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Production of Aromatics by Catalytic Fast Pyrolysisof Cellulose in a Bubbling Fluidized Bed Reactor
Pranav U. Karanjkar, Robert J. Coolman, and George W. HuberDept. of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53706
Michael T. Blatnik, Saba Almalkie, and Stephen M. de Bruyn KopsDept. of Mechanical Engineering, University of Massachusetts-Amherst, Amherst, MA 01003
Triantafillos J. Mountziaris and William C. ConnerDept. of Chemical Engineering, University of Massachusetts-Amherst, Amherst, MA 01003
DOI 10.1002/aic.14376Published online February 11, 2014 in Wiley Online Library (wileyonlinelibrary.com)
Catalytic fast pyrolysis of cellulose was studied at 500C using a ZSM-5 catalyst in a bubbling fluidized bed reactor con-structed from a 4.92-cm ID pipe. Inert gas was fed from below through the distributor plate and from above through avertical feed tube along with cellulose. Flowing 34% of the total fluidization gas through the feed tube led to the optimalmixing of the pyrolysis vapors into the catalyst bed, which experimentally corresponded to 29.5% carbon aromatic yield.Aromatic yield reached a maximum of 31.6% carbon with increasing gas residence time by changing the catalyst bedheight. Increasing the hole-spacing in the distributor plate was shown to have negligible effect on average bubble diame-ter and hence did not change the product distribution. Aromatic yields of up to 39.5% carbon were obtained when allstudied parameters were optimized. VC 2014 American Institute of Chemical Engineers AIChE J, 60: 13201335, 2014Keywords: biomass conversion, catalytic fast pyrolysis, gassolid fluidization, K-L model
Lignocellulosic biomass has attracted significant attentionas a feedstock for production of renewable liquid fuels andvaluable chemicals due to its low cost and abundance.119
Catalytic fast pyrolysis (CFP) allows the direct conversion ofsolid biomass into aromatics.2025 CFP has numerous advan-tages compared to other approaches for biomass conversionbecause it can produce five major feedstocks that petroleumindustry uses including benzene, toluene, xylene, ethylene,and propylene in a single step process that uses inexpensivezeolite catalysts.17,20,21,2632 Toluene and xylenes may alsobe directly blended at high levels into gasoline and at lowlevels into distillate fuels. CFP of biomass is carried out in afluidized bed reactor (FBR) where biomass is rapidly heatedto high temperatures (450650C) where it forms oxygenatedpyrolysis vapors.3335 These vapors subsequently diffuse intothe pores of the zeolite catalyst where they are converted toaromatics, olefins, CO, CO2, and water. Coke is the majorundesired byproduct that competes with aromaticsformation.36
ZSM-5 based catalysts exhibit the highest aromatic yieldsfor CFP of biomass because of their pore size, low internalpore volume, and structure.26,3742 The aromatic yield ofCFP processes using ZSM-5 catalysts can be increased fur-
ther by the addition of metal oxides such as GaO andZnO.43,44 The p-xylene selectivity can be increased whiledecreasing the coke yield by silyation of the catalyst so thatover 90% of the xylenes are p-xylene.45
Different feedstocks have been used for CFP includingwoods,20,21,26,27,46 grasses,47 and model compounds.44,48 Jaeet al. reported a maximum aromatic yield of 15.5% carbonfrom CFP of pine wood in a bubbling FBR using an unmodi-fied spray-dried ZSM-5 catalyst, the same that is used in thisstudy.46 Plant biomass is composed of three main compo-nentscellulose, hemicellulose, and lignin. It has beenshown that cellulose primarily contributes toward aromaticproduction.49,50 Cellulose is a good model compound forraw woody biomasses because woods contain 40% wt ofcellulose. The pyrolysis of cellulose has been widely stud-ied.36,5156 The primary product of cellulose pyrolysis attemperatures of 400600C is levoglucosan which is formedby depolymerization of cellulose.51 Char, CO2, and water areformed from cellulose pyrolysis at lower temperature.36
Other products that are formed from cellulose pyrolysisinclude anhydrosugars, furans, light oxygenates, and noncon-densable gases.51,53
Several types of reactor configurations have been used forCFP including a microgram-scale resistively heated batchreactors, fixed bed reactors, and several FBR configurationsincluding (1) bubbling fluidized beds, (2) spouting fluidizedbeds, and (3) circulating fluidized beds.20,26,27,48,57,58 FBRsare ideal for CFP because they allow for maintaining con-stant catalyst activity through continuous addition of freshcatalyst and removal of coked catalyst.46 FBRs also provide
Additional Supporting Information may be found in the online version of thisarticle.
Correspondence concerning this article should be addressed to G. W. Huber firstname.lastname@example.org.
VC 2014 American Institute of Chemical Engineers
1320 AIChE JournalApril 2014 Vol. 60, No. 4
good heat transfer (for rapid heating of biomass) and goodmass transfer (compared to other modes of gassolid contact-ing). The absence of moving parts also makes FBRs idealfor CFP of biomass.5961 The flow regime in which an FBRis operated depends on the fluidization velocity of the gas.We have previously reported that the production of aro-matics by CFP of biomass is highest in a fluidized reactorthat has a biomass weight hourly space velocity (WHSV)between 0.1 h21 and 0.35 h21.20,46,62 These low space veloc-ities can realistically only be achieved at an industrial scaleby using reactor configurations with low void fractions, suchas, bubbling beds (e 0.50) or turbulent beds (e 0.70).Fast-fluidized beds (e 0.90) and pneumatic transport beds(e> 0.99) are not feasible at the desirable range of spacevelocities. For example, a 2000 metric ton of biomass feedper day reactor, at a WHSV of 0.3 h21 requires 278 metrictons of catalyst, which at a density of 1250 kg m23, requiresa solid volume of 222 m3. A 2-m diameter reactor with avoid fraction typical of fast fluidization (e 5 0.96), wouldrequire an implausible height of 1800 m.
Figure 1 shows a schematic of a bubbling FBR consistingof two phases: (1) a lean bubble phase containing mostly gasbubbles and (2) a well-mixed dense emulsion phase of solidcatalyst particles and gas. At the minimum fluidizationvelocity, all the gas goes through the emulsion phase.63 Asthe fluidization velocity increases above the minimum fluid-ization velocity, the gas in excess of minimum fluidizationgoes through the bubble phase. The bubble size increaseswith catalyst bed height as the bubbles coalesce. Betweenthe bubble and emulsion phase, a cloud occurs wherein masstransfer takes place (see Figure 1).59,6466 Understanding thehydrodynamics of this process is very important for thescale-up of CFP reactors, which is a relatively unexploredtopic for CFP of biomass, as well as for elucidating thekinetics of this complex process and improving upon thistechnology.
The objective of this work is to study the CFP of cellulosein a FBR. We have collected data for CFP of cellulose underdifferent hydrodynamic conditions and compared them witha hydrodynamic model to explain the evolution and role ofbubbles. Compilation of various empirical models allowed
us to calculate hydrodynamic parameters including bedexpansion, bubble diameter, and bubble residence time.
Industrial-grade cellulose with an average particle size of 200mm (LatticeVR NT Microcrystalline Cellulose, FMC biopolymer,99%) was used without pretreatment as the feedstock for thisstudy. C6H10O5 was used as an empirical formula for cellulose.The catalyst used in these experiments was a commercial spray-dried 40% ZSM-5 catalyst (Intercat) with an average particlesize of 99 mm and a standard deviation of 23 mm. Between 90and 250 g of catalyst were loaded into the reactor. These load-ings correspond to about 1540% of the reactor volume. Priorto reaction, the catalyst was calcined in situ at 500C in a mix-ture with a 1:4 oxygen-to-helium ratio flowing at 880 sccm.Equation 1 shows the WHSV of cellulose
WHSV h 21 5 cellulose flow rate g h21
weight of catalyst g (1)
The WHSV is calculated by dividing the cellulose flowrate by the amount of catalyst present inside the FBR. Selec-tivity toward a particular aromatic compound is defined byEq. 2 obtained by dividing the number of moles of carbon inthat aromatic product by the number of moles of carbon inall the aromatic products
5moles of carbon in an aromatic product
moles of carbon in all aromatic products3 100%
Equation 3 defines the selectivity toward an olefin com-pound in a similar way
5moles of carbon in an olefinic product
moles of carbon in all olefinic products3 100%
(3)As shown in Eq. 4, the residence time of the gas was cal-
culated by dividing the catalyst bed volume by the total gas
Figure 1. Schematic of a gassolid FBR with two carrier gas inlets.
AIChE Journal April 2014 Vol. 60, No. 4 Published on behalf of the AIChE DOI 10.1002/aic 1321
flow rate (Qt) which is the sum of carrier gas flow rate (Qc)and the product gas flow rate (Qp)
Gas residence time s
5Catalyst bed volume cm 3 3 60 s min 21
Total gas flow rate cm 3 min 21(4)
Figure 2 shows a schematic of the FBR system used forthe CFP of cellulose. The FBR is a 316L stainless steel4.92-cm ID pipe with a freeboard height of 40.64 cm. Abovethe freeboard is a disengaging zone which includes anexpansion to a 7.79-cm ID pipe. The catalyst bed is sup-ported by a distributor plate made of two layers of stainlesssteel perforated plates sandwiched around a 400 mesh stain-less steel cloth. Cellulose is fed into the reactor via a