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摘要: 通过烷烃芳构化可将催化裂化汽油深度脱硫工艺和煤制油工艺中产生的大量低辛烷值饱和直链烷烃转化成芳烃，从而提升油品质量和芳烃产能，是制备芳烃的重要非石油路线，具有显著的社会经济价值。其中，C2−C5轻烃芳构化技术相对成熟，已进入到工业应用阶段；而针对
${\rm{C}}_6^+ $ 直链烷烃芳构化，由于反应过程复杂、多种基元反应相互竞争，导致芳烃收率偏低、催化剂易结焦失活。为此，本工作综述了近年来有关${\rm{C}}_6^+ $ 正构烷烃芳构化的研究进展，重点讨论了${\rm{C}}_6^+ $ 直链烷烃芳构化的反应机理以及单功能及双功能催化体系中金属位点分散度、电子状态及载体的酸性、形貌和孔道结构等对反应性能的影响。-
关键词:
- C6 +正构烷烃芳构化 /
- 反应机理 /
- 单(双)功能催化剂 /
- 金属位点 /
- 载体
Abstract: Conversion of saturated straight-chain alkanes generated in the deep desulfurization process of fluid catalytic cracking (FCC) gasoline and the coal-to-oil processes into aromatics via alkane aromatization is an important non-petroleum route for the preparation of aromatics that effectively improves the quality of oil. The aromatization technology of C2−C5 light hydrocarbons is relatively mature and has been used in industry. However, for the aromatization of${\rm{C}}_6^+ $ n-alkanes, the aromatics yield is still very low due to the complex reaction process and the competition of various elemental reactions. In addition, the catalysts usually suffer from rapid deactivation. In this work, we summarize the recent advances in the aromatization of${\rm{C}}_6^+ $ n-alkanes. The reaction mechanism of aromatization of${\rm{C}}_6^+ $ alkanes and the effects of the dispersion of metal sites, electronic state, and acidity, morphology and pore structure of the support on the catalytic performance are discussed in detail. -
Figure 2 Pathways of n-heptane reforming over Pt/BaKL catalyst[30] (with permission from Elsevier)
Figure 3 Bifunctional reaction scheme for reforming of C6 hydrocarbons[32] (with permission from Elsevier)
Figure 4 Reaction pathways for aromatization (a), hydro-isomerization (b) and cracking (c) of n-heptane on Pt/meso-Kβ-0.05-4 catalyst[33] (with permission from Elsevier)
Figure 5 (A) H2-TPR profiles of virous samples; (B) n-octane conversion in n-octane dehydrocyclization (DHC) at 823 K on (e) ZrO2 in water vapor-hydrogen (WVH2) atmosphere, (f) ZrO2 in H2 atmosphere, (g) Pt/ZrO2 in H2 atmosphere, (h) Pt/ZrO2 in WVH2 atmosphere, (i) Pt-Sn/ZrO2 in H2 atmosphere and (j) Pt-Sn/ZrO2 in WVH2 atmosphere [36] (with permission from Elsevier)
Figure 6 (a) Selectivity of aromatics and C6-C8 alkanes in octane conversion over various Pt/ZSM-5 catalysts; (b) Energy profiles for n-octane dissociation to form 1-C8H16 and H2 on the Pt(111) surface and Pt8 clusters distributing in the inner pores of the catalyst[38] (with permission from American Chemical Society)
Figure 7 Aromatization of n-octane over CZ (CrOx/ZrO2) and CLZ (CrOx/La2O3-ZrO2) catalyst at 823 K, W/F = 58 and TOS = 90 min [44] (with permission from Elsevier)
Figure 8 (A) Conversion and products distribution for n-heptane aromatization over different Pt/ZSM-5 catalysts at TOS of 12 h (a), catalytic stability of Pt/KZSM-5(deAl) catalyst for the aromatization of n-heptane (b), n-octane (c) and n-nonane (d); (B) pore size distributions (a) and NH3-TPD profiles (b) of various Pt/ZSM-5 catalysts[51] (with permission from Royal Society of Chemistry)
Figure 9 (A) Schematic process for the synthesis of bimetallic PtCo-n/KL (n = 1, 5, and 20) and CoPt/KL catalysts; (B) Catalytic performances of the catalysts: (a) Conversion of n-heptane and product selectivity over the catalysts after 5 h test and (b) Catalytic results as a function of reaction time in the aromatization of n-heptane over PtCo-5/KL catalyst[57] (with permission from Royal Society of Chemistry)
Figure 10 (A) NH3-TPD profiles (I) and Py-IR spectra (II); (B) Pt 4f XPS spectra of various catalysts[61] (with permission from Elsevier)
Table 1 Conversion of n-heptane, selectivity to aromatics and lifetime of various catalysts in the aromatization of n-heptane[61] (with permission from Elsevier)
Catalyst C7
conv. /%Arom. sel. /% Lifetime /h C-depos. rate /(pct·h−1) Pt/H-Beta-NS
Pt/K-Beta-NS-1.0M
Pt/H-Beta-HS
Pt/K-Beta-HS-0.2M
Pt/K-Beta-HS-0.6M
Pt/K-Beta-HS-0.8M
Pt/K-Beta-HS-1.0M
Pt/K-Beta-HS-1.2M97.2
78.8 (58.8)
94.5
98.7
97.6 (88.7)
98.8 (82.1)
91.8 (80.0)
78.4 (60.0)30.6
74.4 (59.9)
45.9
80.0
69.1 (64.2)
66.2 (65.7)
69.3 (67.8)
70.0 (57.0)12
60
21
11
166
175
205
552.53
0.41
1.33
1.06
0.35
0.24
0.16
0.35Note: (1) reaction was conducted at 550 ℃ and atmospheric pressure, with a weight hourly space velocity (WHSV) of 2 h−1 and H2/n-heptane mole ratio of 6. (2) conversion of n-heptane (C7 conv.) and selectivity to aromatics (Arom. sel.) were obtained after 4 h time on stream (the values for TOS = 60 h were provided in parentheses). (3) coking rate (C-depos. rate) was estimated with the TG analysis 
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