酸、盐处理对Pt/SAPO-11物化及其催化性能的影响

刘强; 杜君臣; 张爱敏; 郝亚杰; 张少朋; 陈玉保; 赵云昆

酸、盐处理对Pt/SAPO-11物化及其催化性能的影响

1.
昆明贵金属研究所稀贵金属综合利用新技术国家重点实验室, 云南昆明 650106
2.
云南师范大学能源与环境科学学院, 云南昆明 650500

基金项目:

国家自然科学基金 21266032

详细信息

通讯作者:
张爱敏, Tel:0871-68322030, E-mail:aimin.zhang@126.com

中图分类号: O643.3
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- 被引次数: 0
出版历程
- 收稿日期: 2016-11-14
- 修回日期: 2017-02-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-03-10

Study on the physicochemical properties and catalytic performance of Pt/SAPO-11 catalysts treated by acid and salt

1.
State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Kunming Institute of Precious Metals, Kunming 650106, China
2.
College of Energy and Environmental Science, Yunnan Normal University, Kunming 650500, China

Funds:

the National Natural Science Foundation of China 21266032

摘要

摘要: 采用不同酸和盐浸渍处理SAPO-11分子筛，然后负载Pt制成改性的Pt/SAPO-11催化剂，用XRF、XRD、N₂吸附-脱附、SEM、NH₃-TPD和Py-IR对催化剂进行表征，分析其物理化学性能。结果表明，酸和盐处理没有破坏SAPO-11的骨架结构，还提高了催化剂的孔容、孔径、比表面积等性质，催化剂的酸性、酸量也明显发生了改变。在固定床反应器中，评价了改性的Pt/SAPO-11催化小桐子油一步加氢制异构烷烃性能；结合催化剂表征数据表明，颗粒粒径、比表面积、孔径、酸性和酸量影响催化剂的活性及产物分布。对比发现，经0.5 mol/L柠檬酸处理的Pt/SAPO-11催化剂孔径大小、酸性、B酸和L酸量分布合适，因此，一步加氢催化处理小桐子油性能优异；其中，生物航油组分（C_8-16）的收率为32.47%，异构烷烃（C_8-16）选择性为53.13%。
- Pt/SAPO-11催化剂 /
- 改性 /
- 异构 /
- 柠檬酸
Abstract: SAPO-11 molecular sieves were treated with different acids and salts and the modified Pt/SAPO-11 catalysts were prepared by loading platinum on the pre-treated SAPO-11. The catalyst samples were characterized with XRF, XRD, N₂ adsorption-desorption, SEM, NH₃-TPD and pyridine Py-IR to analyze their physicochemical properties. The results showed that the modification of acid and salt did not destroy the structure of SAPO-11, but improved the pore volume, pore size and specific surface area of the catalysts, meanwhile, the acidity and acid amount of the zeolite were also changed obviously. In a fixed-bed reactor, one-step hydrgenation of Jatropha curcas oil to iso-alkanes over modified Pt/SAPO-11 catalyst was carried out. Combined with catalyst characterization results, it was concluded that those parameters, such as particle size, specific surface area, pore diameter, acidity and acid amount, would affect the activity and product distribution of the catalysts. Among these modified catalysts, it is found that the Pt/SAPO-11 catalyst treated with 0.5 mol/L citric acid solution exhibited an excellent catalytic performance in one-step hydrogenation of Jatropha curcas oil, owing to its appropriate pore size, acidity, B acid and L acid distribution. The yield of bio-jet fuel components (C_8-16) was 32.47% and the selectivity of isoparaffins was 53.13%.
- Pt/SAPO-11 catalyst /
- modification /
- isomerism /
- citric acid

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图 1 改性Pt/SAPO-11分子筛的XRD谱图

Figure 1 XRD patterns of modified Pt/SAPO-11 molecular sieves

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图 2 Pt-S (a)、Pt-S-H-0.1(b)、Pt-S-C-0.25(c) 和Pt-S-C-0.75(d) 的SEM照片

Figure 2 SEM images of Pt-S (a), Pt-S-H-0.1 (b), Pt-S-C-0.25 (c) and Pt-S-C-0.75 (d)

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图 3 改性Pt/SAPO-11的NH₃-TPD谱图

Figure 3 NH₃-TPD profiles of modified Pt/SAPO-11

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图 4 小桐子油一步加氢生成异构烷烃的路线示意图

Figure 4 Plausible pathways of one-step hydrogenation of lipids to produce iso-alkanes

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表 1 改性SAPO-11的化学组成

Table 1 Chemical composition of modified SAPO-11 by XRF

Sample	Composition w/%				n(SiO₂)/n(Al₂O₃)
Sample	P₂O₅	Al₂O₃	SiO₂	others	n(SiO₂)/n(Al₂O₃)
S	46.8	42.6	10.3	0.3	0.41
S-N-0.1	47.6	40.9	11	0.5	0.46
S-H-0.1	48.0	40.4	11	0.6	0.46
S-C-0.1	47.8	38.9	12.5	0.8	0.54
S-C-0.25	46.3	38.5	14.7	0.5	0.65
S-C-0.5	42.3	37.4	19.8	0.5	0.9
S-C-0.75	40.3	36.9	22.2	0.6	1.02

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表 2 改性催化剂的比表面积及孔结构

Table 2 Surface area and pore structure of modified catalysts

Sample	Surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore size d/nm	Micropore volume^* v/(cm³·g^-1)	Micropore area^* A/(m²·g^-1)
Pt-S	195.31	0.15	3.1	0.063	154.22
Pt-S-N-0.1	184.87	0.19	4.2	0.056	137.41
Pt-S-H-0.1	208.86	0.17	3.4	0.064	157.11
Pt-S-C-0.1	223.16	0.21	3.6	0.069	168.50
Pt-S-C-0.25	259.18	0.29	4.5	0.059	131.44
Pt-S-C-0.5	215.99	0.22	4.1	0.054	121.73
Pt-S-C-0.75	164.71	0.23	5.7	0.048	117.10
^*：micropore volume, micropore area calculated by t-plot method

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表 3 Py-IR获得的改性催化剂的酸型分布

Table 3 Acid type distributions of modified catalysts by Py-IR analysis

Sample	Acid sites /(μmol·g^-1)
	weak acid site (200 ℃)		medium strong acid site (300 ℃)
	Lewis	Brønsted	Lewis	Brønsted
Pt-S	10.76	27.94	7.45	12.05
Pt-S-N-0.1	21.27	35.38	19.63	18.05
P-S-C-0.1	21.82	39.72	21.27	18.77
Pt-S-C-0.25	14.73	42.60	11.45	14.44
Pt-S-C-0.5	15.13	33.84	10.96	9.67
Pt-S-C-0.75	6.50	23.61	5.40	10.02

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表 4 改性催化剂催化加氢产物分布

Table 4 Hydrocarbon distribution of modified catalysts

Sample	Hydrodeoxygenation rate /%	Cracking rate /%	Bio-jet fuel component /%	>C₁₈/%	Isoparaffin selectivity /%	Aromatic hydrocarbons /%
Pt-S	91.25	7.74	24.22	7.70	47.25	0.92
Pt-S-N-0.1	62.10	3.28	15.71	12.4	28.75	2.23
Pt-S-H-0.1	60.00	5.87	26.17	13.1	35.05	0.57
Pt-S-C-0.1	90.44	11.82	31.51	28.54	40.83	2.30
Pt-S-C-0.25	97.84	8.91	30.07	18.9	53.30	0
Pt-S-C-0.5	97.09	9.13	32.47	14.7	53.13	2.32
Pt-S-C-0.75	74.72	9.75	12.22	8.06	39.30	0.62

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