Effect of reaction conditions on the hydrogenation of naphthalene to decalin over Ni/Al2O3 catalyst
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摘要: 采用Ni/Al2O3催化剂，在高压固定床反应器中考察了反应温度、压力、空速和氢油体积比比等因素对萘饱和加氢反应行为的影响，尤其是反应条件对反式十氢萘和顺式十氢萘选择性的影响。研究表明，反式十氢萘和顺式十氢萘的选择性与反应操作条件密切相关；反式十氢萘与顺式十氢萘的比例随着氢油比和温度的升高而增加，而随着压力和空速的增加而减小。在反应温度260-290℃、反应压力为5-7 MPa、空速为1-1.5 h-1及氢油体积比大于250时，十氢萘的选择性最高可达99%以上，萘的转化率接近100%，产物中反式和顺式十氢萘的比例最高，可达4.0左右。对Ni/γ-Al2O3催化剂稳定性进行了考察，初步发现催化活性组分的烧结或流失是催化剂失活和影响产物中反式十氢萘和顺式十氢萘比例的主要原因。
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关键词:
- 反应条件 /
- 萘加氢 /
- Ni/Al2O3催化剂 /
- 十氢萘
Abstract: The effect of reaction conditions, including temperature, pressure, space velocity and hydrogen to oil ratio, on the hydrogenation of naphthalene to decalin over Ni/Al2O3 catalyst was investigated in a high pressure fixed bed reactor. The results indicate that the conversion of naphthalene and the selectivity to tran-decalin and cis-decalin are closely related to the reaction conditions. The ratio of tran-decalin to cis-decalin increases with an increase in the hydrogen to oil ratio and reaction temperature, but decreases with an increase in the liquid hourly space velocity (LHSV) and reaction pressure. Under a temperature 260-290℃, 5-7 MPa, a LHSV 1-1.5 h-1, and a hydrogen to oil ratio higher than 250, the conversion of naphthalene is 100% and the selectivity to decalin is close to 100%, with a tran-decalin to cis-decalin ratio of about 4.0. Meanwhile, it was found that the sintering and/or loss of active component are the main factors that cause the deactivation of Ni/Al2O3 catalyst in naphthalene hydrogenation and influence the ratio of tran-decalin to cis-decalin in the products.-
Key words:
- reaction conditions /
- naphthalene hydrogenation /
- Ni/Al2O3 /
- decalin
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图 2 催化剂的表征
Figure 2 Characterization of catalyst of the Ni/Al2O3 catalysts
(a): SEM; (b): nitrogen sorption isotherms; (c): XRD patterns; (d): H2-TPR profiles
图 3 氢油体积比对萘饱和加氢活性的影响
Figure 3 Influence of hydrogen to oil ratio on the hydrogenation of naphthalene over the Ni/Al2O3 catalyst
■: naphthalene conversion; ●: selectivity to tran-decalin; ▲: selectivity to cis-decalin; ▼: selectivity to tetralin
图 4 空速对萘饱和加氢活性的影响
Figure 4 Influence of LHSV on the hydrogenation of naphthalene over the Ni/Al2O3 catalyst
■: naphthalene conversion; ●: selectivity to tran-decalin; ▲: selectivity to cis-decalin; ▼: selectivity to tetralin
图 5 压力对萘饱和加氢活性的影响
Figure 5 Influence of pressure on the hydrogenation of naphthalene over the Ni/Al2O3 catalyst
■: naphthalene conversion; ●: selectivity to tran-decalin; ▲: selectivity to cis-decalin; ▼: selectivity to tetralin
图 6 温度对萘饱和加氢活性的影响
Figure 6 Influence of temperature on the hydrogenation of naphthalene over the Ni/Al2O3 catalyst
■: naphthalene conversion; ●: selectivity to tran-decalin; ▲: selectivity to cis-decalin; ▼: selectivity to tetralin
图 7 Ni/γ-Al2O3催化剂的稳定性
Figure 7 Stability of the Ni/γ-Al2O3 catalyst in naphthalene hydrogenation
■: naphthalene conversion; ●: selectivity to tran-decalin; ▲: selectivity to cis-decalin; ▼: selectivity to tetralin
图 8 Ni/γ-Al2O3催化剂反应200 h前后的XRD谱图
Figure 8 XRD patterns of the Ni/γ-Al2O3 catalysts before and after reaction for 200 h
●: C; ○: NiO; ■: γ-Al2O3
表 1 催化剂表征仪器表
Table 1 A list of instruments for the catalyst characterization
Name Model Manufacturer XRD Rigaku Max-2600 Japan Science Corp. SEM Quanta 400F Thermo Fisher Scientific Inc. BET Quadrasor SI Quantachrome Ins H2-TPR Chemisorb 2750 Micromeritics Instrument Corp. 
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表 2 Ni/γ-Al2O3催化剂反应200 h前后的比表面积和孔道结构参数
Table 2 Specific surface area and pore volumes of Ni/γ-Al2O3 catalysts before and after reaction for 200 h
Catalyst Surface area A/(m2·g-1) Pore volume v/(mL·g-1) Pore width d/nm Before 172.5 0.38 5.64 After 171.9 0.41 5.16
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