钴离子对阳离子交换树脂氧化裂解反应的催化作用

doi:10.11949/0438-1157.20190253

摘要/Abstract

摘要：

氧化裂解能有效增大放射性废阳离子交换树脂的减容比，但是较高的裂解温度易导致核素挥发。为了降低裂解温度，以硝酸钴和阳离子交换树脂为原料，制备了不同钴含量的含钴树脂，在热重分析仪上考察了钴含量对树脂裂解反应的影响。采用离子交换的方法掺入10~40 g/L的钴离子，可以使树脂共聚物基体裂解峰的峰值温度降低232~263℃，而对减容比的影响较小。通过对残渣的XRD、FT-IR、XPS及元素分析，发现由钴离子转化形成的氧化钴对共聚物基体的裂解具有催化作用，促进了硫键（—S—）的断裂，使裂解温度降低。

关键词: 废物处理, 阳离子交换树脂, 催化, 裂解, 氧化钴, 热重分析

Abstract:

Oxidative pyrolysis can effectively increase the volume reduction ratio of radioactive waste cation exchange resin, but higher pyrolysis temperature is likely to cause nuclides to volatilize. However, the high pyrolysis temperature can easily lead to the volatilization of nuclide. To lower the pyrolysis temperature, a series of resins containing an increasing Co loading were prepared by ion exchange method, using Co(NO₃)₂·6H₂O and cation exchange resin (Amberlite IRN-97H) as raw materials. The effect of Co with different contents on the pyrolysis of resin was investigated on a thermogravimetric analyzer. When the Co content was 10－40 g/L, the peak temperature of the mass loss peak of the copolymer matrix of resin was reduced by 232－263℃ compared to that of pure resin, while the volume reduction ratios were almost the same. The XRD, FT-IR, XPS and elemental analysis of the solid residue were performed. The results showed that the CoO formed by the conversion from Co²⁺ had a catalytic effect on the oxidative pyrolysis of the copolymer matrix, which promoted the breakdown of sulfurbridge (—S—).

Key words: waste treatment, cation exchange resin, catalysis, pyrolysis, cobalt oxide, thermogravimetric analysis

中图分类号:

TL 941⁺.39

沈建华, 宋琦, 姚兵, 黄正梁, 王靖岱, 阳永荣. 钴离子对阳离子交换树脂氧化裂解反应的催化作用[J]. 化工学报, 2019, 70(7): 2548-2555.

Jianhua SHEN, Qi SONG, Bing YAO, Zhengliang HUANG, Jingdai WANG, Yongrong YANG. Catalytic effect of cobalt ion on oxidative pyrolysis of cation exchange resin[J]. CIESC Journal, 2019, 70(7): 2548-2555.

图/表 7

图1 典型TG及DTG曲线

Fig.1 Typical TG and DTG curves

图2 纯树脂及不同钴含量的含钴树脂的热重曲线

Fig.2 Thermogravimetric curves of pure resin and Co-containing resins with different Co contents

表1 纯树脂与不同钴含量的含钴树脂裂解行为对比

Table 1 Comparison of pyrolysis between pure resin and Co-containing resins with different Co contents

失重峰		钴含量/(g/L)
失重峰		0	0.1	10	20	30	40
1	T_i /℃	280	280	280	280	280	280
	T_f /℃	396	393	390	395	395	393
	T_e/℃	354	352	352	355	356	354
	w/%	15.2	15.3	13.0	12.4	12.1	11.1
2	T_i /℃	396	393	390	395	395	393
	T_f /℃	483	480	480	484	482	475
	T_e/℃	444	446	440	450	455	458
	w/%	16.5	16.8	18.3	17.3	16.8	16.2
3	T_i /℃	483	480
	T_f /℃	546	545
	T_e/℃	515	510
	w/%	6.4	6.1
4	T_i /℃	730	730	480	484	482	475
	T_f /℃	830	830	830	800	820	660
	T_e/℃	777	774	535	545	543	514
	w/%	39.2	38.9	46.3	48.6	48.9	50.1
w_R/%		20.0	20.1	21.8	21.6	21.3	20.2
ρ₀/(g/cm³)		1.42	1.42	1.43	1.44	1.42	1.44
ρ_R/(g/cm³)		1.56	1.57	1.58	1.58	1.57	1.60
α		5.5	5.5	5.1	5.1	5.2	5.5

图3 不同温度下纯树脂及含钴树脂裂解残渣的XRD谱图

Fig.3 XRD patterns of residues of pure resin and Co-containing resin at different temperature

图4 不同温度下纯树脂及含钴树脂裂解残渣的FT-IR谱图

Fig.4 FT-IR spectra of residues of pure resin and Co-containing resin at different temperature

图5 不同温度下纯树脂及含钴树脂裂解残渣的XPS谱图

Fig.5 XPS spectra of residues of pure resin and Co-containing resin at different temperature

表2 不同温度下纯树脂和含钴树脂裂解残渣的元素分析

Table 2 Elemental analysis of residues of pure resin and Co-containing resin at different temperature

反应温度/℃	碳含量（质量分数）/%		氢含量（质量分数）/%		硫含量（质量分数）/%
反应温度/℃	纯树脂	含钴树脂	纯树脂	含钴树脂	纯树脂	含钴树脂
反应前	42.8	41.4	6.3	4.6	14.0	13.4
350	47.2	44.2	4.4	4.1	13.3	11.3
445	37.8	39.2	2.3	2.4	10.0	8.5
515	32.9	11.5	1.7	0.6	10.8	6.0
630	4.9	0.7	0.4	0.3	6.6	3.9

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