焙烧温度对MgAlO<sub><i>x</i></sub>复合氧化物催化甲醛和乙醛合成正丙醛反应性能的影响

程福龙; 郭荷芹; 崔静磊; 侯博; 李德宝

焙烧温度对MgAlO_x复合氧化物催化甲醛和乙醛合成正丙醛反应性能的影响

程福龙^{1, 2},
郭荷芹^1, ,,
崔静磊³,
侯博¹,
李德宝^1, ,

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
山西大学资源与环境工程研究所, 山西太原 030001

基金项目:

国家自然科学基金 21736007

国家自然科学基金 21303241

详细信息

中图分类号: O643
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出版历程
- 收稿日期: 2018-01-15
- 修回日期: 2018-05-11
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-07-10

Effect of calcination temperature on MgAlO_x mixed oxides for converting formaldehyde and acetaldehyde to propanal

CHENG Fu-long^{1, 2},
GUO He-qin^{1
, ,},
CUI Jing-lei³,
HOU Bo¹,
LI De-bao^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Institute of Resources and Environment Engineering, Shanxi University, Taiyuan 030006, China

Funds:

the National Natural Science Foundation of China 21736007

the National Natural Science Foundation of China 21303241

More Information

Corresponding author: GUO He-qin, Tel:0351-4040499, E-mail:heqinguo@sxicc.ac.cn; LI De-bao, E-mail:dbli@sxicc.ac.cn

摘要

摘要: 采用共沉淀法制备了镁铝水滑石前驱体，通过在不同温度下焙烧得到系列MgAlO_x复合氧化物催化剂，采用XRD、TG、N₂吸附-脱附、NH₃-TPD和CO₂-TPD等技术对催化剂的物理和化学性质进行了表征，采用甲醛和乙醛缩合反应对催化剂反应性能进行了评价。结果表明，随着焙烧温度的提高，乙醛转化率以及正丙醛时空收率先增加后减少，C-550催化剂最大，分别达到39.22%和103.86 g/（kg·h），这与催化剂中强碱和强碱数目变化趋势一致。此外，提高催化剂中强碱和强碱数目还会促进副产物甲醇和CO₂的生成。
- 甲醛和乙醛 /
- 正丙醛 /
- MgAlO_x复合氧化物 /
- 焙烧温度
Abstract: A series of MgAlO_x mixed oxides were prepared by calcination of hydrotalcite materials at various temperatures ranging from 400 to 700℃. The physical and chemical properties of the catalysts were characterized by XRD, TG, N₂ adsorption/desorption, NH₃-TPD, and CO₂-TPD techniques. The catalytic activity was evaluated by the condensation of formaldehyde and acetaldehyde. The results show that as the calcination temperatures increase, both the conversion of acetaldehyde and the space time yield of propanal first increase and then decrease, which shows the same trend with the amount of moderate basic sites, and the C-550 catalyst has the maximum of 39.22% and 103.86 g/(kg·h), respectively. Moreover, the yields of by-products including methanol and CO₂ are also significantly related to the moderate and strong basic sites.
- formaldehyde and acetaldehyde /
- propanal /
- MgAlO_x mixed oxides /
- calcination temperature

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图 1 催化剂的XRD谱图

Figure 1 XRD patterns of the samples

(a): precursor; (b): calcined catalysts

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图 2 镁铝前驱体的TG-DTG曲线

Figure 2 TG-DTG curves of the precursor

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图 3 催化剂的织构表征

Figure 3 Textural characterization of the samples

(a): nitrogen adsorption/desorption isotherms; (b): pore size distributions

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图 4 催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of the catalysts

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图 5 催化剂的CO₂-TPD谱图

Figure 5 CO₂-TPD profiles of the catalysts

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图 6 乙醛转化率以及正丙醛时空收率与中强碱数目的关系

Figure 6 Correlation between the conversion of acetaldehyde and the STY of propanal with the amount of moderate basic sites

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表 1 催化剂的织构参数以及表面酸碱分布

Table 1 Textural properties, acidity, and alkalinity of the samples

Sample	A_BET /(m²·g^-1)	v_p /(cm·g^-1)	d_p /nm	Amount of acid sites /(μmol·g^-1)^a			Amount of basic sites /(μmol·g^-1)^b
Sample	A_BET /(m²·g^-1)	v_p /(cm·g^-1)	d_p /nm	total	weak	moderate	total	weak	moderate	strong
HT	116.2	0.67	10.86	-	-	-	-	-	-	-
C-400	208.6	0.34	6.71	105.68	38.12	67.56	198.76	24.91	141.53	32.32
C-500	226.7	0.49	7.57	171.54	51.69	119.85	267.29	23.69	176.26	67.35
C-550	249.2	0.48	6.53	115.23	38.47	76.76	276.30	6.14	182.93	87.22
C-600	223.8	0.55	8.30	175.43	46.36	129.07	242.11	19.46	162.65	60.00
C-700	165.2	0.13	6.62	135.07	39.65	95.42	213.40	28.35	148.60	36.45
A_BET: BET surface area; v_p: BJH pore volume; d_p: average pore diameter; ^a: calculated from NH₃-TPD; ^b: calculated from CO₂-TPD

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表 2 催化剂催化甲醛和乙醛反应的评价

Table 2 Catalytic performance of the catalysts in condensation of formaldehyde and acetaldehyde

Catalyst	x/%	s/%							STY/(g·kg^-1·h^-1)
Catalyst	x/%	propanal	methanol	CO₂	isobutanal	1-propanol	MF	ethanol	propanal	methanol	CO₂
C-400	22.12	77.54	9.01	9.60	1.72	0.45	0.75	0.93	60.42	11.61	17.00
C-500	35.69	60.17	18.35	16.32	2.35	0.92	1.05	0.84	95.19	48.04	58.70
C-550	39.22	56.59	19.17	17.80	2.68	1.05	1.98	0.73	103.86	58.23	74.28
C-600	29.27	62.18	15.11	17.11	2.73	0.99	0.87	1.01	77.55	31.19	48.52
C-700	24.21	69.09	13.40	13.00	1.86	0.67	1.06	0.92	65.54	21.04	28.03
reaction conditions: t=260 ℃, p=0.1 MPa, reaction time=5 h, formaldehyde/acetaldehyde (molar ratio)=4, GHSV=1000 h^-1, LHSV=2.0 h^-1; x: acetaldehyde conversion, s: selectivity, STY: space time yield, MF: methyl formate

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焙烧温度对MgAlO_x复合氧化物催化甲醛和乙醛合成正丙醛反应性能的影响

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Effect of calcination temperature on MgAlO_x mixed oxides for converting formaldehyde and acetaldehyde to propanal

Corresponding author: GUO He-qin, Tel:0351-4040499, E-mail:heqinguo@sxicc.ac.cn; LI De-bao, E-mail:dbli@sxicc.ac.cn

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2023年《燃料化学学报（中英文）》评优结果公布！

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焙烧温度对MgAlOx复合氧化物催化甲醛和乙醛合成正丙醛反应性能的影响

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Effect of calcination temperature on MgAlOx mixed oxides for converting formaldehyde and acetaldehyde to propanal

Corresponding author: GUO He-qin, Tel:0351-4040499, E-mail:heqinguo@sxicc.ac.cn; LI De-bao, E-mail:dbli@sxicc.ac.cn

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出版历程

目录

2023年《燃料化学学报（中英文）》评优结果公布！

焙烧温度对MgAlO_x复合氧化物催化甲醛和乙醛合成正丙醛反应性能的影响

Effect of calcination temperature on MgAlO_x mixed oxides for converting formaldehyde and acetaldehyde to propanal