丁腈橡胶非均相加氢催化剂失活原因及再生性能研究

doi:10.11949/0438-1157.20190113

摘要/Abstract

摘要：

对丁腈橡胶非均相催化加氢制备高附加值氢化丁腈橡胶过程中催化剂失活的原因进行了探究，发现造成催化剂活性下降的原因并不是贵金属纳米颗粒的流失、团聚或中毒，而是催化剂表面的活性位被聚合物覆盖而无法与反应物接触，因此将覆盖在活性位上的聚合物进行脱除才是催化剂再生和重复利用的关键。根据相似相容原理选择单溶剂或者混合溶剂对反应后催化剂进行处理，结果表明经过乙酸乙酯、丁酮、N,N-二甲基甲酰胺以及N-甲基吡咯烷酮这四种有机溶剂处理后，其催化加氢活性可以恢复至新鲜催化剂活性的90%；当用混合溶剂处理后，其催化活性可以提高至新鲜催化剂活性的95%，且循环利用4次其催化活性仍能保持不变。

关键词: 聚合物, 多相反应, 加氢, 失活, 再生, 溶剂, 丁腈橡胶

Abstract:

The reason for the deactivation of catalysts in the process of preparing high value-added hydrogenated nitrile rubber by heterogeneous catalytic hydrogenation of nitrile rubber was investigated. It was found that the cause of the decrease in catalyst activity was not the loss, agglomeration or poisoning of noble metal nanoparticles. The reactants could not contact with the active sites, which was the real reason for the reduced activity. Therefore, the effective removal of the polymers from the active sites was the key to catalyst regeneration and reuse. Secondly, based on the similarity-intermiscibility theory, the recycled catalyst was treated with a single or a mixed solvent to elute the polymers and recover its activity. The results showed that the catalyst activity could be restored to 90% of the fresh catalyst activity by washing with ethyl acetate, butanone, N,N-dimethylfirmamide or N-methylpyrrolidone. When treated with a mixed solvent, its catalyst activity could be increased to 95% of the fresh catalyst activity, and could remain steady after recycling 4 times. SEM and TG characterization results showed that after the organic solvent regeneration, Pd active sites on the surface of the catalyst were exposed, thus its hydrogenation activity was remarkably improved.

Key words: polymers, multiphase reaction, hydrogenation, deactivation, regeneration, solvents, nitrile butadiene rubber

中图分类号:

TQ 530.99

阴义轩, 成婷婷, 鲍晓军, 袁珮. 丁腈橡胶非均相加氢催化剂失活原因及再生性能研究[J]. 化工学报, 2019, 70(7): 2528-2539.

Yixuan YIN, Tingting CHENG, Xiaojun BAO, Pei YUAN. Deactivation and regeneration of heterogeneous catalysts for hydrogenation of nitrile butadiene rubber[J]. CIESC Journal, 2019, 70(7): 2528-2539.

图/表 16

表1 NBR及HNBR红外特征峰[33]

Table 1 Characteristic peaks for NBR and HNBR FT-IR spectra [33]

波数/cm^-1	基团种类	吸收因子	峰强度变化
3500	—NH₂ 或 —NH—	—	—CN被加氢还原后新出现的峰
2236	—CN	1.0	此为内标计算加氢度
970	1,4-trans unit, —CH=CH—	2.3	加氢度增加，峰强度减弱或消失
920	1,2 unit, —CH=CH₂	2.24	加氢度增加，峰强度减弱或消失
750	1,4-cis unit, —CH=CH—	0.36	加氢度增加，峰强度减弱或消失
723	—[CH₂] _n — (n?4)	0.25	C=C被加氢还原，出现亚甲基的特征峰

表2 NBR及HNBR中不同结构对应的H化学位移[33]

Table 2 Chemical shifts of H protons in different microstructures of NBR or HNBR [33]

样品	结构类型	H种类	化学位移
NBR	1,4 单元	—CH=CH—	5.50
		—CH₂—	2.15
		—CH(CN) —	2.65
		—CH₂CH(CN) —	1.70
	1,2 单元	=CH—和=CH₂	4.90—5.10
HNBR		—CH₃	0.90
		—CH₂—	1.30
		—CH(CN) —	2.60
		—CH₂—CH(CN) —	1.50

图1 NBR和HNBR的红外谱图

Fig.1 FT-IR spectra for NBR and HNBR

图2 NBR和HNBR的1H NMR谱图

Fig.2 1H NMR spectra of NBR and HNBR

图3 反应前和反应后催化剂的STEM图（插图由STEM计算得到相应的粒径分布）

Fig.3 STEM micrographs of catalysts before and after reaction

图4 反应前后催化剂N2吸脱附等温线及基于吸附支的孔径分布

Fig. 4 N2 adsorption-desorption isotherms and pore diameter distribution curves obtained from adsorption branches of catalyst before and after reaction

表3 反应前后催化剂的物性数据

Table 3 Physical properties of catalyst before and after reaction

催化剂	比表面积/(m²/g)	孔容/(cm³/g)	平均孔径/nm
反应前	494	1.55	12.5
反应后	281	0.87	12.3

图5 催化剂的SEM图

Fig.5 SEM micrographs of catalysts

图6 样品的红外谱图

Fig.6 FT-IR spectra of samples

图7 热重谱图

Fig.7 TG spectra

图8 催化剂吸附NBR或HNBR后的热重和红外谱图

Fig.8 TG and FT-IR spectra for catalyst after adsorption of NBR or HNBR

图9 不同单一溶剂处理后的催化剂再次用于NBR加氢得到的加氢产物的红外谱图和加氢度

Fig.9 FT-IR spectra of HNBR and hydrogenation degree of HNBR produced by regenerated catalysts treated with different single solvent

图10 催化剂和聚合物的TG谱图

Fig.10 TG spectra of catalysts and polymer

图11 不同方式回收的催化剂再次用于NBR加氢所得产物的加氢度

Fig.11 Hydrogenation degree of HNBR produced by regenerated catalysts treated through different methods

图12 不同混合溶剂处理后的催化剂再次用于NBR加氢得到的加氢产物的红外谱图和加氢度

Fig.12 FT-IR spectra of HNBR and hydrogenation degree of HNBR produced by regenerated catalysts treated with mixed solvents

图13 混合溶剂(EA+NMP)处理的催化剂循环利用4次得到的加氢产物红外谱图和加氢度

Fig.13 FT-IR spectra of HNBR and hydrogenation degree of HNBR produced by regenerated catalysts treated with (EA+NMP) for recycling 4 times

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