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摘要: 通过均匀沉淀法制备了以锆-金属有机骨架化合物（Zr-metal organic framework，Zr-MOF）为载体的Ni/Zr-MOF催化剂，并用于湿污泥和秸秆混合催化热解实验。采用元素分析、X射线荧光光谱（XRF）、热重分析（TG）、X射线衍射（XRD）、扫描电镜（SEM）和N2吸附-脱附等温（BET）对载体和催化剂进行表征分析，通过一系列实验来探讨热解温度、秸秆添加量和Ni负载量对于湿污泥和秸秆混合催化热解制备富氢合成气的影响。结果表明，Zr-MOF载体颗粒均匀呈八面体，比表面积高达805.93 m2/g，平均孔径为20.14 nm，为介孔结构。Ni/Zr-MOF催化剂具有较高的热稳定性和催化活性。与不添加催化剂相比，使用Ni/Zr-MOF催化剂在500 ℃下热解，H2的产量从0.39 mol/kg显著提高到12.65 mol/kg。随着热解温度的升高，催化剂出现团聚现象，同时在反复使用之后其表面产生了少量的积炭，导致催化剂催化活性逐渐降低。因此，Ni/Zr-MOF催化剂适用于生物质低温催化热解。Abstract: The catalytic co-pyrolysis of wet sewage sludge and wheat straw for hydrogen-rich gas production was experimentally investigated in a fixed bed reactor with Ni/Zr-MOF catalyst. The Ni/Zr-MOF catalyst was characterized by ultimate analysis, XRF, TG, XRD, SEM and BET. The effects of reactor temperature, straw content and Ni loading on the composition and yield of gasification gases were explored. The experimental results indicate that the mesoporous Zr-MOF support particles are octahedral with a specific surface area of 805.93 m2/g and an average pore diameter of 20.14 nm. The Ni/Zr-MOF catalyst has high thermal stability and catalytic activity. Compared with the pyrolysis without catalyst, the H2 yield increases significantly from 0.39 mol/kg to 12.65 mol/kg using Ni/Zr-MOF catalyst at 500 ℃. After reuse, the carbon deposits are formed on the surface of catalyst. With the increase in reactor temperature, the catalytic activity decreases gradually due to the agglomeration of the catalyst. Therefore, the Ni/Zr-MOF catalyst is suitable for catalytic pyrolysis of biomass at lower temperature.
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图 2 Zr-MOF载体和Ni/Zr-MOF催化剂的热重分析
Figure 2 Thermogravimetric analysis of Zr-MOF carrier and Ni/Zr-MOF catalyst
图 3 Ni/Zr-MOF催化剂和废Ni/Zr-MOF催化剂的XRD谱图
Figure 3 XRD patterns of Ni/Zr-MOF catalyst and waste Ni/Zr-MOF catalyst
图 4 Zr-MOF载体、Ni/Zr-MOF催化剂和废Ni/Zr-MOF催化剂的SEM照片
Figure 4 SEM images of Zr-MOF, Ni/Zr-MOF catalyst and waste Ni/Zr-MOF catalyst
图 5 Zr-MOF、Ni/Zr-MOF和废Ni/Zr-MOF的N2吸附-脱附等温线以及BJH孔径分布
Figure 5 N2 adsorption-desorption isotherm plots and BJH cumulative pore distribution of various catalysts
(a): Zr-MOF; (b): Ni/Zr-MOF; (c): waste Ni/Zr-MOF
图 7 秸秆添加量对于合成气含量和H2产量的影响
Figure 7 Influence of straw content on syngas content and H2 yield
表 1 干污泥和小麦秸秆的工业分析和元素分析
Table 1 Proximate and ultimate analysis of dry sludge and wheat straw
Sample Proximate analysis wad/% Ultimate analysis w/% M A V FC C H N S O* Sludge 4.15 50.69 35.33 9.83 25.20 5.62 3.82 0.15 14.52 Wheat straw 10.88 6.91 67.11 15.10 31.04 4.22 0.40 0.06 57.37 *: by difference 
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表 2 样品的元素分析和XRF分析
Table 2 Ultimate analysis and XRF analysis of samples
Sample Main composition and content w/% C H N ZrO2 NiO K2O Zr-MOF 33.16 3.57 3.29 58.34 - - Ni/Zr-MOF 0.13 - - 29.63 65.89 3.01 Waste Ni/Zr-MOF 5.47 - - 26.73 63.89 2.54
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表 3 Zr-MOF载体、Ni/Zr-MOF催化剂和废Ni/Zr-MOF催化剂的结构参数
Table 3 Textural parameters of Zr-MOF, Ni/Zr-MOF and waste Ni/Zr-MOF
Sample BET surface area A/(m2·g-1) Total pore volume v/(cm3·g-1) Average pore diameter d/nm Zr-MOF 805.93 0.47 20.14 Ni/Zr-MOF 17.96 0.13 102.11 Waste Ni/Zr-MOF 4.01 0.02 132.58
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表 4 催化剂对于气体组成和特性的影响
Table 4 Influence of catalyst on gas composition and gas characterization
Catalyst No catalyst 30%Ni/Zr- MOF catalyst Pyrolysis temperature t/℃ 500 500 Catalytic temperature t/℃ 500 500 H2 content φ/% 1.94 52.48 CO content φ/% 55.07 12.03 CH4 content φ/% 20.03 5.74 CO2 content φ/% 21.12 29.38 CnHm content φ/% 1.83 0.37 Dry gas yield /(m3·kg-1) 0.45 0.54 H2 yield /(mol·kg-1) 0.39 12.65 QLHV/(MJ·m-3) 15.51 9.87
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