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Citric Acid-Assisted Synthesis of Nanoparticle Copper Catalyst - Supported On An Oxide System For The Reduction of Furfural To - Furfuryl Alcohol in The Vapor Phase
Citric Acid-Assisted Synthesis of Nanoparticle Copper Catalyst - Supported On An Oxide System For The Reduction of Furfural To - Furfuryl Alcohol in The Vapor Phase
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Cite This: Ind. Eng. Chem. Res. 2018, 57, 1506−1515 pubs.acs.org/IECR
1. INTRODUCTION mental pollution because of its high toxic nature and its higher
In the present situation, there is a growing awareness for the temperature with pressurized conditions; these are the main
use of renewable feed stock and the development of new disadvantage of this catalyst.5,6,10 Presently there are several
catalytic processes for the preparation of fuel and fine research groups working on this reaction using various
chemicals. Furfural is one of the biomass derived starting metallics, such as Pt, Pd, Ru, Cu, Ni, Cu, Zn, Ca, Al, Na,
materials obtained from the rice husk and corn core, this was bimetallic, Pd−Cu, Cu−Co, Pt−Sn, and ultrafine amorphous
used for the production of various industrially important alloys Ni−P, Ni−B, Ni−P−B, Co−B, Fe(NiFe)O4, and Ni−
chemicals.1,2 Furfural [FAL] can used to produce furfuryl Fe−B. Cu−Al layered double hydroxide (LDH) and Cu on
alcohol [FOL] as an intermediate to the manufacture of lysine, different supports Cr2O3, Al2O3, SiO2, SBA-15, and CaO11−18
ascorbic acid, numerous lubricants,3,4 tetrahydrofurfuryl alco- used as catalysts for FAL hydrogenation has been reported,19
hol, 2-methylfuran, and tetrahydrofuran. The FOL was The reported catalytic systems involve the preparation of the
produced through the hydrogenation reaction using both catalyst in metal oxide form, and before the reaction occurs, the
vapor and liquid phase reactors. Among the various products, catalyst is to be reduced at harsh conditions with molecular
FOL finds a variety of applications in the chemical industry; it hydrogen for several hours. This process consumes much
was mainly used for the production of various synthetic resins, hydrogen and energy; the former is found to be the future
rubbers, fibers, and chemical resistant thermostatic resins which alternative energy.20−22
are used for strengthening ceramics, molds for metal castings, In the present study a catalyst is prepared by the simplest
impregnating solutions, and carbon binders. It is also used as a method and does not require further reduction before reaction,
solvent for furan resins, pigments, varnishes, and as rocket fuel. making it economically viable for sustainable development. It
Also important, it is an intermediate for the manufacture of shows smaller metallic Cu particles, and their maximum (111)
lysine, vitamin C, lubricants, dispersing agents, and plasti-
cizers.5−9 Received: November 13, 2017
In an industrial process copper chromite has been used Revised: December 22, 2017
commercially for the selective hydrogenation of furfural to Accepted: January 15, 2018
furfuryl alcohol. The presence of Cr6+ causes severe environ- Published: January 15, 2018
plane orientation on the surface showed deactivation free that, it was heated from 50 to 800 °C with a rate of 10 °C/min.
catalytic activity of the CZA-based catalysts for the FAL The amount of hydrogen consumed as a function of
hydrogenation to FOL under reduction-free conditions. temperature was monitored by a thermal conductivity detector
Various organic compounds as hydrogen sources such as (TCD) detector.
hydrazine, citric acid, and formic acid were used for in situ The XPS analyses were performed on a SSX 100/206
reduction of Cu, and the the prepared catalysts were photoelectron spectrometer from Surface Science Instruments
characterized by temperature programmed reduction (TPR), (USA) equipped with a monochromatized microfocused Al X-
high-resolution transmission electron spectroscopy (HRTEM), ray source (powered at 20 mA and 10 kV). The samples
scanning transmission electron microscopy (STEM), X-ray powder pressed in small stainless steel troughs of 4 mm
photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), diameter were placed on an aluminum conductive carousel.
Brunauer−Emmett−Teller (BET) surface area analysis, and The pressure in the analysis chamber was around 10−6 Pa, and
powder X-ray diffraction (pXRD). the pass energy was set at 150 eV. The C-(C,H) component of
the C 1s peak of carbon was fixed to 284.8 eV to set the binding
2. EXPERIMENTAL SECTION energy scale. Data treatment was performed with the Casa XPS
2.1. Materials. Furfural and furfuryl alcohol was procured program (Casa Software Ltd., UK), molar fractions were
from Sigma-Aldrich, India. Al(NO3)3·9H2O, Cu (NO3)2·3H2O, calculated using peak areas normalized on the basis of
and Zn(NO3)2·6H2O were purchased from SD fine chemicals. acquisition parameters and sensitivity factors provided by the
Hydrazine hydrate, citric acid, and formic acid were obtained manufacturer.
from Merck, India, and used without further purification. TEM images of the fresh and used catalysts were obtained by
2.2. Catalyst Preparation. The catalysts were prepared by using FEI TITAN3 80−300 kV aberration corrected trans-
taking 50 wt % of Cu(NO3)2, 20 wt % of Zn(NO3)2, and 30 wt mission electron microscope having both HRTEM and STEM-
% of Al(NO3)2. To this mixture, 70 wt % organic compounds Z contrast imaging facility.
was added and the mixture was ground well using mortar and Dispersion of metallic Cu atoms were determined by pulsed
pestle. The sample was then dried at 120 °C for 3 h and titration of N2O using BELCAT-2 TPX instrument Japan, the
calcined under inert gas atmosphere for 4 h at 300 °C (with a catalysts of 200 mg were placed in the quartz tube (reduced
ramp rate of 5°/min). After that, the sample was cooled to form). Helium gas was used as carrier gas at 10 mL min−1 and
room temperature by maintaining the N2 flow at 20 mL per the successive doses of 10% N2O/He gas were subsequently
min. The samples were stored in vacuum desiccator in airtight titered into the He stream by means of a calibrated injection
bottles. The samples were designated as CZA, CZAC, CZAH, valve (15 μL N2O pulse) at 60 °C temperature. The product
and CZAF for samples without organic compound, and with gases N2 and retained N2O were analyzed by TCD. The
citric acid, hydrazine hydrate, and formic acid, respectively. The amount of N2 and N2O was calibrated with the ZA sample,
CZA sample was reduced using H2 at 300 °C for 4 h and N2O consumption and N2 liberated were calculated, both
designated as CZAD. giving good agreement values within 1% error.
2.3. Catalyst Characterization. The prepared CZA Bulk Cu elemental analysis was carried out using a Horiba
samples using organic compounds were characterized using XGT X-ray fluorescence instrument. A Shimadzu IRAffinity-1
various techniques, such as XRD, BET, field emission scanning FT-IR instrument was used to record the spectra of the samples
electron microscopy (FE-SEM), TPR, XRF, Fourier transform by the KBr pellet method with 4.0 cm−1 resolution in the
infrared (FT-IR), HRTEM, STEM and XPS. wavenumber range 4000−500 cm−1 to study the presence of
Powder XRD measurements were performed for fresh and carbonaceous compounds in the catalysts after calcination
spent catalysts, the 2θ values were between 10−80° obtained by under N2 atmosphere. A complex formation was confirmed.
scanning at 2θ = 0.020° per step using a PAN alytical X’pert 2.4. Catalytic Activity Test. The vapor phase hydro-
PRO X-ray diffractometer with graphite monochromatized Cu genation of furfural was carried out in a fixed-bed down flow
Kα radiation source (λ = 1.5406 Å). The Debye−Scherrer quartz reactor (400 mm long and 20 mm inner diameter)
equation was used to estimate the mean Cu crystallite size under atmospheric pressure. The catalyst of 1.5 g was packed at
based on the diffraction peaks of the Cu (111) plane. the center of the reactor between the plugs of glass wool and
Surface and pore characteristics of the catalysts were the reactor was set to the desired reaction temperature (160−
measured using a Quanta Chrome Nova-1000 surface analyzer 280 °C). Furfural (LHSV 3.6 s−1) 1.8 mL/h was fed
under liquid nitrogen temperature. Prior to the measurements continuously from the syringe pump (model NE-1000) to a
sample were degassed at 300 °C for 4 h to remove preadsorbed vaporizer, the vapors formed were mixed with H2 gas with a
gas and moisture. The BET method was employed to measure ratio 15:1 of H2/furfural. This mixed gaseous stream was passed
the quantity of nitrogen absorbed, and the cumulative volumes through the reactor. The products were condensed in an ice-
of pores were obtained by the BJH method from the desorption cooled trap and analyzed by a chemito GC-1000 gas
isotherms. chromatograph with TR-WAX capillary column (30 m length,
Morphology of the samples was recorded using a JEOL JSM- 0.32 mm thickness, and 0.5 μm internal diameter) attached
6490 FESEM under high vacuum mode. with flame ionization detector. The calibration and quantifica-
The reducibility of the sample was determined using a tion of reactant (FAL) conversion and products (FOL, MF)
BELCAT-II Microtrac (made in Japan) temperature-pro- yield was made using standard samples purchased from Sigma
grammed reduction analyzer. The measurements were Aldrich, India.
performed by placing 50 mg of catalyst sample to the quartz
tube and ramping the temperature with a rate 10 °C/min, 3. RESULTS AND DDISCUSSION
under 20 mL/min of Ar up to 500 °C, and holding for 1 h. 3.1. Catalyst Characteristics. 3.1.1. Surface Character-
Then the sample was cooled to room temperature and a stream istics. Surface area and pore characteristics of CZA samples
of 10% H2/Ar was flushed with a flow rate of 20 mL/min. After were provided in Table1. The CZA sample prepared without
1507 DOI: 10.1021/acs.iecr.7b04701
Ind. Eng. Chem. Res. 2018, 57, 1506−1515
Industrial & Engineering Chemistry Research Article
Table 1. Surface Characteristics of the Prepared Catalysts 3.1.2. XRD Analysis. Powder X-ray diffraction patterns for all
the prepared catalysts are shown in Figure 2. The CZA catalyst
surface pore pore average TPR-H2
area volume diameter particle size consumption
catalyst (m2/g) (cm3/g) (Å) (nm) (mmol/g)
CZA 28.3 0.049 66 28 1.86
CZAC 48.3 0.083 54 14 0.13
CZAF 36.0 0.051 63 20 0.32
CZAH 38.0 0.061 62 20 0.45
Figure 3. HRTEM images of CZA samples: (A) CZA, (B) CZAC, (C) CZAF, and (D) CZAH.
Figure 5. STEM images of CZA and CZAC and SAED patterns of CZAC.
Figure 6. SEM images of (A) CZA, (B) CZAC, (C) CZAF, (D) CZAH, and (E) EDXA pattern of CZAC.
representing together with the absence of typical satellite peaks of small amount of unreduced species (Cu2O). The formic acid
at 940−945 eV for the Cu2+ species related to the unoccupied used may not be sufficient enough to reduce all the copper
3d states, the reduced copper species in the form of Cu and/or present in the catalyst species (it will produce the least amount
Cu+. CZAC samples give only a single sharp peak at 932.34 eV of hydrogen during calcination among the reducing agents
and the absence of a satellite peak confirms the presence of used). Hydrazine being a strong reducing agent, still resulted in
only Cu metallic species. However, CZAF samples showed an three kinds of copper being present after the calcination under
additional peak along with Cu species. There is a small peak inert atmosphere. The sample CZAH showed a broad peak
which is due to (deconvoluted peak at 933.34 eV) the presence which is in the range that falls to all three kinds of Cu species,
1510 DOI: 10.1021/acs.iecr.7b04701
Ind. Eng. Chem. Res. 2018, 57, 1506−1515
Industrial & Engineering Chemistry Research Article
Table 3. Conversion and Yield of Products under Different Catalysts for Hydrogenation of FALa
200 °C 240 °C
CZA CZAD CZAC CZAF CZAH CZA CZAD CZAC CZAF CZAH
FAL conversion (%) 34 80 88 78 75 38 86 91 84 83
yield (%) FOL 23 65 83 70 69 20 62 77 70 68
MF 11 10 05 08 06 08 16 11 12 10
furan 05 08 03 03 05
a
Reaction conditions: H2/FAL ratio = 3; atmospheric pressure, LHSV, 3.6 h−1.
Table 4. Correlation between the Different Factors with FAL Conversion and FOL Yield
catalysts surface area of Cu atoms (m2/g) average particle size (nm) % Cu dispersion ESHOa (103) FAL conversion FOL yield TOF (h−1)
CZA 11.71 28 18 5.90 34 23 14.6
CZAC 36.14 14 58 29.34 88 83 32.4
CZAF 24.57 20 39 21.50 78 70 26.3
CZAH 26.82 20 44 24.78 78 69 25.8
correlation r 0.98 0.94 0.96 0.999
a
ESHO: Efficiency surface H2 occupancy
particle influence on a higher surface area, and showed better 16.6 nm, which confirms deactivation free activity for more
catalytic activity for the FAL hydrogenation to yield FOL. than 30 h of reactants stream.
3.5. Characteristics of Used Catalysts. The used catalyst
sample was characterized to know the deactivation and stability 4. CONCLUSION
using XRD, N2-physisorption, and HRTEM. The results
showed stable and deactivation free catalytic activity. The The solid state dry synthesis of metallic copper on mixed oxides
XRD pattern (Figure 11) showed major peaks at 43.317 (111), using organic compound as reducing agents was reported. The
metal complexes decomposed during the calcination, produces
hydrogen which results in situ reduction of copper on the oxide
cluster surface. The structure and composition of organic the
compound used play an important role in morphology and
reduction behavior of the final catalyst. Citric acid-assisted
synthesis (CZAC) resulted in better dispersion of metallic
copper nanoparticles on mixed oxides with higher surface area.
The CZAC catalyst showed the best performance more than 30
h on-stream for the catalytic hydrogenation of furfural to
furfuryl alcohol with higher selectivity. The term efficiency
surface hydrogen occupancy (ESHO) was coined to correlate
the effect of metallic dispersion, particle size, and their surface
Figure 11. XRD pattern of (CZACR) used catalysts. area for the hydrogenation reaction; it showed a better
correlation coefficient. This can be extended to industrial
50.449 (200), and 74.126 (220) responsible for the Cu metallic catalysis. This method of synthesis showed to be less energetic
species and minor peaks for the CuO and Cu2O, which and more economic for industrial catalyst synthesis.
■
indicates that the catalyst retained almost all its characteristics
after use. The surface and pore characteristics measured by the ASSOCIATED CONTENT
BET method showed a slightly decreased surface area of 43 m2/
g with a pore volume of 0.076 cm3/g and average pore diameter * Supporting Information
S
of 53.12 Å. The HRTEM images of CZAC (Figure 12) showed The Supporting Information is available free of charge on the
some agglomeration of particles with increased particle size of ACS Publications website at DOI: 10.1021/acs.iecr.7b04701.
Figure 12. HRTEM images of (A) CZAC and (B) CZACR catalysts.
Comparison of different catalysts with our catalyst, UV− (13) Sitthisa, S.; Sooknoi, T.; Ma, Y.; Balbuena, P. B.; Resasco, D. E.
visible spectra of CZAs catalysts for the confirmation of Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2
catalysts. J. Catal. 2011, 277, 1−13.
complex formation and reaction mechanism (PDF) (14) Sitthisa, S.; Resasco, D. E. Hydrodeoxygenation of Furfural Over
■ AUTHOR INFORMATION
Corresponding Author
Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni.
Catal. Lett. 2011, 141, 784−791.
(15) Wu, J.; Shen, Y.; Liu, C.; Wang, H.; Geng, C.; Zhang, Z. Vapor
phase hydrogenation of furfural to furfuryl alcohol over environ-
*E-mail: venkatesha.312@gmail.com. Tel.: 9901003120. mentally friendly Cu-Ca/SiO2 catalyst. Catal. Commun. 2005, 6, 633−
ORCID 637.
(16) Chen, X.; Li, H.; Luo, H.; Qiao, M. Liquid phase hydrogenation
N. J. Venkatesha: 0000-0002-9091-9744 of furfural to furfuryl alcohol over Mo-doped Co-B amorphous alloy
Notes catalysts. Appl. Catal., A 2002, 233, 13−20.
The authors declare no competing financial interest. (17) Antunes, M. M.; Lima, S.; Neves, P.; Magalhaes, A. L.; Fazio, E.;
■
Fernandes, A.; Neri, F.; Silva, C. M.; Rocha, S. M.; Ribeiro, M. F.;
ACKNOWLEDGMENTS Pillinger, M.; Urakawa, A.; Valente, A. A. One-pot conversion of
furfural to useful bio-products in the presence of a Sn,Al-containing
The authors would like to thank the Rajya Vokkaligara Sangha zeolite beta catalyst prepared via post-synthesis routes. J. Catal. 2015,
and Principal of Bangalore Institute of Technology for the 329, 522−537.
facilities provided. The authors also extended their thanks to (18) Halilu, A.; Ali, T. H.; Atta, A. Y.; Sudarsanam, P.; Bhargava, S.
Prof. S. M. Shivaprasad, ICMS JNCASR, Mr. G. Vijaykumar K.; Abd Hamid, S. B. Highly Selective Hydrogenation of Biomass-
and Mr. Eranjaneya, Central College BUB, for XRD, Mr. Derived Furfural into Furfuryl Alcohol Using a Novel Magnetic
Srikanth, NCL Pune, for TPR measurements and Mr. M. Nanoparticles Catalyst. Energy Fuels 2016, 30, 2216−2226.
Shivakumar, BMSCE, for SEM. (19) Lee, S. P.; Chen, Y. W. Selective Hydrogenation of Furfural on
■
Ni−P, Ni−B, and Ni−P−B Ultrafine Materials. Ind. Eng. Chem. Res.
1999, 38, 2548−2556.
REFERENCES (20) Ramesh, S.; Venkatesha, N. J. Template Free Synthesis of Ni-
(1) Adam, J.; Blazso, M.; Meszaros, E.; Stocker, M.; Nilsen, M. H.; Perovskite: An Efficient Catalyst for Hydrogen Production by Steam
Bouzga, A.; Hustad, J. E.; Gronli, M.; Oye, G. Pyrolysis of biomass in Reforming of Bioglycerol. ACS Sustainable Chem. Eng. 2017, 5, 1339−
the presence of Al-MCM-41 type catalysts. Fuel 2005, 84, 1494−1502. 1346.
(2) He, R.; Ye, X. P.; English, B. C.; Satrio, J. A. Influence of pyrolysis (21) Yan, K.; Liao, J.; Wu, X.; Xie, X. A noble-metal free Cu-catalyst
condition on switchgrass bio-oil yield and physicochemical properties. derived from hydrotalcite for highly efficient hydrogenation of
Bioresour. Technol. 2009, 100, 5305−5311. biomass-derived furfural and levulinic acid. RSC Adv. 2013, 3,
(3) Luo, H. S.; Li, H. I.; Zhuang, L. Furfural Hydrogenation to 3853−3856.
Furfuryl Alcohol over a Novel Ni−Co−B Amorphous Alloy Catalyst. (22) Yfanti, V. L.; Vasiliadou, E. S.; Lemonidou, A. A. Glycerol
Chem. Lett. 2001, 30, 404−405. hydro-deoxygenation aided by in situ H2 generataion via methanol
(4) Audemar, M.; Ciotonea, C.; Vigier, K. O.; Royer, S.; Ungureanu, aqueous reforming over a Cu-ZnO-Al2O3 catalysts. Catal. Sci. Technol.
A.; Dragoi, B.; Dumitriu, E.; Jerome, F. Selective Hydrogenation of 2016, 6, 5415−5426.
Furfural to Furfuryl Alcohol in the Presence of a Recyclable Cobalt/ (23) Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans, J.;
SBA-15 Catalyst. ChemSusChem 2015, 8, 1885−1891. Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.; Sanz, J. F.;
(5) Kijenski, J.; Winiarek, P.; Paryjczak, T.; Lewicki, A.; Mikolajska, Rodriguez, J. A. Highly active copper-ceria and copper-ceria-titania
A. Platinum deposited on monolayer supports in selective hydro- catalysts for methanol synthesis from CO2. Science 2014, 345, 546−
genation of furfural to furfuryl alcohol. Appl. Catal., A 2002, 233, 171− 551.
182. (24) Petitjean, L.; Gagne, R.; Beach, E. S.; Xiao, D.; Anastas, P. T.
(6) Rao, R. S.; Baker, R. T. K.; Vannice, M. Furfural hydrogenation
Highly selective hydrogenation and hydrogenolysis using a copper-
over carbon-supported copper. Catal. Lett. 1999, 60, 51−57.
doped porous metal oxide catalyst. Green Chem. 2016, 18, 150−156.
(7) Thomas, D. Catalyst comprising Raney nickel with adsorbed
(25) Hu, Q.; Yang, L.; Fan, G.; Li, F. Hydrogenation of biomass-
molybdenum compound. U.S. Patent No. 4153578, 1979.
derived compounds containing a carbonyl group over a copper-based
(8) Leo, F. J.; Herman, F. J. Copper chromite catalyst for preparation
of furfuryl alcohol from furfural.U.S. Patent No. 4251396, 1981. nanocatalyst: Insight into the origin and influence of surface oxygen
(9) Elizaveta, P. A.; Juldash, M.; Ivan, P. P.; Lidia, G. G.; vacancies. J. Catal. 2016, 340, 184−195.
Jormukhamat, A. G.; Ildgam, B. A.; Aexei, D. M.; Larisa, C. J.; (26) Chanquia, C. M.; Sapag, K.; Rodriguez-Castellon, E.; Herrero, E.
Lazar, P. D.; Bassheva, B. B. Method for preparing furfuryl alcohol. R.; Eimer, G. A. Nature and Location of Copper Nanospecies in
U.S. Patent No. 4261905, 1981. Mesoporous Molecular Sieves. J. Phys. Chem. C 2010, 114, 1481−
(10) Rao, R.; Dandekar, A.; Baker, R. T. K.; Vannice, M. A. 1490.
Properties of Copper Chromite catalysts in hydrogenation reaction. J. (27) Lou, L. L.; Liu, S. X. CuO-containing MCM-48 as catalysts for
Catal. 1997, 171, 406−419. phenol hydroxylation. Catal. Commun. 2005, 6, 762−765.
(11) (a) Liu, H.; Hu, Q.; Fan, G.; Yang, L.; Li, F. Surface synergistic (28) Hao, X. Y. A novel approach to prepare MCM-41 supported
effect in well-dispersed Cu/MgO catalysts for highly efficient vapor- CuO catalyst with high metal loading and dispersion. Microporous
phase hydrogenation of carbonyl compounds. Catal. Sci. Technol. Mesoporous Mater. 2006, 88, 38−47.
2015, 5, 3960−3969. (b) Lesiak, H.; Binczarski, M.; Karski, S.; (29) Niu, X.; Zhao, T.; Yuan, F.; Zhu, Y. Preparation of hollow
Maniukiewicz, W.; Rogowski, J.; Szubiakiewicz, E.; Berlowska, J.; CuO@SiO2 spheres and its catalytic performances for the NO + CO
Dziugan, P.; Witonska, I. Hydrogenation of furfural over Pd−Cu/ and CO oxidation. Sci. Rep. 2015, 5, 9153.
Al2O3 catalysts. The role of interaction between palladium and copper (30) Valencia, D.; Klimova, T. Citric acid loading for MoS2-based
on determining catalytic properties. J. Mol. Catal. A: Chem. 2014, 395, catalysts supported on SBA-15. New catalytic materials with high
337−348. hydrogenolysis ability in hydrodesulfurization. Appl. Catal., B 2013,
(12) Vaidya, P. D.; Mahajani, V. V. Kinetics of Liquid-Phase 129, 137−145.
Hydrogenation of Furfuraldehyde to Furfuryl Alcohol over a Pt/C (31) Jimenez-Gomez, C. P.; Cecilia, J. A.; Martin, D. D.; Tost, R. M.;
Catalyst. Ind. Eng. Chem. Res. 2003, 42, 3881−3885. Gonzalez, J. S.; Robles, J. M.; Mariscal, R.; Torres, P. M. Gas-phase