CaO对Cu-ZnO-ZrO2催化CO2加H2合成甲醇性能影响

陈俊军; 高文桂; 王华; 纳薇

CaO对Cu-ZnO-ZrO₂催化CO₂加H₂合成甲醇性能影响

陈俊军^{1, 2},
高文桂^{1, 3, ,},
王华^{1, 3},
纳薇^{1, 3}

1.
昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室, 云南昆明 650093
2.
昆明理工大学化学工程学院, 云南昆明 650093
3.
昆明理工大学冶能与能源工程学院, 云南昆明 650093

基金项目:

国家自然科学基金 51304099

云南省应用基础研究计划 2013FZ035

国家科技支撑计划 2011BAC01B03

详细信息

中图分类号: O643.3
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- 被引次数: 0
出版历程
- 收稿日期: 2015-10-28
- 修回日期: 2016-01-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-04-30

Effect of CaO on the performance of Cu-ZnO-ZrO₂ catalyst for methanol synthesis from CO₂ and H₂

CHEN Jun-jun^{1, 2},
GAO Wen-gui^{1, 3
, ,},
WANG Hua^{1, 3},
NA Wei^{1, 3}

1.
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China
2.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650093, China
3.
Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China

More Information

Corresponding author: E-mail: gao_wengui@126.com.

摘要

摘要: 用CaO作为改性助剂,采用并流共沉淀法制备了CuO:ZnO:ZrO₂为5:4:1(物质的量比),CaO添加量为0、1%、2%、4%、8%、16%(摩尔分数)的六组催化剂。用X射线衍射(XRD)、微商热重(TG-DTG)、傅里叶红外(FT-IR)、N₂吸附脱附(BET)、X射线光电子能谱(XPS)、氢气程序升温还原(H₂-TPR)、CO₂程序升温脱附(CO₂-TPD)、NH₃程序升温脱附(NH₃-TPD)对催化剂进行了表征。用自制固定床评价了催化剂活性。结果表明,添加CaO后,催化剂路易斯酸性和表面碱性增强;催化剂母体中高温碳酸盐含量增加,热稳定性增强,CuO颗粒粒径变小,Cu-Zn协同作用增强,Cu比表面积增大,分散性变好。催化剂活性受到表面酸碱性、铜比表面积、Cu-Zn协同作用和铜分散性共同影响。当CaO为2%时,铜比表面积为79.3 m²/g、铜分散度为34.8%、CO₂转化率为24.55%、甲醇选择性为19.01%、甲醇收率为0.044 g/(g_cat·h),催化剂活性最好。过量CaO占据催化剂孔道和覆盖表面活性位,使催化剂路易斯酸性和表面碱性过强,CuO与H₂有效接触减少,CO₂难以脱附,催化活性下降。因此,适量CaO(2%)添加可促进CO₂加氢反应合成甲醇。
- 并流共沉淀法 /
- CaO /
- Cu-ZnO-ZrO₂ /
- CO₂加H₂ /
- 甲醇
Abstract: CuO:ZnO:ZrO₂=5:4:1 (molar ratio) catalysts were prepared with CaO doping of 0,1%, 2%, 4%, 8%, 16% (molar fraction) by cocurrent-flow co-precipitation. X-ray diffraction (XRD), thermal analysis(TG-DTG), Fourier infrared (FT-IR), N₂ adsorption desorption (BET), X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H₂-TPR), CO₂ temperature programmed desorption (CO₂-TPD) and NH₃ temperature programmed desorption (NH₃-TPD) were used to characterize the catalysts. The catalyst activity was evaluated with a lab-made fixed bed reactor. Results show that CaO doping enhances Lewis acid and surface alkaline of the catalyst, increases the amount of high temperature carbonate in the catalysts, improves the thermal stability, reduces the CuO particle size, enhances the synergistic effect of Cu-Zn, increases the Cu specific surface area and the Cu dispersion. The catalyst activity is influenced by the surface acidity, the specific surface area of copper, the synergistic effect of Cu-Zn and the dispersion of copper. When the doping amount of CaO is 2%, the copper specific surface area is 79.3 m²/g, the dispersion degree of copper is 34.8%, the CO₂ conversion is 19.01%, the selectivity of methanol is 24.55% and the yield of methanol is 0.044 g/(g_cat·h), catalyst activity is the highest. With the amount of CaO increasing, the excessive CaO occupies the catalyst pore and covers the surface active sites, the Lewis acid and the surface alkaline of the catalysts become so strong that the effective contact of CuO and H₂ is reduced, CO₂ is difficult to desorb, resulting in decrease of catalytic activity. Therefore, the proper doping amount of CaO (2%) can promote the synthesis of methanol through CO₂ hydrogenation.
- cocurrent-flow co-precipitation /
- CaO /
- Cu-ZnO-ZrO₂ /
- CO₂ and H₂ /
- methanol

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图 1 催化剂前驱体的XRD谱图

Figure 1 XRD patterns of the catalyst precursors

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图 2 催化剂前驱体热分析曲线

Figure 2 Curves of thermal analysis of the catalyst precursors

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图 3 催化剂前驱体FT-IR 谱图

Figure 3 FT-IR profiles of the catalyst precursors

a: P-CaO16%; b: P-CaO8%; c: P-CaO4%; d: P-CaO2%; e：P-CaO1%; f: P-blank

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图 4 催化剂母体XRD谱图

Figure 4 XRD patterns of the precatalysts

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图 5 催化剂的XRD谱图

Figure 5 XRD patterns of the catalysts

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图 6 催化剂母体SEM照片

Figure 6 SEM images of the catalysts

(a): M-blank; (b): M-CaO2%

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图 7 催化剂母体氮气吸附脱附曲线

Figure 7 Nitrogen adsorption desorption curves of the catalysts

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图 8 催化剂母体孔径分布

Figure 8 Pore size distribution of the catalysts

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图 9 催化剂母体XPS Cu 2p谱图

Figure 9 Cu 2p XPS patterns of the catalysts

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图 10 催化剂母体XPS Zn 2p谱图

Figure 10 Zn 2p XPS patterns of the catalysts

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图 11 催化剂母体红外光谱谱图

Figure 11 FT-IR profiles of the catalysts

a: M-CaO16%; b: M-CaO8%; c: M-CaO4%; d: M-CaO2%; e: M-CaO1%; f: M-blank

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图 12 不同焙烧温度催化剂母体红外光谱谱图

Figure 12 FT-IR profiles of the catalysts calcined at different temperatures

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图 13 催化剂的H₂-TPR谱图

Figure 13 H₂-TPR profiles of the catalysts

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图 14 催化剂的TEM照片

Figure 14 TEM images of the catalysts

(a): CZZblank; (b): CZZCaO2%

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图 15 催化剂的CO₂-TPD谱图

Figure 15 CO₂-TPD profiles of the catalysts

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图 16 催化剂的NH₃-TPD谱图

Figure 16 NH₃-TPD profiles of the catalysts

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表 1 催化剂前驱体热分析

Table 1 Thermal analysis data of the catalyst precursors

Sample	P-blank		P-CaO1%		P-CaO2%		P-CaO4%		P-CaO8%
Decomposition stages	weight loss w/%	DTG maximum peak position t/℃	weight loss w/%	DTG maximum peak position t/℃	weight loss w/%	DTG maximum peak position t/℃	weight loss w/%	DTG maximum peak position t/℃	weight loss w/%	DTG maximum peak position t/℃
60-200℃	8.22		3.02		4.98		2.76		3.25
200-400℃	13	308.9	13.63	316.2	16.16	332.8	15.77	313.1,373.6	15.25	319.6
400-560℃	3.29	458.9	5.21	480.3	5.6	512.8	3.36	463.2	4.38	466.0

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表 2 催化剂母体孔结构参数

Table 2 Pore structure parameters of the catalysts

Catalyst	M-blank	M-CaO1%	M-CaO2%	M-CaO4%	M-CaO8%	M-CaO16%
A_BET/(m²·g^-1)	77.4	97.3	99.8	100.6	94	89.1
v/(mL·g^-1)	0.237	0.305	0.321	0.322	0.298	0.252
d(CuO) /nm	10.9	7.3	6.0	9.0	10.5	10.7
d(ZnO) /nm	16.8	12.3	6.3	15.7	15.4	16.2

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表 3 催化剂H₂-TPR还原峰数据

Table 3 H₂-TPR reduction peaks of the catalysts

Catalyst	α		β		α/(α+β)
Catalyst	Area /(mV·℃)	t_max /℃	Area /(mV·℃)	t_max /℃	α/(α+β)
CZZblank	2574	230.4	6223	266.9	0.29
CZZCaO1%	2487	229	5704	260.6	0.30
CZZCaO2%	2871	226.9	5277	258.2	0.35
CZZCaO4%	2359	233	5565	264	0.30
CZZCaO8%	1963	217.4	5880	251.1	0.25
CZZCaO16%	1652	226.3	4555	254.8	0.27

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表 4 催化剂的催化性能

Table 4 Reaction performance of the catalysts

Catalyst	s(CH₃OH) /%	x(CO₂) /%	w(CH₃OH) /(g·g_cat^-1·h^-1)	A(Cu) /(m²·g^-1)	D(Cu) /%
CZZblank	12.09	22.06	0.022	48.6	17.8
CZZCaO1%	16.08	25.1	0.038	50.86	20.5
CZZCaO2%	19.01	24.55	0.044	79.3	34.8
CZZCaO4%	14.09	24.44	0.032	14.9	7.1
CZZCaO8%	13.69	24.07	0.026	27.8	11.6
CZZCaO16%	13.21	23.1	0.027	22.5	10.2
A(Cu): the copperspecific surface area; D(Cu): the dispersion degree of copper; reaction conditions: t= 250℃,p=3MPa,H₂ /CO₂= 3∶1(volume ratio) and SV=3000mL/(g·h)

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