Pt/SAPO-11催化剂载体的改性对正十四烷临氢转化性能的影响

杨娜; 王海峰; 柳云骐; 刘晨光

Pt/SAPO-11催化剂载体的改性对正十四烷临氢转化性能的影响

1.
航天长征化学工程股份有限公司兰州分公司, 甘肃兰州 730010
2.
中国石油化工股份有限公司济南分公司, 山东济南 250101
3.
中国石油大学(华东) 重质油国家重点实验室, CNPC催化重点实验室, 山东青岛 266580

基金项目:

国家自然科学基金 21676300

详细信息

中图分类号: TQ424.81
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- 文章访问数: 83
- HTML全文浏览量: 40
- PDF下载量: 9
- 被引次数: 0
出版历程
- 收稿日期: 2017-08-09
- 修回日期: 2017-10-17
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Study on the transformation rule of n-tetradecane hydroisomerization over modified Pt/SAPO-11 catalyst

1.
Changzheng Engineering Co., LTD Lanzhou Branch, Lanzhou 730010, China
2.
Jinan Branch, China Petroleum & Chemical Corporation, Jinan 250101, China
3.
State Key Laboratory of Heavy Oil Processing in China University of Petroleum(East China), Key Laboratory of Catalysis CNPC, Qingdao 266580, China

Funds:

the National Natural Science Foundation of China 21676300

More Information

Corresponding author: LIU Yun-qi, E-mail:Liuyq@upc.edu.cn

摘要

摘要: 以Pt/SAPO-11双功能催化剂为基础, 对催化剂载体进行柠檬酸、炭黑改性, 以正十四烷为模型化合物, 通过催化剂表征和反应评价, 探索了催化剂载体的改性对正十四烷临氢转化性能的影响。结果表明, 异构化产物以单甲基异构物为主, 改性没有改变催化剂的酸强度, 但使得酸浓度有所下降。通过柠檬酸调变催化剂的酸性使得催化剂的低温催化活性显著提高, 采用炭黑扩孔改性, 有效改善了催化剂的传质性能, 提高了催化剂的单甲基异构体选择性。柠檬酸和炭黑改性的催化剂裂化产物均以C₆为主, 改性并没有改变SAPO-11分子筛的孔道限制效应, 裂化产物呈现一定的择型效应, 裂化产物分布呈现出不对称分布的特点。
- 临氢转化 /
- 改性 /
- 传质效应 /
- 酸性
Abstract: Pt/SAPO-11 bifunctional catalyst was modified with citric acid and carbon black.The effects of different modified methods on the catalytic activity of Pt/SAPO-11 catalysts were investigated using n-tetradecane as the probe reaction.Results indicated that the isomerization products were mainly composed of monomethyl isomer, the modification has not changed the acid strength of the catalyst, but the acid concentration has decreased.The citric acid significantly improved the low temperature catalytic activity of the catalysts, while carbon black effectively promoted the mass transfer performance and monomethyl isomer selectivity of the catalysts.The cracking products were mainly composed of C₆ compounds, and modification did not change the shape selective effects of SAPO-11 molecular sieve.Carbon number distribution of cracking products was obvious asymmetric distribution.
- hydrotransformation /
- modification /
- mass transfer effect /
- acidity

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图 1 改性前后Pt/SAPO-11催化剂的吡啶红外光谱谱图

Figure 1 Py-FTIR spectra of different modified Pt/SAPO-11 catalysts

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图 2 改性前后Pt/SAPO-11催化剂的NH₃-TPD谱图

Figure 2 NH₃-TPD profiles of different modified Pt/SAPO-11 catalysts

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图 3 改性前后Pt/SAPO-11催化剂的CO FT-IR光谱图

Figure 3 CO FT-IR spectra of different modified Pt/SAPO-11 catalysts

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图 4 改性前后催化剂的异构化反应产物分布

2, 5-DM-C12, 3, 5-DM-C12, 6M-C13, 5M-C13, 4M-C13,
2M-C13, 3M-C13 respectively represent
2, 5-dimethyl dodecane, 3, 5-dimethyl dodecane,
6-methyl tridecane, 5-methyl tridecane,
4-methyl tridecane, 2-methyl tridecane, 3-methyl tridecane

Figure 4 Product distribution of isomerization reaction on different modified catalysts

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图 5 正十四烷在改性前后催化剂上反应的裂化产物的碳数分布(转化率为97.5%)

Figure 5 Carbon-number distribution in hydrocracked products on different modified catalysts

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表 1 不同改性方法所得载体的孔结构数据

Table 1 Pore structure of different modified supports

Sample	Specific surface area A/(m²·g^-1)			Pore volume v/(mL·g^-1)
Sample	BET	micropore	mesoporous	total	micropore	mesoporous
SAPO-11	202	96	106	0.27	0.04	0.23
SAPO-11G	186	98	88	0.29	0.04	0.25
SAPO-11S	175	91	84	0.26	0.04	0.22
SAPO-11Y	237	119	118	0.35	0.05	0.30
SAPO-11N	248	135	112	0.32	0.06	0.26
SAPO-11C	226	111	115	0.46	0.05	0.41
SAPO-11J	98	8	90	0.25	0.01	0.24
SAPO-11X represents modified support; (G, Y, N, S, C and J respectively represent high temperature heat treatment, hydrochloric acid modification, citric acid modification, hydrothermal treatment, carbon black modification and polyacrylamide modification)

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表 2 不同催化剂的孔结构数据

Table 2 Pore structure of different catalysts

Sample	Specific surface area A/(m²·g^-1)			Pore volume v/(mL·g^-1)
Sample	BET	micropore	mesoporous	total	micropore	mesoporous
SA	167	82	85	0.25	0.03	0.22
SAN	211	125	86	0.29	0.05	0.24
SAC	190	96	94	0.44	0.04	0.40

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表 3 改性前后Pt/SAPO-11催化剂的吡啶红外光谱谱图积分

Table 3 Integral area of Py-FTIR spectra of different modified Pt/SAPO-11 catalysts

Sample	A_{1450 cm^-1}	A_{1540 cm^-1}
SA	40.51	27.24
SAN	33.64	22.66
SAC	39.44	26.37
A_{1450 cm^-1}、A_{1540 cm^-1} respectively represent the integral areas of wave number 1450 cm^-1、1540 cm^-1

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表 4 改性前后Pt/SAPO-11催化剂的酸性表征

Table 4 Acidity characterization on different modified Pt/SAPO-11 catalysts

Sample	Acid site/(μmol·g^-1)		Total(acid site)/(μmol·g^-1)
Sample	t₁	t₂	Total(acid site)/(μmol·g^-1)
SA	298.26	585.01	883.27
SAN	208.16	349.36	557.52
SAC	278.79	487.07	765.86

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表 5 不同催化剂的分散度计算

Table 5 Degree of dispersion of different modified Pt/SAPO-11 catalysts

Sample	Degree of dispersion(R)
SA	0.233
SAN	0.269
SAC	0.280

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表 6 改性前后催化剂对异构化反应活性的影响

Table 6 Influence of different modified Pt/SAPO-11 catalysts on the reaction activity

Temperature t/℃	Catalyst	Conversion x/%	Selectivity s/%	Cracking η/%
300	SA	64.06	80.24	19.76
	SAN	86.86	82.79	17.21
	SAC	63.48	90.06	9.94
320	SA	90.54	72.68	27.32
	SAN	97.86	55.82	44.18
	SAC	91.46	84.37	15.63
340	SA	97.94	37.73	62.27
	SAN	98.90	38.80	61.20
	SAC	97.20	59.24	40.76

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