磷前驱体对金属磷化物甲烷化催化性能的影响

WANG Bao-wei; WANG Ting-ting; ZHAO Jun; LI Zhen-hua; XU Yan; MA Xin-bin

doi:10.1016/S1872-5813(21)60110-X

磷前驱体对金属磷化物甲烷化催化性能的影响

doi: 10.1016/S1872-5813(21)60110-X

天津大学化工学院绿色合成与转化教育部重点实验室天津 300072

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中图分类号: TQ032.4
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出版历程
- 收稿日期: 2021-01-13
- 修回日期: 2021-02-10
- 网络出版日期: 2021-06-01
- 刊出日期: 2021-07-15

Effect of phosphorus precursor on the catalytic performance of metal phosphides in the methanation of syngas

Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Funds: The project was supported by the National High Technology Research and Development Program of China (863 Project, 2015AA050504)

More Information

Corresponding author: Tel: +086-22-87401818, E-mail: wangbw@tju.edu.cn

摘要

摘要: 采用氢气程序升温还原方法制备了系列金属磷化物催化剂，研究了磷前驱体和H₂/CO比对其甲烷化催化性能的影响。结果表明，与磷酸氢二铵相比，由植酸制备的金属磷化物催化剂具有较高的甲烷化活性；植酸作为螯合剂可以有效地分散金属前驱体，降低还原温度，使催化剂具有较高的比表面积和较小的晶粒尺寸，并更好地还原为纯磷化物晶相。不同金属磷化物催化剂的活性顺序为MoP > WP > CoP > NiP。高H₂/CO比有利于甲烷化反应进行，随着反应物H₂/CO比的增加，所有磷化物催化剂的甲烷选择性都增加。
- 植酸 /
- 甲烷化 /
- 磷酸盐 /
- 金属磷化物 /
- H₂/CO比 /
- 催化性能
Abstract: A series of metal phosphides including MoP, WP, CoP and NiP was prepared by temperature-programmed reduction with hydrogen from different phosphorus precursors. The effect of phosphorus precursor and feed H₂/CO ratio on the catalytic performance of metal phosphides in the methanation was investigated. In comparison with diammonium hydrogen phosphate (DAP), phytic acid (PA) as a chelating agent can effectively disperse the metal precursor, reduce the reduction temperature, promote to form pure phosphide phase, and give the phosphide catalyst a higher surface area and a smaller particle size; as a result, the metal phosphides prepared with PA as a phosphorus precursor exhibit higher catalytic activity in methanation. In addition, the catalytic activity of various metal phosphides in methanation follows the sequence of MoP > WP > CoP > NiP. A high H₂/CO ratio in the feed is favorable for the methanation over the phosphide catalysts; the selectivity to methane increases with an increase in the H₂/CO ratio.
- phytic acid /
- methanation /
- phosphate /
- metal phosphide /
- H₂/CO ratio /
- catalytic performance

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FIG. 801. FIG. 801.

FIG. 801.

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Figure 1 Methanation performance of various metal phosphide catalysts

(a): with DAP as phosphorus precursor; (b): with PA as phosphorus precursorreaction conditions: 550 °C, 3.0 MPa, 5000 mL/(g·h)

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Figure 2 XRD patterns of various metal phosphide catalysts

(a): with DAP as precursor; (b): with PA as precursor

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Figure 3 H₂-TPR profiles of various metal phosphide catalysts

(a): with DAP as precursor; (b): with PA as precursor

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Table 1 Methanation performance of various metal phosphide catalysts at 550 °C, 3.0 MPa, and 5000 mL/(g·h)

Catalyst	H₂/CO = 1				H₂/CO = 3
Catalyst	$x_{ {\rm{CO} } }$/%	$ s_{{\rm{CO}}_2} $/%	$ s_{{\rm{CH}}_4} $/%	$ s_{{\rm{C}}_2{\rm{H}}_6} $/%	$ x_{{\rm{CO}}} $/%	$ s_{{\rm{CO}}_2} $/%	$ s_{{\rm{CH}}_4} $/%	$ s_{{\rm{C}}_2{\rm{H}}_6} $/%
MoP-DAP	50.1	45.8	53.1	1.1	59.6	41.9	57.2	0.9
MoP-PA	65.6	46.8	51.9	1.3	72.5	31.9	67.5	0.6
WP-DAP	17.3	41.9	57.5	0.6	22.8	32.0	67.5	0.5
WP-PA	21.3	43.0	56.0	1.0	23.8	32.9	66.2	0.9
CoP-DAP	5.8	20.0	78.1	1.9	9.4	10.1	88.8	1.1
CoP-PA	12.4	23.6	75.8	0.4	17.3	16.8	82.1	1.1
NiP-DAP	3.2	13.4	84.0	2.6	3.4	7.0	90.3	2.7
NiP-PA	3.2	14.3	84.1	1.6	4.3	12.0	86.3	1.7

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Table 2 Textural properties determined by N₂ sorption of various phosphide catalysts

Catalyst	Surface area A/(m²·g⁻¹)	Pore volume v/(cm³·g⁻¹)	Average pore size d/nm	Particle size d/nm
MoP-DAP	3.7	0.022	27.0	19.7
MoP-PA	40.1	0.010	8.9	14.7
WP-DAP	3.2	0.024	55.5	35.5
WP-PA	27.4	0.083	11.1	22.9
CoP-DAP	1.0	0.003	52.6	90.8
CoP-PA	10.9	0.062	30.2	38.1
NiP-DAP	4.0	0.029	48.1	25.8
NiP-PA	8.1	0.021	38.3	19.7

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