsorption capacity; K_L—Langmuir equilibrium constant of adsorption; R²—Linear regression coefficient; 1/n—Inverse of the concentration index; K_F—Freundlich adsorption equilibrium constant; R—Thermodynamic gas constant(8.314 J·mol⁻¹·K⁻¹); T—Temperature; b—Related constant; K_T—Temkin adsorption equilibrium constant.

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表 3 氨基硫脲/季铵木质素吸附PtCl₆²⁻的动力学模型参数

Table 3. Kinetic model parameters of PtCl₆²⁻ adsorption by thiosemicarbazide/quaternary ammonium lignin

Kinetic models	Parameters
Pseudo first order	K₁/(min⁻¹)	q_e,cal/(mg·g⁻¹)	R²
Pseudo first order	0.0608	227.77	0.938
Pseudo second order	K₂/(g·mg⁻¹·min⁻¹)	q_e,cal/(mg·g⁻¹)	R²
Pseudo second order	0.000759	106.00	0.998
W-M	K₃₁/(mg·g⁻¹·min^−1/2)	A₁	R₁²
	5.74	41.68	0.966
	K₃₂/(mg·g⁻¹·min^−1/2)	A₂	R₂²
	0.55	90.15	0.652
Elovich	K₄₁/(mg·g⁻¹·min^−1/2)	B₁	R₁²
	20.91	1.59	0.993
	K₄₂/(mg·g⁻¹·min^−1/2)	B₂	R₂²
	3.04	81.68	0.718
Notes: K₁—Pseudo-first-order rate constant; q_e,cal—Adsorption capacity at equilibrium; R²—Linear regression coefficient; K₂—Pseudo-second-order rate constant; K₃₁—Diffusion rate constants in the first stage; K₃₂—Diffusion rate constant in the second stage; A₁—First stage boundary layer thickness constant; A₂—Second stage boundary layer thickness constant; R₁²—First stage linear regression coefficient; R₂²—Second stage linear regression coefficient; K₄₁—First stage of the surface distribution of heterogeneous rate constant; K₄₂—Second stage of the surface distribution of heterogeneous rate constant; B₁—First stage Elovich constant; B₂—Second stage Elovich constant.

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