2013-SALL-Reforming of Ethanol With Exhaust Heat at Automotive Scale

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Article
REFORMING OF ETHANOL WITH EXHAUST HEAT AT AUTOMOTIVE SCALE
Erik D Sall, David A. Morgenstern, James P Fornango,
James W Taylor, Nichilos Chomic, and Jennifer Wheeler
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef4011274 • Publication Date (Web): 06 Aug 2013
Downloaded from http://pubs.acs.org on August 10, 2013
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15 Ethanol intake plenum Second feed plenum to catalyst tubes Reformate plenum
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First tube bank, Second tube bank, Third tube bank, Fourth tube bank,
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31 Figure 1: Schematic of the reformer test system used for finned tube and shoebox reformers. The system
enabled testing of two reformers in parallel, supplying each reformer with exhaust from four cylinders of a
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V8 engine operating on gasoline. Black lines show the exhaust path. Fuel paths (ethanol and gasoline to
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Figure 7: A finned tube reformer: Above, left to right: (a) An end view showing the finned, annular exhaust
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channel, the ethanol inlet tube (at left) and the endcap of the reforming bed, (b) catalyst coated onto
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REFORMING OF ETHANOL WITH EXHAUST
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12 HEAT AT AUTOMOTIVE SCALE
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17 Erik D. Sall, David A. Morgenstern*, James P. Fornango, James W Taylor
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20 MONSANTO Co.
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23 800 N. Lindbergh Blvd
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27 St. Louis, MO 63167
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33 Nichilos Chomic, Jennifer Wheeler
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37 AVL POWERTRAIN ENGINEERING
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40 47519 Halyard Dr.
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43 Plymouth, MI 48170
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50 ABSTRACT
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55 *
56 Corresponding author. Tel: 314 694 8786, david.a.morgenstern@monsanto.com
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3 A low-temperature ethanol reforming pathway, catalyzed by copper-nickel powder catalysts, transforms
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6 ethanol into a mixture of H2, CO, and CH4 at temperatures between 300°C and 350°C. Blending 25-50%
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8 of this gas mixture, known as “low-temperature ethanol reformate,” with ethanol or E85 fuels, enables
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10 dilute engine operation, resulting in substantial improvements in fuel economy and emissions. It is
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13 thermodynamically feasible to drive low-temperature reforming with exhaust heat, but this requires an
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15 onboard reformer providing adequate heat exchange between exhaust and fuel while retaining the
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17 catalyst. Three low-temperature ethanol reformer architectures (representing a design evolution) were
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developed and tested at automotive scale with exhaust from a V8 engine. The best catalyst retention
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22 and heat transfer properties were achieved by embedding the catalyst in fibrous metal media with a
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24 density gradient. Longitudinal shell-and-tube and finned tube reformers achieved effective heat
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transfer and adequate initial conversion, but proved inadequate for vehicular applications due to high
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29 thermal mass, catalyst settling, and unacceptable pressure build. A transverse shell-and tube design in
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31 which banks of parallel, vertical catalyst tubes extended through a transverse stack of exhaust side heat
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33 exchange plates exhibited sustained high conversion with low and stable fuel-side pressure throughout
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36 a 500-hour test period. This design has relatively low thermal mass and can be readily packaged on a
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38 vehicle. Thus, onboard reforming of ethanol or methanol-rich fuels appears to be a feasible pathway to
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40 improved fuel economy and emissions in light-duty vehicles.
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44 INTRODUCTION
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48 Onboard Reforming
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50 Since the 1970’s there has been interest in converting liquid fuels to hydrogen onboard a vehicle, a
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52 process known as “onboard reforming.”1,2 This approach to hydrogen vehicles provides consumers with
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55 the convenience of liquid fueling and avoids the cost and weight penalties incurred by high pressure
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57 hydrogen storage on board a passenger vehicle. The first wave of research, which lasted into the early
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1980’s, focused almost exclusively on methanol reforming. Methanol can be converted to two moles of
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6 hydrogen and one mole of CO at around 300°C (eq. 1), a temperature low enough to enable this
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endothermic process to be driven by exhaust heat. Copper is the most common catalytic metal.
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13 Several studies (generally employing bottled, or “simulated reformate”5,6) showed that the product,
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15 “methanol reformate,” enabled internal combustion engines (ICEs) to operate at significantly improved
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efficiency compared to gasoline. The efficiency gains approached 50% at mid-load, although the
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20 improvement was partially due to increased compression ratio. Reforming is expected to be most
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22 beneficial in city driving, since the engine is almost always operating at low to mid-load with heavy
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24 throttling.
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27 CH3OH(g) → CO + 2H2 ∆H = +90.6 kJ/mol (1)
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29 The value of reformate to internal combustion engines is due to three factors, one of which is exhaust
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heat recovery. Reforming reactions are endothermic, capturing thermal energy from exhaust in the
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form of increased enthalpy of combustion. Most importantly, even quite modest levels of hydrogen
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36 greatly improve flammability of the fuel, enabling the engine to tolerate signficant dilution of the fuel-air
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mixture, either with excess air (lean operation), or with exhaust gas recirculation. Dilute operation
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improves efficiency by reducing throttling losses and heat loss to coolant.
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45 Since these early studies, research on exhaust-driven reforming has been largely dormant for the past
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quarter century due to waning interest in methanol as a motor fuel accompanied by the evolution of
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50 highly efficient hydrogen fuel cells. Hydrogen fuel cells do not generate useful amounts of waste heat.
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52 Instead, reformers for fuel cell vehicles have generally been designed to operate on hydrocarbon fuels
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54 (typically gasoline) which require reforming temperatures near 600°C.9 A fraction of the fuel is burned
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57 to generate the heat, incurring a fuel economy penalty. Several concepts for high temperature gasoline
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reforming for internal combustion engines have also surfaced, such as the plasmatron and reforming
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6 at the cylinder exhaust ports, but these approaches have not been demonstrated at vehicular scale.
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In 2003, the Department of Energy abandoned support for onboard reforming for fuel cell vehicles,
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13 citing cost, thermal mass and startup energy issues. Reformers, particularly for fuel cells, tend to be
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15 massive, and the energy required to heat them to 600°C represents a substantial loss of overall
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17 efficiency, particularly over a short drivecycle. Heatup time was also a concern. No hydrogen is
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20 produced until the reformer has reached temperature, which would require the driver either to wait
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22 through the heatup period or to run the vehicle on a battery or other backup system. Virtually all fuel
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24 cell passenger vehicle development efforts now utilize tanks of high pressure hydrogen on board the
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vehicle.
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29 Low-temperature Ethanol Reforming
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31 This paper represents a return to lower-temperature reforming driven by exhaust heat, but utilizing
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ethanol rather than methanol as the fuel. The past two decades have witnessed a massive expansion in
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36 ethanol production in the US and Brazil with a total capacity approaching twenty billion gallons, all
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38 derived from sustainable biological sources, primarily maize and sugarcane. Unlike methanol, ethanol is
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non-toxic, which has enabled it to displace methyl-tert-butyl ether as the primary oxygenate in US
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43 gasoline. Continuing gains in yield and agricultural productivity ensure continuing growth in ethanol
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45 capacity over the next two decades.13
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50 Many papers have described high temperature steam reforming of ethanol at around 600°C (eq. 2),14
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52 but as noted above this temperature is too high to be driven by engine exhaust. Coking is also an issue
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54 due to the dehydration of ethanol at acid sites on the catalyst at high temperature (eq. 3) generating
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57 ethylene which then carbonizes.15
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5 CH3CH2OH(g) + 3H2O(g) → 2CO2 + 6H2 ∆H = +173 kJ/mol (2)
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7 CH3CH2OH → H2O + C2H4 (3)
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10 A 2005 paper in this journal reported that ethanol could be reformed by a different pathway at about
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13 300°C (eq. 4), enabling the reaction to be sustained by exhaust heat.16 Unlike high temperature
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15 reforming, supplementary water is not required. Thus the reaction is compatible with anhydrous
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17 ethanol fuels such as E85 without requiring a secondary water tank. The reaction was catalyzed by a
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novel catalyst, copper-plated nickel sponge (Raney nickel). Due to the low reforming temperature and
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22 lack of acidic sites, reforming could be conducted over this catalyst for hundreds of hours without coking
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24 or significant catalyst degradation.
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28 CH3CH2OH(g) → CH4 + CO + H2 ∆H = +49.1 kJ/mol (4)
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31 The low-temperature pathway shown in eq. 4 produces only one mole of hydrogen and is therefore
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33 unsuitable for conventional fuel cell vehicles, although hybrid fuel cell-ICE powertrains are a possibility.
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35 17,18
36 As a result, although ethanol reforming has been extensively studied, catalysis of reaction 4 has
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38 remained almost unexplored, although an iridium complex was recently reported to enable this reaction
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40 to procedure non-catalytically .19
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43 Despite its much lower hydrogen content, research in single-cylinder engines over the last four years
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45 has demonstrated that the H2/CO/CH4 mixture, “ethanol reformate,” enables engine efficiency
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47 improvements comparable to those seen in reformed methanol engines.20 Further work revealed that
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50 due to the enhanced flammability range of hydrogen, only 25-50% of the fuel needed to be reformed in
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52 order to obtain the efficiency benefits of highly dilute engine operation.21 This finding, along with the
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54 observation that reformate was not required at high engine load, implies that a reformer of modest size
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57 could be developed for automotive applications. Unlike reformers for fuel cell vehicles, low
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3 temperature ethanol reformers need only provide a fraction of the fuel over the low and mid-load
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6 portions of the drivecycle in order to achieve significant fuel economy and emissions benefits.
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10 A recent study demonstrated greatly improved fuel economy and startup emissions when fueling a V8
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13 engine with a 50/50 mixture (on a mass basis) of E85 and ethanol reformate supplied from gas
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15 cylinders.22 In addition, as will be described below, the engine was fueled with reformate from a
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17 prototype reformer at a part load engine operating point. This paper will describe the design and
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20 operation of this and later reformers with improved designs which provide confidence in the feasibility
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22 of automotive-scale reforming using ethanol-rich fuels.
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Challenges in exhaust-driven reformer design
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29 As discussed above, high temperature reformers must burn a portion of the fuel in order to maintain
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31 reforming temperatures. Exhaust-driven reforming utilizes only waste engine heat and is therefore not
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subject to this type of efficiency drag. However, this benefit comes at the cost of a substantial design
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36 complication: The reformer must serve both as a reactor and as a heat exchanger between the fuel and
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38 the exhaust stream.
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43 For automotive applications, the difficulty is magnified by several further considerations. First, it must
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45 exhibit low thermal mass in order to reach operating temperature early in the drive cycle. This can be a
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47 challenge when designing for enough surface area to enable adequate heat exchange while ensuring a
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50 pressure rating sufficient to withstand the fuel-side backpressure created by the catalyst bed. In
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52 addition, the design must minimize exhaust backpressure to negligible values (inches of water) since
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54 exhaust backpressure places a load on the engine and reduces efficiency. For high-volume automotive
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3 applications, low cost and weight are essential as is a compact design which enables packaging in a
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6 vehicle exhaust train.
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10 Although the early literature on reformed methanol engines includes several reports of successful
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13 operation of engine-reformer systems, all of the examples are at steady state and reformer design
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15 details and performance data are scarce. From the information available, it would appear that all
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17 automotive-scale methanol reformers are essentially shell-and-tube reformers with ceramic (typically
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alumina-based) catalyst pellets on either the shell or tube side. Reformer mass, when reported, ranges
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22 from approximately 22 kg23,24 to 50 kg25 for engine displacements ranging from 0.5 to 2.0 liters. No
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24 heatup times have been reported for exhaust-driven methanol reformers. Recently, reformers of this
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type have been developed for fuel cell vehicles in which some of the methanol is burned to provide the
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29 heat. The reformers have heatup times in excess of 20 minutes.26,27
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In the work described in this paper, variants of the shell-and-tube architecture were used because
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36 negligible exhaust backpressure can be achieved. However, the copper-plated nickel sponge catalyst is a
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38 granular powder, requiring modifications to the design in order to retain the catalyst in the reformer
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40 and provide efficient heat transfer. To these ends, the catalyst was impregnated into metal mesh
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43 materials. Heat transfer through powder beds, even metal powders is slow, but networks of metal
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45 fibers in the bed provide pathways for heat transfer. In addition, horizontal reformer designs with a
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47 maximum width of six inches were used to enable integration with the exhaust system of the vehicle.
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51 Catalyst Temperature and Selectivity
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53 Unlike methanol reforming or high temperature steam reforming of hydrocarbons and ethanol, the
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55 desired reaction, eq. 4, is not the thermodynamically preferred pathway. Instead, as seen in Scheme 1,
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58 the first step of the process is an endothermic dehydrogenation of ethanol, which is catalyzed by copper
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3 alone. The aldehyde product can then undergo decarbonylation to methane and CO, catalyzed by the
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6 copper-nickel catalyst. This second step is mildly exothermic. Overall, the low temperature reforming
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8 reaction described here is net endothermic (eq. 4), but not to the extent that can’t be easily supplied by
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10 the engine waste heat. In fact, at anticipated operating points the heat required to vaporize and reform
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13 the ethanol represents only about 7% of the enthalpy of combustion, or roughly 15% of the heat of
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15 combustion in the engine after heat loss to sinks other than the exhaust gas are considered.
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However, at high temperature or in the presence of active nickel, a far more exothermic reaction can
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22 convert CO and hydrogen to methane (“methanation”). Methanation does not occur on the copper-
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24 nickel catalyst below 350°C, apparently because of the high kinetic barrier coupled with destruction of
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nickel ensembles by copper plating. Unfortunately, as shown in Scheme 1, at elevated temperature,
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29 methanation coupled to water-gas shift results in destruction of all of the hydrogen and conversion of
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31 ethanol to methane and CO2 (eq. 5).
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2CH3CH2OH(g) → 3CH4 + CO2 ∆H = -149 kJ/mol (5)
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37 The methanation pathway is exothermic and potentially self-sustaining if excursions in local catalyst
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39 temperature exceed about 350°C. Balancing heat flow from exhaust with heat uptake by the reforming
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41 process is a significant challenge in reformer design, since, in practice, reformers are far from
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44 isothermal. Maintaining incomplete conversion is helpful since endothermic dehydrogenation reactions
45
46 prevails throughout the reformer, but control of the catalyst distribution to avoid hot spots proved to be
47
48 essential.
49
50
51
Scheme 1
52
53
54
55
56
57
58
59
60
8
1
2
3
+68.1 kJ/mol -19.0 kJ/mol
4
CH3CH2OH(g) CH3CHO + H2 CH4 + CO + H2
5 Cu Cu-Ni
6
7
8 2H2 + CO
9 methanation
10 H2 Ni -206 kJ/mol
11 CH4
12 Cu
13 CO2 H2O
14
15 water-gas shift
-41 kJ/mol CO
16
17
18 EXPERIMENTAL
19
20
21
22 Catalyst Preparation
23
24 Raney® nickel grades 2800 and 4200 were obtained from Grace Davison, Chattanooga, TN. The
25
26 copper-plating procedure was the same as that described in our earlier publication.16 The same
27
28
29 procedure was used for both Raney nickel grades. Typical chemisorption data for this catalyst has been
30
31 reported previously.
32
33
34
35
36
Copper plating of Pd/C catalyst was performed by electroless plating. The following procedure was
37
38 used to prepare a catalyst with a nominal 15% copper content from 185 g of 1% Pd on carbon pellets
39
40 (Evonik Noblyst 1006). A solution of 128 g CuSO4•5H2O (0.51 mol, 32.6 g. copper) in 800 ml of water
41
42
was combined with a solution of 507 g Rochelle salt (3.5 equivalents), 54 g Na2CO3 (1.0 equiv.), and 123
43
44
45 g of 50% NaOH (3.0 equiv.) in 1.5 liters of water. The Pd/C catalyst was added with gentle mechanical
46
47 stirring, just sufficient to keep the granules suspended. A mixture of 83 g. of 37% CH2O (2.0 equiv.) and
48
49 17 ml DI water was added in 10-ml aliquots spaced three minutes apart. Three minutes after the
50
51
52 addition of the final portion of the reducing agent, the catalyst was recovered by filtration and rinsed
53
54 with water. The catalyst was a bright metallic copper color. The catalyst was dried overnight at 120°C
55
56 under 24” Hg vacuum with nitrogen purge. 202 g of copper-colored pellets were recovered (9% weight
57
58
59
60
9
1
2
3 gain on plating). Elemental analysis (Huffman Labs): Cu 4.8%, Pd, 0.78%). Langmuir surface area: 1308
4
5
6 m2/g (substrate), 1161 m2/g (catalyst). CO uptake: 18 µmol/g (substrate), 7.8 µmol/g (catalyst).
7
8
9 Reformer Fabrication
10
11
12 The shell of the shell-and-tube reformer was a 24-inch length of Schedule 10 type 304 stainless steel
13
14 tubing with a 6.3-inch internal diameter (Schoeller Bleckmann, Houston). Exhaust flowed through
15
16 nearly 200 ¼-inch type 316 stainless steel tube with a thin (0.020-inch) wall. The tubes were welded
17
18
into tubesheets at either end of the reformer. The tubesheets consisted of ¼-inch stainless steel disks
19
20
21 with an array of ¼-inch holes cut by water-jet.
22
23
24
25
The same pattern of holes was cut into the baffles and other internals through which the tubes
26
27
28 passed. The internals included baffles cut from 1/16-inch stainless steel plate with a maximum
29
30 clearance of 0.3 inches. Two types of Bekaert “Bekipor®” sintered fiber mats were used as internal
31
32 filters, both fabricated from Fecralloy. Type NPF-09013-000 with a one-inch thickness (porosity 96.3%)
33
34
35 was used for the final filter below the reformate exit. A ½-inch thick material, type NPF-09012-000
36
37 (porosity 93.8%) was used between catalyst stages to prevent catalyst movement. Disks of sintered
38
39 Fecralloy fiber sheet were used for heat transfer (semi-sintered S-Mat from Micron Fiber Tech, Debary,
40
41
42
FL). The catalyst, copper-plated Raney nickel 2800, was applied wet to disks of a Fecralloy screen (G-
43
44 Mat, also from Micron Fiber Tech) into which the array of holes had been cut by water-jet. The catalyst
45
46 disks, baffles and other internal components were assembled into a stack before insertion into the shell
47
48
and inserting exhaust tubes into the assembly. A shroud around the outside of the reformer bypassed a
49
50
51 portion of the exhaust around the shell to avoid thermal stress during heatup.
52
53
54
55 The finned tube reformers used mostly the same materials for the internals as the shell-and-tube
56
57
58 reformer. As before, catalyst was loaded by applying wet catalyst to G-Mat disks. Bekaert and Micron
59
60
10
1
2
3 Fiber Tech materials were used for internal filtration and heat transfer as before, but the baffles were
4
5
6 stamped out of 21 gauge (0.032-inch) copper sheet with an open area 10% of the tube cross-section.
7
8
9
10 The finned tube reformer was fabricated from a three-foot length 1.5-inch diameter type 304 stainless
11
12
13 steel tube with 0.065-inch wall. 0.45-inch L-fins (0.014 or 0.024-inch thickness) were applied in a spiral
14
15 pattern at 120 fins per inch by Class Ten Industries (Pryor, OK). The finned tube was mounted inside an
16
17 exhaust sleeve with a 2.45-inch internal diameter (Eagle Tube), providing a tight clearance between the
18
19
20
fins and the interior of the sleeve in order to minimize exhaust bypass.
21
22
23
24 The shoebox reformer was assembled by R&D Enterprises (Plymouth, MI) by expansion of four banks
25
26
of 10, 5-inch long,1-inch diameter tubes into a stack of copper fins between two stainless steel headers.
27
28
29 The tubes were hand-welded into the headers which were then sealed by hand welding a
30
31 “compartmentalized” cover over the top and bottom headers. Once welded, the cover compartments
32
33 formed a series of top and bottom plena, arranged in such a way that the exit gas from one bank of
34
35
36 reactor tubes was directed to the inlet of the next bank. The fin stack was encased to form a rectangular
37
38 chamber through which exhaust could pass.
39
40
41
42
Reformer testbed
43
44 The shell-and-tube, finned tube, and shoebox reformers were tested using exhaust from a production,
45
46 flex-fuel, MY 2009 5.4-liter V8 engine supplied by Ford Motor Company. The base engine is used in the
47
48 Ford F150 pickup truck, but the compression ratio was increased from 9.8:1 to 12:1 as described in an
49
50
51 earlier paper.22 Reformer testing was performed in the Ann Arbor facility of AVL Powertrain. A
52
53 schematic diagram of the reformer test system used for finned tube and shoebox reformers is shown in
54
55 Figure 1.
56
57
58
59
60
11
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 1: Schematic of the reformer test system used for finned tube and shoebox reformers. The
33
34 system enabled testing of two reformers in parallel, supplying each reformer with exhaust from four
35
36 cylinders of a V8 engine operating on gasoline. Black lines show the exhaust path. Fuel paths (ethanol
37
38
39
and gasoline to the 5.4L V6 engine) are shown in green. The reformate path through the buffer tanks
40
41 and to vent is shown in yellow. Small arrows show thermocouple and pressure probe locations.
42
43
44 With the exception of the shell-and-tube reformer, which was tested with E85, the reformers were
45
46 fed neat, denatured ethanol (96.4% minimum ethanol by volume by ASTM D5501). Ethanol feed rates
47
48
49 to the reformer were varied throughout the day, generally from 0.5 to 2.5 kg/hr. Fuel was supplied with
50
51 a digital piston pump. The fuel passed through a 2-ft2 heat plate-and-frame heat exchanger prior to
52
53 entering the reformer. This heat exchanger cooled the reformate gas and heated the liquid ethanol to
54
55
56
57
58
59
60
12
1
2
3 assist the vaporization process. A second heat exchanger was used to further cool the reformate gas to
4
5
6 a targeted 25°C ensuring that any ethanol vapors were condensed and collected in the buffer tank.
7
8
9
10 Two exhaust diverter valves were designed and installed for control of exhaust flow through the
11
12
13 reformers in order to control the catalyst temperatures. The reformers were installed upstream of the
14
15 exhaust diverter valves on each side, as shown in Figure 2.
16
17
18
19
20
The reformer test protocol utilized a daily repeating 20-hour test cycle that would repeat every 24-
21
22 hour period with a four hour cool down phase in between. The four-hour cool down phase allowed for
23
24 cold start characteristics to be monitored on a daily basis. Reformate exit temperature was controlled
25
26
at setpoints of 300°C, 325°C, or 350°C via the exhaust bypass valves.
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48 Figure 2: Reformer installation in the exhaust train, showing a shoebox reformer and the exhaust
49
50
bypass line. Part of the exhaust diverter valve is under the insulation on the right of the picture. In
51
52
53 operation, the reformer and fuel lines were insulated.
54
55
56
57
58
59
60
13
1
2
3 The composition of the reformate stream was monitored by a custom gas chromatograph connected
4
5
6 to the reformer outlet by heat-traced lines. Some condensation occurred during reformer cool-down,
7
8 leading to spurious high ethanol values shortly after daily startup. The GC system was engineered by
9
10 Custom Solutions Group (Katy, TX) and was based on a Varian 450-GC gas chromatograph. The system
11
12
13 utilized heated multi-port valves for pressure equilibration and to provide backflush of the column used
14
15 for permanent gas analysis (Varian Carboplot P7).
16
17
18 RESULTS AND DISCUSSION
19
20
21
22 Shell and tube reformer with a V8 engine: A 2010 paper22 described the operation of a 5.4L V8
23
28
24 engine using a 50:50 mixture of E85 and “simulated” reformate: a 1:1:1 molar mixture of H2, CO, and
25
26 methane. As an extension of the study, the engine was also run using reformate from the shell-and-
27
28
29 tube reformer shown in Figure 3. The reformer was packed with 2.5 kg of copper-plated Raney® nickel
30
31 4200 coated onto wire mesh disks sandwiched between pads of metal mesh. The catalyst was divided
32
33 into six stages separated by baffles so that flow through the catalyst stages was alternately upflow and
34
35
36 downflow. Bulk gas transport was most likely intermediate between mixed and plug flow.
37
38
39
40 198 ¼-inch tubes conducted exhaust through the reformer and provided heat transfer area. The
41
42
43
reformer weighed 75 pounds, primarily due to the mass of the exhaust tubes. As a result, the reformer
44
45 heatup time with typical exhaust flowrates and temperatures was about 20 minutes.
46
47
48
49
At this stage of the project, no GC had been installed. Conversion was estimated based on the
50
51
52 accumulation of liquid (gasoline and unreacted ethanol) in the buffer tank between the reformer and
53
54 the engine. On this basis, conversion dropped from 85% to 40% over two months of operation. The
55
56
57
58
59
60
14
1
2
3 primary cause was found to be catalyst bypass. The dense metal powder catalyst slowly sifted to the
4
5
6 bottom of the reformer.
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 Figure 3: Shell-and-tube reformer used with the V8 engine.
43
44
45 The remainder of this paper describes a program to develop ethanol reformers with lower thermal
46
47 mass and sustained high ethanol conversion. After initial studies in model reformers, automotive-scale
48
49
reformers were tested in pairs using the same V8 engine, effectively receiving the exhaust of a four-
50
51
52 cylinder engine as shown in Figure 1. Conversion was measured by a GC system developed for the
53
54 program and confirmed based on condensate collected in the buffer tank. Neat denatured ethanol was
55
56 used for these studies instead of E85 because gasoline interferes with reformate GC analysis.
57
58
59
60
15
1
2
3
4
5 A Model Reformer Using a Single Powder Catalyst Stage
6
7 The first studies were conducted at about 10% of automotive scale, utilizing a single relatively massive
8
9 bed of copper-plated nickel sponge powder catalyst in order to observe the influence of simulated
10
11
12 exhaust temperature, ethanol flowrate, and heat transfer on the temperature distribution and
13
14 performance of the catalyst bed. Packed beds of particulates do not transmit heat by simple conduction
15
16 like homogeneous solid.29 The tests were conducted in a cylindrical reformer two inches in diameter,
17
18
19
shown in Figure 4. The ethanol was preheated to about 150°C, but the heat of reaction was supplied
20
21 through the cylinder walls by hot nitrogen. 267 g of dry copper-plated Raney nickel was poured into the
22
23 reformer forming an even cylindrical bed with a depth of 2.25 inches. Temperature distribution in the
24
25
catalyst bed during reforming was determined by an array of thermocouple at selected radial and axial
26
27
28 positions.
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Figure 4. Top view of packed powder reformer showing protruding thermocouples. Hot nitrogen,
47
48 simulating exhaust, passed through the annular chamber around the outside of the catalyst zone. The
49
50 objects seen against the white background in the reactor tube form a three dimensional array of intra-
51
52
53
reactor temperature points. The diameters of the catalyst chamber and the exhaust annulus were 2
54
55 inches and 6 inches respectively.
56
57
58
59
60
16
1
2
3
4
5 Figure 5 shows temperatures measured near the wall, at the center, and at an intermediate radius for
6
7 the catalyst bed when passing steam or ethanol through the reformer and stepwise increases in the
8
9 temperature of the nitrogen passing through the outer annulus. The temperature of the catalyst drops
10
11
by nearly 100°C from the wall to the center of the catalyst bed even with quite modest ethanol
12
13
14 flowrates. The catalyst bed cannot conduct heat as fast as the reforming reaction consumes it. No
15
16 temperature gradient was observed in the axial direction for either feed. As seen in the lower panel of
17
18 Figure 5, introduction of copper mesh into the catalyst bed nearly eliminates the radial temperature
19
20
21 gradient.
22
23
24
25
26 550
27
28 500
29
30 450
31
400
°C
32
33
34 350
35
36 300
37
38 250
39 100 200 300 400
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
17
1
2
3
4
5
6 550
7
8 500
9
10 450
11
12
°C 400
13
14
350
15
16
300
17
18
19 250
20 0 100 200 300 400
21 Minutes
22
23 N2 into annulus
24 Wall
25 Intermed
26 Center
27
28
29
30 Figure 5: Temperature distribution in a packed bed of copper-plated nickel sponge reforming 5 ml/min
31
32
33 of neat ethanol (top) using a powder catalyst bed. The lower panel shows the same catalyst with 5
34
35 ml/min of ethanol but with copper mesh in the bed.
36
37
38
39 The temperature distribution in a powder bed is determined by the competition between heat
40
41
supplied from the wall and heat consumed by reforming, mediated by the thermal conductivity of the
42
43
44 bed. Figure 6 shows the effect of stepwise reductions in ethanol flow from 10 to 2 ml/min, using the
45
46 same reformer and catalyst while maintaining a constant nitrogen temperature (535°C). As the ethanol
47
48 flowrate is reduced, catalyst temperature and conversion increase. At the lowest flowrate, methane
49
50
51 production increases and hydrogen drops due to the onset of methanation near the wall at
52
53 temperatures above 350°C. This event occurs when the ethanol flowrate drops to 2 ml/min at 300
54
55 minutes.
56
57
58
59
60
18
1
2
3
4
5
6 40
7
8
9 30
psi or ml / min
10
11
12 20
13
14
15 10
16
17
18
0
19 100 200 300 400
20
21 Minutes
22
23 EtOH Flow (ml/min)
24 psi - Reformer_In
25 psi - Reformer_Out
26
27
28
29
30
31 400
32 380
33 360
34 340
35
36 320
°C
37 300
38 280
39 260 Wall
40
240 Mid
41 Center
42 220
43 200
44 100 150 200 250 300 350 400
45
46 Minutes
47
48
49
50
51
52
53
54
55
56
57
58
59
60
19
1
2
3
4
5
6 35
7
8 30
9
10 25
11
Mol %
20
12
H2
13 15 CO
14 CH4
15 10
EtOH
16 Acet
17 5
18
0
19
20 100 200 300 400
21 Minutes
22
23
24
Figure 6. Temperature distribution and reformate composition for ethanol reforming at a constant
25
26 nitrogen temperature of 535°C with ethanol flow reduced stepwise from 10 to 2 ml/min (0.47 to 0.094
27
28 kg/hr).
29
30
31
32 Based on these findings, powder catalyst was embedded in fibrous Fecralloy media in the automotive
33
34
35 scale reformers. The temperature of reformate exiting the reformer was limited to 350°C in order to
36
37 avoid methanation. The reformers are far from isothermal, because the reformate is heated
38
39 downstream of the last catalyst stage while passing through about 3 cm of final filter.
40
41
42
43
44 Gross Reformer Design
45
46 In the model reformer just discussed and the automotive-scale reformers which follow, we have
47
48 consistently observed that methanation is significant only at high conversion and generally at
49
50
51
temperatures above 350°C. The presence of ethanol appears to suppress methanation by reducing local
52
53 catalyst temperature via the endothermic dehydrogenation reaction, although blocking of active sites
54
55 for methanation cannot be ruled out.
56
57
58
59
60
20
1
2
3 Whatever the mechanism, it remains true that as reforming proceeds there is a general trend from
4
5
6 net endothermic chemistry (dehydrogenation of ethanol) at low to medium conversion to net
7
8 exothermic chemistry (decarbonylation of the acetaldehyde intermediate) at higher conversions. The
9
10 practical implication is that, for most reactor designs, ethanol reforming is controlled by the ability to
11
12
13 transfer heat into and distribute heat within the reactor at low and medium conversion, while at high
14
15 conversion it is the ability to transfer heat within and out of the reactor that governs rate and ultimate
16
17 selectivity by keeping the catalyst from getting too hot.
18
19
20
21
22 For this reason we have found it advantageous to utilize co-current flow of ethanol and exhaust. Co-
23
24 current design is optimal for heat transfer in the ethanol vaporization and low conversion stages, and
25
26
serves to limit catalyst temperature at high conversion at the exit end of the reformer, thus reducing the
27
28
29 risk of methanation.
30
31
32
33 Three co-current reformer designs have been tested at automotive scale, beginning with the shell-
34
35
36 and-tube design described above. With experience, it has proven possible to dramatically reduce the
37
38 mass of the reformer by relying on turbulent heat transfer. The first reformer using turbulent heat
39
40 transfer used powder catalyst packed in a finned tube which was mounted concentrically in a 3-inch
41
42
43
exhaust tube, as shown in Figure 7. The fins create mild turbulence in the exhaust annulus as well as
44
45 heat transfer area. Exhaust pressure drop across the reformer was less than 4 kPa at a 400 kPa brake
46
47 mean effective pressure (BMEP) engine operating point. Packing of the interior of the finned tube is
48
49
discussed in the next section.
50
51
52
53
54
55
56
57
58
59
60
21
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 7: A finned tube reformer: Above, left to right: (a) An end view showing the finned, annular
24
25
26 exhaust channel, the ethanol inlet tube (at left) and the endcap of the reforming bed, (b) catalyst
27
28 coated onto stacks of Fecralloy screen disks, (c) catalyst packed into a “copper crown” for heat transfer,
29
30 (d) an insertable “bottlecap” copper baflle. An overall view of the reformer is shown below.
31
32
33 Thermocouple taps are seen on the exhaust sleeve.
34
35
36 The final and most successful design also utilized fins for heat transfer. Vertical tubes packed with
37
38 catalyst were embedded in horizontal copper fins with a profile which promote heat transfer via mild
39
40 turbulence, but without producing measurable exhaust backpressure. The design was designated the
41
42
43 “shoebox” and is shown in Figure 8. Although copper is not normally the metal of choice at automotive
44
45 exhaust temperatures (up to 600°C), mechanical strength is not a concern for fins, while the high
46
47 thermal conductivity and excellent corrosion resistance of copper recommend it for this application.
48
49
50
51
52
53
54
55
56
57
58
59
60
22
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Figure 8: Schematic diagram of the “shoebox” reformer design and a picture of the core, after insertion
35
36
37 of catalyst.
38
39
40 The finned tube and shoebox designs were tested using exhaust from one the four cylinder banks of a
41
42 V8 engine as described in the experimental section. Conversion and selectivity were monitored by an
43
44
online GC monitoring the composition of the reformer product. Heat transfer in both the finned tube
45
46
47 and the shoebox operated at “pinch.” Exhaust and reformate exit temperatures were equal,
48
49 demonstrating that heat transfer was adequate in both designs. Since exhaust flow is controlled by a
50
51 diverter valve, it is therefore possible to regulate the reformate exit temperature. This control strategy
52
53
54 was used throughout the study.
55
56
57 Table 1. Automotive-scale reformer dimensions
58
59
60
23
1
2
3
Design Length Width Catalyst Total
4
5 Mass Mass
6
7 Shell-and-tube 54” 7” 2.5 kg 34 kg
8
9 Finned tube 36” 2.8” 0.4 kg 6 kg
10
11
Shoebox 18” 6” 0.3 kg 8 kg
12
13
14
15 Catalyst Stage Structure
16
17 Copper-plated nickel sponge is uniquely capable of catalyzing the complete low-temperature ethanol
18
19
20
reforming pathway, eq. 4. Although extrudates and other structured forms are commercially available,
21
22 only the powder form can withstand reforming conditions. The key design goal for the interior of the
23
24 reformer is to pack the powder in a way that resists movement of the catalyst, which leads to pressure
25
26
buildup and bypass. Catalyst movement is driven primarily by ethanol and reformate flow, but
27
28
29 gravitational setting of the dense metal powder occurs as well. Maintaining adequate heat transfer is
30
31 also critical.
32
33 The key to retaining and distributing the powder catalyst was the use of steel wools and foams into
34
35
36 which the catalyst was dispersed by ethanol and reformate flow. The media also served to transmit
37
30
38 heat to the powder. The effective thermal conductivities of randomly packed fiber beds can be
39
40 estimated by the methods of Tsai and Streider. We estimate that the incorporation of fibers improves
41
42
43 the thermal conductivity of the catalyst bed by an order of magnitude.
44
45
46
47 In the finned tube design, metal mesh was inserted downstream of the catalyst which was packed wet
48
49
50
onto Fecralloy mesh disks or copper crowns which served as catalyst carriers and heat transfer media, as
51
52 shown in Figure 7. Three additional strategies were employed within the shoebox architecture to
53
54 achieve stable backpressure and high conversion.
55
56
57
58
59
60
24
1
2
3
1. The Cu/Ni sponge catalyst was sieved after passivation and the coarse (>53 µm) retained
4
5 fraction was used.
6 2. A “gradient” packing was positioned downstream of the powder beds. The powder was driven
7
into metal mesh layers with progressively tighter porosity. Typically a semi-sintered S-Mat was
8
9 positioned directly downstream of the powder bed followed by one or more layers of Bekaert
10 media.
11 3. In one shoebox reformer (Shoebox H), the powder loading was reduced and Cu/Pd/C pellets
12
13 used in its place, as described above. One finned tube reformer (M) used only Cu/Pd/C pellets
14 without copper-nickel powder.
15
16 Incorporation of the pellet catalysts effectively splits the reforming chemistry into endothermic and
17
18
19
exothermic stages. Copper-on-carbon pellets with a palladium adhesion layer were used for this
20
21 purpose,31 allowing the loading of powder catalyst to be greatly reduced, since the powder was only
22
23 required to catalyze the decarbonylation of acetaldehyde (eq. 7).
24
25
26
27 CH3CH2OH → CH3CHO + H2 (copper-catalyzed) (6)
28
29 CH3CHO → CH4 + CO (Cu/Ni-catalyzed) (7)
30
31
32
33 Backpressure Stability
34
35
36 The major obstacle to reliable long-term performance of the reformers proved to be gradual buildup
37
38 of backpressure due to movement of the powder catalyst. Figure 9 compares backpressure versus time
39
40 for finned tube and shoebox reformers at an ethanol feed rate of 0.5 kg/hr. The shoebox reformer
41
42
maintained constant backpressure for 500 hours onstream while all of the finned tube reformers
43
44
45 exhibited relentless pressure build which was accompanied by a steady loss of conversion. This included
46
47 finned tube M, which was packed only with copper-plated Pd/C pellets. Much higher ethanol feed rates,
48
49 up to 4 kg/hr, could be used in the shoebox reformer without excessive developing excessive inlet
50
51
52 pressure. The pressure did not increase linearly with feed rate.
53
54
55
56
57
58
59
60
25
1
2
3
4
5
6 5000
7
8
9 4000
Fuel Inlet P (kPa)

10
11 3000
12
13
2000
14
15
16 1000
17
18
0
19
20 0 100 200 300 400 500
21 Hours on stream
22
23 Shoebox E, powder & pellet cats
24 Finned tube, powder cat
25 Finned tube, Cu-Pd pellet cat
26
27
28
29
30
31 2500
32
33
34 2000
Fuel Inlet P(kPa)
35
36
37 1500
38
39
40 1000
41
42
43 500
44
45
46 0
47
0 100 200 300 400 500
48
49
Hours On Stream
50
51
52 0.5 kg/hr
53 1 kg/hr
54 1.5 kg/hr
3 kg/hr
55
4 kg/hr
56
57
58
59
60
26
1
2
3 Figure 9: Above: Inlet pressure for ethanol fed to finned tube and shoebox reformer E with an ethanol
4
5
6 feed rate of 0.5 kg/hr. Note that 400 kPa backpressure is due to the pressure in the buffer tank
7
8 downstream from the reformer. Below: Reformer inlet pressure with ethanol feed rates up to 4 kg/hr
9
10 for shoebox reformer E.
11
12
13
The parallel flow paths provided by the shoebox design thus proved superior to the sequence of
14
15
16 narrow baffle openings in the finned tube design for maintaining steady backpressure.
17
18
19 Conversion and Selectivity
20
21
Shoebox reformer H, loaded with a mixture of Cu/Pd/C pellet and Cu/nickel sponge powder catalyst
22
23
24 provided the best conversion of any reformer tested. Figure 10 shows data from the online GC over the
25
26 lifetime of the test. As noted above, the ethanol feed rate was stepped up from 0.5 to 2.5 kg/hr over
27
28 the course of each day’s testing. Conversion of ethanol to acetaldehyde (eqn 6) and of acetaldehyde to
29
30
31 CH4 and CO (eqn 7) were determined from the GC data. The temperature setpoint for reformate exiting
32
33 the reformer was varied between 300°C and 350°C as shown in Figure 10. The conversion could also be
34
35 assessed by measuring the amount of condensate collected. This approach, which was only used
36
37
38
occasionally for safety reasons, indicated that complete conversion of ethanol to H2, CO, and CH4 (eqn 4)
39
40 fell from about 90% at 0.5 kg/hr to about 70% at 2.5 kg/hr.
41
42 The conversion data demonstrates that the shoebox design overcomes the primary failure mode seen
43
44
in other designs: catalyst movement leading to backpressure. Catalyst activity is clearly adequate to
45
46
47 maintain activity, but the conversion data cannot be interpreted as a measurement of catalyst stability,
48
49 because the catalyst bed is highly non-isothermal.
50
51
52
53
54
55
56
57
58
59
60
27
1
2
3
4
5
6 120 5
7
Ethanol Flow (kg/hr)

8 100 4
9
Conversion %
10 80
11 3
12 60
13 2
14 40
15
16 20 1
17
18 0 0
19 0 50 100 150 200 250 300 350
20
21 EtOH Flow (kg/hr) Hours on stream
22 EtOH Conv %
23 Acet Conv %
24
25
26
27 400
28
29 380
30
Reformate °C
31
360
32
33
340
34
35
36 320
37
38 300
39
40 280
41 0 50 100 150 200 250 300 350
42
43 Hours on stream
44 Figure 10: Shoebox H conversion and selectivity based on GC data (above) and reformate temperature
45
46 at the exit plenum (below).
47
48
49
50
51
The finned tube reformers provided high ethanol conversion, but once the pressure began to
52
53 increase, severe methanation was observed (eqn 5). Although we have not examined the question in
54
55 detail, high pressure would be expected to favor methanation, formally a third-order reaction, over the
56
57
uni-molecular reforming reactions.
58
59
60
28
1
2
3
4
5 CONCLUSIONS
6
7
8 Onboard reforming has long been recognized as, in principle, an attractive means to recover the
9
10 energy value of the ~500°C exhaust stream produced by light-duty vehicles, provided that the fuel can
11
12
13 be reformed below 400°C. Although other fuels, such as methylcyclohexane,32 have been explored,
14
15 virtually all research in this area has focused on alcohol fuels, particularly methanol. However, prior to
16
17 the present work, we are not aware of any reports of exhaust-driven alcohol reformers suitable for
18
19
20 incorporation into conventional passenger vehicles or practical ethanol reformers.
21
22
23
24 The use of copper-plated nickel sponge catalyst embedded in metal mesh materials for heat transfer
25
26
27
and catalyst retention has now been shown to provide high conversion of ethanol to hydrogen and
28
29 other gases when utilizing exhaust heat. But the linear finned tube reformers failed due backpressure
30
31 resulting from slow migration of the powder catalyst and the inexorable rise in backpressure that
32
33
resulted. Both the shoebox and the earlier shell-and-tube designs allow ethanol and reformate to flow
34
35
36 vertically through the catalyst via multiple pathways. This strategy enables stable backpressure to be
37
38 achieved over hundreds of hours of operation, but only the shoebox design provided sustained high
39
40 conversion and relatively low mass.
41
42
43
44
45 The ethanol reformate produced by the copper/nickel sponge catalyst has been shown in earlier
46
47 studies to enable very low emissions at cold start along with substantial improvements in fuel economy.
48
49
50 At steady state, the shoebox reformer provides sufficient reformate to realize these benefits in a
51
52 passenger vehicle. E85 and hydrous ethanol motor fuels are now widely available in the US and Brazil
53
54 respectively, making this approach practical in these two countries, at least for vehicles with longer drive
55
56
cycles such as taxicabs or delivery vehicles, for which reformer heatup time is less of a concern.
57
58
59
60
29
1
2
3
4
5
6 For ordinary passenger vehicle with relatively short drivecycles, reduced heatup time is clearly
7
8 necessary. For experimental convenience, relatively long and massive exhaust lines connected the
9
10 engine to the reformers in this study, resulting in heatup times approaching 20 minutes. Even with
11
12
13 substantial reductions in exhaust line thermal mass, downsizing of the reformer is likely to be required
14
15 to achieve heatup times significantly below five minutes. The excellent heat transfer and conversion
16
17 observed in the shoebox reformers, particularly reformer H with reduced catalyst volume, make us
18
19
20
confident that this can be achieved, although closer coupling to the engine and catalytic converters will
21
22 likely be required. Experimental work in this direction is ongoing.
23
24
25 ACKNOWLEDGMENTS
26
27
28
29
30 The finned tube, shell-and-tube, and model reformer and their components were fabricated by the
31
32 Monsanto shop. The authors would like to acknowledge their gratitude to Dale Beaver, Josh Kary, Rick
33
34 Bailey, Craig Mierkowski, Ted Ahrens, Tavis Aholt, Kevin Brinker, and Steve Gambino. Durai Swamy and
35
36
37 Mel Miller provided an initial testbed for the shell-and-tube reformer. The shoebox reformer was
38
39 fabricated by R&D Enterprises in Plymouth, MI who also contributed significantly to the design. We
40
41 thank Roger Smith, Brian Ralph, and Rick Cox of R&D for their contribution as well as Brian Guth, Zach
42
43
McMichael, Andy Singleton and Kevin Depperman of Monsanto for CAD and assembly support of the
44
45
46 project. Catalyst characterization data was provided by Venu Arunatesan of Evonik.
47
48
49
50
51
52 At Monsanto, Jamie Davis, Yi Hu, Jing Lo, Kevin Coffman, Beth Calabotta, Greg Hartmann, Brad Storrs,
53
54
Dan Wright, Eric Haupfear, Sherri Brown, Tom Adams, Mark Deadwyler, and Robb Fraley, played
55
56
57
58
59
60
30
1
2
3 essential legal and supervisory roles. At R&D, Roger Smith, Brian Ralph, and Rick Cox were responsible
4
5
6 for the design and fabrication of the shoebox reformers.
7
8
9
10
11
12 We would also like to acknowledge the significant contributions of the AVL operations team who
13
14 designed and executed the test cell set-up. Gary Darst was the lead technician for the duration of
15
16
17 project testing and his efforts are especially appreciated. Additionally, the work could not have been
18
19 accomplished without the efforts of the engine controls team, led by Nick Zayan.
20
21
22 REFERENCES
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34

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Fuel Inlet P (kPa)

Ethanol Flow (kg/hr)

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