碱溶透析和酸析处理对碱木质素物化性质和Pb2+去除性能的影响

doi:10.11949/j.issn.0438-1157.20181386

摘要/Abstract

摘要：

采用XPS、静态接触角、颗粒表面电荷、扫描电镜、官能团分析等方法来研究碱木质素经过碱溶透析和碱溶酸析处理后的物化性质的差异，探讨碱木质素分子聚集程度对Pb²⁺去除性能的影响。结果表明，碱溶透析木质素的比表面积是碱溶酸析木质素的4.77倍，碱溶透析样品较酸析样品的表面氧含量高48%、水/木质素薄膜的静态接触角低13°，反映出碱溶透析处理后的木质素比碱溶酸析处理后的木质素分子聚集程度低、分子链疏松、羧基和羟基等含氧官能团裸露程度增加。碱溶透析处理后的木质素与Pb²⁺的静电作用增强，对Pb²⁺的去除能力显著提高。Pb²⁺浓度为100 mg·L^-1时，碱溶透析木质素对Pb²⁺的去除量达136 mg·g^-1，去除率为81.8%，且去除性能受体系pH的影响小。与化学改性和表面功能化相比，利用碱溶透析处理以提高木质素对Pb²⁺的去除性能具有操作简单、无毒、能耗低的优点。

关键词: 碱木质素, 碱溶透析, 碱溶酸析, 聚集程度, 废水, 去除

Abstract:

XPS, static contact angle, particle surface charge, scanning electron microscopy, functional group analysis and other methods were used to study the difference of physicochemical properties of alkali lignin after alkali-soluble dialysis and alkali-soluble acid precipitation treatment, and to explore the degree of alkali lignin molecular aggregation to Pb²⁺ removal. The results indicate that (1) after alkali-dialysis treatment, the specific surface area is 4.77 times compared with alkali-acid precipitation, and the contact angle of the water/lignin film decreased by 13° compared with alkali-acid precipitation, reflecting the degree of aggregation of lignin molecular is low and the molecular chain is loose; (2) the surface oxygen content increased by 48% compared with alkali-acid precipitation, reflecting the exposed degree of oxygen-containing functional groups such as carboxyl groups and hydroxyl groups are increased, so that the electrostatic interaction between the sample and Pb²⁺ is enhanced; (3) the lead ions removal performance is remarkably enhanced, while the removal capacity can reach 136 mg·g^-1 and the removal rate can reach 81.8% at the concentration of Pb²⁺ was 100 mg·L^-1, and the removal performance is little affected by the pH of the system. Compared with the chemical modifications and surface functionalizations which aim at improving the removal performance of lignin, the alkali-dialysis treatment has the characteristics of low toxicity and low energy consumption in the preparation process.

Key words: alkali lignin, alkali-dialysis, alkali-acid precipitation, aggregation degree, waste water, removal

中图分类号:

O 636.2

赵汝斌, 蔡猛, 庞煜霞. 碱溶透析和酸析处理对碱木质素物化性质和Pb²⁺去除性能的影响[J]. 化工学报, 2019, 70(5): 1894-1903.

Rubin ZHAO, Meng CAI, Yuxia PANG. Effects of dialysis and acid precipitation treatment on physicochemical properties of alkali lignin and its lead ions removal properties[J]. CIESC Journal, 2019, 70(5): 1894-1903.

图/表 11

表1 碱溶透析和碱溶酸析处理对木质素元素、组分的影响

Table 1 Effect of alkali-dialysis and alkali-acid precipitation on element and components of lignin

Sample	C/%	H/%	N/%	S/%	Lignin/%	Cellulose/%	Ash/%	Phenolic hydroxyl content/(mmol·g^-1)	Carboxyl group content/(mmol·g^-1)	M _w/(g·mol^-1)
AL	60.03	5.65	1.31	0.55	63.64	<1	2.42	1.76	1.63	3800
SX-AL	58.65	5.08	0.06	0.66	64.91	<1	0.90	2.14	1.94	4300
TX-AL	58.00	5.13	0.08	0.42	74.30	<1	0.34	2.27	2.21	4500

图1 碱溶酸析和碱溶透析处理对木质素样品比表面积、表面氧含量和亲疏水性的影响（插图为水在木质素薄膜上的静态接触角测试结果）

Fig.1 Effect of alkali-dialysis and alkali-acid precipitation on surface area, oxygen content and hydrophilicity of lignin(Insets show contact angle of water on SX-AL and TX-AL film)

图2 两种物理处理方法对木质素表面形貌的影响

Fig.2 Effect of alkali-dialysis and alkali-acid precipitation on surface appearance of lignin

图3 碱溶透析和碱溶酸析处理对木质素溶解性的影响

Fig.3 Effect of alkali-dialysis and alkali-acid precipitation on solution property of lignin

图4 pH对木质素颗粒表面电荷的影响

Fig.4 Effect of pH on surface charge of lignin

图5 pH对木质素去除Pb2+性能的影响

Fig.5 Effect of pH on removal performance of lignin

表2 碱溶酸析木质素样品用量对Pb2+去除量和去除率的影响

Table 2 Effects of SX-AL mass on removal capacity and removal rate

Sample	Sample mass/mg	Lignin mass/mg	Removal rate/%	Removal capacity /(mg·g^-1)
SX-AL	30	19.5	23.6	39.3
SX-AL	40	26.0	31.4	39.2
SX-AL	50	32.4	38.9	38.8
TX-AL	30	22.3	81.8	136.0

图6 两种木质素与Pb2+结合前后的红外光谱图

Fig.6 Infrared spectra of lignins before and after combined with lead ions

图7 碱溶透析木质素与Pb2+结合后的XPS(a)及O 1s分峰（b）

Fig.7 XPS spectra of TX-AL-Pb2+

表3 木质素基吸附剂对Pb2+的去除能力对比

Table 3 Removal capacities toward Pb(II) by some lignin-based adsorbent

Adsorbent	Adsorption capacity/(mg·g^-1)	Surface charge of lignin(pH=5.5)/(mmol·g^-1)	Ref.
TX-AL	136.0	0.79	present study
SAL	165.4	1.00	present study
CMAL	159.9	0.95	present study
aminated lignin	60.5	—	[10]
modified lignin by amination and sulfomethylation	53.9	—	[11]
modified lignin by amination, sulfomethylation and phenolation	130.2	—	[12]
microwave-assisted carboxymethyl lignin	323.6	—	[14]
polycondensation resins by lignin reaction with glucose	194.6	—	[15]
lignin microspheres	33.9	—	[19]
porous lignin-based sphere	27.1	—	[20]
porous lignin based poly (acrylic acid)/organo-montmorillonite nanocomposites	223.8	—	[21]
lignin grafted carbon nanotubes	235.0	—	[22]
chitin/lignin hybrid material	91.7	—	[31]

图8 两种物理处理对木质素去除Pb2+的作用差异机理模型图

Fig.8 Model diagram of effect of SX-AL and TX-AL for lead ions removal performance

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碱溶透析和酸析处理对碱木质素物化性质和Pb²⁺去除性能的影响

Effects of dialysis and acid precipitation treatment on physicochemical properties of alkali lignin and its lead ions removal properties

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