改性HZSM-5分子筛上噻吩烷基化反应和失活再生性能的研究

刘冬梅; 蒋涵博; 曲圣涛; 王海彦; 杨占旭; 张玉嵩

改性HZSM-5分子筛上噻吩烷基化反应和失活再生性能的研究

1.
辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
2.
抚顺职业技术学院, 辽宁抚顺 113122

基金项目:

辽宁省教育厅基本科研项目 L2017LQN012

博士启动项目 1100130210

辽宁省大型仪器设备共享服务平台能力建设研究基金 2016LD0106

详细信息

通讯作者:
LIU Dong-mei, E-mail: ldmwain1234@126.com

中图分类号: TE991
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- 文章访问数: 94
- HTML全文浏览量: 29
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- 被引次数: 0
出版历程
- 收稿日期: 2017-11-27
- 修回日期: 2018-01-18
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-03-10

Study on the alkylation of thiophene and catalyst deactivation and regeneration with modified HZSM-5 zeolite

1.
School of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Fushun Vocational Technology Institute, Fushun 113122, China

Funds:

The project was supported by the Liaoning Education Department of Basic Research Program of China L2017LQN012

Ph.D. Start-up Funding 1100130210

Liaoning Province Large-Seale Instrument Equipment Sharing Service Platform Capacity-Building Research Fund Project of China 2016LD0106

摘要

摘要: 采用不同碱单独处理和两种碱不同方式联合处理HZSM-5分子筛，制备微孔-介孔多级孔HZSM-5分子筛催化剂并应用于噻吩烷基化反应中。结果表明，不同碱单独处理和两种碱不同方式联合处理HZSM-5分子筛后，均能够在分子筛上造出介孔孔道且能够调变分子筛的酸性，其中，采用Na₂CO₃溶液和TPAOH溶液分开处理得到的分子筛催化剂织结构最适合噻吩烷基化反应；其次考察具有最佳织结构分子筛催化剂的噻吩烷基化反应稳定性，并分析催化剂失活的原因和再生条件。结果表明，当噻吩烷基化反应进行到1050 h后，催化剂已基本失活，催化剂失活的主要原因是，在反应过程中原料中反应组分间发生烯烃齐聚、环化、脱氢和芳烃烷基化等副反应生成的大分子化合物沉积在催化剂上，堵塞催化剂的孔道和遮盖催化剂的活性中心所致；对失活催化剂进行高温再生，从高温再生的能耗较大以及多次高温再生对催化剂酸性和骨架结构不利的角度考虑，选定催化剂的再生温度为550 ℃。
- 碱改性 /
- 噻吩烷基化 /
- HZSM-5 /
- 失活与再生
Abstract: HZSM-5 zeolites were treated by different alkalis alone or different combining ways with two kind of alkalis to prepare micro-meso hierarchical pore HZSM-5 catalysts for thiophene alkylation reaction. The result show that mesopores are created in molecular sieves and the acidity of catalysts after treated is modulated by single alkali or different combining methods of double alkalis. Simultaneously, the structure of catalyst obtained by the separate treatment of Na₂CO₃ solution and TPAOH solution is most suitable for the thiophene alkylation reaction. Furthermore, the stability of the thiophene alkylation reaction over the catalyst with the best microstructure was investigated, and the reason of catalyst deactivation and the regeneration conditions were determined. The results show that the catalysts are basically inactivated after thiophene alkylation reaction for 1050 h. During the reaction, the macromolecular compounds such as olefin oligomerization formed by the cyclization, dehydrogenation and aromatics alkylation are deposited on the catalyst, blocking the pore and then covering the active site of the catalyst. From the viewpoint of the high energy consumption in regeneration at high temperature and the adverse effect of repeated high temperature regeneration on the acidity and skeleton structure of the catalyst, the catalyst should be regenerated at the temperature of 550℃.
- alkali modified /
- thiophene alkylation /
- HZSM-5 /
- inactivation and regeneration

HTML全文

图 1 不同碱处理前后分子筛的XRD谱图

a：HZ(50); b：HZ(CO₃^2--TPA⁺-50); c：HZ(T-50); d：HZ(CO₃^2--50); e：HZ(CO₃^2-/TPA⁺-50); f：HZ(OH^-/TPA⁺-50); g：HZ(OH^--TPA⁺-50); h：HZ(OH^--50)

Figure 1 XRD spectra of zeolites before and after different alkali treatment

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图 2 不同反应时间下Cat-f催化剂的噻吩烷基化转化率

Figure 2 Thiophene alkylation conversion over Cat-f catalyst under different reaction times

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图 3 失活分子筛催化剂上萃取物的气相色谱图

Figure 3 Gas chromatogram of the extract from deactivated zeolites catalyst

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图 4 失活前后分子筛催化剂的TGA-DTA曲线

(a): Cat-f; (b): Cat-d

Figure 4 TGA-DTA curves of the catalyst before and after inactivation

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图 5 失活前后催化剂的NH₃-TPD谱图

a: Cat-d-650; b: Cat-f; c: Cat-d-600; d: Cat-d-550

Figure 5 NH₃-TPD spectra of the catalyst before and after inactivation

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图 6 再生催化剂的噻吩烷基化转化率

a: Cat-f; b: Cat-d-550; c: Cat-d-600; d: Cat-d-650

Figure 6 Thiophene alkylation conversion over regenerated catalyst

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表 1 不同碱处理前后分子筛的孔结构性质

Table 1 Pore structure of zeolites before and after different alkali treatment

Sample	A_BET/(m²·g^-1)	v_micro/(cm³·g^-1)	v_total/(cm³·g^-1)	d_aver/nm
HZ(50)	317.9	0.15	0.19	1.5
HZ(T-50)	357.6	0.14	0.28	3.6
HZ(CO₃^2--50)	401.3	0.14	0.42	5.3
HZ(OH^--50)	398.6	0.09	0.45	5.6
HZ(CO₃^2--TPA⁺-50)	450.8	0.15	0.49	5.9
HZ(OH^--TPA⁺-50)	401.1	0.10	0.47	5.7
HZ(CO₃^2-/TPA⁺-50)	395.6	0.13	0.40	4.2
HZ(OH^-/TPA⁺-50)	402.5	0.13	0.46	5.8

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表 2 不同碱处理前后分子筛的相对酸量

Table 2 Relative acidity of zeolites before and after different alkali treatments

Catalyst	Relative acid density /(mmol·g^-1)
Catalyst	strong	weak
HZ(50)	1.00	1.00
HZ(T-50)	1.08	1.06
HZ(CO₃^2--50)	1.63	1.53
HZ(OH^--50)	1.30	1.26
HZ(CO₃^2--TPA⁺-50)	1.73	1.52
HZ(OH^--TPA⁺-50)	1.42	1.36
HZ(CO₃^2-/TPA⁺-50)	1.21	1.15
HZ(OH^-/TPA⁺-50)	1.65	1.57

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表 3 不同碱处理前后分子筛的噻吩转化率和选择性

Table 3 Thiophene conversion and selectivity of zeolites before and after different alkali treatments

Sample	x/%	s/%	Sample	x/%	s/%
HZ(50)	39.2	85.1	HZ(CO₃^2--TPA⁺-50)	98.6	62.1
HZ(T-50)	86.3	72.1	HZ(OH^--TPA⁺-50)	96.3	66.2
HZ(CO₃^2--50)	96.0	66.8	HZ(CO₃^2-/TPA⁺-50)	90.1	68.7
HZ(OH^--50)	95.1	67.5	HZ(OH^-/TPA⁺-50)	97.8	63.9
reaction condition: t=120 ℃，p=1.0 MPa，VHSV=1.0 h^-1，t=24 h

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表 4 失活分子筛催化剂上萃取物的主要成分

Table 4 Main components of the extract from deactivated zeolites catalyst

Number	Component	Number	Component
1	C₁₈n-olefin	6	C₄₀ polycyclic aromatic hydrocarbon
2	2, 4-dihexyltoluene	7	C₄₈ polycyclic aromatic hydrocarbon
3	C₂₄n-paraffin	8	C₅₄ polycyclic aromatic hydrocarbon
4	C₃₀n-paraffin	9	C₆₀ polycyclic aromatic hydrocarbon
5	C₃₆n-paraffin	10	C₆₆ polycyclic aromatic hydrocarbon

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表 5 失活前后分子筛催化剂的孔结构性质

Table 5 Pore structural properties of the catalysts before and after deactivation

Sample	A_BET/(m²·g^-1)	v_micro/(cm³·g^-1)	v_meso/(cm³·g^-1)	d_aver/nm
Cat-f	450.8	0.15	0.49	5.9
Cat-d	218.6	0.05	0.14	2.3
Cat-d-550	420.9	0.13	0.46	5.4
Cat-d-600	437.6	0.14	0.47	5.5
Cat-d-650	445.3	0.15	0.48	5.7

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