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A Feasibility Analysis of Hydrogen Delivery System Using Liquid

A Feasibility Analysis of Hydrogen Delivery System Using Liquid

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Published by: Anshu Shukla on Oct 05, 2011
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Afeasibilityanalysisofhydrogendeliverysystemusingliquidorganic hydrides
 Ameya U. Pradhan, Anshu Shukla, Jayshri V. Pande, Shilpi Karmarkar, Rajesh B. Biniwale*
National Environmental Engineering Research Institute (NEERI), Council of Scientific and Industrial Research (CSIR), Nagpur 440020, India
a r t i c l e i n f o
Article history:
Received 8 June 2010Received in revised form17 September 2010Accepted 19 September 2010Available online xxx
Keywords:
Hydrogen storageHydrogen deliveryCycloalkanesDehydrogenationHydrogen stationFeasibility analysis
a b s t r a c t
The paper discusses the techno-economic feasibility of a hydrogen storage and deliverysystemusingliquidorganichydrides(LOH).Wherein,LOH(particularlycycloalkanes)areusedfortransportingthehydrogeninchemicalbondedformatambienttemperatureandpressure.The hydrogen is delivered through a catalytic dehydrogenation process. The aromaticsformed in the process are used for carrying more hydrogen by a subsequent hydrogenationreaction. Cost economics were performed on a system which produces 10 kg/h of hydrogenusing methylcyclohexane as a carrier. With proprietary catalysts we have demonstrated thepossibility of hydrogen storage of 6.8 wt% and 60 kg/m
3
of hydrogen on volume basis. Theenergy balance calculation reveals the ratio of energy transported to energy consumed isabout 3.9. Moreover, total carbon footprint calculation for the process of hydrogen deliveryincluding transportation of LOH is also reported. The process can facilitate a saving of 345tons/year of carbon dioxide emissions per delivery station by replacing gasoline withhydrogenforpassengercars.Thereisanimmensetechno-economicpotentialfortheprocess.
ª
2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
1. Introduction
Hydrogen is a fascinating energy carrier. It can be producedfrom water by electrolysis. Its conversion to heat or power issimple and clean. When combusted with oxygen, hydrogenforms water; hence no pollutants are generated. Hydrogen isbeing pursued as a future fuel all around the world for auto-motive applications in internal combustion engines and infuel cells[1,2]. Hydrogen-fuelled vehicles will use fuel cells,which can provide much higher energy conversion efficiencyas comparedtointernalcombustion (IC) engineswith zerotailpipe emissions[1]. Nevertheless, its storage and delivery(or in-situ production) is still a challenge[3,4]The four major factors on which conversion of automotivefossil fuel economy to hydrogen economy will dependinclude: bulk production of hydrogen, transportation of hydrogen from production facility to fuelling station, onboardstorage of hydrogen and utilization of hydrogen for energygeneration[1]. Production of hydrogen from hydrocarbon viasteam reforming or auto-thermal reforming is relativelydeveloped[5]. Similarly, as evident from the literature, thedevelopments in the field of fuel cell or IC engines using hydrogen as fuel have reached a considerable level[2].Hydrogen being a very flammable gas, its storage and trans-port involves several safety issues. The major safety issue iswide span of lower and higher explosion limits for H
2
concentration in air. Transporting hydrogen using high pres-sure (typically 300
e
500 psi) cylinders for storage is not anattractive option as it involves high pressure hazards andpotential explosion hazards. Carrying hydrogen in liquefiedform attracts an energy penalty and thus is not viable. Theseproblems can be overcome if hydrogen is either adsorbed onmaterials such as carbon based materials[6], metal hydrides[7,8], magnesium alloys[9]or boranes[10]. While developing 
*
Corresponding author
. Tel.:
þ
91 712 2249885x410; fax:
þ
91 712 2249900; Mobile:
þ
91 9822745768.E-mail address:rb_biniwale@neeri.res.in(R.B. Biniwale).
e
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Please cite this article in press as: Pradhan AU, et al., A feasibility analysis of hydrogen delivery system using liquid organichydrides, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.09.054
0360-3199/$
e
see front matter
ª
2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.doi:10.1016/j.ijhydene.2010.09.054
 
such hydrogen storage materials, capacity of the material interms of weight and volume is an important factor to beconsidered. With a limited capacity it would result in a weightpenalty and CO
2
emissions associated with transportation.Also the adsorption and desorption kinetics has to be suffi-ciently fast to provide a continuous H
2
supply. Anotherimportantrequisiteistotransporthydrogencontainingmediaat close to atmospheric temperature and pressure.A novel approach for the supply of hydrogen is throughliquid organic hydrides (LOH) using a catalytic reaction pair of dehydrogenation of cycloalkanes such as methylcyclohexane,cyclohexane and decalin; and hydrogenation of correspond-ing aromatics is a useful process for supply of hydrogen toPEMFC[11
e
20]. This is one of the most promising methodsto store, transport and supply with in-situ generation of hydrogen. The advantages of this system are: CO freehydrogen at fuelling stations, reversible catalytic reactions,recyclable reactants and products and relatively highhydrogencontents(6
e
8wt%)[19].Duetohighboilingpointsof cycloalkanes, the present infrastructure such as oil tankersand tank lorries can be used for the long-term storage andlong-distance transportation of hydrogen in the form of LOH.Theproposedsystemof hydrogen storage usingliquidorganichydrides will serve the transportation of hydrogen fromproduction facility to fuelling stations. Whereas for onboardstorage of hydrogen other methods such as gas cylinders orsystems based on metal hydrides will be useful.In order to implement the process of hydrogen deliveryusing LOH technology, it is important to examine the techno-economical feasibility of the method. This study targets thefeasibility of the hydrogen transportation and delivery using LOH as hydrogen carriers and a dehydrogenation reaction asmeansofproducinghydrogenatfuellingstations.Thepresentapproach particularly focuses on the transportation of hydrogen from production facility to fuelling stations.
2. Description of process
Hydrogenisproducedinrefineriesandchloroalkaliindustries.This hydrogen can be reacted with aromatics to form cyclo-alkanes. Cycloalkanes can be transported by lorries or pipe-lines to fuelling station site, and can be stored in storagetanks. A detailed description of the proposed process is givenin our earlier report[19]. At the fuelling station a subsequentdehydrogenation reaction supplies hydrogen to fuel cellvehicles and recycles back the toluene to the hydrogenproduction facility. Literature reports high selectivity andstability for some noble metal and non-noble metal-basedcatalysts for the dehydrogenation reaction[11
e
20]. Hydroge-nation and dehydrogenation reactions are well established.However R & D efforts are being devoted towards the devel-opment of appropriate systems for achieving these reactionsat low temperatures with low energy inputs.Fig. 1depicts a system based on methylcyclohexane (MCH)and toluene for the transportation of hydrogen. The systemboundary for the estimation of techno-economic feasibilityencloses the dehydrogenation setup at the fuelling station.The MCH is fed to the reactor and exposed to the catalystheated at 350
C. MCH on dehydrogenation give toluene andhydrogen. These products are separated using a condenser.Hydrogen is passed through a hydrocarbon trap. With subse-quent compression the clean hydrogen, free from CO
x
, can besupplied to the fuel cell vehicles. Liquid products thusobtained are then sent to an extractive distillation unit, whichseparates aromatics from unreacted cycloalkanes which arerecycled back to their respective storage. Pure toluene is sentback to the refinery for hydrogenation or can be directly soldin the market as a solvent.
3. Results and discussions
Several factors are considered while proposing the abovediscussed method for hydrogen transportation froma hydrogen production facility to fuel station. These include:
Use of various cycloalkanes
Development of an effective catalytic system consisting of active, selective and stable catalysts
Development of reactors for effectively carrying out theendothermic dehydrogenation reaction
Easy product purification, particularly to obtain cleanhydrogen
Economic estimations
Carbon footprint of the system
3.1. Cycloalkanes as candidates for hydrogentransportation
Several cycloalkanes including cyclohexane, methyl-cyclohexane, tetralin, decalin, cyclohexylbenzene, bicyclo-hexyl,1-methyldecalin,etc.maybeusedasahydrogencarrieras liquid organic hydrides. Each mole of cycloalkane haspotentialtotransport3
e
6molesofhydrogen.Thisresultsintoahighhydrogencapacitybetween3and7.5wt%[19].Catalyticdehydrogenation of these cycloalkanes delivers the hydrogen.The endothermic energy requirement for these reactions is inthe range of 64
e
69 kJ/mol of H
2
. This is much lower thanenergy that could be obtained by oxidation of H
2
(248 kJ/mol).Hydrogen storage capacities of cycloalkanes, boiling points,and endothermic energy required for dehydrogenation arecompared inTable 1. Due to high boiling points of cyclo-alkanes, the present infrastructure such as oil tankers andtank lorries can be used for the long-term storage and long-distance transportation of hydrogen in the form of LOH[19].Methylcyclohexane was selected for feasibility study as thedehydrogenation product toluene is relatively safe solventas compared to benzene produced during dehydrogenationof cyclohexane. Further, both the methylcyclohexane andtoluene are liquid at ambient conditions unlike naphthaleneproduced by dehydrogenation of decalin. The ready avail-ability of methylcyclohexane was also an importantconsideration.
3.2. Development of catalysts for dehydrogenation of cycloalkanes
The dehydrogenation of cycloalkanes can be effectivelycarried out using the metal catalysts well dispersed on
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Please cite this article in press as: Pradhan AU, et al., A feasibility analysis of hydrogen delivery system using liquid organichydrides, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.09.054
 
a high surface area support[11
e
20]. The mechanism of reaction involves adsorption of cycloalkanes on metallic sitewith rapid or simultaneous abstraction of the hydrogenatom via tetrahedral metal atom and formation of a pi-bond.Thus the products of the reaction include hydrogen andaromatics. Rapid removal of the hydrogen atom from theactive site and subsequent formation of molecular hydrogenis an essential step to avoid the reverse reaction on thecatalyst’s surface. Several monometallic and bimetalliccatalysts are proposed for this reaction. A brief review forthe catalysts reported has been covered in our earlier report[19]. A proprietary catalyst (i.e. NEERI DeH2) developed byour group exhibits excellent activity in terms of hydrogenproduction rates, 958 mmol/g 
met
 /min as compared to thebest reported 744 mmol/L
cat
 /min for a continuous fixed bedreactor system using MCH.
Fig. 1
e
Schematic diagram for hydrogen delivering plant delivering 10 kg/h using dehydrogenation of methylcyclohexane.Table 1
e
Hydrogen storagecapacityof various cycloalkanes,their boilingpointsand endothermicenergyrequirementfordehydrogenation.
Storage Media Hydrogen storage capacity Boling point(
C)Endothermic dehydrogenationenergy (kJ/mol of H
2
)wt% mol/L
Cyclohexane 7.2 27.77 80.7
þ
68.8Methylcyclohexane 6.2 23.29 101
þ
68.3Tetralin 3.0 14.72 207
þ
64.2cis-Decalin 7.3 32.44 193
þ
64.0trans-Decalin 7.3 31.46 185
þ
66.7Cyclohexylbenzene 3.8 17.63 237
þ
65.9Bicyclohexyl 7.3 32.0 227
þ
66.6cis-syn-1-Mehtyldecalin 6.6 29.31 213.2
þ
63.9trans-anti-1-Mehtyldecalin 6.6 28.52 204.9
e
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Please cite this article in press as: Pradhan AU, et al., A feasibility analysis of hydrogen delivery system using liquid organichydrides, International Journal of Hydrogen Energy (2010), doi:10.1016/j.ijhydene.2010.09.054

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