N_2O一步氧化苯制苯酚Fe-ZSM-5分子筛催化剂失活与再生研究
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摘要
本文以实验分析和TG-DTA、BET、TPO以及C/H元素分析等表征技术相结合的方式,系统开展了N_2O一步氧化苯制苯酚Fe-ZSM-5分子筛催化剂的失活规律和再生工艺研究。
对液相离子交换法制备并经水热法预处理的Fe-ZSM-5分子筛催化剂的活性评价结果表明,尽管Fe-ZSM-5分子筛催化剂在N_2O一步氧化苯制苯酚反应中具有较高的初始活性和苯酚产率,但是随着反应时间的延长催化剂活性逐步降低,特别是在反应初期的4 h内,活性下降速率很快,积炭量迅速增加。结合TG-DTA等表征结果可见,失活催化剂上存在着低温炭和高温炭两种形式的积炭,这是导致催化剂失活的主要原因。对失活的Fe-ZSM-5催化剂进行再生实验结果表明,失活催化剂在N_2O气氛下、723 K进行40 min烧炭处理,可使催化剂的活性基本恢复。
基于固定床反应装置,以单因素实验法分别考察了微量水蒸气、NO、O_2和NO_2对Fe-ZSM-5分子筛催化剂活性的影响。结果表明:(1)微量水蒸气的存在对分子筛催化剂活性几乎没有影响;(2)微量NO的存在对提高Fe-ZSM-5分子筛催化剂的活性有利;(3)微量O_2的存在将导致Fe-ZSM-5分子筛催化剂活性降低,且随着O_2含量的增加,分子筛催化剂的活性下降更为迅速;(4)微量NO_2的存在也导致分子筛催化剂活性的降低,但降低幅度较小。
The object of this paper was to investigate the deactivation rule and regenerated technology of Fe-ZSM-5 zeolite catalyst in the one-step oxidation of benzene to phenol with nitrous oxide.Based on the experimental investigation and some characterized methods such as TG-DTA,BET,TPO and C/H element analysis.
Fe-ZSM-5 zeolite catalyst was prepared through liquid ion-exchanged method and hydrothermal pretreatment.The results of the performance evaluation of Fe-ZSM-5 zeolite showed that the initial activity of catalyst and the productivity of phenol were high,but they gradually decreased along with the run time.By the characterization means it could be found that the coke formed on the activity sites of catalyst was the main reason to lead catalyst deactivation,and two species of coke exited:high temperature carbon and low temperature carbon.The regenerating research indicated that the activity of deactivated Fe-ZSM-5 zeolite catalyst almost restored in nitrous oxide atmosphere and 723 K conditions.
Based on the experiments in the isothermal integral reactor,the effect of tiny H_2O,NO,O_2 and NO_2 on the Fe-ZSM-5 zeolite catalyst were investigated by the method of single-factor.The results demonstrated that:(1)the addition of tiny H_2O almost had no influence on the activity of the zeolite catalyst.(2) the addition of tiny NO enhanced the activity of the zeolite catalyst.(3)the addition of tiny O_2 decreased the activity of the zeolite catalyst,and the activity dropped more obviously with the increase of O_2.(4)the addition of tiny NO_2 also decreased the activity of the zeolite catalyst.
对液相离子交换法制备并经水热法预处理的Fe-ZSM-5分子筛催化剂的活性评价结果表明,尽管Fe-ZSM-5分子筛催化剂在N_2O一步氧化苯制苯酚反应中具有较高的初始活性和苯酚产率,但是随着反应时间的延长催化剂活性逐步降低,特别是在反应初期的4 h内,活性下降速率很快,积炭量迅速增加。结合TG-DTA等表征结果可见,失活催化剂上存在着低温炭和高温炭两种形式的积炭,这是导致催化剂失活的主要原因。对失活的Fe-ZSM-5催化剂进行再生实验结果表明,失活催化剂在N_2O气氛下、723 K进行40 min烧炭处理,可使催化剂的活性基本恢复。
基于固定床反应装置,以单因素实验法分别考察了微量水蒸气、NO、O_2和NO_2对Fe-ZSM-5分子筛催化剂活性的影响。结果表明:(1)微量水蒸气的存在对分子筛催化剂活性几乎没有影响;(2)微量NO的存在对提高Fe-ZSM-5分子筛催化剂的活性有利;(3)微量O_2的存在将导致Fe-ZSM-5分子筛催化剂活性降低,且随着O_2含量的增加,分子筛催化剂的活性下降更为迅速;(4)微量NO_2的存在也导致分子筛催化剂活性的降低,但降低幅度较小。
The object of this paper was to investigate the deactivation rule and regenerated technology of Fe-ZSM-5 zeolite catalyst in the one-step oxidation of benzene to phenol with nitrous oxide.Based on the experimental investigation and some characterized methods such as TG-DTA,BET,TPO and C/H element analysis.
Fe-ZSM-5 zeolite catalyst was prepared through liquid ion-exchanged method and hydrothermal pretreatment.The results of the performance evaluation of Fe-ZSM-5 zeolite showed that the initial activity of catalyst and the productivity of phenol were high,but they gradually decreased along with the run time.By the characterization means it could be found that the coke formed on the activity sites of catalyst was the main reason to lead catalyst deactivation,and two species of coke exited:high temperature carbon and low temperature carbon.The regenerating research indicated that the activity of deactivated Fe-ZSM-5 zeolite catalyst almost restored in nitrous oxide atmosphere and 723 K conditions.
Based on the experiments in the isothermal integral reactor,the effect of tiny H_2O,NO,O_2 and NO_2 on the Fe-ZSM-5 zeolite catalyst were investigated by the method of single-factor.The results demonstrated that:(1)the addition of tiny H_2O almost had no influence on the activity of the zeolite catalyst.(2) the addition of tiny NO enhanced the activity of the zeolite catalyst.(3)the addition of tiny O_2 decreased the activity of the zeolite catalyst,and the activity dropped more obviously with the increase of O_2.(4)the addition of tiny NO_2 also decreased the activity of the zeolite catalyst.
引文
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