活性炭负载Pt-Ni双金属催化剂上甘油水溶液原位加氢反应性能

doi:10.7503/cjcu20150857

摘要/Abstract

摘要：

采用KBH₄液相还原法制备了系列活性炭(AC)负载的Pt-M(M=Fe, Ni, Co, Zn, Cu)双金属催化剂, 考察了该系列催化剂对甘油水溶液原位加氢制备1,2-丙二醇反应的催化性能. 结果表明, 当Pt负载量(质量分数)为2.0%, Pt/Ni质量比为1∶1时, 在220 ℃和1.0 MPa氮气压力下反应8 h, 2%Pt-2%Ni/AC催化剂上甘油转化率和1,2-丙二醇选择性分别达到98.7%和60.5%; 且在5次重复使用过程中, 催化剂保持较高的稳定性. 采用氮气物理吸附-脱附实验、 X 射线衍射(XRD)、透射电子显微镜(TEM)、选区电子衍射(SAED)及X射线光电子能谱(XPS)等对催化剂的结构和形貌进行了表征. 结果表明, 粒径约为2 nm的纳米颗粒在活性炭载体上均匀分散, 纳米粒子中金属多以还原态形式存在, Ni原子进入Pt晶格中形成的Pt-Ni物种使Pt与Ni之间表现出强相互作用力. 通过比较Pt/AC, Ni/AC与Pt-Ni/AC双金属催化剂的催化性能, 推断Pt能够促进甘油水溶液重整而Ni有利于氢解反应, Pt-Ni金属间协同作用是Pt-Ni/AC催化剂对甘油原位加氢反应具有优良催化性能的重要原因.

关键词: 甘油水溶液, 原位加氢, 双金属催化剂, 液相还原, 1, 2-丙二醇

Abstract:

A series of activated carbon supported Pt-M(M=Fe, Ni, Co, Zn, Cu) bimetallic catalysts was prepared via KBH₄ reduction method for glycerol in situ hydrogenolysis to produce 1,2-propanediol. The results showed that Pt-Ni/AC catalyst with a Pt loading(mass fraction) of 2.0% and a Pt/Ni mass ratio of 1∶1 displayed excellent performance at 220 ℃ under 1.0 MPa of N₂ after 8 h reaction time, with a high selectivity of 60.5% and a conversion of 98.7%. In addition, the prepared Pt-Ni/AC had a good catalytic stability, which kept a high activity even after five cycles catalytic evaluation. The results from the characterization of catalysts by N₂ physisorption, XRD, TEM and XPS indicated that nanoparticles with an average size of ca. 2 nm were uniformly dispersed on the support. And the majority of metals in nanoparticles are present in the zerovalent metallic state. The formation of Pt-Ni phase due to the incorporation of Ni in the Pt lattice was responsible for the strong interaction between Pt and Ni metal. The catalytic performance of Pt-Ni/AC was compared with that of Pt/AC and Ni/AC, it was clearly observed that Pt could promote the aqueous phase reforming of glycerol to hydrogen, and Ni could facilitate the hydrogenolysis of glycerol. The unique perfor-mance of Pt-Ni/AC bimetallic catalysts was attribute to the the synergistic effect between Pt and Ni.

Key words: Glycerol aqueous solution, In situ hydrogenolysis, Bimetallic catalyst, Liquid phase reduction, 1, 2-Propanediol

中图分类号:

O643

TrendMD:

孔丹旎, 江涛, 张一颖, 曹发海. 活性炭负载Pt-Ni双金属催化剂上甘油水溶液原位加氢反应性能. 高等学校化学学报, 2016, 37(6): 1140.

KONG Danni, JIANG Tao, ZHANG Yiying, CAO Fahai. Catalytic Performance of Activated Carbon Supported Pt-Ni Bimetallic Catalyst for Glycerol in situ Hydrogenolysis^†. Chem. J. Chinese Universities, 2016, 37(6): 1140.

图/表 11

Table 1 Physicochemical property of Pt-M/AC catalysts

Catalyst	Specific surface area^a/(m²·g^-1)	Pore volume^a/(cm³·g^-1)	Average pore diameter^a/nm	Mean particle size^b/nm
AC	806	0.53	5.3
Pt-Fe/AC	783	0.45	5.1	2.3
Pt-Ni/AC	768	0.49	5.1	2.1
Pt-Co/AC	763	0.51	5.2	2.3
Pt-Zn/AC	691	0.52	5.2	2.3
Pt-Cu/AC	523	0.49	4.7	4.9

Fig.1 XRD patterns of the Pt-M/AC catalysts before(A) and after(B) reactiona. AC; b. Pt/AC; c. Pt-Ni/AC; d. Pt-Co/AC; e. Pt-Fe/AC; f. Pt-Zn/AC; g. Pt-Cu/AC.

Fig.2 TEM image(A), HRTEM image(B) and particle size distribution(C) of Pt-Ni/AC fresh catalystInset of (A): corresponding SAED pattern.

Fig.3 TEM image(A) and particle size distribution(B) of Pt-Ni/AC catalyst used for five times

Fig.4 XPS spectra of Pt4f(A) and Ni2p(B) for Pt-Ni/AC catalyst

Table 2 Glycerol in situ hydrogenolysis on different Pt-M/AC catalystsa

Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	Selectivity(%)
Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	1,2-PDO	EG	2-PO	1-PO	CH₄	CO₂	Others^b
2%Pt-2%Fe/AC	99.8	169.6	48.7	7.5	9.8	9.0	1.5	13.0	10.5
2%Pt-2%Ni/AC	98.3	167.0	60.5	9.1	9.9	7.8	1.1	10.5	1.1
2%Pt-2%Co/AC	94.2	159.9	60.1	6.9	10.5	9.5	0.5	10.4	2.1
2%Pt-2%Zn/AC	85.1	144.6	50.3	10.7	12.0	9.8	0.8	10.1	6.3
2%Pt-2%Cu/AC	54.7	92.9	58.5	12.2	9.1	3.1	0.1	2.6	14.4

Table 3 Glycerol in situ hydrogenolysis on Pt-Ni/AC catalysts with different mass ratios of Pt/Nia

Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	Selectivity(%)
Catalyst	Conversion(%)	Reaction rate/ (μmol·g^-1·min^-1)	1,2-PDO	EG	2-PO	1-PO	CH₄	CO₂	Others^b
2%Ni/AC	45.7	77.6	50.6	35.8	13.6	0	0	0	0
2%Pt/AC	80.5	136.7	45.1	4.6	15.4	14.2	2.9	14.9	2.9
1%Pt-1%Ni/AC	85.6	145.4	56.3	5.8	11.6	11.9	1.6	11.5	1.3
2%Pt-1%Ni/AC	93.0	158.0	60.9	8.2	10.6	5.6	1.0	12.6	1.1
5%Pt-1%Ni/AC	98.5	167.3	56.8	8.2	11.2	7.6	1.4	13.2	1.6
2%Pt-2%Ni/AC	98.3	167.0	60.5	9.1	9.9	7.8	1.3	10.3	1.1
2%Pt-3%Ni/AC	98.0	166.4	58.3	8.8	9.7	7.2	2.3	12.3	1.4
2%Pt-5%Ni/AC	97.8	166.1	57.8	9.4	9.3	7.1	2.7	12.1	1.6

Fig.5 Effect of reaction temperature on glycerol in situ hydrogenolysisReaction conditions: 0.2 g catalyst(2%Pt-2%Ni/AC), 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution, 8 h.

Fig.6 Effect of N2 pressure on glycerol in situ hydrogenolysisReaction conditions: 0.2 g catalyst(2%Pt-2%Ni/AC), 220 ℃, 15 g 10%(mass fraction) glycerol aqueous solution, 8 h.

Fig.7 Effect of reaction time on glycerol in situ hydrogenolysisReaction condition: 0.2 g catalyst(2%Pt-2%Ni/AC), 220 ℃, 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution

Fig.8 Reuse of Pt-Ni/AC catalyst for glycerol in situ hydrogenolysiReaction condition: 0.2 g catalyst(2%Pt-2%Ni/AC), 1.0 MPa N2 pressure, 15 g 10%(mass fraction) glycerol aqueous solution, 220 ℃, 8 h.

参考文献 27

[1]	Zhou C. H., Beltramini J. N., Fan Y. X., Lu G. Q., Chem. Soc. Rev., 2008, 37, 527—549
[2]	Dam J. T., Hanefeld D., Chem. Sus. Chem., 2011, 4, 1017—1034
[3]	Wang S., Yin K.H., Zhang Y. C., Liu H. C., ACS Catalysis, 2013, 3, 2112—2121
[4]	Yu W. Q., Zhao J., Ma H., Miao H., Song Q., Xua J., Appl. Catal. A, 2010, 383, 73—78
[5]	Kurosaka T., Maruyama H., Naribayashi I., Sasaki Y., Catal. Commun., 2008, 9, 1360—1363
[6]	Martin A., Armbruster U., Gandarias I., Arias P. L., Eur. J. Lipid Sci. Technol., 2013, 115, 9—27
[7]	D’Hondt E., de Vyver S. V., Sels B. F., Jacobs P. A.,Chem. Commun., 2008, 6011—6012
[8]	Roy D., Subramaniam B., Chaudhari R. V., Catal. Today, 2010, 156, 31—37
[9]	Yin A. Y., Guo X. Y., Dai W. L., Fan K. N., Green Chem., 2009, 11, 1514—1516
[10]	Barbelli M. L., Santori G. F., Nichio N. N., Bioresour. Technol., 2012, 111, 500—503
[11]	Meryemoglu B., Hesenov A., Irmak S., Atanur O. M., Erbatur O., Int. J. Hydrogen Energy, 2010, 35(22), 12580—12587
[12]	Venkateswara R. C., Viswanathan B., J. Phys. Chem. C, 2009, 113, 18907—18913
[13]	Antolini E., Salgado J. R. C., da Silva R. C., Gonzalez E. R., Mater. Chem. Phys., 2007, 101, 395—403
[14]	Hu Y. J., Wu P., Zhang H., Cai C. X., Electrochim. Acta, 2012, 85, 314—321
[15]	Zhao Y. C., Yang X. L., Tian J. N., Wang F. Y., Zhan L., Int. J. Hydrogen Energy, 2010, 35, 3249—3257
[16]	Kyung W. P., Jong H. C., Boo K. K., Seol A. L., Yung E. S., J. Phys. Chem. B, 2002, 106, 1869—1877
[17]	Dasari M. A., Kiatsimkul P. P., Sutterlin W. R., Suppes G. J., Appl. Catal. A, 2004, 281, 225—231
[18]	Wang S., Zhang D., Ma Y. Y., Zhang H., Gao J., Nie Y. T., Sun X. H., Appl. Mater. Interfaces, 2014, 6, 12429—12435
[19]	Wang Z. B., Zuo P. J., Wang G. J., Du C. Y., Yin G. P., J. Phys. Chem. C, 2008, 112, 6582—6587
[20]	Gao J., Hou Z. Y., Liu X. S., Zeng Y. W., Luo M. F., Zheng X. M., Int. J. Hydrogen Energy, 2009, 34(9), 3734—3742
[21]	Zhang H., Yin Y. J., Hu Y. J., Li C.Y., Wu P., Wei S.H., Cai C. X., J. Phys. Chem. C, 2010, 114, 11861—11867
[22]	Liang Y. M., Zhang H. M., Zhong H. X., Zhu X. B., Tian Z. Q., Xu Q. Y., Yi B. L., J. Catal., 2006, 238, 468—476
[23]	Hu Y. J., He F. Y., Ben A. L., Chen C. Y., J. Electroanal. Chem., 2014, 726, 55—61
[24]	Mu R., Fu Q., Xu H., Zhang H., Huang Y.Y., Jiang Z., Zhang S., Tan D. L., Bao X. H., J. Am. Chem. Soc., 2011, 133,1978—1986
[25]	Jiang T., Huai Q., Geng T., Ying W. Y., Xiao T. C., Cao F. H., Biomass Bioenergy, 2015, 78, 71—79
[26]	Gordon D., Weather B., Calvin H., J. Catal., 1982, 77, 460—472
[27]	Feng J., Fu H. Y., Wang J. B., Li R. X., Chen H., Li X. J., Catal. Commun., 2008, 9, 1458—1464