混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能

刘冬梅; 铁大兴; 高晨义; 毛艳红; 王海彦; 于海兵

混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能

1.
辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
2.
中国石油抚顺石化公司, 辽宁抚顺 113001

基金项目:

辽宁省自然科学基金 201202126

详细信息

通讯作者:
Tel:13842357629,E-mail:ldmwain1234@126.com.

中图分类号: G643
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- 文章访问数: 148
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- 被引次数: 0
出版历程
- 收稿日期: 2016-08-16
- 修回日期: 2016-11-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-02-10

Preparation of micro-mesoporous ZSM-5 zeolite through mixed alkali treatment and its catalytic performance in the alkylation of thiophene

1.
Collelege of Chemistry, Chemical Engineering and Environmental Engineering, Fushun 113001, China
2.
CNPC Fushun Petrochemical, Fushun 113001, China

Funds:

Natural Science Foundation of Liaoning Province 201202126

摘要

摘要: 以SiO₂/Al₂O₃物质的量比为50的H-ZSM-5分子筛为母体，分别采用Na₂CO₃溶液处理后加入TPAOH溶液进行二次晶化法以及Na₂CO₃/TPAOH混合溶液同时处理法，制备了微孔-介孔多级孔HZSM-5催化剂，对其噻吩烷基化反应催化性能进行了研究。结果表明，采用4 mol/L的Na₂CO₃溶液处理后的催化剂在TPAOH溶液中发生了二次晶化；当TPAOH溶液浓度为0.3 mol/L、晶化温度为170℃、晶化时间为24 h时，得到的HZ（CO₃^2--TPA⁺，0.3-24-170）催化剂具有适宜的孔径和酸性，其噻吩烷基化转化率最高（99.1%）。而Na₂CO₃/TPAOH同时处理HZSM-5分子筛所得的催化剂，由于生成大量SiO₂堵塞了孔道，覆盖了催化剂表面，降低了催化剂的平均孔径和酸性，不适合噻吩烷基化反应。
- 混合碱处理 /
- 多级孔 /
- 二次晶化 /
- ZSM-5 /
- 烷基化
Abstract: ZSM-5 zeolite with a SiO₂/Al₂O₃ mol ratio of 50 as the raw material was treated either by adding tetrapropylammonium hydroxide solution for secondary crystallization after pre-treating with Na₂CO₃ solution or directly by Na₂CO₃/TPAOH mixed solution, to prepare the micro-mesoporous hierarchical HZSM-5 catalyst;the catalytic performance of resultant micro-mesoporous HZSM-5 in thiophene alkylation was then investigated.The results showed that if the raw ZSM-5 material is first pre-treated with 4 mol/L Na₂CO₃ and then crystallized for the second time in the presence of 0.3 mol/L TPAOH and at 170℃ for about 24 h, the resultant micro-mesoporous HZSM-5(CO₃^2--TPA⁺, 0.3-24-170) has a moderate pore diameter and acidity and exhibits the highest conversion of thiophene (99.1%) in alkylation.However, if the raw ZSM-5 is treated by the mixed solution of Na₂CO₃ and TPAOH, the dissolved SiO₂ may block the pores and channels, leading to lower acidity and smaller pores, which is not suitable for the thiophene alkylation.
- mixed alkali treatment /
- hierarchical /
- secondary crystallization /
- ZSM-5 /
- alkylation

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图 1 催化剂的XRD谱图

a: HZ(50); b: HZ(CO₃^2-,4-2-80); c: HZ(CO₃^2--TPA⁺,0.1-24-170); d: HZ(CO₃^2--TPA⁺,0.3-24-170); e: HZ(CO₃^2--TPA⁺,0.5-24-170)

Figure 1 XRD patterns of various catalysts

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图 2 催化剂的SEM照片

(a): HZ(50); (b): HZ(CO₃^2-,4-2-80); (c): HZ(CO₃^2--TPA⁺,0.1-24-170); (d): HZ(CO₃^2--TPA⁺,0.3-24-170)； (e): HZ(CO₃^2--TPA⁺,0.5-24-170)

Figure 2 SEM images of various catalysts

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图 3 催化剂的 ²⁹Si MAS NMR 谱图

a: HZ(CO₃^2-,4-2-80);b: HZ(CO₃^2--TPA⁺,0.1-24-170); c: HZ(CO₃^2--TPA⁺,0.3-24-170); d: HZ(CO₃^2--TPA⁺,0.5-24-170)

Figure 3 ²⁹Si MAS NMR spectra of various catalysts

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图 4 催化剂的N₂吸附-脱附等温线

■: HZ(50); ●: HZ(CO₃^2-,4-2-80); : HZ(CO₃^2--TPA⁺,0.1-24-170); ◆: HZ(CO₃^2--TPA⁺,0.3-24-170); : HZ(CO₃^2--TPA⁺,0.5-24-170)

Figure 4 N₂ adsorption desorption isotherms of various catalysts

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图 5 催化剂的NH₃-TPD谱图

a: HZ(50); b: HZ(CO₃^2-,4-2-80); c: HZ(CO₃^2--TPA⁺,0.1-24-170);d: HZ(CO₃^2--TPA⁺,0.3-24-170);e: HZ(CO₃^2--TPA⁺,0.5-24-170)

Figure 5 NH₃-TPD profiles of various catalysts

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图 6 催化剂的XRD谱图

a: HZ(50); b: HZ(CO₃^2-,4-2-80);c: HZ(CO₃^2--TPA⁺,0.3-12-170); d: HZ(CO₃^2--TPA⁺,0.3-24-170); e: HZ(CO₃^2--TPA⁺,0.3-36-170);f: HZ(CO₃^2--TPA⁺,0.3-48-170)

Figure 6 XRD patterns of various catalysts

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图 7 催化剂的NH₃-TPD谱图

a: HZ(CO₃^2--TPA⁺,0.3-36-170); b: HZ(CO₃^2--TPA⁺,0.3-48-170); c: HZ(CO₃^2-,4-2-80); d: HZ(CO₃^2--TPA⁺,0.3-24-170);e: HZ(CO₃^2--TPA⁺,0.3-12-170)

Figure 7 NH₃-TPD profiles of various catalysts

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图 8 催化剂的XRD谱图

a: HZ(50); b: HZ(CO₃^2-,4-2-80); c: HZ(CO₃^2--TPA⁺,0.3-24-120);d: HZ(CO₃^2--TPA⁺,0.3-24-150); e: HZ(CO₃^2--TPA⁺,0.3-24-170); f: HZ(CO₃^2--TPA⁺,0.3-24-190)

Figure 8 XRD patterns of the catalysts

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图 9 催化剂的NH₃-TPD谱图

a: HZ(50); b: HZ(CO₃^2--TPA⁺,0.3-24-190); c: HZ(CO₃^2--TPA⁺,0.3-24-120); d: HZ(CO₃^2--TPA⁺,0.3-24- 150); e: HZ(CO₃^2--TPA⁺,0.3-24-170);f: HZ(CO₃^2-,4-2-80)

Figure 9 NH₃-TPD profiles of the catalysts

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图 10 噻吩烷基化催化剂的稳定性

a: HZ(50); b: HZ(CO₃^2-,4-2-80);c: HZ(CO₃^2--TPA⁺,0.3-24-170)

Figure 10 Stability of various catalyst in the thiophene alkylation

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图 11 催化剂的XRD谱图

a: HZ(CO₃^2--TPA⁺,0.3-24-170);b: HZ(CO₃^2-,4-2-80); c: HZ(TPA⁺/CO₃^2-,0.025-24-170);d: HZ(TPA⁺/CO₃^2-,0.075-24-170);e: HZ(TPA⁺/CO₃^2-,0.125-24-170);f: HZ(TPA⁺/CO₃^2-,0.25-24-170);g: HZ(TPA⁺/CO₃^2-,0.075-24-120);h: HZ(TPA⁺/CO₃^2-,0.075-24-190)

Figure 11 XRD patterns of various catalysts

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表 1 催化剂的相对结晶度和SiO₂/Al₂O₃物质的量比

Table 1 Relative crystallinity and SiO₂/Al₂O₃ mol ratio of various catalysts

Sample	Relative crystallinity /%	SiO₂/Al₂O₃ (mol ratio)
HZ(50)	100	50
HZ(CO₃^2-,4-2-80)	82	38
HZ(CO₃^2--TPA⁺,0.1-24-170)	86	41
HZ(CO₃^2--TPA⁺,0.3-24-170)	95	43
HZ(CO₃^2--TPA⁺,0.5-24-170)	90	40

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表 2 催化剂的表面硅铝物质的量比

Table 2 Ratio of silicon to aluminum of catalysts

Catalyst	Si/Al (mol ratio)
HZ(50)	9.4
HZ(CO₃^2-,4-2-80)	10.5
HZ(CO₃^2--TPA⁺,0.1-24-170)	14.7
HZ(CO₃^2--TPA⁺,0.3-24-170)	15.6
HZ(CO₃^2--TPA⁺,0.5-24-170)	15.7

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表 3 催化剂的孔结构性质

Table 3 Textural properties of various catalysts

Sample	A_BET/ (m²·g^-1)	A_ext/ (m²·g^-1)	v_micro/ (cm³·g^-1)	v_meso/ (cm³·g^-1)	d_aver/nm
HZ(50)	317.9	11.1	0.15	0.04	1.5
HZ(CO₃^2-,4-2-80)	401.3	76.4	0.14	0.28	5.3
HZ(CO₃^2--TPA⁺,0.1-24-170)	416.7	88.2	0.14	0.32	5.5
HZ(CO₃^2--TPA⁺,0.3-24-170)	449.6	120.2	0.15	0.33	5.8
HZ(CO₃^2--TPA⁺,0.5-24-170)	458.5	128.5	0.13	0.35	6.2

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表 4 催化剂的相对结晶度和SiO₂/Al₂O₃物质的量比

Table 4 Relative crystallinity and SiO₂/Al₂O₃ molar ratios of various catalysts

Sample	Relative crystallinity /%	SiO₂/Al₂O₃ (mol ratio)
HZ(50)	100	50
HZ(CO₃^2-,4-2-80)	82	38
HZ(CO₃^2--TPA⁺,0.3-12-170)	92	41
HZ(CO₃^2--TPA⁺,0.3-24-170)	95	43
HZ(CO₃^2--TPA⁺,0.3-36-170)	93	43
HZ(CO₃^2--TPA⁺,0.3-48-170)	90	44

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表 5 催化剂的孔结构性质

Table 5 Textural properties of various catalysts

Sample	A_BET/ (m²·g^-1)	A_ext/ (m²·g^-1)	v_micro/ (cm³·g^-1)	v_meso/ (cm³·g^-1)	d_aver/nm
HZ(50)	317.9	11.1	0.15	0.04	1.5
HZ(CO₃^2-,4-2-80)	401.3	76.4	0.14	0.28	5.3
HZ(CO₃^2--TPA⁺,0.3-12-170)	417.2	103.2	0.14	0.29	5.4
HZ(CO₃^2--TPA⁺,0.3-24-170)	449.6	120.2	0.15	0.33	5.8
HZ(CO₃^2--TPA⁺,0.3-36-170)	452.8	128.7	0.13	0.34	5.6
HZ(CO₃^2--TPA⁺,0.3-48-170)	443.2	132.3	0.10	0.35	6.0

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表 6 不同晶化温度下的孔结构性质

Table 6 Pore structural properties of the catalysts under different crystallization temperature

Sample	A_BET/ (m²·g^-1)	A_ext/ (m²·g^-1)	v_micro/ (cm³·g^-1)	v_meso/ (cm³·g^-1)	d_aver/nm	SiO₂/Al₂O₃ (mol ratio)
HZ(50)	317.9	11.1	0.15	0.04	1.5	50
HZ(CO₃^2-,4-2-80)	401.3	76.4	0.14	0.28	5.3	38
HZ(CO₃^2--TPA⁺,0.3-24-120)	409.6	87.2	0.13	0.29	5.4	35
HZ(CO₃^2--TPA⁺,0.3-24-150)	412.8	90.7	0.14	0.30	5.4	36
HZ(CO₃^2--TPA⁺,0.3-24-170)	449.6	120.2	0.15	0.33	5.8	43
HZ(CO₃^2--TPA⁺,0.3-24-190)	368.5	68.7	0.13	0.25	5.1	41

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表 7 催化剂的噻吩烷基化反应物转化率及产物分布

Table 7 Thiophene conversion and product distribution for the thiophene alkylation over various catalysts

Sample	Conversion x/%		HTs distribution w/%			1-hexene selectivity s/%
Sample	thiophene alkylation	1-hexene	HT	DHT	THT	alkylation
HZ(50)	41.2	27.3	99.2	1.2	0.0	88.7
HZ(CO₃^2-,4-2-80)	97.2	71.2	14.7	56.2	29.1	67.5
HZ(CO₃^2--TPA⁺,0.1-24-170)	97.9	74.7	13.5	54.8	31.7	66.1
HZ(CO₃^2--TPA⁺,0.3-24-170)	99.1	87.6	10.9	51.5	37.6	63.4
HZ(CO₃^2--TPA⁺,0.5-24-170)	98.3	80.4	11.2	51.6	37.2	63.3
HZ(CO₃^2--TPA⁺,0.3-12-170)	97.6	78.5	13.3	54.2	32.5	62.3
HZ(CO₃^2--TPA⁺,0.3-36-170)	98.5	82.6	10.7	53.4	35.9	64.1
HZ(CO₃^2--TPA⁺,0.3-48-170)	95.8	69.8	11.6	51.8	36.6	68.7
HZ(CO₃^2--TPA⁺,0.3-24-120)	98.2	80.6	11.2	51.3	37.5	62.4
HZ(CO₃^2--TPA⁺,0.3-24-150)	98.8	83.1	11.0	50.6	38.4	63.9
HZ(CO₃^2--TPA⁺,0.3-24-190)	94.2	65.7	15.6	53.2	3.2	69.1
HTs: alkylthiophene; HT: hexylthiophene; DHT: di-hexylthiophene; THT: tri-hexylthiophene

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表 8 催化剂的相对结晶度和SiO₂/Al₂O₃物质的量比

Table 8 Relative crystallinity and SiO₂/Al₂O₃ mol ratios of various catalysts

Sample	Relative crystallinity /%	SiO₂/Al₂O₃ (mol ratio)
HZ(CO₃^2-,4-2-80)	82	38
HZ(CO₃^2--TPA⁺,0.3-24-170)	95	43
HZ(TPA⁺/CO₃^2-,0.025-24-170)	73	43
HZ(TPA⁺/CO₃^2-,0.075-24-170)	75	42
HZ(TPA⁺/CO₃^2-,0.125-24-170)	84	44
HZ(TPA⁺/CO₃^2-,0.25-24-170)	87	45
HZ(TPA⁺/CO₃^2-,0.075-24-120)	72	43
HZ(TPA⁺/CO₃^2-,0.075-24-190)	74	44

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表 9 催化剂的孔结构性质

Table 9 Textural properties of various catalysts

Sample	A_BET/ (m²·g^-1)	A_ext/ (m²·g^-1)	v_micro/ (cm³·g^-1)	v_meso/ (cm³·g^-1)	d_aver/nm
HZ(CO₃^2-,4-2-80)	401.3	76.4	0.14	0.28	5.3
HZ(CO₃^2--TPA⁺,0.3-24-170)	449.6	120.2	0.15	0.33	5.8
HZ(TPA⁺/CO₃^2-,0.025-24-170)	382.8	67.7	0.10	0.23	3.3
HZ(TPA⁺/CO₃^2-,0.075-24-170)	395.6	85.2	0.12	0.25	4.2
HZ(TPA⁺/CO₃^2-,0.125-24-170)	388.5	78.6	0.11	0.23	3.8
HZ(TPA⁺/CO₃^2-,0.25-24-170)	397.4	89.3	0.13	0.26	4.0
HZ(TPA⁺/CO₃^2-,0.075-24-120)	376.5	60.1	0.10	0.22	3.7
HZ(TPA⁺/CO₃^2-,0.075-24-190)	393.7	80.9	0.12	0.24	3.9

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