Fuel 89 (2010) 12211229

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Combined pre-reformingdesulfurization of high-sulfur fuels for distributed hydrogen applications

Nazim Muradov a,*, Karthikeyan Ramasamy a, Clovis Linkous a, Cunping Huang a, Ibrahim Adebiyi a, Franklyn Smith a, Ali T-Raissi a, James Stevens b
a b

Florida Solar Energy Center, University of Central Florida, Cocoa, FL 32922, USA Chevron Technology Ventures, LLC, Houston, TX 77042, USA

a r t i c l e

i n f o

a b s t r a c t
A major challenge facing the future Hydrogen Economy is the issue of hydrogen fuel delivery and distribution. In the near term, it may be necessary to deliver high-density hydrocarbon fuels (e.g., diesel fuel) directly to the end-user (e.g., a fueling station) wherein it is reformed to hydrogen, on demand. This approach has the advantages of utilizing the existing fuel delivery infrastructure, and the fact that more energy can be delivered per trip when the tanker is lled with diesel instead of liqueed or compressed hydrogen gas. Reforming high-sulfur hydrocarbon fuels (e.g., diesel, JP-8, etc.) is particularly challenging due to rapid deactivation of conventional reforming catalysts by sulfurous compounds. A new on-demand hydrogen production technology for distributed hydrogen production is reported. In this process, rst, the diesel fuel is catalytically pre-reformed to shorter chain hydrocarbons (C1C6) before being fed to the steam reformer, where it is converted to syngas and further to high-purity hydrogen gas. In the pre-reformer, most sulfurous species present in the fuel are converted to H2S. Desulfurization of the pre-reformate gas is carried out in a special regenerative redox system, which includes an iron-based scrubber coupled with an electrolyzer. The integrated pre-reformer and sulfur-scrubbing unit operated successfully for 100 h at desulfurization efciency of greater than 95%. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 15 June 2009 Received in revised form 23 October 2009 Accepted 28 October 2009 Available online 14 November 2009 Keywords: Hydrogen Diesel fuel Reforming Desulfurization Catalyst

1. Introduction Considerable research and development efforts are underway, worldwide, to substitute hydrogen for gasoline and diesel fuel in transportation sectors. Due to the relatively low volumetric energy density of hydrogen, its delivery to fueling stations and storage present major challenges facing the future Hydrogen Economy. In the near term, it may be economically more feasible to deliver high energy density hydrocarbon fuels, such as diesel, gasoline, etc., directly to the end-user wherein it is reformed to hydrogen, on demand. This approach has the following advantages: (1) no change to the existing fuel delivery infrastructure is necessary, (2) more energy is delivered per trip when the tanker carries diesel instead of liquid or compressed hydrogen, and (3) the fuel dispensing station would be able to service both internal combustion and fuel cell powered vehicles at the same time.

Reforming of liquid hydrocarbon fuels to hydrogen has been a focus of intensive worldwide R&D efforts with a particular emphasis on vehicular (on-board) applications (e.g., [14]). The objective of on-board reforming is to convert liquid fuels into hydrogen-rich gas for use in an internal combustion engine (ICE) or a fuel cell (FC). In many respects, liquid hydrocarbon fuels represent a more attractive means of carrying hydrogen than compressed H2 itself, promising greater vehicle range, shorter refueling times, increased safety, and perhaps most importantly, utilization of the current fuel distribution infrastructure. The drawbacks of on-board reformers include their inherent complexity, weight, high cost, the need for an elaborate purication of hydrogen from impurities (e.g., CO, H2S) that could degrade FC performance (although, H2 purity requirements for the ICE applications are much less stringent than those required for FC [5]).Three main fuel reforming strategies for H2 production from hydrocarbons are: steam reforming (SR), partial oxidation (POx) and autothermal reforming (ATR). A generalized chemical reaction for ATR of hydrocarbon fuel (CnHm) is shown below:

* Corresponding author. Fax: +1 321 638 1010. E-mail address: Muradov@fsec.ucf.edu (N. Muradov). 0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2009.10.030

Cn Hm xO2 2n 2xH2 O ! nCO2 2n 2x m=2H2

DH  0

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POx and ATR have a number of advantages over SR, namely, shorter startup time, better transient behavior, and less weight. They can reform a wide range of fuels, including gasoline and diesel fuel. However, the POx and ATR reformers suffer from some shortcomings compared to SR: (i) the reformate gases from POx and ATR become diluted with N2 (since air is used in the process) resulting in lower FC performance compared to SR, (ii) H2 in FC anode exhaust is not easily integrated with the POx or ATR system, (iii) due to high exothermicity of the POx process, the reformer may be subject to greater thermal loses, etc. Different fuels impose different constraints on the reformer design, catalysts used and operating conditions. For example, it is more difcult to reform diesel fuel than gasoline due to a number of factors, e.g., the former has lower H/C ratio (thus, the potential for soot formation), higher energy consumption due to lower volatility of diesel fuel, higher temperatures in the reformer, higher sulfur content, etc. The effect of fuel composition on the fuel processor performance was investigated by Borup et al. [6]. It was demonstrated that short-chain aliphatic hydrocarbons tend to have favorable reforming characteristics for catalytic ATR compared to longer-chain and aromatic components. The Argonne National Laboratory researchers have investigated the reactor characteristics and the efciency of a catalytic autothermal reformer using surrogates of diesel fuel (dodecane and hexadecane) as feedstock [7]. The catalyst used was 1 wt.% Pt supported on cerium and gadolinium oxides. The reforming of these hydrocarbons was examined at the range of oxygen-to-carbon ratios of 0.180.5 and steam-to-carbon ratios of 13 and space velocities ranging from 10,000 to 100,000 h1 with H2 selectivity reaching up to 86%. Reforminghigh-sulfur(orhigh-S)hydrocarbonfuels(e.g.,diesel,JP8, etc.) is particularly challenging due to rapid deactivation of conventionalreformingcatalystsbycokedepositsandsulfurouscompounds. Moreover,ifsulfurouscompounds(mostly,H2S)arenotremovedfrom thereformategas,theycouldpoisonthecatalystsintheanodecompartment of FC substantially decreasing its performance or permanently damaging it. Thus, R&D efforts in this area have been focused either on desulfurization of liquid hydrocarbon fuels before reforming or on the development of sulfur-tolerant reforming catalysts. Fukunaga etal.havereportedanefcientNi-basedadsorbentthatloweredsulfur impuritiesfromhigh-Skerosenedowntolessthan1 ppm[8].Ithasbeen shown in a number of publications that traditional Ni-based steam reforming catalysts rapidly deactivate during processing of high-S liquid fuels. Although noble metal based catalysts (e.g., supported Ru, Pd,Rh,etc.)showedsomeimprovedtolerancetowardsulfurpoisoning andcokingcomparedtoNi-basedcatalysts,theirlongtermstabilitystill was not acceptable. For example, the authors [9] reported that supported Rh catalyst initially demonstrated a relatively good performance in steam reforming of high-S jet fuel, but over a longer period of operation showed signs of enhanced deactivation. Florida Solar Energy Center (FSEC), in collaboration with the Chevron Technology Ventures (CTV), has developed a new on-demand hydrogen production technology for distributed applications. The objective of this work is to catalytically convert high-S liquid hydrocarbon fuels to an essentially sulfur-free gaseous feedstock for steam reformation, while consuming only a fraction of hydrogen product. The experimental results on the development and performance testing of the catalytic pre-reformer and desulfurization systems are presented in this paper.

was obtained from Alpha Aesar and used as received. Commercial diesel fuel was purchased from a local Chevron gas station. Since commercial diesel fuel contains low levels of sulfur (approximately 5.5 ppmw), the fuel was supplemented with thiophene (C4H8S) to elevate the sulfur content to 31805240 ppmw level. This thiophene-spiked diesel was then used in all experiments as a surrogate high-S fuel. The same was carried out with hexadecane. Alumina-supported NiMo hydroprocessing catalyst in the form of 1 mm by 5 mm extruded pellets was provided by Haldor Topsoe. The composition of the NiMo catalyst was (%w/w): NiO (25), MoO3 (1218), Al2O3 (6880) and AlPO4 (511). In order to produce catalytically active form of the NiMo catalyst it was sulded using 6% dimethyl disulde, (CH3)2S2, (DMDS) in n-heptane as a sulding agent according to the following procedure. The NiMo catalyst (115 g) was placed inside a stainless steel reactor (2.5 cm diameter). H2 was introduced at pressure of 6.7 atm and temperature of 235 C for 1 h. Then, 6% DMDS in heptane was pumped to the reactor at a owrate of 25 mL/h for 0.5 h. The catalyst bed temperature was increased to 235 C and maintained for 1 h at that temperature. H2 pressure was increased to 54.5 atm and catalyst remained under that pressure for 1 h. The catalyst bed temperature was then increased to 340 C and held there for additional 1 h before curtailing the pumping of the DMDS solution into the reactor. The catalyst bed temperature was decreased to 175 C, and H2 ow was maintained overnight at 15 L/h and 54.5 atm pressure. A proprietary zeolite catalyst in the form of 1.5 by 5 mm extruded pellets was supplied by CTV. 2.2. Analysis Analysis of the products of pre-reforming was performed by means of gas chromatography (GC) as follows: the permanent gases, such as H2, CO, CO2 and CH4 were analyzed using an SRI8610A GC (thermal conductivity detector, argon carrier gas, silica gel packed column); gaseous and liquid hydrocarbons were analyzed using a Shimadzu GC-14B (ame ionization detector, helium carrier gas, capillary column). Analysis of sulfurous compounds (H2S, thiophene, methyl-mercaptan) was conducted using Perkin Elmer GC (ame photometric detector, capillary column). Additionally, H2S content in the pre-reformate gases was determined with the use of a set of Sensidyne and RAE Systems gas-detection tubes in the range of 0.25, 160 and 25250 ppmv H2S. X-ray diffraction (XRD) analysis of the NiMo/alumina catalyst samples before and after the pre-reforming experiments was conducted using a Rigaku D-MaxB diffractometer. X-ray photoelectron spectroscopic (XPS) analysis of the catalysts samples was conducted using a Physical Electronics 5400 XPS instrument applying non-monochromatic Mg Ka X-rays for excitation (pass energy for survey 44.75 eV, step size 0.5 eV; for high resolution spectra pass energy 35.75 eV, step size 0.1 eV). The surface morphology of the catalysts before and after pre-reforming were examined by scanning electron microscopy (SEM) (JEOL 6400F). 3. Results and discussion 3.1. Description of the concept Fig. 1 depicts a simplied block-diagram of the process for conversion of a high-S fuel to hydrogen. A high-S liquid hydrocarbon fuel (e.g., diesel fuel) is rst catalytically processed in a pre-reformer 1 to shorter chain hydrocarbons (C1C6, preferably, C1C4) in the presence of hydrogen (this process is similar to a hydrocracking process, therefore, hereafter we will also refer to this process hydro-reforming). Assuming (for the sake of simplication) the diesel fuel empirical formula as C12H23 and propane as the main

2. Experimental 2.1. Reagents and catalysts Hexadecane with greater than 98% purity was obtained from Fisher and used without further purication. Thiophene (99%)

N. Muradov et al. / Fuel 89 (2010) 12211229

1223

Diesel fuel

Reforming unit
H2, C1-C6, H2S 1

Desulfurization unit
Fe2+ 2 Fe3+ 3

3.2. Pre-reforming of high-S hexadecane and diesel fuel Figs. 2 and 3 show, respectively, a schematic diagram and a photograph of the bench-scale experimental unit employed for pre-reforming and desulfurization of high-S hydrocarbon fuels. In this section, the results of catalytic pre-reforming experiments using hexadecane and commercial diesel fuel spiked with thiophene in the amount corresponding to 31805240 ppmw sulfur are described (the data on the desulfurization sub-unit will presented in the next section). The pre-reformer sub-unit consists of four zones: (1) a fuel metering and delivery zone, (2) a reaction zone, (3) a products separation zone, and (4) a products metering and analysis zone. In the fuel delivery zone, diesel (or hexadecane) is pumped to the reactor at 13.614.3 atm pressure using high performance liquid chromatography pump (Lab Alliance) at a owrate of 0.20.4 mL/min. Hydrogen ow is controlled by a high-pressure mass ow controller (Parker) and varied in the range of 0.723.50 L/min. The prereforming reactor (ID = 25 mm, wall thickness 2 mm, length 45 cm) was fabricated out of 316 stainless steel with a maximum pressure rated at 200 atm at 540 C. Three quarters of the reactor was lled with catalyst. The hydrogen entered at the bottom of the reactor and the diesel vapor owed in at the top of the catalyst layer within the reactor. The reactor had an adjustable catalyst support system. The adjustable catalyst support system provided exibility in varying the length of the catalyst zone, which allowed capability to vary reactants residence time in the reactor. Fluid pressures and temperatures were monitored, in real time, at the inlet as well as at the outlet of the reactor using a LabView data acquisition system. The temperature in the upper section of the reactor maintained at 400450 C and in the lower part (where diesel entered the reaction zone) at 450500 C. In the products separation zone, the product mixture passed through a shell-andtube type condenser (kept at a temperature around 1520 C) where most of C6 + hydrocarbons condensed and reuxed back to the reactor and the gaseous hydrocarbons (predominantly, C1 C4), H2S and excess H2 entered a knock-out vessel where the escaped high hydrocarbons from the condenser were trapped and collected. The efuent gas owed through in-line lters that removed any particulates or aerosols that may have been produced in the reaction zone, passing through a back-pressure regulator to reduce pressure to near atmospheric. The pre-reformate then entered into a metering and analysis zone wherein most of the gaseous product passed through a gas meter (Shinagawa W-NK-2), that metered the volume of the gas generated. For safety reasons, several pressure relief valves were installed, and corrosion resistant stainless steel 316 tubing and ttings were used throughout the system. Three series of experiments with different catalytic systems were conducted including: (i) zeolite catalyst, (ii) NiMo/alumina catalyst and (iii) the mixture of zeolite and NiMo/alumina catalysts. The rational for selecting these particular catalysts is as follows. In order to convert long-chain hydrocarbons and sulfurorganic compounds present in diesel fuel to short-chain hydrocarbons (e.g., C1C6) and H2S, catalysts with hydrocracking and hydrotreating activities are needed. Zeolite and NiMo/alumina based catalysts are widely being utilized in oil rening and chemical industries for these particular applications. The composition of the efuent gas from hexadecane hydro-reforming over zeolite catalyst at 450 C and 14 atm is depicted in Fig. 4 (left). It can be seen that C1C7 saturated hydrocarbons (parafns) were produced in the reaction, with propane being a main component in the mixture followed by butanes. The stability of the zeolite catalyst, however, was not adequate, and after about 2030 h of operation there were signs of deactivation manifested by the appearance of a liquid product in the knock-out vessel. Indeed,

H2,C1-C6 H2 5 4 Steam

Sulfur

H2

Fig. 1. Schematic of the concept for conversion of high-sulfur diesel fuel to hydrogen. (1) Pre-reforming reactor, (2) H2S scrubber, (3) electrolyzer, (4) steam reforming reactor, (5) gas conditioning/separation unit.

product of the reaction, then, the diesel hydro-reforming process can be described as follows:

C12 H23 4:5H2 ! 4C3 H8

catalyst

In the pre-reformer, most sulfurous species present in the fuel are catalytically converted to hydrogen sulde (H2S):

RS 2H2 ! H2 S RH2

catalyst

where R refers to an organic moiety. The sulfur removal from the pre-reformate gas is required in order to avoid deactivation of the Ni-based catalyst in the steam reformer 4. Desulfurization of the pre-reformate gas is carried out in a special regenerative redox system, which includes a Fe-based scrubber 2 coupled with an electrolyzer 3. In particular, ferrous/ ferric (Fe2+/Fe3+) redox couple is used for oxidizing H2S to elemental sulfur as follows:
2 2Fe3 aq H2 Sg ! 2Feaq Ss 2Haq

The resulting ferrous ion is electrochemically oxidized back to the ferric state, releasing H2, in a closed loop process:
3 2Fe2 aq 2Haq ! 2Feaq H2g

The overall reaction is decomposition of H2S to H2 and elemental sulfur:

H2 Sg ! H2g Ss

Desulfurized pre-reformate gas is fed to the main reformer 4, where it is mixed with steam and processed over a Ni-catalyst to syngas (again, assuming propane as the main product of prereforming):

C3 H8 3H2 O ! 3CO 7H2

The syngas is further conditioned (or shifted) and puried (via pressure swing adsorption process) to high-purity H2 via conventional steam methane (or naphtha) reforming processes. A fraction of the output hydrogen product is recycled to the prereformer and used to conduct hydro-reforming of the high-S feedstock. The required amount of recycled hydrogen depends on the composition of the feedstock and hydro-reforming products. For example, assuming an empirical formula of C12H23 for diesel, the fraction of hydrogen product needed in the pre-reforming process for generating propane and butane would be about 16% and 13%, respectively.

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Vent Line

17 9 5 8 3 7 6
Gas out

10

19
To analysis

18
Liquid in

16

20

2 1 4

15

12 11

To desulfurization unit
14 13

Fig. 2. Schematic of the bench-scale experimental unit for high-sulfur diesel pre-reforming. (1) Diesel fuel storage, (2) nitrogen tank, (3) hydrogen tank, (4) HPLC pump, (5) mass ow controller, (6) two-way valve, (7) in-line lter, (8) check valve, (9) pressure relief valve, (10) pressure gauge, (11) three zone furnace, (12) reactor, (13) hydrogen inlet, (14) diesel inlet, (15) thermocouple, (16) catalyst, (17) condenser, (18) knock-out vessel, (19) back-pressure regulator, (20) gas meter.

Fig. 3. Photo of the combined diesel (hexadecane) pre-reformingdesulfurization experimental unit.

zeolite catalyst dislodged from the reactor after the experiment had turned black, apparently due to coke deposition. The amount of coke accumulated on the catalyst surface was measured to be about 10 wt.% of the original catalyst weight. The coked catalyst could be easily reactivated by burning coke off the catalyst surface by air at 450 C for 4 h. Fig. 4 (right) shows the product distribution of hexadecane hydro-reforming over NiMo/alumina catalyst at conditions similar to that of the zeolite catalyst. In contrast to the zeolite-produced gas, the product gas from hexadecane hydro-reforming was rich in higher hydrocarbons, in particular, C4C7 parafns, with butanes being the main products, followed by heptanes. Similar to the zeolite, the NiMo catalyst activity was not satisfactory, deactivating much faster than the zeolite catalyst. After about 5 h of run time, liquid product appeared in the condenser, indicating the loss of hydro-reforming activity of the NiMo/alumina catalyst. At the end of the experiment, the catalyst color had turned from light green to black.

In the following series of experiments, the mixture of zeolite catalyst and NiMo/alumina catalyst in the weight ratio of 2:1 was utilized. The experimental conditions were as follows: temperatures in the upper and lower parts of the reactor were 400 and 470 C, respectively, pressure of 13.7 atm, thiophene-added hexadecane feed ow 0.3 mL/min. The results revealed that the composition of the pre-reformate gas changed with time during rst 2530 h of the experimental run, reaching a steady state after about 50 h. Fig. 5a and b illustrates the results of a typical experiment presenting the data in two forms: (a) the time dependence of the molar fraction of the individual (or the family of) hydrocarbons, and (b) the composition of the product gas after 4, 20, 32 and 56 h of operation. The gure shows that at the beginning of the process (while the catalyst is fresh), methane is by far the main component of the pre-reformate gas, followed by ethane, propane and butanes. There are practically no higher hydrocarbons in the efuent gas. As the experiment progresses, the concentration of methane gradually decreases and the concentrations of higher hydrocarbons

N. Muradov et al. / Fuel 89 (2010) 12211229

1225

0.4 CH4 C2 H6 C3 H8 C4 C5 0.2 C6 C7 C8 + 0.1

CH4 C8+ CH4 C8+

0.3

0.0

Zeolite

Ni-Mo/Al2 O3

Fig. 4. Hexadecane hydro-reforming products distribution using zeolite (left) and NiMo/alumina (right) catalysts. T = 450 C, P = 14 atm.

1.0

0.8

after 4 hrs after 20 hrs after 32 hrs after 56 hrs

0.6

0.4

0.2

A similar experiment was conducted by passing the thiophenecontaining diesel fuel feedstock over mixed zeolite and NiMo/alumina catalysts. The reaction was operated at two temperature regimes: 450 and 500 C (temperature measured in the middle section of the reactor) with other parameters remaining the same as in hexadecane experiment. As in the case with hexadecane, initially, the pre-reformate gas was rich with methane; however, after about 1216 h the steady state regime was achieved which was maintained for the duration of the experiment (100 h). Average conversion of diesel to gaseous hydrocarbon products during the experiment was 9597%. Fig. 6 depicts the distribution of the pre-reformate products at 450 (left) and 500 C (right) after reaching a steady state regime. It is noteworthy that the distribution of C1C6 products of diesel and hexadecane hydro-reforming over the same catalytic system and at the same temperature range showed some similarities: in both systems, propane was the main product followed by butanes. In contrast to hexadecane, the diesel-derived gas contained a slightly higher content of heavier hydrocarbons (C6C8+). It is evident from Fig. 6 that increase in temperature resulted in an increase in methane concentration in the pre-reformate gas. A relatively stable operation of a binary mixture of catalysts with different types of catalytically active sites demonstrated in the above experiments is an interesting observation, which is yet to be fully understood. A similar observation was made by Chevron researchers [10], who pointed out that a physically intermixed catalyst system comprising hydrodesulfurization and hydrocracking catalyst particles of the same size demonstrated a surprisingly good stability against fouling when used in combined hydrotreating and hydrocracking applications. In agreement with this observation, in our binary zeolite + NiMo/alumina catalytic system, the both catalysts particles are substantially of the same size, which may explain their improved stability against coking. 3.3. Desulfurization of pre-reformate gas The analysis of the pre-reformate gas produced by the zeolite catalyst revealed that the thiophene-to-H2S conversion yield was very low. On the other hand, the combined zeolite/NiMo catalyst almost quantitatively hydrogenated thiophene to H2S using thiophene-laden hexadecane and diesel feedstocks. The latter prereformate gas, containing H2, H2S and light hydrocarbons (C1C6), was directed to the desulfurization sub-unit.

Molar fraction

Molar fraction

0.0 1 2 3 4 5 6

Carbon number
1.0

0.8

CH4 C2 H 6 C3 H 8 C4 C5 C6 +

Molar fraction

0.6

0.4

0.4 CH4 C2 H 6 C3H 8 C4 C5 0.2

CH4 CH4

0.2

0.3
0.0

Molar fraction

C6 C7 C8 +

Fig. 5. Hexadecane hydro-reforming over zeolite/NiMo catalyst. T = 400470 C, P = 13.7 atm. Hexadecane and thiophene feeding rates are 0.3 mL/min and 1.21 mg/ min, respectively. The gas samples were analyzed after: (A) 4, (B) 20, (C) 32 and (D) 56 h.

0.1

increase. After about 50 h a steady state regime is reached characterized by production of the pre-reformate gas consisting of C1C6 hydrocarbons with propane being the main component of the product gas. Overall, the experiment was run for 80 h, and only a small amount of liquid hydrocarbon was collected from the knock-out vessel, which corresponded to 98% conversion of hexadecane to gaseous products.

C8+

C8+

0.0

Zeolite/Ni-Mo (450oC)

Zeolite/Ni-Mo (500oC)

Fig. 6. Diesel hydro-reforming over zeolite/NiMo catalyst at 450 C (left) and 500 C (right). P = 13.7 atm. Diesel and thiophene feeding rates are 0.3 mL/min and 0.81 mg/min, respectively.

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Fig. 7A provides a schematic diagram of the desulfurization subunit for the continuous removal of hydrogen sulde from the prereformate gas and its splitting to hydrogen and sulfur. A gaseous mixture from the pre-reformer enters into a scrubbing unit, which includes an absorption column lled with aqueous ferric sulfate solution, Fe2(SO4)3(aq) (total volume of solution 2.3 L). H2S when dissolved in the aqueous solution is oxidized by ferric ion (Fe3+) to elemental sulfur, and simultaneously ferric sulfate is reduced into ferrous sulfate, FeSO4 (see Eq. (4)). (Note that the kinetics of the Fe3+ reaction with saturated hydrocarbons and hydrogen present in the pre-reformate gas is negligible, whereas the reaction with sulde ion is almost diffusion controlled.) Elemental sulfur is removed from the system by a lter, and the remaining ferrous sulfate solution is fed to an electrolyzer, where ferrous sulfate is oxidized back to ferric sulfate, and protons are reduced to hydrogen gas at the cathode. The regenerated ferric sulfate solution is then fed back to the absorption column of the scrubber for scrubbing hydrogen sulde, forming a closed cycle with the net reaction being hydrogen sulde decomposition to elemental sulfur and hydrogen gas. Electrolysis of acidic FeSO4 aqueous solutions was carried out using a modied proton exchange membrane (PEM) electrolyzer as shown in Fig. 7B. Platinum catalyst was spray-deposited onto the cathode side of a Naon lm to form a membrane electrode assembly (MEA). The cathode section consisted of a stainless steel

H2 Iron (III) sulfate

Desulfurized prereformate gas 6 To analysis

2 1 Iron (II) sulfate 4 5 Sulfur

Pre-reformate gas

plate used as current collector in a contact with water for hydrogen evolution. This conguration eliminated the need for a carrier gas to sweep hydrogen from the cathode side of the electrolyzer. An electrolyzer potential of 0.801.03 V was necessary for the electrochemical process to regenerate the scrubber solution at a rate sufcient to match the H2S ow rate into the scrubber. The electrolytic system can be operated at the range of temperatures from ambient to 90 C. In our experiments, desulfurization of the pre-reformate gas occurred optimally at the following process conditions: iron sulfate (total) concentration of 0.1 M, pH of 1.71.8 (adjusted by addition of 5 N sulfuric acid), and electrolyte temperature of 50 C. It should be noted that no Pt catalyst is needed for the oxidation of ferrous ions in the anodic section of the electrolyzer. Experimental results depicted in Fig. 8 imply that oxidation of ferrous to ferric ions is not affected by the lack of Pt catalyst at the anode. A plain carbon cloth can be used at the anode to allow distribution of both current and electrolyte. The experimental results demonstrated that both H2SO4 and FeSO4 concentrations have a signicant effect on the electrolytic hydrogen production rate. In particular, it was found that while the hydrogen evolution rate increased almost linearly with the increase in H2SO4 concentration (within the range of [H2SO4] = 0.250.75 N), the same dependence on the FeSO4 concentration goes through a maximum with respect to hydrogen production rate corresponding to about 0.15 M (Fig. 9). This was attributed to the generation of polysulfate species at higher concentrations that were less active toward charge transfer at the carbon anode surface. During initial testing of the combined scrubberelectrolyzer system, the bench-scale desulfurization unit was continuously operated for more than 300 h using a model H2SN2 mixture with 2500 ppmv H2S at the inlet and practically no H2S at the outlet of the scrubber (which corresponded to several turnovers of the Fe2+/ Fe3+-redox system). In the diesel pre-reforming experiment using the zeolite/NiMo catalytic system, diesel with 3180 ppmw of thiophene produced the pre-reformate gas with H2S content of 185 ppmv (determined by GC-PFD method and conrmed by gasdetection tubes). The chromatogram showed the presence of H2S as the only product of hydrogenation of thiophene; no unreacted thiophene or other sulfurous compounds were detected. On average, about 3 ppmv of H2S was detected exiting the ferric sulfate scrubber during the experiment. A similar experiment using the zeoliteNiMo mixed catalyst and hexadecane containing 5240 ppmw of thiophene produced largely desulfurized pre-refor-

B
600 500 400 300 200 100 0 0 20 40 60 80 100

Hydrogen volume, mL

one-side Pt-loaded membrane two-sides Pt-loaded membrane

Time, min
Fig. 7. Schematic of desulfurization unit (A) and electrolyzer (B). (1) Hydrogen sulde scrubber, (2) electrolyzer, (3) heating coil, (4) lter, (5) peristaltic pump, (6) three-way valve. Fig. 8. Electrolysis of acidic FeSO4 solution using one-side and two-sides Pt loaded MEA. Pt loading: 1.8 mg/cm2, current density: 3050 mA/cm2, electrolyte: 0.5 N H2SO4 + 0.18 M FeSO4, potential: E = 0.95 V.

N. Muradov et al. / Fuel 89 (2010) 12211229

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Hydrogen evolution rate, mL/min

5000

4000

O1s

N (E)

3000

2000

1
1000
Mo3p C1s Mo3d Al2s Al2p

0 0.0 0.1 0.2 0.3 0.4 0.5 0.6

0 700

600

500

400

300

200

100

[FeSO4], mol/L
Fig. 9. Hydrogen evolution rate as a function of FeSO4 concentration. One-side Ptloaded MEA, Pt loading: 1.8 mg/cm2, 0.325 N H2SO4, E = 0.95 V.

Binding energy, eV
Fig. 11. XPS spectrum of NiMo/alumina catalyst.

mate gas with H2S content of less than 5 ppmv. The sulfur balance of the pre-reforming reaction and the degree of the feedstock desulfurization was determined by comparing the amount of sulfur in feedstock (in moles) entering the reactor with the amount

of H2S (in moles) detected in the efuent gas after the scrubber. The sulfur balance for the above experiments was closed within the margin of error of 68% using two independent analytical methods for the gas analysis (GC and gas-detection tubes). The fuel desulfurization yield was dened as follows:

C4 H8 Sin H2 Sout 100% C4 H8 Sin

where g is fuel desulfurization yield, (C4H8S)in is number of thiophene moles in the fuel entering the pre-reformer, (H2S)out is the number of H2S moles exiting the sulfur scrubber.

Mo4+ B

Mo 3d5/2

Intensity

Mo 3d3/2

240

238

236

234

232

230

228

226

224

Binding energy, eV
Fig. 10. SEM images of NiMo/alumina catalyst before (A) and after (B) high-sulfur diesel hydro-reforming. Diesel hydro-reforming temperature: 450 C. Fig. 12. High resolution XPS spectra of NiMo/alumina catalyst before (A) and after (B) high-sulfur diesel hydro-reforming (224240 eV range).

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3.4. Characterization of pre-reforming catalyst Characterization of the zeolite/NiMo catalyst before and after pre-reforming of high-S diesel was carried out by SEM, XPS and XRD analyses. Fig. 10 shows SEM images of the Ni Mo/alumina catalyst before (A) and after (B) hydro-reforming of high-S diesel (at 450 C and time on stream of 100 h). It can be seen that no signicant changes in the catalyst surface morphology occurred during the hydro-reforming reaction. The XPS spectrum of the original NiMo/alumina pre-reforming catalyst in the region of 0700 eV is depicted in Fig. 11. The effect of operating conditions during the high-S fuel pre-reforming on the oxidation state of Mo and Ni was investigated. Fig. 12 compares the XPS spectra of the oxidized (original) (A) and reduced (after exposure to H2 and high-S diesel fuel) (B) forms of Mo in the NiMo catalyst. The XPS spectrum of the Mo3d5/2 and Mo3d3/2 transitions for the oxidized form of catalyst (Fig. 12A) shows only Mo6+ species, corresponding to binding energies of 233 and 236 eV, respectively. After exposure of the catalyst to reducing and sulding environment, the reduced Mo4+ species appeared in the XPS spectrum with Mo3d5/2 binding energy of about 229 eV (Fig. 12B). The peaks at 229229.6 eV in the suld-

Intensity

Based on the collected data from high-S diesel and hexadecane pre-reformingdesulfurization experiments, the fuel desulfurization yields were determined to be in the range of 9698% (averaged over a multi-day operation). The value of the parasitic load related to the electrolyzer operation (i.e., percentage of the heating value of diesel used to operate the electrolyzer) was estimated at 0.3% (LHV basis).

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Fig. 14. XRD pattern of NiMo/alumina catalyst after high-sulfur diesel hydroreforming.

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ed catalyst indicate the presence of MoS2. The spectrum shows that after hydro-reforming, a signicant amount of Mo in the catalyst remains in its oxidized form, which may point to a strong interaction of oxidized Mo species with the alumina support. Fig. 13A and B shows the XPS spectra of the oxidized and reduced/sulded form of the pre-reforming catalyst, respectively, in the region of 850866 eV. Interpretation of the Ni2p region of the XPS spectra as it relates to oxidized and reduced forms of the NiMo/alumina catalyst poses some challenges, because of proximity of Ni2p binding energies for different Ni species [11]. Indeed, it is very difcult to distinguish between different Ni species (e.g., NiO, Ni2O3, NiAl2O4) in the XPS spectrum, as all may appear in the same region. The weak peak at the binding energy of 854 eV in the reduced/sulded form of the catalyst may be attributed to NiS. The absence of a peak at a binding energy of 852.4 eV indicates that nickel was not reduced to its metallic state, and most likely, remained in its Ni2+ oxidation state. The XRD pattern of the NiMo/alumina catalyst after high-S diesel pre-reforming is shown in Fig. 14. Two most prominent diffraction peaks appearing at 2h values of 46 and 67 can be assigned to c-Al2O3. The XRD pattern does not indicate XRDobservable Ni oxides; however, it is commonly observed that NiO and Ni2O3 may also exist in amorphous or microcrystalline phases [12]. Identication of a NiAl2O4 phase is rather difcult because of proximity of its reection to that of alumina. Peaks corresponding to Mo compounds are apparently too weak to be distinguishable on the XRD pattern of the catalyst.

Intensity

4. Conclusions A novel process for converting high-sulfur diesel to hydrogen that employs a catalytic pre-reformer coupled with an efcient sulfur-scrubbing unit suitable for distributed hydrogen production and dispensing applications has been developed. A robust bi-functional catalytic system for pre-reforming high-sulfur fuels (sulfur content up to 5240 ppm) to short-chain hydrocarbons (predominantly, propane) at an average yield of 97% has been developed and demonstrated. A regenerable Fe2+/Fe3+-redox/electrolyzer system capable of scrubbing H2S from the pre-reformate gas and its splitting to H2 and elemental sulfur has also been developed and tested for 300 h of continuous operation. Electrolysis of acidic

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Fig. 13. High resolution XPS spectra of NiMo/alumina catalyst before (A) and after (B) high-sulfur diesel hydro-reforming (850866 eV range).

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FeSO4 aqueous solution was shown to be highly efcient with a columbic efciency approaching 100% at applied voltage of 1.0 V or lower. The effect of reaction conditions, such as pH, FeSO4 concentration, and temperature on the desulfurization efciency has been determined. It was shown that the electrolytic process can be conducted with a Pt-free anode capable of oxidizing ferrous to ferric ions, thereby reducing the cost of the electrolytic system. The integrated pre-reformer and sulfur-scrubbing unit operated successfully for 100 h, while achieving the desulfurization efciencies of 95% or greater for removing sulfur (i.e., [H2S] < 5 ppmv in the pre-reformate gas). Acknowledgements Financial support for this work was provided by the Florida Hydrogen Initiative (FHI) and Chevron Technology Ventures (CTV). Authors thank Haldor Topsoe and CTV for providing the samples of catalysts used in the experiments, and Kirk Scammon (UCF Materials Characterization Facility) for conducting analyses of the catalysts. Authors also wish to acknowledge contributions of Ms. Pam Portwood (FHI), Stephen Adams (FHI) and Dr. David Block (FSEC) toward completion of this work. References
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