纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应

王彦博; 贺雷; 李文翠

doi:10.1016/S1872-5813(23)60332-9

纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应

doi: 10.1016/S1872-5813(23)60332-9

大连理工大学化工学院, 精细化工国家重点实验室, 辽宁省低碳资源高值化利用国家重点实验室, 大连, 116024

详细信息

通讯作者:
E-mail: helei@dlut.edu.cn

wencuili@dlut.edu.cn

中图分类号: O643.3
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-07
- 录用日期: 2022-12-25
- 修回日期: 2022-12-24
- 网络出版日期: 2023-01-10

Morphology Effect of Nano-hydroxyapatite as Support for Loading Ni in Methane Dry Reforming

State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024

摘要

摘要: 甲烷干重整能同时将甲烷与二氧化碳两种主要温室气体转化为合成气(CO和H₂)，衔接费托过程生产燃料及化学品，实现高值转化利用，减少碳足迹，是“双碳”背景下含碳资源利用的重要反应。高效、稳定的催化剂是甲烷干重整实现工业应用的关键之一。载体的结构性质会影响活性组分的稳定固载和积碳–消碳反应的平衡，从而影响催化剂在甲烷干重整中的活性和稳定性。本文通过对羟基磷灰石(HAP)的形貌调控，得到表面Ca、O、P分布不同的纳米棒状、片状和线状的HAP载体，负载1.25wt%的活性组分镍后，得到Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂进行甲烷干重整性能研究。其中，Ni/HAP-R催化剂表现出最优的活性和抗积碳性能。利用XRD、氮吸附、FT–IR、XPS及CO₂–TPD，对催化剂晶相结构、电子性质及表面酸碱性进行表征，证实棒状HAP具有最高的比表面积，有利于Ni的分散锚定，因此活性最佳。且棒状HAP表面富Ca–O–P碱性位点，能够有效活化CO₂，促进积碳消除。TPSR实验进一步证实Ni/HAP-R催化剂上甲烷的深度裂解生成积碳的过程受到抑制，且在CO₂存在时能够迅速转化为CO和H₂，因此具有良好的抗积碳性能。该研究为高稳定负载型催化剂的设计合成提供了新的思路。
- 羟基磷灰石 /
- 镍 /
- 甲烷干重整 /
- 形貌效应
Abstract: Methane dry reforming (MDR) can simultaneously convert methane and carbon dioxide, two major greenhouse gases, into syngas (CO and H₂), which can further produce fuels and chemicals through Fischer-Tropsch process. It is an important reaction for the utilization of carbon-containing resources with low carbon footprint. The design of efficient and stable MDR catalyst is one of the bottlenecks for industrial application. The properties of supports affect the stability of the active components and the carbon deposition-elimination rates, thus influencing the activity and stability of the catalyst. In this paper, hydroxyapatite (HAP) with nanorod, nanosheet and nanowire morphologies were synthesized with different Ca, O and P distributions over the surface. After loading 1.25wt% of nickel, Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts were obtained and applied for MDR studies. Among them, the Ni/HAP-R catalyst showed best performance. The geometric structure, electronic properties and surface acidity and alkalinity of the catalyst were characterized by XRD, N₂ sorption, FT–IR, XPS and CO₂–TPD. It proved that HAP-R possesses the larges surface area, thus, beneficial for Ni dispersion to obtain high MDR activity. Meanwhile, it was rich in Ca–O–P which can accelerate CO₂ activation for coke elimination. TPSR experiments further confirmed that the deep cracking of methane on Ni/HAP-R catalyst was inhibited, but can be accelerated in the presence of CO₂ to produce CO and H₂. In this case, Ni/HAP-R catalyst showed excellent anti-coking performance. This study provides inspiration for the design and synthesis of highly stable heterogeneous catalysts.
- hydroxyapatite /
- nickel /
- methane dry reforming /
- morphology effect

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图 1 (a, d) HAP-R，(b, e) HAP-S，(c, f) HAP-W的SEM照片

Figure 1 SEM images for (a, d) HAP-R，(b, e) HAP-S，(c, f) HAP-W

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图 2 三种不同形貌羟基磷灰石的(a) XRD结果和(b) FT–IR谱图

Figure 2 (a) XRD patterns and (b) FT–IR results for the as-prepared HAP samples

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图 3 (a) Ni/HAP-R，(b) Ni/HAP-S，(c) Ni/HAP-W还原后催化剂的TEM照片，以及(d)对应的XRD结果

Figure 3 TEM images for reduced (a) Ni/HAP-R, (b) Ni/HAP-S and (c) Ni/HAP-W catalysts; (d) the corresponding XRD results

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图 4 Ni/HAP-R，Ni/HAP-S，Ni/HAP-W还原后催化剂的氮气吸脱附曲线以及对应的比表面积和孔容

Figure 4 Nitrogen sorption isotherms of reduced Ni/HAP-R，Ni/HAP-S，Ni/HAP-W catalysts and the corresponding specific surface area and pore volume

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图 5 (a) HAP-R、HAP-S和HAP-W的CO₂–TPD质谱(m/z=44)结果；(b) Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的H₂–TPR结果

Figure 5 (a) Mass spectra (m/z=44) of CO₂–TPD for HAP-R, HAP-S and HAP-W; (b) H₂–TPR results for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

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图 6 Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的(a) Ni 2p XPS谱图和(b) UV–vis–DRS

Figure 6 (a) Ni 2p XPS and (b) UV–vis–DRS results for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

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图 7 Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂在800 ℃甲烷干重整反应中的(a) CH₄和(b) CO₂的转化率

Figure 7 (a) CH₄ and (b) CO₂ conversion for Ni/HAP-R、Ni/HAP-S和Ni/HAP-W catalysts in MDR tests

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图 8 反应后Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的(a)TG曲线和(b)对应的质谱(m/z=44)结果

Figure 8 (a) TG curves and (b) corresponding mass spectra (m/z=44) for the spent Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

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图 9 (a) Ni/HAP-R催化剂的800 ℃稳定性测试; (b) 稳定性测试后的XRD结果; (c) 稳定性测试后的TG及质谱结果

Figure 9 (a) stability test of Ni/HAP-R catalyst at 800 ℃; (b) XRD for the catalyst after stability test; (c) TG and the corresponding mass spectra (m/z=44)

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图 10 Ni/HAP-R, Ni/HAP-S和Ni/HAP-W催化剂的程序升温反应质谱结果: (a–c) CH₄–TPSR, (d–f) CH₄/CO₂–TPSR

Figure 10 Mass spectra of (a–c) CH₄–TPSR and (d–f) CH₄/CO₂–TPSR for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

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