Mg修饰锌孔雀石催化甲醇合成的性能研究

袁治国; 张凡; 杨世礼; 徐晓颖; 刘晨阳; 邱正璞; 魏伟

doi:10.1016/S1872-5813(24)60455-X

Mg修饰锌孔雀石催化甲醇合成的性能研究

doi: 10.1016/S1872-5813(24)60455-X

袁治国^1,,
张凡^2,,
杨世礼^1,,
徐晓颖^2, ,,
刘晨阳^1,,
邱正璞^2,,
魏伟^1,

1.
国能蒙西煤化工股份有限公司, 内蒙古鄂尔多斯 016100
2.
北京低碳清洁能源研究院, 北京 102211

基金项目: 国家能源集团科技创新项目(ST930023003N)资助

详细信息

通讯作者:
Tel: 010-57337302, E-mail: xiaoying.xu.d@chnenergy.com.cn

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2024-02-21
- 修回日期: 2024-04-07
- 录用日期: 2024-04-07
- 网络出版日期: 2024-05-13

Effect of Mg modification on the catalytic performance of zinc malachite for methanol synthesis

YUAN Zhiguo^1
,,
ZHANG Fan^2
,,
YANG Shili^1
,,
XU Xiaoying^{2
, ,},
LIU Chenyang^1
,,
QIU Zhengpu^2
,,
WEI Wei^1
,

1.
Guoneng Mengxi Coal Chemical Co., LTD., Inner Mongolia Autonomous Region, Ordos 016100, China
2.
National Institute of Clean-and-low-carbon Energy, Beijing 102211, China

Funds: The project was supported by Science and Technology Innovation Project of CHN ENERGY Group (ST930023003N).

摘要

摘要: 焦炉煤气制甲醇的复杂工况给铜基甲醇合成催化剂的稳定性和寿命带来挑战。本工作制备了一系列不同镁含量的锌孔雀石样品，采用原位X射线衍射、热重-质谱、N₂物理吸附、H₂程序升温还原、CO₂程序升温脱附等方法对锌孔雀石及焙烧后的样品进行表征，考察镁元素的添加对锌孔雀石结构和甲醇合成催化性能的影响。结果发现，镁元素的添加提高了锌孔雀石结构内部的铜取代程度，促进了焙烧后催化剂内部高温碳酸盐的形成。随着镁含量的增加，焙烧后催化剂的比表面积逐渐增大，还原后的单质铜晶粒尺寸逐渐减小。原位XRD结果表明，少量镁元素在催化剂热处理过程中能有效抑制单质铜晶粒尺寸生长。评价显示催化剂的初始活性随着镁元素的添加呈现先升高后降低的趋势，热处理后含镁催化剂活性仍保持在相对较高的水平。镁元素的适量添加有助于提高铜基甲醇合成催化剂初始活性和热稳定性。
- 铜晶粒 /
- 镁元素 /
- 热稳定性
Abstract: The complex conditions of methanol production from coke-oven gas have brought challenges to the copper-based methanol synthesis catalyst. In this work, a series of zinc-malachite samples with different Mg contents were prepared. The zinc-malachite and calcined samples were characterized by in-situ X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS), N₂ physical adsorption, H₂ programmed temperature reduction (H₂-TPR), CO₂ programmed temperature desorption (CO₂-TPD) and other methods. The effects of Mg addition on the structure of zinc-malachite and its catalytic performance of methanol synthesis were investigated. The results showed that the addition of Mg increased the degree of Cu substitution inside the zinc-malachite structure and promoted the formation of high temperature carbonates in the catalyst after roasting. With the increase of Mg content, the specific surface area of the calcined catalyst increased gradually, and the Cu grain size decreased simultaneously. In-situ XRD results showed that a small amount of Mg could effectively inhibit the growth of copper grain size during the heat treatment. The evaluation showed that the initial activity of the catalyst increased first and then decreased with Mg addition, and the activity of the Mg-doped catalyst remained at a relatively high level after heat treatment. The appropriate Mg addition is beneficial to the initial activity and thermal stability of Cu-based methanol synthesis catalyst.
- copper nanoparticle /
- magnesium /
- thermostability

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图 1 不同镁含量的前驱体样品的XRD谱图

Figure 1 XRD results of precursor samples with different Mg contents

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图 2 催化剂前驱体的热重质谱联用分析

Figure 2 Thermogravimetric mass spectrometry results of catalyst precursors (10 ℃/min, air atmosphere)

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图 3 焙烧后（a）和230 ℃还原后（b）催化剂样品的XRD谱图

Figure 3 XRD results of catalyst samples after calcination (a) and reduction at 230 ℃ (b)

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图 4 CuZn和CuZnMg_0.25样品的原位XRD谱图

Figure 4 In-situ XRD results of CuZn and CuZnMg_0.25 samples

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图 5 CuZn和CuZnMg_0.25样品热处理过程中的Cu晶粒尺寸变化

Figure 5 Variation of Cu grain sizes of CuZn and CuZnMg_0.25 samples during heat treatment

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图 6 不同镁含量催化剂样品的H₂-TPR谱图

Figure 6 H₂-TPR results of catalyst samples with different Mg contents

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图 7 不同镁含量催化剂样品的CO₂-TPD谱图

Figure 7 CO₂-TPD results of catalyst samples with different Mg contents

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图 8 催化剂样品的初始活性和热稳定性

Figure 8 Evaluation results of initial activity and thermal stability of catalyst samples

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表 1 甲醇合成催化剂样品的设计元素组成

Table 1 Designed atomic ratio of the methanol synthesis catalyst samples

Sample	Cu²⁺∶Zn²⁺∶Mg²⁺ (mole ratio)	CuO∶ZnO∶MgO (mass ratio)
CuZn	7∶ 3∶ 0	69.5∶30.5∶0
CuZnMg_0.25	7∶ 3∶ 0.25	68.7∶30.1∶1.2
CuZnMg_0.50	7∶ 3∶ 0.50	67.8∶29.7∶2.5

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表 2 不同镁含量样品的物化性质表征

Table 2 Physicochemical characterization results of samples with different Mg contents

Sample	Grain size^a/nm			Specific surface area /(m²·g⁻¹)	Elemental composition^c w/%
Sample	precursor	CuO	Cu ^b	Specific surface area /(m²·g⁻¹)	CuO	ZnO	MgO	CO₂
CuZn	24.78	9.45	13.2	38.6	68.6	26.9	0.0	4.5
CuZnMg_0.25	18.06	7.85	10.5	46.1	66.6	27.2	0.4	5.8
CuZnMg_0.50	13.91	6.93	7.81	65.7	65.4	26.5	1.0	7.1
^a: Precursors calculated by the $12\bar0 $> reflection, CuO and Cu calculated by the $11\bar1 $ reflection; ^b: In-situ XRD results at 230 ℃; ^c: Normalized results of XRF analyses.

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表 3 不同镁含量样品的CO₂-TPD曲线分峰拟合

Table 3 Peak fitting results of CO₂-TPD curves of samples with different Mg contents

Sample	Amount of total basic sites /(µmol·g⁻¹)	α peak		β peak		γ peak
Sample	Amount of total basic sites /(µmol·g⁻¹)	t/℃	basic sites / (µmol·g⁻¹)	t/℃	basic sites / (µmol·g⁻¹)	t/℃	basic sites / (µmol·g⁻¹)
CuZn	245	93	34 (13.8%)	143	57 (23.1%)	385	155 (63.1%)
CuZnMg_0.25	336	93	52 (15.4%)	150	107 (31.9%)	389	177 (52.7%)
CuZnMg_0.50	409	95	54 (13.1%)	157	153 (37.4%)	391	203 (49.5%)

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