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In order to promote hydrocarbon production and catalyst stability in catalytic fast pyrolysis (CFP) of
biomass, HZSM-5 catalysts were treated with alkali solutions to introduce mesopores into the
microporous system. Parent and hierarchical catalysts were tested in catalytic conversion of furan as an
important intermediate from biomass fast pyrolysis (BFP). Controlled desilication with mole
concentration of NaOH of 0.3 M resulted in sheet-like mesopores on the external sphere, enhancing
mass transfer in the catalyst, and it specifically promoted the carbon yield of hydrocarbons by 21.6%.
Though the coke content on these HZSM-5-0.3M catalysts increased gradually by 11.6%, the tolerance
Received 3rd December 2015
Accepted 20th April 2016
toward deactivation by coke deposition was improved. Cyclic tests of catalysis-regeneration process
over hierarchical HZSM-5-0.3M over 20 cycles revealed that it can withstand long-running with a stable
DOI: 10.1039/c6ra05356d
yield of hydrocarbons being achieved. Thus, hierarchical HZSM-5 is a suitable catalyst for CFP of biomass
www.rsc.org/advances and its derivatives to hydrocarbons by this simple synthetic process.
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template are burned away resulting in intracrystalline meso- using Cu Ka radiation at 40 kV and 40 mA with a scanning speed
pores in the zeolite.19 Some templates are very expensive, which of 0.02 min1 in the range of 5 # q # 80 .
determines its limited application in industry. Removal of silica Energy Dispersive Spectrometry (EDS) was used to determine
from the crystal framework with alkali solutions is an easily the element content, and then the Si/Al ratio was obtained,
operated method that may cause the appearance of meso- which conrmed that little Cl was le. EDS was performed on
porosity.20–22 Selective dissolving and removal of silica from the a Vantage IV system, Thermo Fisher Scientic, USA.
zeolite framework can be realized by alkaline treatment. Silica Nitrogen physisorption isotherms were measured using an
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extraction leads to the formation of structural defects in the Autosorb-iQ gas adsorption analyzer (Quantachrome, USA) at
lattice.23,24 Thus, desilication by alkaline treatment is a prefer- 196 C. Each sample was outgassed at 200 C for 6 h before
ential method to introduce mesopores. These hierarchical measurement. The specic surface area (SBET) was calculated
zeolites enhance the utilization of their active volume and have using the Brunauer–Emmett–Teller equation (P/P0 ¼ 0.05–0.20).
attained superior yields of targeted products in many catalysis The total pore volume (Vtotal) was taken as the total uptake at
reactions.25 P/P0 ¼ 0.995. The Barrett–Joyner–Halenda (BJH) method was
To improve carbon yield of hydrocarbons in CFP of biomass used to determine the micropore volume and micropore size
and promote catalyst stability, alkali treatment was carried out distribution. And the mesoporous volume was obtained by
on HZSM-5 catalysts to introduce some mesopores into the subtracting the micropore volume from the overall pore
microporous catalyst system. The hierarchical HZSM-5 catalyst volume.
showed better mass transfer. In our study, N2 adsorption and Scanning electron microscopy (SEM) experiments were per-
transmission electron microscopy were used to investigate the formed to obtain the morphology of the fresh and modied
existence of mesopores, and the morphology was greatly catalysts. The measurements were performed with a FEI Inspect
dependent on the treatment conditions. The parent and hier- F50 system at 10 kV. Prior to each measurement, the samples
archical HZSM-5 catalysts were employed in the catalytic were prepared on a carbon pad and sputtered with gold to
conversion of furan as an important intermediate from BFP. obtain the necessary conductivity. The morphology and pore
The effect on hydrocarbon production was studied and the size of zeolites were also examined by transmission electron
catalyst performance in cycle runs of the catalysis-regeneration microscopy (TEM) on a Tecnai G2 microscope operated at an
process was discussed. electron acceleration voltage of 200 kV. A small amount of
catalyst was dispersed in ethanol, sonicated, and dispersed over
a micrograte.
Experimental The acidity of the catalysts was estimated by the NH3
temperature programmed desorption (TPD) technique. The
Catalyst and desilication procedure
sample was pre-treated at 600 C in owing He for 0.5 h. Aer
In this study, two series of HZSM-5 catalyst samples were pre-treatment, the sample was cooled to 100 C and saturated
compared: a commercial catalyst (purchased from catalyst plant with NH3 gas. The physical absorbed NH3 was then blown out.
of Nankai University, stated Si/Al ratio of 25) and its hierarchical Finally, NH3-TPD was carried out under a constant ow of He
counterpart. The hierarchical catalyst was prepared by desili- (20 mL min1). The temperature was raised from 100 to 600 C
cation according to the following procedure: 2 g of the parent at a heating rate of 15 C min1.
sample was treated in stirred aqueous NaOH solutions (0.1–1 M, Deactivated catalysts were regenerated in a owing air
70 C, 30 min, 33 mL solution per gram catalyst material). The atmosphere of 50 mL min1 in a thermogravimetric analyzer to
mixtures were washed and ltered several times until the pH determine the coke content by weight loss during oxidation.
was neutral, and the isolated solids were dried at 110 C for Typically, 15 mg of the sample was placed in the alumina
12 h. All modied zeolites were converted to the protonated crucible and heated from ambient temperature to 800 C at
form by ion exchange in aqueous NH4Cl solution (1 M, 80 C, a rate of 15 C min1.
4 h, 10 mL solution per gram catalyst material, 3 consecutive
treatments) and washed several times followed by calcination in
air at 600 C for 5 h. These catalysts will be referred to as HZSM- Catalyst tests
5-P and HZSM-5-X respectively. X stands for the mole concen- All catalytic tests were performed in a quartz glass xed-bed
tration of the NaOH solution used for preparation. It should be reactor that has been described elsewhere.26 The catalyst bed
mentioned that Cl content of the nal modied catalysts has was activated by pure air ow (200 mL min1) at 600 C for 1 h
been tested in the following section to eliminate the inuence prior to each run. Then, the nitrogen ow was mixed with 1.68 g
of Cl on the catalytic performance. h1 furan via a spring pump, resulting in a weight hourly space
velocity (WHSV) of 11.2 g furan per gram catalyst per hour. All
experiments were carried out under atmospheric pressure and
Catalyst characterization a furan partial pressure of Pfuran ¼ 12.30 Torr. Aer 20 minutes
The parent and desilicated samples were characterized by of catalysis, furan feeding was stopped and air was introduced
several techniques. into the reactor with ow rate of 500 mL min1 for 30 minutes,
The structures of the ZSM-5 samples were determined which should ensure that the coke was removed completely.
through X-ray powder diffraction (XRD) by a Bruker instrument During the coke combustion process, CO was converted into
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CO2 in the copper converter that was full of copper oxide and
then trapped by ascarite. The coke amount was measured by the
weight increase in the CO2 capturer. Product analysis was per-
formed using gas chromatography. The product composition
was determined with gas chromatography/mass spectrometry
(GC/MS) (Agilent, 7890A-5975C) equipped with an HP-5 capil-
lary column (30 m 0.25 mm 0.25 mm) and quantied by GC-
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Table 2 Product distribution in the catalytic conversion of furan over analysis as shown in Fig. 7. Mass loss of the deactivated cata-
HZSM-5 lysts was shown during coke combustion. First, total coke
content of the catalysts showed some differences among all
Parent 0.1 M 0.3 M 0.5 M 0.8 M 1 M
catalysts. Compared with the parent catalyst, treated catalysts
Carbon yield (mol%) almost had more coke content, and this observation can also be
Olens 5.41 6.74 8.78 7.10 5.12 3.82 found in other coked catalysts with hierarchical structure.36,37
Aromatic hydrocarbons 13.79 14.25 14.57 15.65 14.66 13.31 This suggests that the mesopores may act as spaces for coke to
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the HZSM-5-0.3M was 40 C lower. First, it is understandable desilicated HZSM-5 catalyst showed higher selectivity to olens
that the carbon yield of hydrocarbons for HZSM-5-0.3M was and more serious coke deposition, but a higher tolerance
higher than that of HZSM-5-P because of the appearance of towards coking. Moreover, the cyclic tests of the catalysis-
mesopores in HZSM-5, which provided more chances for regeneration process indicated that hierarchical HZSM-5
contact between reactant and catalyst acid sites. The parent zeolites are potentially suitable for long-term operation. The
HZSM-5 catalyst showed more serious overheating than HZSM- hierarchical HZSM-5 catalyst successfully combined the high
5-0.3M. On one hand, the loose and porous coke determines its selectivity of the microporous system and promoted mass
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relatively lower burning temperature.39 Svelle and Schmidt re- transfer of mesopores in CFP of biomass for hydrocarbon
ported that coke distribution of microporous HZSM-5 showed production.
a gradient over the catalyst particle and the carbonaceous
molecules mainly deposited in the microporous near-surface
area that led to the rapid deactivation of catalysts, while hier- Acknowledgements
archical HZSM-5 catalysts showed a homogeneous distribution
over the whole particle due to the improved accessibility of The authors acknowledge the nancial support of the National
active sites and higher catalyst utilization.19,40 Therefore, the Natural Science Foundation of China (Grant No. 51561145010,
more uniform deactivation of the desilicated catalyst due to 51525601 and 51306036), the National Basic Research Program
a complex interplay among alterations of porosity, activity and of China (973 Program, Grant 2012CB215306), the Jiangsu
rate of deactivation upon desilication, makes combustion gas Natural Science Foundation (Grant No. BK20130615) and the
easily diffuse out of catalysts channels.40 Actually, accurate Scientic Research Foundation of Graduate School of Southeast
temperature within the catalyst particle was much higher than University (YBJJ1324).
the detected value. Thus, lots of heat during coke combustion
resulted in extraction of the framework Al to generate octahe-
drally coordinated Al species out of the zeolite framework.41 References
Dealumination occurred, and the removed aluminum was
retained in the pores. Generally, the mesopores in the treated 1 P. S. Rezaei, H. Shafaghat and W. M. A. W. Daud, RSC Adv.,
HZSM-5 catalyst will decrease the burning temperature and also 2015, 5, 65408–65414.
the particle interior temperature, weaken the dealumination 2 A. Veses, M. Aznar, I. Martı́nez, J. D. Martı́nez, J. M. López,
effect and nally promote the cycle stability. Coke content was M. V. Navarro, M. S. Callén, R. Murillo and T. Garcı́a,
also recorded online during regeneration. The coke amount Bioresour. Technol., 2014, 162, 250–258.
determined by combustion online only includes carbon while 3 K. G. Wang and R. C. Brown, Green Chem., 2013, 15, 675–681.
the TG analysis of deactivated catalysts in air can determine the 4 H. Y. Zhang, T. R. Carlson, R. Xiao and G. W. Huber, Green
full composition amounts including carbon, hydrogen and Chem., 2012, 14, 98–110.
oxygen. Previous studies revealed that coke species at high 5 E. L. Kunkes, D. A. Simonetti, R. M. West, J. C. Serrano Ruiz,
temperature (>400 C) are mainly hydrogen-poor carbon species C. A. Gärtner and J. A. Dumesic, Science, 2008, 322, 417–421.
with no oxygen.42 Therefore, the coke amount obtained by the 6 T. P. Vispute, H. Y. Zhang, A. Sanna, R. Xiao and
above method may be just a little smaller than TG analysis. G. W. Huber, Science, 2012, 330, 1222–1227.
Coke content of original catalysts and those used for cycles has 7 Á. Ibarra, A. Veloso, J. Bilbao, J. M. Arandes and P. Casta,
been added into Fig. S4.† It is obvious that the coke content Appl. Catal., B, 2016, 182, 336–346.
decreased with increasing cycle numbers, and the decrease rate 8 H. Y. Zhang, M. M. Luo, R. Xiao, S. S. Shao, B. S. Jin,
of parent ZSM-5 catalysts seems higher. For the parent ZSM-5, G. M. Xiao, M. Zhao and J. Y. Liang, Bioresour. Technol.,
the high burning temperature leads to hotspots in the catalyst 2014, 155, 57–62.
particles and dealumination may happen.43,44 Dealumination is 9 D. Chen, K. Moljord and A. Holmen, Microporous Mesoporous
usually accompanied by the decrease of strong acid sites, which Mater., 2012, 164, 239–250.
easily causes serious coke formation.41 Thus, the decrease of 10 K. G. Wang, K. H. Kim and R. C. Brown, Green Chem., 2014,
coke content with cycle numbers is understandable. Hierar- 16, 727–735.
chical catalyst (HZSM-5-0.3M) showed relatively lower 11 S. Vitolo, B. Bresci, M. Seggiani and M. G. Gallo, Fuel, 2001,
combustion temperature and thus lower degree of deal- 80, 17–26.
umination, which explains the slight decrease in coke content. 12 C. A. Mullen and A. A. Boateng, ACS Sustainable Chem. Eng.,
2015, 7, 1623–1631.
Conclusion 13 S. S. Shao, H. Y. Zhang, L. J. Heng, M. M. Luo, R. Xiao and
D. K. Shen, Ind. Eng. Chem. Res., 2014, 53, 15871–15878.
Catalytic conversion of furan, as an important intermediate 14 M. Firoozi, M. Baghalha and M. Asadi, Catal. Commun.,
from BFP, was conducted on a micro-mesoporous HZSM-5 2009, 10, 1582–1585.
catalyst, created by alkali treatment, to obtain hydrocarbons. 15 Y. M. Ni, A. M. Sun, X. L. Wu, G. Hai, J. L. Hu, T. Li and
The prepared sample of HZSM-5-0.3M, with sheet-like meso- G. X. Li, Microporous Mesoporous Mater., 2011, 143, 435–442.
pores, presented the best catalytic performance with carbon 16 H. Mochizuki, T. Yokoi, H. Imai, S. Namba, J. N. Kondo and
yields of hydrocarbons boosted to 21.6%. The appropriately T. Tatsumi, Appl. Catal., A, 2012, 449, 188–197.
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44320 | RSC Adv., 2016, 6, 44313–44320 This journal is © The Royal Society of Chemistry 2016