Abstract
A series of Cu, Ni monometallic and bimetallic catalysts supported on γ-Al2O3 and activated carbon were synthesized by incipient wetness impregnation method and examined for hydrogenolysis and esterification of glycerol. Hydrogenolysis reaction was carried out in a 250 ml Teflon-coated stainless steel batch reactor at 250°C and 10 bar H2 pressure, whereas esterification of glycerol with acetic acid was carried out at 120°C at atmospheric pressure. The physiochemical properties of the catalysts were investigated by various techniques such as surface area, X-ray diffraction (XRD), NH3-temperature-programmed desorption (TPD). Characterization results dictated that the reduction behavior, acidic nature and the metal support interactions were varied with the support as well as Cu/Ni weight ratio. The XRD results confirmed the formation of mixed oxide Cu0.75Ni0.25 Al2O4 phase in Cu–Ni (3:1)/γ-Al2O3 catalyst. Among the catalysts tested, Cu–Ni bimetallic catalysts showed superior performance as compared to monometallic catalysts in both the reactions. The glycerol hydrogenolysis activity of γ-Al2O3 supported Cu–Ni catalysts was higher than the activated carbon-supported catalysts. 1,2-PDO was obtained as the main hydrogenolysis product independent of the support as well as Cu/Ni weight ratio and its selectivity was in the range of 92.8–98.5%. The acidic nature of γ-Al2O3 and the mixed oxide (Cu0.75Ni0.25Al2O4) phase played an important role for hydrogenolysis activity. Cu–Ni (3:1)/γ-Al2O3 catalyst showed the maximum 1,2-PDO selectivity to 97% with 27% glycerol conversion after a reaction time of 5 h. On the other hand, Cu–Ni(1:3)/C catalyst showed the highest glycerol conversion of 97.4% for esterification and obtained selectivity to monoacetin, diacetin and triacetin were 26.1%, 67.2% and 6.5%, respectively.
Acknowledgment
The authors are grateful to DEAN, SRIC, Indian Institute of Technology Roorkee, Uttarakhand, India for supporting this work from SRIC-Fund under F.I.G (Scheme-A).
References
1. GoncalvesVL, PintoBP, SilvaJC, MotaCJ. Acetylation of glycerol catalyzed by different solid acids . Catal Today2008;133:673–7.10.1016/j.cattod.2007.12.037Search in Google Scholar
2. WerpyT, PetersenG. Top value added chemicals from biomass-results of screening for potential candidates from sugars and synthesis gas . US DOE Report, vol. 1, 2004.10.2172/15008859Search in Google Scholar
3. PagliaroM, RossiM. The future of glycerol: new usages for a versatile raw material. Cambridge: RSC Publishing, 2008.Search in Google Scholar
4. BehrA, EiltingJ, IrawadiK, LeschinskiJ, LindnerF. Improved utilisation of renewable resources: new important derivatives of glycerol . Green Chem2008;10:13–30.10.1039/B710561DSearch in Google Scholar
5. ZhouCH, BeltraminiJN, FanYX, LuGQ. Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals . Chem Soc Rev2008;37:527–49.10.1039/B707343GSearch in Google Scholar PubMed
6. ChaminandJ, DjakovitchL, GallezotP, MarionP. Glycerol hydrogenolysis on heterogeneous catalysts . Green Chem2004;6:359–61.10.1039/b407378aSearch in Google Scholar
7. DasariMA, KiatsimkulPP, SutterlinWR, SuppesGJ. Low pressure hydrogenolysis of glycerol to propylene glycol . Appl Catal A: Gen2005;281:225–31.10.1016/j.apcata.2004.11.033Search in Google Scholar
8. KusunokiY, MiyazawaT, KunimoriK, TomishigeK. Highly active metal–acid bifunctional catalyst system for hydrogenolysis of glycerol under mild reaction conditions . Catal Commun2005;6:645–9.10.1016/j.catcom.2005.06.006Search in Google Scholar
9. FurikadoI, MiyazawaT, KosoS, ShimaoA, KunimoriK, TomishigeK. Catalytic performance of rh/SiO2 in glycerol reaction under hydrogen . Green Chem2007;9:582–8.10.1039/b614253bSearch in Google Scholar
10. MarisEP, DavisRJ. Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts . J Catal2007;249:328–37.10.1016/j.jcat.2007.05.008Search in Google Scholar
11. MiyazawaT, KosoS, KuminoriK, TomishigeK. Development of a Ru/C catalyst for glycerol hydrogenolysis in combination with an ion-exchange resin . Appl Catal A: Gen2007;318:244–51.10.1016/j.apcata.2006.11.006Search in Google Scholar
12. MiyazawaT, KosoS, KunimoriK, TomishigeK. Glycerol hydrogenolysis to 1,2-propanediol catalyzed by a heat resistant ion-exchange resin combined with Ru/C . Appl Catal A: Gen2007;329:30–5.10.1016/j.apcata.2007.06.019Search in Google Scholar
13. WangS, LiuH. Selective hydrogenolysis of glycerol to propylene glycol on Cu–ZnO catalysts . Catal Lett2007;117:62–7.10.1007/s10562-007-9106-9Search in Google Scholar
14. AlhanashA, KozhevnikovaEF, KozhevnikovIV. Hydrogenolysis of glycerol to propanediol over Ru: polyoxometalate bifunctional catalyst . Catal Lett2008;120:307–11.10.1007/s10562-007-9286-3Search in Google Scholar
15. MaL, HeD, LiZ. Promoting effect of rhenium on catalytic performance of Ru catalysts in hydrogenolysis of glycerol to propanediol . Catal Commun2008;9:2489–95.10.1016/j.catcom.2008.07.009Search in Google Scholar
16. SatoS, AkiyamaM, TakahashiR, HaraT, InuiK, YokotaM. Vapor-phase reaction of polyols over copper catalysts . Appl Catal A: Gen2008;347:186–91.10.1016/j.apcata.2008.06.013Search in Google Scholar
17. BalarajuM, RekhaV, PrasadPS, Prabhavathi DeviBL, PrasadRB, LingaiahN. Selective hydrogenolysis of glycerol to 1, 2-propanediol over Cu–ZnO catalysts . Appl Catal A: Gen2009;354:82–7.Search in Google Scholar
18. VasiliadouES, HeracleousE, VasalosIA, LemonidouAA. Ru-based catalysts for glycerol hydrogenolysis-effect of support and metal precursor . Appl Catal B: Environ2009;92:90–9.10.1016/j.apcatb.2009.07.018Search in Google Scholar
19. GandariasI, AriasPL, RequiesJ, GuemezMB, FierroJL. Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: the role of acid and metal active sites on product selectivity and the reaction mechanism . Appl Catal B: Environ2010;97:248–56.10.1016/j.apcatb.2010.04.008Search in Google Scholar
20. GongL, LuY, DingY, LinR, LiJ, DongW, et al. Selective hydrogenolysis of glycerol to 1,3-propanediol over a Pt/WO3/TiO2/SiO2 catalyst in aqueous media . Appl Catal A: Gen2010;390:119–26.10.1016/j.apcata.2010.10.002Search in Google Scholar
21. RoyD, SubramaniamB, ChaudhariRV. Aqueous phase hydrogenolysis of glycerol to 1,2-propanediol without external hydrogen addition . Catal Today2010;156:31–7.10.1016/j.cattod.2010.01.007Search in Google Scholar
22. ShinmiY, KosoS, KubotaT, NagakawaY, TomishigeK. Modification of Rh/SiO2 catalyst for the hydrogenolysis of glycerol in water . Appl Catal B: Environ2010;94:318–26.10.1016/j.apcatb.2009.11.021Search in Google Scholar
23. HamzahN, NordinNM, NadzriAH, NikYA, KassimMB, YarmoMA. Enhanced activity of Ru/TiO2 catalyst using bisupport, bentonite-TiO2 for hydrogenolysis of glycerol in aqueous media . Appl Catal A: Gen2012;419:133–41.10.1016/j.apcata.2012.01.020Search in Google Scholar
24. PerosaA, TundoP. Selective hydrogenolysis of glycerol with Raney Nickel . Ind Eng Chem Res2005;44:8535–7.10.1021/ie0489251Search in Google Scholar
25. GandariasI, AriasPL, RequiesJ, DoukkaliME, GüemezMB. Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under nitrogen pressure using 2-propanol as hydrogen source . J Catal2011;282:237–47.10.1016/j.jcat.2011.06.020Search in Google Scholar
26. GandariasI, RequiesJ, AriasPL, ArmbrusterU, MartinA. Liquid-phase glycerol hydrogenolysis by formic acid over Ni–Cu/Al2O3 catalysts . J Catal2012;290:79–89.10.1016/j.jcat.2012.03.004Search in Google Scholar
27. MeleroJA, Van GriekenR, MolaresG, PaniaguaM. Acidic mesoporous silica for the acetylation of glycerol: synthesis of bioadditives to petrol fuel . Energy Fuels2007;21:1782–91.10.1021/ef060647qSearch in Google Scholar
28. LiaoX, ZhuY, WangSG, LiY. Producing triacetylglycerol with glycerol by two steps: esterification and acetylation . Fuel Process Technol2009;90:988–93.10.1016/j.fuproc.2009.03.015Search in Google Scholar
29. FerreiraP, FonsecaIM, RamosAM, VitalJ, CastanheiroJE. Esterification of glycerol with acetic acid over dodecamolybdophosphoric acid encaged in USY zeolite . Catal Commun2009;10:481–4.10.1016/j.catcom.2008.10.015Search in Google Scholar
30. FerreiraP, FonsecaIM, RamosAM, VitalJ, CastanheiroJE. Glycerol acetylation over dodecatungstophosphoric acid immobilized into a silica matrix as catalyst . Appl Catal B: Environ2009;91:416–22.10.1016/j.apcatb.2009.06.009Search in Google Scholar
31. JagadeeswaraiahK, BalarajuM, Sai PrasadPS, LingaiahN. Selective esterification of glycerol to bioadditives over heteropoly tungstate supported on Cs-containing zirconia catalysts . Appl Catal A: Gen2010;386:166–70.10.1016/j.apcata.2010.07.046Search in Google Scholar
32. FerreiraP, FonsecaIM, RamosAM, VitalJ, CastanheiroJE. Acetylation of glycerol over heteropolyacids supported on activated carbon . Catal Commun2011;12:573–6.10.1016/j.catcom.2010.11.022Search in Google Scholar
33. RodríguezID, AdrianyC, GaigneauxEM. Glycerol acetylation on sulphated zirconia in mild conditions . Catal Today2011;167:56–63.10.1016/j.cattod.2010.11.057Search in Google Scholar
34. TrejdaM, StawickaK, DubinskaA, ZiolekM. Development of niobium containing acidic catalysts for glycerol esterification . Catal Today2012;187:129–34.10.1016/j.cattod.2011.10.033Search in Google Scholar
35. KhayoonMS, HameedBH. Synthesis of hybrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives . Appl Catal A: Gen2012;433–434:152–61.10.1016/j.apcata.2012.05.013Search in Google Scholar
36. XuJ, YuW, MaH, WangF, LuF, GhavreM, et al. Catalytic conversion of glycer--ol. In: XieH, GathergoodN, editors. The role of green chemistry in biomass processing and conversion. Hoboken, NJ: John Wiley & Sons, Inc, 2011:357.Search in Google Scholar
37. HuS, LuoX, WanC, LiY. Characterization of crude glycerol from biodiesel plants . J Agric Food Chem2012;60:5915−21.10.1021/jf3008629Search in Google Scholar
38. HierlR, KnozingerH, UrbachHP. Surface properties and reduction behavior of calcined CuO/Al2O3 and CuO-NiO/Al2O3 catalysts . J Catal1981;69:475–86.10.1016/0021-9517(81)90183-4Search in Google Scholar
39. WangX, PanX, LinR, KouS, JouW, MaJX. Steam reforming of dimethyl ether over Cu–Ni/γ-Al2O3 bi-functional catalyst prepared by deposition–precipitation method . Int J Hydrogen Energy2010;35:4060–8.10.1016/j.ijhydene.2010.01.142Search in Google Scholar
40. LiuY, LiuD. Study of bimetallic Cu–Ni/γ-Al2O3 catalysts for carbon dioxide hydrogenation . Int J Hydrogen Energy1999;24:351–4.10.1016/S0360-3199(98)00038-XSearch in Google Scholar
41. AriasAM, GarciaMF, BallesterosV, SalamancaLN, ConesaJC, OteroC, et al. Characterization of high surface area Zr-Ce (1:1) mixed oxide prepared by a microemulsion method . Langmuir1999;15:4796–802.10.1021/la981537hSearch in Google Scholar
42. DandekarA, BakerRT, VanniceMA. Carbon-supported copper catalysts I. characterization . J Catal1999;183:131–54.10.1006/jcat.1999.2390Search in Google Scholar
43. RaoRS, BakerRT, VanniceMA. Furfural hydrogenation over carbon-supported copper . Catal Lett1999;60:51–7.Search in Google Scholar
44. LiuZ, ZhouR, ZhengX. Comparative study of different methods of preparing CuO-CeO2 catalysts for preferential oxidation of CO in excess hydrogen . J Mol Catal A: Chem2007;267:137–42.10.1016/j.molcata.2006.11.036Search in Google Scholar
45. MeherLC, GopinathR, NaikSN, DalaiAK. Catalytic hydrogenolysis of glycerol to propylene glycol over mixed oxides derived from a hydrotalcite-type precursor . Ind Eng Chem Res2009;48:1840–6.10.1021/ie8011424Search in Google Scholar
46. YuanZ, WuP, GaoJ, LuX, HouZ, ZhengX. Pt/solid-base: a predominant catalyst for glycerol hydrogenolysis in a base-free aqueous solution . Catal Lett2009;130:261–5.10.1007/s10562-009-9879-0Search in Google Scholar
47. BalarajuM, RekhaV, PrasadPS, PrasadRB, LingaiahN. Selective hydrogenolysis of glycerol to 1, 2-propanediol over Cu–ZnO catalysts . Catal Lett2008;126:119–24.10.1007/s10562-008-9590-6Search in Google Scholar
48. HaoSL, PengWC, ZhaoN, XiaoFK, WeiW, SunYH. Hydrogenolysis of glycerol to 1,2-propanediol catalyzed by Cu-H4SiW12O40/Al2O3 in liquid phase . J Chem Technol Biotechnol2010;85:1499–503.10.1002/jctb.2456Search in Google Scholar
49. HuangZ, CuiF, KangH, ChenJ, ZhangX, XiaC. Highly dispersed silica-supported copper nanoparticles prepared by precipitation-gel method: a simple but efficient and stable catalyst for glycerol hydrogenolysis . Chem Mater2008;20:5090–9.10.1021/cm8006233Search in Google Scholar
50. YuanZ, WangJ, WangL, XieW, ChenP, HouZ, et al. Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts . Biores Technol2010;101:7088–92.10.1016/j.biortech.2010.04.016Search in Google Scholar PubMed
51. GuoL, ZhouJ, MaoJ, GuoX, ShuguangZ. Supported cu catalysts for the selective hydrogenolysis of glycerol to propanediols . Appl Catal A: Gen2009;367:93–8.10.1016/j.apcata.2009.07.040Search in Google Scholar
52. VilaF, GranadosML, OjedaM, FierroJL, MariscalR. Glycerol hydrogenolysis to 1,2-propanediol with Cu/γ-Al2O3: effect of the activation process . Catal Today2012;187:122–8.10.1016/j.cattod.2011.10.037Search in Google Scholar
53. ManeRB, HengneAM, GhalwadkarAA, VijayanandS, MohitePH, Pot-darHS, et al. Cu:Al nano catalyst for selective hydrogenolysis of glycerol to 1,2-propanediol . Catal Lett2010;135:141–7.10.1007/s10562-010-0276-5Search in Google Scholar
54. YadavGD, ChandanPA, DevendraPT. Hydrogenolysis of glycerol to 1,2-propanediol over nano-fibrous Ag-OMS-2 catalysts . Ind Eng Chem Res2012;51:1549–62.10.1021/ie200446ySearch in Google Scholar
55. MontassierC, DumasJM, GrangerP, BarbierJ. Deactivation of supported copper based catalysts during polyol conversion in aqueous phase . Appl Catal A: Gen1995;121:231–44.10.1016/0926-860X(94)00205-3Search in Google Scholar
56. YuanZ, WangL, WangJ, XiaS, ChengP, HouZ, et al. Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts . Appl Catal B: Environ2011;101:431–40.10.1016/j.apcatb.2010.10.013Search in Google Scholar
©2014 by De Gruyter