Al<sub>2</sub>O<sub>3</sub>载体负载的铂和钨双功能催化剂在甘油氢解制1,3-丙二醇中的性能研究

徐文峰; 牛鹏宇; 郭荷芹; 贾丽涛; 李德宝

doi:10.1016/S1872-5813(21)60101-9

Al₂O₃载体负载的铂和钨双功能催化剂在甘油氢解制1,3-丙二醇中的性能研究

doi: 10.1016/S1872-5813(21)60101-9

徐文峰^{1, 2,},
牛鹏宇^1, ,,
郭荷芹¹,
贾丽涛^{1, 3, ,},
李德宝^{1, 3}

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.
中国科学院洁净能源创新研究院，辽宁大连 116023

基金项目: 山西省重点研发计划(201903D121033)资助

详细信息

作者简介:
徐文峰：1716521419@qq.com

通讯作者:
Tel: 0351-4040499，E-mail: niupy@sxicc.ac.cn

litaojia@sxicc.ac.cn

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-11
- 修回日期: 2021-04-13
- 网络出版日期: 2021-05-31
- 刊出日期: 2021-09-30

Study on the performance of platinum and tungsten bifunctional catalyst supported on Al₂O₃ in the hydrogenolysis of glycerol to 1,3-propanediol

XU Wen-feng^{1, 2
,},
NIU Peng-yu^{1
, ,},
GUO He-qin¹,
JIA Li-tao^{1, 3
, ,},
LI De-bao^{1, 3}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Dalian National Laboratory of Clean Energy, Dalian 116023, China

Funds: The project was supported by the Key Research Project of Shanxi Province, China (201903D121033)

摘要

摘要: 采用水热晶化法合成了一种高比表面积且富含不饱和五配位铝位点的棒状Al₂O₃，并利用等体积顺序浸渍法使钨物种先以低聚合态纳米簇的形式锚定在Al₂O₃载体表面。通过高温热处理方式使铂物种以小粒径高分散的形式与钨物种紧密接触，极大地加强了铂和钨物种之间的相互作用程度，有利于更多活性位结构的产生，显著地提高了甘油氢解制1,3-丙二醇（1,3-PDO）的催化活性。其催化反应性能评价结果表明，在固定床反应器中，反应温度160 ℃，压力5.0 MPa，10%甘油水溶液连续进液时，Pt-WO_x/Al₂O₃催化剂的甘油转化率为75.2%，1,3-PDO的收率达到了33.1%。
- Al₂O₃ /
- 甘油氢解 /
- 1,3-丙二醇 /
- 铂 /
- 钨
Abstract: In this work, a rod-shaped Al₂O₃ with high specific surface area and rich in unsaturated pentahedral coordination Al³⁺ sites was synthesized by hydrothermal crystallization method, and the tungsten species was anchored on the surface of the Al₂O₃ support in the form of oligomeric nanoclusters using the incipient-wetness impregnation method. Then the platinum species were in close contact with the tungsten species in the form of small particle size and high dispersion through high temperature heat treatment. It greatly enhances the degree of interaction between platinum and tungsten species, is conducive to the generation of more active site structures, and significantly improves the catalytic activity of glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO). In a fixed-bed reactor, when the reaction temperature is 160 ℃, the pressure is 5.0 MPa, and the 10% glycerol aqueous solution is continuously added, the catalytic reaction performance evaluation results show that the glycerol conversion of the Pt-WO_x/Al₂O₃ catalyst is 75.2%, and the yield of 1,3-PDO reach 33.1%.
- Al₂O₃ /
- glycerol hydrogenolysis /
- 1,3-propanediol /
- Pt /
- W

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FIG. 912. FIG. 912.

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图 1 催化剂的XRD谱图

Figure 1 XRD patterns of the catalysts

a: WO_x/Al₂O₃-600; b: WO_x/Al₂O₃-700; c: WO_x/Al₂O₃-800; d: WO_x/Al₂O₃-850; e: Pt-WO_x/Al₂O₃-800; A = Al₂W₃O₁₂

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图 2 样品的N₂吸附-脱附曲线（a）和孔径分布（b）

Figure 2 N₂ adsorption-desorption isotherms (a) and pore size distribution (b) of samples

a: Al₂O₃; b: WO_x/Al₂O₃-800; c: Pt-WO_x/Al₂O₃-600; d: Pt-WO_x/Al₂O₃-700; e: Pt-WO_x/Al₂O₃-800; f: Pt-WO_x/Al₂O₃-850

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图 3 不同Al₂O₃和WO_x/Al₂O₃样品的 ²⁷Al MAS NMR谱图

Figure 3 ²⁷Al MAS NMR spectra of different Al₂O₃ and WO_x/Al₂O₃ samples

a: Al₂O₃-300; b: Al₂O₃-600; c: Al₂O₃-700; d: Al₂O₃-800; e: WO_x/Al₂O₃-600; f: WO_x/Al₂O₃-700; g: WO_x/Al₂O₃-800; h: WO_x/Al₂O₃-850

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图 4 催化剂的Raman吸收光谱谱图

Figure 4 Raman spectra of the catalysts

a: WO_x/Al₂O₃-600; b: WO_x/Al₂O₃-700; c: WO_x/Al₂O₃-800; d: WO_x/Al₂O₃-850

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图 5 不同WO_x/Al₂O₃载体的紫外-可见吸收光谱谱图（a）；根据紫外-可见吸收光谱谱图得到的禁带宽度（b）

Figure 5 UV-vis absorption spectra of different WO_x/Al₂O₃ supports (a); Electronic edge values based on UV-vis spectra (b)

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图 6 Al₂O₃载体的SEM照片和不同催化剂的HR-TEM照片及粒径分布

Figure 6 SEM image of Al₂O₃ support (a); HR-TEM images and particle size distribution of differentcatalysts(b), (d) WO_x/Al₂O₃-800; (c), (e) Pt-WO_x/Al₂O₃-800

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图 7 Pt-WO_x/Al₂O₃-800催化剂的EDS表征

Figure 7 EDS of Pt-WO_x/Al₂O₃-800 catalyst

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图 8 Pt/Al₂O₃和Pt-WO_x/Al₂O₃催化剂在不同载体热处理温度下的Pt分散度

Figure 8 Pt dispersion of Pt/Al₂O₃ and Pt-WO_x/Al₂O₃ catalysts at different support heat treatment temperatures

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图 9 不同催化剂的H₂-TPR谱图

Figure 9 H₂-TPR profiles of variouscatalysts

a: Pt/Al₂O₃; b: WO_x/Al₂O₃-800; c: Pt-WO_x/Al₂O₃-600; d: Pt-WO_x/Al₂O₃-700; e: Pt-WO_x/Al₂O₃-800; f: Pt-WO_x/Al₂O₃-850

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图 10 Pt-WO_x/Al₂O₃催化剂的吡啶吸收红外谱图

Figure 10 Py-FTIR spectra of pyridine adsorption of Pt-WO_x/Al₂O₃ catalysts

a: Pt-WO_x/Al₂O₃-600; b: Pt-WO_x/Al₂O₃-700; c: Pt-WO_x/Al₂O₃-800; d: Pt-WO_x/Al₂O₃-850; e: Pt-WO_x/Al₂O₃-800 (co-feeding H₂ with pyridine)

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图 11 Pt/Al₂O₃和Pt-WO_x/Al₂O₃催化剂的Pt 4d (a)和W 4f (b) XPS谱图

Figure 11 Pt 4d (a) and W 4f (b) XPS spectra of Pt/Al₂O₃ and Pt-WO_x/Al₂O₃ catalysts

a: Pt/Al₂O₃; b: Pt-WO_x/Al₂O₃-600; c: Pt-WO_x/Al₂O₃-700; d: Pt-WO_x/Al₂O₃-800; e: Pt-WO_x/Al₂O₃-850

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图 12 不同催化剂的Pt分散度与1,3-PDO收率之间的相关性

Figure 12 Correlation between Pt dispersion of different catalysts and the yield of 1,3-PDO

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表 1 载体和催化剂的物化性质

Table 1 Physico-chemical properties of the supports and the catalysts

Sample	A_BET/(m²·g⁻¹)	v_p/(cm³·g⁻¹)	d_p/nm	Pt content^a w/%	W content^b w/%
Al₂O₃	260	0.24	3.6	−	−
WO_x/Al₂O₃-800	82	0.45	19.3	−	−
Pt-WO_x/Al₂O₃-600	225	0.45	6.8	1.9	7.8
Pt-WO_x/Al₂O₃-700	176	0.50	9.4	2.0	8.1
Pt-WO_x/Al₂O₃-800	62	0.28	18.7	1.9	8.0
Pt-WO_x/Al₂O₃-850	103	0.38	14.1	2.1	7.4
A_BET: BET surface area; v_p: BJH pore volume; d_p: average pore diameter; ^a,b: Pt and W content is detected by ICP

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表 2 不同载体和催化剂中Al³⁺的配位态

Table 2 Coordination states of Al³⁺ in different supports and catalysts

Sample	Percentage of different coordinated Al³⁺ sites/%^a
Sample	${\rm{Al}}_{{\rm{octa}}}^{3 + } $	${\rm{Al}}_{{\rm{penta}}}^{3 + } $	${\rm{Al}}_{{\rm{tetra}}}^{3 + } $
Al₂O₃-300	59	22	17
Al₂O₃-600	53	24	23
Al₂O₃-700	65	10	25
Al₂O₃-800	69	0	31
WO_x/Al₂O₃-600	70	0	30
WO_x/Al₂O₃-700	68	0	32
WO_x/Al₂O₃-800	65	0	35
WO_x/Al₂O₃-850	63	0	37
^a: percentages of various coordination states are calculated according to the peak areas of different coordination Al³⁺ sites

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表 3 催化剂的甘油氢解制1,3-PDO反应性能

Table 3 Catalysis performance of catalysts in hydrogenolysis of glycerol to 1,3-PDO

Catalyst	Conversion/%	Selectivity/%				Selectivity ratio(1,3/ 1,2)
Catalyst	Conversion/%	1,3-PDO	1,2-PDO	1-PO	2-PO	Selectivity ratio(1,3/ 1,2)
Pt/Al₂O₃	5.5	3.4	50.0	2.1	0.2	0.07
Pt-WO_x/Al₂O₃-600	18.9	49.8	15.8	11.5	5.6	3.15
Pt-WO_x/Al₂O₃-700	56.8	53.8	6.1	19.8	9.1	8.82
Pt-WO_x/Al₂O₃-800	75.2	44.0	3.9	32.8	11.5	11.28
Pt-WO_x/Al₂O₃-850	54.9	40.2	4.9	28.4	9.6	8.20
reaction conditions: 160 ℃, 5.0 MPa, 10% GLY, glycerol aqueous solution (0.05 mL/min), 1,3-PDO: 1,3-propanediol, 1,2-PDO: 1,2-propanediol, 1-PO: 1-propanol, 2-PO: 2-propanol

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