Citation: XIAO Zhu-qian, MAO Jian-wei, JI Jian-bing, SHA Ru-yi, FAN Yu, XING Chuang. Preparation of nano-scale nickel-tungsten catalysts by pH value control and application in hydrogenolysis of cellulose to polyols[J]. Journal of Fuel Chemistry and Technology, ;2017, 45(6): 641-650. shu

Preparation of nano-scale nickel-tungsten catalysts by pH value control and application in hydrogenolysis of cellulose to polyols

XIAO Zhu-qian ^1,2 ,
MAO Jian-wei ^1,2,*,, ,
JI Jian-bing ³ ,
SHA Ru-yi ^1,2 ,
FAN Yu ^1,2 ,
XING Chuang ^1,2

1.
Zhejiang Provincial Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing, Hangzhou 310023, China
2.
Zhejiang Provincial Key Laboratory of Chemical and Biological Processing Technology of Farm Products, Hangzhou 310023, China
3.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Corresponding author: MAO Jian-wei, zjhzmjw@163.com
Received Date: 10 February 2017
Revised Date: 7 April 2017

Fund Project: Scientific Research Project of Zhejiang Provincial Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing 2016KF0035Science and Technology Project of Zhejiang Province 2017C37049

Figures(9)

The Ni-W/SBA-15 catalysts prepared by incipient-wetness impregnation method and controlled by the pH value were developed. Potassium hydroxide and citric acid regarded as the pH value regulators were added to the solution before impregnation to provide an acidic or basic condition at different pH values (0.83, 1.00, 3.09, 5.00, 7.03, 8.97 and 11.0). The 74.5% yield of total low carbon (C_{2, 3}) polyols including ethylene glycol (EG), 1, 2-propylene glycol (1, 2-PG) and glycerol (Gly) was obtained over 10%Ni-20%W/SBA-15 catalyst prepared at pH value of 1.00 and 518 K under H₂ pressure of 5.0 MPa. Furthermore, the physical properties of this series of nickel-tungsten catalysts were characterized by BET and SEM. The results demonstrated that the catalysts showed excellent thermal stability and the surface area was mainly in range of 330-450 m²/g. The particles had a good dispersion on the surface of SBA-15 but some aggregations were existed which could be characterized by TEM and SEM-EDX. However, the reduction of metallic oxides especially for NiO was obviously influenced by pH value control and some metallic species characterized by XRD. According to XRD results, the impregnation pH value influenced the reduction of NiO and the phase states of nickel and tungsten species.
- cellulose,
- hydrogenolysis,
- pH value control,
- nickel-tungsten catalysts,
- polyols
1. [1]
  JUBEN N C, GEORGE W H, JAMES A D. Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbon to fuels and chemicals[J]. Angew Chem Int Ed, 2007,46(38):7164-7183. doi: 10.1002/(ISSN)1521-3773
2. [2]
  YABUSHITA M, KOBAYASHI H, FUKUOKA A. Catalytic transformation into platform chemicals[J]. Appl Catal B:Environ, 2014,145(1):1-9.
3. [3]
  SCHWARTZ T J, O'NEILL B J, SHANKS B H, DUMESIC J A. Bridging the chemical and biological catalysis gap:Challenges and outlook for producing sustainable chemicals[J]. ChemInform, 2014,45(31):2060-2069.
4. [4]
  WANGA Q, ZHANG T. One-pot conversion of cellulose to ethylene glycol with multi-functional tungsten-based catalysts[J]. Accounts Chem Res, 2013,46(7):1377-1386. doi: 10.1021/ar3002156
5. [5]
  JI N, ZHENG M Y, WANG A Q, ZHANG T, CHEN J G. Ni-promoted tungsten carbide for cellulose conversion:Effect of preparation methods[J]. ChemSusChem, 2012,5(5):939-944. doi: 10.1002/cssc.201100575
6. [6]
  PANG J F, ZHENG M Y, WANG A Q, ZHANG T. Catalytic hydrogenation of corn stalk to ethylene glycol and 1, 2-propylene glycol[J]. Ind Eng Chem Res, 2011,50(11):6601-6608. doi: 10.1021/ie102505y
7. [7]
  ABDEL-AZIM S M, ABOUL-GHEIT A K, AHMED S M, EL-DSOUKI D S, ABDEL-MOTTALEB M S. Preparation and application of mesoporous nanotitania photocatalysts using different templates and pH media[J]. Int J Photoenergy, 2014,2014(5):1-6.
8. [8]
  BAE J W, LEE Y J, PARK J Y, JUN K W. Influence of pH of the impregnation solution on the catalytic properties of Co/γ-alumina for Fischer-Tropsch synthesis[J]. Energy Fuels, 2008,22(5):2885-2891. doi: 10.1021/ef800155v
9. [9]
  HUANG Y P, DONG X Q, YU Y Z. The influence of surface xygen and hydroxyl groups on the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate on pure Pd(100):A DET study[J]. Appl Surf Sci, 2016,388(12):455-460.
10. [10]
  LI G N, PIDKO E A, HENSEN J M. A periodic DFT study of glucose to fructose isomerization on tungstite (WO₃ center dot H₂O):Influence of group Ⅳ-Ⅳ dopants and cooperativity with hydroxyl groups[J]. ACS Catal, 2016,6(7):4162-4169. doi: 10.1021/acscatal.6b00869
11. [11]
  ENGELBREKT C, MALCHO P, ANDERSEN J, ZHANG L J, STAHL K, LI B, HU J, ZHANG J D. Selective synthesis of clinoatacammite Cu₂(OH)₃Cl and tenorite CuO nanoparticle by pH control[J]. J Nanopart Res, 2014,16(8):2562-2574. doi: 10.1007/s11051-014-2562-4
12. [12]
  LIU Q Y, LIAO Y H, WANG T J, CAI C L, ZHANG Q, TSUBAKI N, MA L L. One-pot transformation of cellulose to sugar alcohols over acidic metal phosphates combined with Ru/C[J]. Ind Eng Chem Res, 2014,53(32):12655-12664. doi: 10.1021/ie5016238
13. [13]
  SUN R Y, ZHENG M Y, PANG J F, LIU X, WANG J H, PAN X L, WANG A Q, WANG X D, ZHANG T. Selectivity-switchable conversion of cellulose to glycols over Ni-Sn catalysts[J]. ACS Catal, 2016,6(1):191-201. doi: 10.1021/acscatal.5b01807
14. [14]
  XIAO Z Q, GE Q W, XING C, JIANG C J, FANG S, JI J B, MAO J W. Self-reducing bi-functional Ni-W/SBA-15 catalyst for cellulose hydrogenolysis to low carbon polyols[J]. J Energy Chem, 2015,25(3):434-444.
15. [15]
  KOSMULSKI M. The pH-dependent surface charging and points of zero charge[J]. J Colloid Interf Sci, 2011,353(1):1-5. doi: 10.1016/j.jcis.2010.08.023
16. [16]
  NGUYEN VAN T D, SUFIAN S, MANSOR N, YAHYA N. Characterization of carbon nanofibers treated with thermal nitrogen as a catalyst support using point of zero charge analysis[J]. J Nanomater, 2014,2014(12):1-6.
17. [17]
  LI H, FANG Z, LUO J, YANG S. Direct conversion of biomass components to the bio-fuel methyl levulinate catalyzed by acid-base bi-functional zirconia-zeolites[J]. Appl Catal B:Environ, 2017,200:182-191. doi: 10.1016/j.apcatb.2016.07.007
18. [18]
  ZHU S H, GAO X Q, ZHU Y L, ZHU Y F, ZHENG H Y, LI Y G. Promoting effect of boron oxide on Cu/SiO₂ catalyst for glycerol hydrogenolysis to 1, 2-peopanediol[J]. J Catal, 2013,303(7):70-79.
19. [19]
  FABICOVICOVA K, LUCAS M, CLAUS P. From microcrystalline cellulose to hard-and softwood-based feedstocks:Their hydrogenolysis to polyols over a highly efficient ruthenium-tungsten catalyst[J]. Green Chem, 2015,17(5):3075-3083. doi: 10.1039/C5GC00421G
20. [20]
  PAN G Y, MA Y L, MA X X, SUN Y G, LV J M, ZHANG J L. Catalytic hydrogenation of corn stalk into polyols over Ni-W/MCM-41 catalyst[J]. Chem Eng J, 2016,299(1):386-392.
21. [21]
  SUAREZ-TORILLO V A, SANTOLALLA-VARGAS C E, DE LOS REYES J A, VAZQUEZ-ZAVALA A, VRINAT M, GEANTET C. Influence of the solution pH in impregnation with citric acid and activity of Ni/W/Al₂O₃ catalysts[J]. J Mol Catal A:Chem, 2015,404-405(s):36-46.
22. [22]
  LI Y P, LIAO Y H, CAO X F, WANG T J, MA L L, LONG J X, LIU Q Y, XUA Y. Advances in hexitol and ethylene glycol production by one-pot hydrolytic hydrogenation and hydrogenolysis of cellulose[J]. Bio Bioenergy, 2015,74(1):148-161.
23. [23]
  LEE S, ZHANG Z T, WANG X M, PFEFFERLE L D, HALLER G L. Characterization of multi-walled carbon nanotubes catalyst supports by point of zero charge[J]. Catal Today, 2011,164(1):68-73. doi: 10.1016/j.cattod.2010.10.031
24. [24]
  CAO Y L, WANG J W, KANG M Q, ZHU Y L. Efficient synthesis of ethylene glycol from cellulose over Ni-WO₃/SBA-15 catalyst[J]. J Mol Catal A Chem, 2014,381:46-53. doi: 10.1016/j.molcata.2013.10.002
25. [25]
  ZHENG M Y, WANG A Q, JI N, PANG J F, WANG X D, ZHANG T. Transition metal-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol[J]. ChemSusChem, 2010,3(1):63-66. doi: 10.1002/cssc.v3:1
26. [26]
  SUN R Y, ZHENG M Y, PANG J F, LIU X, WANG J H, PAN X L, WANG A Q, WANG X D, ZHANG T. Selectivity-switchable conversion of cellulose yo glycols over Ni-Sn catalysts[J]. ACS Catal, 2016,6(1):191-201. doi: 10.1021/acscatal.5b01807
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