Layered double hydroxide-derived catalyst of Zn-Ni-Al-Fe-O for hydrogen production via auto-thermal reforming of acetic acid
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摘要: 采用共沉淀法制备了Zn2.4Ni0.6AlxFe1-xO4.5±δ（x=1/0.5/0）系列类水滑石型镍基催化剂，用于乙酸自热重整制氢，并利用XRD、H2-TPR、BET、XPS等表征手段对催化剂进行了表征。结果表明，Zn2.4Ni0.6Al0.5Fe0.5O4.5±δ催化剂在乙酸自热重整中乙酸转化率维持在100%，氢气产率为2.39 mol-H2/mol-HAc。Zn-Al水滑石前驱体经焙烧后形成了ZnO为骨架的复合氧化物，铁的适量添加增大了催化剂的比表面积，经还原后形成FeNiZn合金，Fe以及Zn的给电子作用提高了Ni的抗氧化能力，催化剂的抗氧化烧结和抗积炭能力得到提高。
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关键词:
- FeNiZn合金 /
- 类水滑石型镍基催化剂 /
- 乙酸自热重整制氢
Abstract: Zn2.4Ni0.6AlxFe1-xO4.5±δ catalysts were prepared by co-precipitation, tested in auto-thermal reforming (ATR) of HAc, and characterized by XRD, H2-TPR, BET and XPS. The result showed that the Zn2.4Ni0.6Al0.5Fe0.5O4.5±δ catalyst presented a better performance in ATR of HAc. The HAc conversion and hydrogen yield remained at 100% and 2.39 mol-H2/mol-HAc, respectively. The characterization results indicated that the better performance can be attributed to the addition of Fe, which was helpful to increase surface area and formation of FeNiZn alloy after reduction, while resistance to oxidation and coking was improved as well.1) 本文的英文电子版由 Elsevier 出版社在 ScienceDirect 上出版(http://www.sciencedirect.com/science/journal/18725813). -
图 1 ZNAF系列类水滑石型镍基催化剂用于乙酸自热重整反应
Figure 1 Catalytic performance of catalysts for ATR of HAc
(a): ZNA; (b): ZNA0.5F0.5; (c): ZNF
: xHAC; ●: sCO2; △: sCO; ▼: sCH4; ★: sCH3COCH3; ○: wH2
图 2 ZNA0.5F0.5催化剂的自热重整反应活性图
Figure 2 ATR of HAc over the catalyst ZNA0.5F0.5
ATR of HAc over the catalyst ZNA0.5F0.5
: xHAC; ▲: sCO2; ▽: sCO; ◄: sCH4; ☆: sCH3COCH3; ○: wH2
图 3 ZNAF系列催化剂的X射线粉末衍射图
Figure 3 XRD patterns of ZNAF catalysts
(a): precursors; (b): calcined
a: ZNA; b: ZNA0.5F0.5; c: ZNF
图 4 ZNAF系列催化剂的BET表征
Figure 4 BET of ZNAF catalysts
(a): nitrogen adsorption-desorption isotherms; (b): pore size distribution
a: ZNA; b: ZNA0.5F0.5; c: ZNF
图 5 ZNAF系列催化剂X射线粉末衍射图
Figure 5 XRD patterns of ZNAF catalysts
(a): reduced; (b): spent
a: ZNA; b: ZNA0.5F0.5; c: ZNF
图 6 ZNAF系列还原后及反应后催化剂光电子能谱分析
Figure 6 XPS spectra of reduced (a) and spent (b) catalysts
a: ZNA-R; b: ZNA0.5F0.5-R; c: ZNF-R; d: ZNA-S; e: ZNA0.5F0.5-S; f: ZNF-S
图 7 ZNAF系列反应后催化剂热重分析图
Figure 7 TG/DTG profiles of the spent catalysts
(a): ZNA; (b): ZNA0.5F0.5; (c): ZNF
表 1 催化剂清单及比表面积、孔体积、平均孔径、粒径
Table 1 List of crystal sizes, partical size and BET data of the catalysts
Catalyst Nominal compisitions Surface area A/
(m2·g-1)Pore volume v/
(cm3·g-1)Average pore size d/nm Particle size measured by XRD d/nm reduced spent ZNA Zn2.4Ni0.6AlO4.5±δ 40.0 0.146 12.3 16.0a 17.9a ZNA0.5F0.5 Zn2.4Ni0.6Al0.5Fe0.5O4.5±δ 48.3 0.145 9.8 16.6b 16.1b ZNF Zn2.4Ni0.6FeO4.5±δ 31.2 0.088 10.2 22.6b 28.0b a: 43.6° for NiZn alloy；b: 51.3° for NiFe alloy 
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