Effect of Ce modified Co/SEP catalyst on hydrogen production via ethanol steam reforming
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摘要: 采用海泡石（SEP）为载体，通过化学沉淀法制备了Co/SEP和Co-Ce/SEP催化剂，对催化剂进行X射线衍射（XRD）、H2-程序升温还原（H2-TPR）和透射电镜（TEM）等表征。结果表明，Ce的加入显著改善催化剂的分散度和还原性；两种催化剂应用于乙醇重整制氢实验，考察Ce的加入、反应时间、反应温度和水碳比（S/C比）对制氢的影响。结果表明，在WHSV为20.5h-1，水碳比（S/C）为3，反应温度600℃时，Co-Ce/SEP乙醇转化率和氢气产率达到最高，分别为85%和65%。同时Ce的添加能使Co-Ce/SEP拥有更优的活性和稳定性。Abstract: Co/SEP and Co-Ce/SEP catalysts were prepared by chemical precipitation method with sepiolite (SEP) as support. X-ray diffraction (XRD), H2-programmed reduction (H2-TPR) and transmission electron microscopy (TEM) were used to characterize the catalysts. It is proved that the addition of Ce significantly improved the dispersion and reducibility of the catalyst. The effects of Ce addition, reaction time, reaction temperature and steam/carbon (S/C) ratio on hydrogen production were investigated. The results show that the ethanol conversion and hydrogen production of Co-Ce/SEP are the highest values, 85% and 65%, respectively, when the WHSV is 20.5 h-1, the S/C ratio is 3 and the reaction temperature is 600℃. Meanwhile, the addition of Ce can make Co-Ce/SEP possess superior activity and stability.
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图 2 Co/SEP和Co-Ce/SEP两种催化剂煅烧和还原后的XRD谱图
Figure 2 XRD spectra of Co/SEP and Co-Ce/SEP catalysts
(a): calcined samples; (b): reduced samples
图 3 Co/SEP和Co-Ce/SEP催化剂的H2-TPR谱图
Figure 3 H2-TPR profiles of the Co/SEP and Co-Ce/SEP catalysts
图 4 还原后催化剂的TEM照片
Figure 4 TEM images of the catalysts after reduction
(a): Co/SEP; (b): Co-Ce/SEP
图 5 10 h反应时间内催化剂对乙醇蒸汽重整制氢的影响
Figure 5 Effect of reaction time on hydrogen production via ethanol steam reforming during the first 10 h TOS
a: Co-Ce/SEP; b: Co/SEP; c: SEP
图 6 温度对乙醇催化重整制氢的影响
Figure 6 Effect of temperature on hydrogen production via ethanol steam reforming
图 7 S/C比对乙醇催化重整制氢的影响
Figure 7 Effect of S/C ratio on hydrogen production via ethanol catalytic reforming
表 1 反应前催化剂的物化性质
Table 1 Physico-chemical properties of the catalysts before reaction
Catalyst Low temperature zone H2 consumption
/(mmol·g-1)High temperature zone H2 consumption
/(mmol·g-1)Total H2 consumption
/(mmol·g-1)Reduction degree/%a dCo3O4
/nmbdCo
/nmcCo/SEP 0.2765 0.5836 0.8601 41.1 13 19.2 Co-Ce/SEP 0.6152 0.5101 1.1253 53.5 10.7 14.1 a: ${\rm{reduction}}\;{\rm{degree}} = \frac{{{\rm{mole}}\;\left( {{\rm{total}}\;{{\rm{H}}_2}\;{\rm{consumption}}} \right)/{{\rm{g}}_{{\rm{catalyst}}}}}}{{4/3 \times {\rm{mole}}\;({\rm{mean}}\;{\rm{Co}}\;{\rm{meatal}}\;{\rm{loading}})/{{\rm{g}}_{{\rm{catalyst}}}}}} \times 100\% $;
b/c: derived from diffraction peak in XRD corresponding to the Co3O4 (440) plane at 65.2° or Co0 (111) plane at 44.2° by the Scherrer formula
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