煤化工废盐中杂质对NaCl和Na2SO4溶剂化影响研究

doi:10.11949/0438-1157.20251182

摘要/Abstract

摘要：

将NaCl和Na₂SO₄为主的煤化工废盐作为研究对象，通过浓度和频次排序筛选了当中的9种典型无机杂质K⁺、NH₄⁺、NO₃^-、HCO₃^-、CO₃^2-、Ca²⁺、Mg²⁺、Al³⁺、Fe³⁺及6种典型有机杂质戊烷、苯酚、苯乙烯、油酰胺、十二烷、氯苯，并采用COSMOtherm软件绘制了它们的电荷密度分布谱图（σ-profile分布图）。随后在273.15 ~ 323.15 K温度范围内，研究了温度、杂质类型、杂质浓度等因素对NaCl和Na₂SO₄溶剂化的影响。结果发现无机杂质中Al³⁺、Fe³⁺、Mg²⁺和CO₃^2-等高价离子的σ值偏离阈值程度大且σ-profile极性峰值高，它们因具有较大的离子半径和较高的电荷密度而具有更强的水分子争夺能力，与低价离子相比它们能显著减弱NaCl和Na₂SO₄溶剂化；有机杂质中油酰胺、十二烷的σ-profile非极性峰值较高，疏水效应强且空间位阻大，能够使得NaCl和Na₂SO₄的溶剂化明显减弱；与NaCl相比，Na₂SO₄的溶剂化自由能对周围理化环境的变化更敏感，即更易通过改变理化条件的方法来调控Na₂SO₄的溶解结晶行为。

关键词: 废盐, 溶解性, 溶剂化, 模拟, 热力学性质

Abstract:

The resource utilization of waste salt generated by the coal chemical industry is a key step in achieving clean and efficient coal utilization. The efficient separation of NaCl and Na₂SO₄ serves as an important pathway for their valorization. In this study, waste salt from the coal chemical industry, primarily composed of NaCl and Na₂SO₄, was taken as the research object. Through concentration and frequency ranking, nine typical inorganic impurities ( K⁺、NH₄⁺、NO₃^-、HCO₃^-、CO₃^2-、Ca²⁺、Mg²⁺、Al³⁺、Fe³⁺ ) and six organic impurities ( pentane, phenol, styrene, oleamide, dodecane, chlorobenzene ) were selected. Surface charge distribution data of these impurities were calculated using the COSMOtherm software, and their charge density distribution spectrum (σ-profile) distribution diagrams were plotted. Subsequently, within the temperature range of 273.15 ~ 323.15 K and impurity concentrations of 0.05 ~ 0.5 mol·L^-1, the effects of temperature, impurity type, and impurity concentration on the solvation of NaCl and Na₂SO₄ were investigated. The results revealed that among the inorganic impurities, multivalent ions such as Al³⁺, Fe³⁺, Mg²⁺ and CO₃^2- exhibited significant deviations in σ-profile from the threshold and displayed high polar peak intensities in their σ-profile. Due to their larger ionic radii and higher charge densities, these ions possess a stronger ability to compete for water molecules, significantly weakening the solvation of NaCl and Na₂SO₄ compared to lower-valence ions. Among the organic impurities, oleamide and dodecane showed high non-polar peak intensities in their σ-profile, indicating strong hydrophobic effects and significant steric hindrance, which notably reduced the solvation of NaCl and Na₂SO₄. Compared to NaCl, the solvation free energy of Na₂SO₄ was found to be more sensitive to changes in the physicochemical environment, suggesting that the dissolution and crystallization behavior of Na₂SO₄ can be more easily regulated by altering physicochemical conditions.

Key words: waste salt, solubility, solvation, simulation, thermodynamic properties

中图分类号:

TQ 115

程文婷, 王恩琪, 程芳琴. 煤化工废盐中杂质对NaCl和Na₂SO₄溶剂化影响研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251182.

Wenting CHENG, Enqi WANG, Fangqin CHENG. Study on impact of impurities in coal chemical waste salt on solvation of NaCl and Na₂SO₄[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251182.

图/表 13

图1 工业废盐重金属含量的相关性分析

Fig. 1 Correlation analysis of heavy metal content in industrial waste salt

表1 典型杂质名称及浓度

Table 1 Typical impurity names and concentrations

物质名称	浓度范围mg·L^-1	物质名称	浓度范围mg·L^-1
K⁺	0.20932 ~ 6452	Al³⁺	0.1276 ~ 71
NH₄⁺	21.54 ~ 43.3	戊烷	0.51 ~ 0.55
NO₃^-	0.25 ~ 2500	苯酚	5 ~ 75
HCO₃^-	0.12 ~ 10990	苯乙烯	0.9 ~ 64.63
CO₃^2-	0 ~ 119.69	油酰胺	2.18 ~ 37
Ca²⁺	0.06 ~ 1960	十二烷	0.6 ~ 17
Mg²⁺	0.2 ~ 1176	氯苯	0.17 ~ 0.5
Fe³⁺	0.06 ~ 9.87

图2 工业废盐成分分析

Fig. 2 Analysis of industrial waste salt composition

图3 无机杂质与Na+、Cl-、SO42-和水的σ分布

Fig. 3 Distribution of inorganic impurities with Na+, Cl-, SO42- and water

图4 有机杂质与Na+、Cl-、SO42-和水的σ分布

Fig. 4 The σ distribution of organic impurities with Na+, Cl-, SO42- and water

图5 温度在273.15 ~ 323.15 K范围内不同无机杂质存在时NaCl的溶剂化自由能

Fig. 5 Solvation free energy of NaCl with different inorganic impurities in the temperature range of 273.15 ~ 323.15 K

图6 不同浓度无机杂质对NaCl的溶剂化自由能的影响

Fig. 6 The effect of different concentrations of inorganic impurities on the solvation free energy of NaCl

图7 温度在273.15 ~ 323.15 K范围内不同无机杂质存在时Na2SO4的溶剂化自由能

Fig. 7 Solvation free energy of Na2SO4 with different inorganic impurities in the temperature range of 273.15 ~ 323.15 K

图8 不同浓度无机杂质对Na2SO4的溶剂化自由能的影响

Fig. 8 The effect of different concentrations of inorganic impurities on the solvation free energy of Na2SO4

图9 温度在273.15 ~ 323.15 K范围内不同有机杂质存在时NaCl的溶剂化自由能

Fig. 9 Solvation free energy of NaCl with different organic impurities in the temperature range of 273.15 ~ 323.15 K

图10 不同浓度有机杂质对NaCl的溶剂化自由能的影响

Fig. 10 The effect of different concentrations of organic impurities on the solvation free energy of NaCl

图11 温度在273.15 ~ 323.15 K范围内不同有机杂质存在时Na2SO4的溶剂化自由能

Fig. 11 Solvation free energy of Na2SO4 with different organic impurities in the temperature range of 273.15 ~ 323.15 K

图12 不同浓度有机杂质对Na2SO4的溶剂化自由能的影响

Fig. 12 The effect of different concentrations of organic impurities on the solvation free energy of Na2SO4

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煤化工废盐中杂质对NaCl和Na₂SO₄溶剂化影响研究

Study on impact of impurities in coal chemical waste salt on solvation of NaCl and Na₂SO₄

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