反气相色谱法研究煤直接液化残渣经分级提取前后的表面性质变化

肖怀德; 王强

反气相色谱法研究煤直接液化残渣经分级提取前后的表面性质变化

肖怀德^{1, 2},
王强^{1, 2, ,}

1.
新疆大学理化测试中心, 新疆乌鲁木齐 830046
2.
新疆大学化学化工学院, 煤炭清洁转化与化工过程自治区重点实验室, 新疆乌鲁木齐 830046

基金项目:

国家自然科学基金 21566036

国家自然科学基金 21366029

详细信息

中图分类号: TQ529.1
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- 被引次数: 0
出版历程
- 收稿日期: 2017-11-30
- 修回日期: 2018-04-02
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-07-10

Determination of surface properties of direct coal liquefaction residue before and after solvent extraction by inverse gas chromatography

XIAO Huai-de^{1, 2},
WANG Qiang^{1, 2
, ,}

1.
Center for Physical and Chemical Analysis, Xinjiang University, Urumqi 830046, China
2.
Key Laboratory of Coal Cleaning Conversion and Chemical Engineering Process, Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China

Funds:

the National Natural Science Foundation of China 21566036

the National Natural Science Foundation of China 21366029

More Information

Corresponding author: WANG Qiang, Tel:18099485055, E-mail:xjuwq@sina.com

摘要

摘要: 采用反气相色谱法（IGC）分别对煤直接液化残渣（DCLR）脱灰处理后不溶物、正己烷不溶物、甲苯不溶物、四氢呋喃不溶物的表面性质进行表征。基于非极性探针净保留体积V_n分别采用Dorris-Gray方法和Schultz方法得到表面色散自由能，基于极性探针V_n得到吸附焓△H^sp，并通过△H^sp作图计算得到酸常数K_a和碱常数K_b。结果表明，经溶剂分级提取后表面色散自由能、K_a和K_b均发生明显变化。而DCLR呈现两性偏碱性这一特征并未随分级提取发生改变。IGC作为一种动力学吸附技术，可快速准确表征DCLR在经分级提取过程中表面性质的变化，相同温度下应用Dorris-Gray方法得到DCLR表面色散自由能略高于Schultz方法。
- 反气相色谱 /
- 煤直接液化残渣 /
- 表面色散自由能 /
- 表面酸碱常数
Abstract: Direct coal liquefaction residue (DCLR) is deashed by hydrochloric acid and hydrofluoric acid to obtain ACLR. The ACLR was extracted with n-hexane, toluene and tetrahydrofuran to obtain n-hexane insoluble matter (HCLR), toluene insoluble matter (TCLR), tetrahydrofuran insoluble (FCLR). The surface properties of ACLR, HCLR, TCLR and FCLR were characterized by inverse gas chromatography (IGC). Based on net residual volume V_n of the non-polar probe, surface dispersion free energy were calculated by Dorris-Gray and Schultz method respectively. The adsorption enthalpy △H^sp of the polar probe on surface of the 4 insoluble solids was obtained by V_n of the polar probe, and the acid constant K_a and the base constant K_b of the 4 insoluble solids were calculated by △H^sp. The results show that the surface dispersion free energy of ACLR are obviously changed after solvent extraction, and the dispersion free energy on surface of the 4 insoluble solids is decreasing from 60 to 100℃. By K_b/K_a> 1 and △H^sp analysis, 4 insoluble solids surfaces are both amphoteric and the alkaline effect is stronger than that of the acid effect. As a kinetic adsorption technique, IGC can quickly and accurately characterize change of surface properties of DCLR during fractionated extraction. At the same temperature the surface dispersion free energy obtained by the Dorris-Gray method is slightly higher than that by the Schultz method.
- inverse gas chromatography /
- direct coal liquefaction residue /
- surface dispersion free energy /
- surface acid base constant

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图 1 以ACLR为固定相正烷烃的RTlnV_n与2Na(γ_L^d)^1/2关系图

Figure 1 Plot of RTlnV_n versus 2Na(γ_L^d)^1/2 for n-alkanes on ACLR column

下载: 全尺寸图片幻灯片

图 2 极性探针在固定相表面的吸附△G^sp

Figure 2 Adsorption free energy △G^sp of polar probe on stationary phase

下载: 全尺寸图片幻灯片

图 3 极性探针在固体不溶物上的吸附

△H^SP/AN^*对DN/AN^*作图

Figure 3 Adsorption of polar probe on insoluble

solids △H^SP/AN^* versus DN/AN^*

下载: 全尺寸图片幻灯片

表 1 伊犁煤的工业分析与元素分析

Table 1 Proximate and ultimate analyses of the Yili coal

Proximate analysis w/%			Ultimate analysis w_daf /%
M_ad	A_d	V_daf	C	H	N	S	O
7.33	8.61	36.79	83.21	4.25	0.98	0.39	11.17

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表 2 探针溶剂的性质

Table 2 Nature of the probe solvent

Probe	a×10²⁰/m²	γ_s^d/(mJ·m^-2)	AN^*/(kJ·mol^-1)	DN/(kJ·mol^-1)
n-C₆	51.5	18.4	-	-
n-C₇	57.0	20.3	-	-
n-C₈	63.0	21.3	-	-
n-C₉	69.0	22.7	-	-
CHCl₃	44.0	25.9	22.7	0
Acet	42.5	16.5	10.5	71.4
Etacet	48.0	19.6	6.3	71.1
THF	45.0	22.5	2.1	84.4

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表 3 分别采用Dorris-Gray(D-G)和Schultz(S)方法计算得到表面色散自由能

Table 3 Surface dispersion free energy calculated by Dorris-Gray and Schultz method

t/℃	ACLRγ_s^d/(mJ·m^-2)		HCLRγ_s^d/(mJ·m^-2)		TCLRγ_s^d/(mJ·m^-2)		FCLRγ_s^d/(mJ·m^-2)
t/℃	D-G	S	D-G	S	D-G	S	D-G	S
60	5.25	4.75	3.95	3.25	8.81	7.95	3.30	2.97
70	3.27	2.90	2.09	1.28	5.98	5.31	1.85	1.64
80	1.84	1.60	0.88	0.76	4.09	3.56	0.77	0.67
90	0.87	0.74	0.56	0.23	2.72	2.32	0.32	0.28
100	0.46	0.38	0.31	0.19	1.72	1.44	0.17	0.14

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表 4 酸碱作用的吸附焓

Table 4 Adsorption enthalpy-△H^sp of acid-base interaction

Probe	-△H^sp/(kJ·mol^-1)
Probe	ACLR	HCLR	TCLR	FCLR
CHCl₃	11.49	13.44	11.60	13.49
Acet	12.55	16.22	9.99	11.63
Etacet	8.78	13.61	9.90	7.66
THF	9.16	11.61	7.47	5.33

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表 5 固体不溶物表面酸碱常数

Table 5 Surface acid-base constant of solid insoluble

	K_b	K_a	K_b/K_a	R²
ACLR	0.458	0.096	4.750	0.994
HCLR	0.687	0.121	5.666	0.998
TCLR	0.543	0.076	7.165	0.988
FCLR	0.684	0.047	14.690	0.986

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