Ni-CeO2-K/γ-Al2O3催化剂上沼气联合重整制合成气

doi:10.16085/j.issn.1000-6613.2019-0933

摘要/Abstract

摘要：

采用超声波辅助等体积浸渍法制备Ni-CeO₂-K/γ-Al₂O₃催化剂用于沼气联合重整反应，采用 BET、XRD、TG/DTG等技术对催化剂性质进行了表征，在微型固定床反应装置中研究了反应温度、体积空速、原料气组成等对沼气联合重整反应特性的影响，并对催化剂的稳定性进行了研究。结果表明，助剂CeO₂的加入，提高了催化剂中Ni的分散度，降低了催化剂还原温度。升高反应温度和减小体积空速，能够提高沼气中CH₄和CO₂的转化率；原料气中加入水蒸气，能够明显提高H₂/CO体积比；加入的O₂容易与H₂、CO发生反应，CH₄转化率稍有提高。在常压、反应温度850℃、体积空速为100000h^-1、摩尔比CH₄∶CO₂∶H₂O∶O₂∶Ar=1∶0.5∶0.5∶0.1∶0.01的优化条件下，沼气中CH₄转化率超过95%，CO₂转化率超过75%，生成合成气H₂/CO体积比约为1.6，反应48h后，催化剂未见积炭，保持稳定的活性。与沼气干重整相比，沼气联合重整不利于沼气中CO₂的转化。

关键词: 沼气, 重整, Ni基, 催化剂, 固定床, 合成气

Abstract:

The Ni-CeO₂-K/γ-Al₂O₃ catalyst used for biogas reforming reaction was prepared by the ultrasonic assisted incipient wetness impregnation method. The catalyst was characterized by BET, XRD and TG/DTG techniques. In addition, the effects of reaction temperature, space velocity, composition on the raw gas to biogas mixed reforming reaction were studied in a micro fixed-bed reactor. The results showed that the addition of CeO₂ increased the dispersion of Ni in the catalyst, and decreased the reduction temperature. The conversion of CH₄ and CO₂ in biogas could be improved by increasing the reaction temperature and reducing the gas space velocity. The addition of water vapor to the raw gas could significantly increase H₂/CO so that the added O₂ reacted easily with H₂ and CO, and the CH₄ conversion rate was slightly improved. The CH₄ conversion was over 95%, the CO₂ conversion was more than 75%, and the ratio of H₂/CO of the generated syngas was about 1.6 in conditions of normal pressure, reaction temperature of 850℃, volume space velocity of 100000h^-1, and CH₄∶CO₂∶H₂O∶O₂∶Ar=1∶0.5∶0.5∶0.1∶0.01. There was no obvious carbon deposition on the catalyst after continuous reaction over 48h, and the activity remained stable. Compared with the dry reforming of methane, the mixed-reforming of biogas is not conducive to the transformation of CO₂.

Key words: biogas, reforming, Ni based, catalyst, fixed-bed, syngas

中图分类号:

S216.4

盖希坤,杨丹,吕鹏,邢闯,吕成学,杨瑞芹. Ni-CeO₂-K/γ-Al₂O₃催化剂上沼气联合重整制合成气[J]. 化工进展, 2020, 39(4): 1357-1362.

Xikun GAI,Dan YANG,Peng LÜ,Chuang XING,Chengxue LÜ,Ruiqin YANG. Mixed-reforming of biogas to syngas over the Ni-CeO₂-K/γ-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1357-1362.

图/表 8

表1 载体和催化剂的物理性质

样品	比表面积/m²·g^-1	孔体积/cm³·g^-1	平均孔径/nm
γ-Al₂O₃	156.104	1.122	17.571
Ni/γ-Al₂O₃	131.553	0.8581	17.504
Ni-CeO₂/γ-Al₂O₃	129.433	0.8298	17.641
Ni-CeO₂-K/γ-Al₂O₃	126.449	0.8391	17.518

图1 载体和催化剂的XRD谱图

a—Ni/γ-Al2O3；b—Ni-CeO2/γ-Al2O3；c—Ni-CeO2-K/γ-Al2O3；d—γ-Al2O3

图2 反应后Ni-CeO2-K/γ-Al2O3催化剂的TG/DTG曲线

图3 反应温度对CH4和CO2转化率和H2/CO体积比的影响（常压，100000h-1，CH4∶CO2∶H2O∶O2∶Ar=1∶0.5∶0.5∶0.1∶0.01）

图4 体积空速对CH4和CO2转化率和H2/CO体积比的影响（常压，850℃，CH4∶CO2∶H2O∶O2∶Ar=1∶0.5∶0.5∶0.1∶0.01）

图5 氧气含量对CH4和CO2转化率和H2/CO体积比的影响（常压，850℃，100000h-1，CH4∶CO2∶H2O∶Ar=1∶0.5∶0.5∶0.01）

图6 水蒸气含量对CH4和CO2转化率和H2/CO体积比的影响（常压，850℃，100000h-1，CH4∶CO2∶O2∶Ar=1∶0.5∶0.1∶0.01）

图7 Ni-CeO2-K/γ-Al2O3催化剂的稳定性（常压，850℃，100000h-1，CH4∶CO2∶H2O∶O2∶Ar=1∶0.5∶0.5∶0.1∶0.01）

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Ni-CeO₂-K/γ-Al₂O₃催化剂上沼气联合重整制合成气

Mixed-reforming of biogas to syngas over the Ni-CeO₂-K/γ-Al₂O₃ catalyst

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