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A feasibility analysis of hydrogen delivery system using liquid organic 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

article info
Article history: Received 8 June 2010 Received in revised form 17 September 2010 Accepted 19 September 2010 Available online xxx Keywords: Hydrogen storage Hydrogen delivery Cycloalkanes Dehydrogenation Hydrogen station Feasibility analysis

abstract
The paper discusses the techno-economic feasibility of a hydrogen storage and delivery system using liquid organic hydrides (LOH). Wherein, LOH (particularly cycloalkanes) are used for transporting the hydrogen in chemical bonded form at ambient temperature and pressure. The hydrogen is delivered through a catalytic dehydrogenation process. The aromatics formed in the process are used for carrying more hydrogen by a subsequent hydrogenation reaction. Cost economics were performed on a system which produces 10 kg/h of hydrogen using methylcyclohexane as a carrier. With proprietary catalysts we have demonstrated the possibility of hydrogen storage of 6.8 wt% and 60 kg/m3 of hydrogen on volume basis. The energy balance calculation reveals the ratio of energy transported to energy consumed is about 3.9. Moreover, total carbon footprint calculation for the process of hydrogen delivery including transportation of LOH is also reported. The process can facilitate a saving of 345 tons/year of carbon dioxide emissions per delivery station by replacing gasoline with hydrogen for passenger cars. There is an immense techno-economic potential for the process. ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Hydrogen is a fascinating energy carrier. It can be produced from water by electrolysis. Its conversion to heat or power is simple and clean. When combusted with oxygen, hydrogen forms water; hence no pollutants are generated. Hydrogen is being pursued as a future fuel all around the world for automotive applications in internal combustion engines and in fuel cells [1,2]. Hydrogen-fuelled vehicles will use fuel cells, which can provide much higher energy conversion efficiency as compared to internal combustion (IC) engines with zero tail pipe 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 automotive fossil fuel economy to hydrogen economy will depend include: bulk production of hydrogen, transportation of hydrogen from production facility to fuelling station, onboard

storage of hydrogen and utilization of hydrogen for energy generation [1]. Production of hydrogen from hydrocarbon via steam reforming or auto-thermal reforming is relatively developed [5]. Similarly, as evident from the literature, the developments 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 transport involves several safety issues. The major safety issue is wide span of lower and higher explosion limits for H2 concentration in air. Transporting hydrogen using high pressure (typically 300e500 psi) cylinders for storage is not an attractive option as it involves high pressure hazards and potential explosion hazards. Carrying hydrogen in liquefied form attracts an energy penalty and thus is not viable. These problems can be overcome if hydrogen is either adsorbed on materials such as carbon based materials [6], metal hydrides [7,8], magnesium alloys [9] or boranes [10]. While developing

* Corresponding author. Tel.: þ91 712 2249885x410; fax: þ91 712 2249900; Mobile: þ91 9822745768. E-mail address: rb_biniwale@neeri.res.in (R.B. Biniwale). 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

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such hydrogen storage materials, capacity of the material in terms of weight and volume is an important factor to be considered. With a limited capacity it would result in a weight penalty and CO2 emissions associated with transportation. Also the adsorption and desorption kinetics has to be sufficiently fast to provide a continuous H2 supply. Another important requisite is to transport hydrogen containing media at close to atmospheric temperature and pressure. A novel approach for the supply of hydrogen is through liquid organic hydrides (LOH) using a catalytic reaction pair of dehydrogenation of cycloalkanes such as methylcyclohexane, cyclohexane and decalin; and hydrogenation of corresponding aromatics is a useful process for supply of hydrogen to PEMFC [11e20]. This is one of the most promising methods to store, transport and supply with in-situ generation of hydrogen. The advantages of this system are: CO free hydrogen at fuelling stations, reversible catalytic reactions, recyclable reactants and products and relatively high hydrogen contents (6e8 wt%) [19]. Due to high boiling points of cycloalkanes, the present infrastructure such as oil tankers and tank lorries can be used for the long-term storage and long-distance transportation of hydrogen in the form of LOH. The proposed system of hydrogen storage using liquid organic hydrides will serve the transportation of hydrogen from production facility to fuelling stations. Whereas for onboard storage of hydrogen other methods such as gas cylinders or systems based on metal hydrides will be useful. In order to implement the process of hydrogen delivery using LOH technology, it is important to examine the technoeconomical feasibility of the method. This study targets the feasibility of the hydrogen transportation and delivery using LOH as hydrogen carriers and a dehydrogenation reaction as means of producing hydrogen at fuelling stations. The present approach particularly focuses on the transportation of hydrogen from production facility to fuelling stations.

hydrogen. These products are separated using a condenser. Hydrogen is passed through a hydrocarbon trap. With subsequent compression the clean hydrogen, free from COx, can be supplied to the fuel cell vehicles. Liquid products thus obtained are then sent to an extractive distillation unit, which separates aromatics from unreacted cycloalkanes which are recycled back to their respective storage. Pure toluene is sent back to the refinery for hydrogenation or can be directly sold in the market as a solvent.

3.

Results and discussions

Several factors are considered while proposing the above discussed method for hydrogen transportation from a 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 the endothermic dehydrogenation reaction  Easy product purification, particularly to obtain clean hydrogen  Economic estimations  Carbon footprint of the system

3.1. Cycloalkanes as candidates for hydrogen transportation
Several cycloalkanes including cyclohexane, methylcyclohexane, tetralin, decalin, cyclohexylbenzene, bicyclohexyl, 1-methyldecalin, etc. may be used as a hydrogen carrier as liquid organic hydrides. Each mole of cycloalkane has potential to transport 3e6 moles of hydrogen. This results into a high hydrogen capacity between 3 and 7.5 wt% [19]. Catalytic dehydrogenation of these cycloalkanes delivers the hydrogen. The endothermic energy requirement for these reactions is in the range of 64e69 kJ/mol of H2. This is much lower than energy that could be obtained by oxidation of H2 (248 kJ/mol). Hydrogen storage capacities of cycloalkanes, boiling points, and endothermic energy required for dehydrogenation are compared in Table 1. Due to high boiling points of cycloalkanes, the present infrastructure such as oil tankers and tank lorries can be used for the long-term storage and longdistance transportation of hydrogen in the form of LOH [19]. Methylcyclohexane was selected for feasibility study as the dehydrogenation product toluene is relatively safe solvent as compared to benzene produced during dehydrogenation of cyclohexane. Further, both the methylcyclohexane and toluene are liquid at ambient conditions unlike naphthalene produced by dehydrogenation of decalin. The ready availability of methylcyclohexane was also an important consideration.

2.

Description of process

Hydrogen is produced in refineries and chloroalkali industries. This hydrogen can be reacted with aromatics to form cycloalkanes. Cycloalkanes can be transported by lorries or pipelines to fuelling station site, and can be stored in storage tanks. A detailed description of the proposed process is given in our earlier report [19]. At the fuelling station a subsequent dehydrogenation reaction supplies hydrogen to fuel cell vehicles and recycles back the toluene to the hydrogen production facility. Literature reports high selectivity and stability for some noble metal and non-noble metal-based catalysts for the dehydrogenation reaction [11e20]. Hydrogenation and dehydrogenation reactions are well established. However R & D efforts are being devoted towards the development of appropriate systems for achieving these reactions at low temperatures with low energy inputs. Fig. 1 depicts a system based on methylcyclohexane (MCH) and toluene for the transportation of hydrogen. The system boundary for the estimation of techno-economic feasibility encloses the dehydrogenation setup at the fuelling station. The MCH is fed to the reactor and exposed to the catalyst heated at 350  C. MCH on dehydrogenation give toluene and

3.2. Development of catalysts for dehydrogenation of cycloalkanes
The dehydrogenation of cycloalkanes can be effectively carried out using the metal catalysts well dispersed on

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Fig. 1 e Schematic diagram for hydrogen delivering plant delivering 10 kg/h using dehydrogenation of methylcyclohexane.

a high surface area support [11e20]. The mechanism of reaction involves adsorption of cycloalkanes on metallic site with rapid or simultaneous abstraction of the hydrogen atom via tetrahedral metal atom and formation of a pi-bond. Thus the products of the reaction include hydrogen and aromatics. Rapid removal of the hydrogen atom from the active site and subsequent formation of molecular hydrogen is an essential step to avoid the reverse reaction on the

catalyst’s surface. Several monometallic and bimetallic catalysts are proposed for this reaction. A brief review for the catalysts reported has been covered in our earlier report [19]. A proprietary catalyst (i.e. NEERI DeH2) developed by our group exhibits excellent activity in terms of hydrogen production rates, 958 mmol/gmet/min as compared to the best reported 744 mmol/Lcat/min for a continuous fixed bed reactor system using MCH.

Table 1 e Hydrogen storage capacity of various cycloalkanes, their boiling points and endothermic energy requirement for dehydrogenation. Storage Media Hydrogen storage capacity wt%
Cyclohexane Methylcyclohexane Tetralin cis-Decalin trans-Decalin Cyclohexylbenzene Bicyclohexyl cis-syn-1-Mehtyldecalin trans-anti-1-Mehtyldecalin 7.2 6.2 3.0 7.3 7.3 3.8 7.3 6.6 6.6

mol/L
27.77 23.29 14.72 32.44 31.46 17.63 32.0 29.31 28.52

Boling point ( C)
80.7 101 207 193 185 237 227 213.2 204.9

Endothermic dehydrogenation energy (kJ/mol of H2)
þ68.8 þ68.3 þ64.2 þ64.0 þ66.7 þ65.9 þ66.6 þ63.9 e

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Another important aspect of catalyst design is use of support for structured catalyst. Besides requiring a high surface area of the support, its structured nature is also important. Using Al2O3 or carbon pellets placement of catalyst in the reactor is difficult, particularly for heating the catalyst, except in the case of a packed bed reactor. As explained in the next section, if plate type heaters are used then the contact between heater and pellets is not continuous and results in poor heat transfer to the catalyst. Earlier, we have reported the use of carbon cloth and alumite plates as support for metal catalysts [18,19]. This structured catalyst is suitable for placement of catalyst in the reactor.

3.3. Development of reactors for catalytic dehydrogenation of cycloalkanes
Dehydrogenation of cycloalkanes being an endothermic reaction demands supply of heat. The catalyst’s surface is thus required to be at temperatures in the range of 300e400  C. Since the reactant, i.e. methylcyclohexane, is fed to the reactor in liquid form the surface temperature of the catalysts may be lowered by losing energy in vaporizing the reactant and product. However, in the case of vapor phase reaction, wherein the cycloalkanes are introduced as vapors, the contact between reactant and solid catalysts may be poor. In our work we have used two different types of reactors e namely a packed column reactor and an advanced spraypulsed reactor. The packed column reactor is simple to operate and particularly useful when the source of heat is a solar concentrator. It is reported in the literature including our earlier studies [16e20] that creation of unsteady state conditions on the surface of the catalysts helps in improving the activity and stability of the catalysts for dehydrogenation of cycloalkanes. Several attempts including superheated film conditions, spray-pulsed reactors, etc. have been reported for creating unsteady conditions. We have used a spray-pulsed reactor, as described in detail elsewhere and briefly herein, to create alternate wet and dry conditions over the catalyst surface. The catalyst is kept on a plate type heater and the reactant is introduced as an atomized spray over the catalysts. A fine nozzle installed at the top of the reactor is used for creating the atomized spray and for injecting cycloalkanes at a controlled injection pulse frequency and pulse width. During the injection step, reactant reaches the heated catalyst’s surface in fine droplets and evaporates to form a dense vapor phase in close vicinity to the catalyst surface. This improves the catalyst-reactant contact. During the interval between two injection pulses, i.e. dry step, the product and unreacted reactant gets removed from the surface of the catalyst. The alternate wet and dry conditions thus help in keeping the catalyst’s surface clean and active for longer stability of the catalyst. Also, the surface of the catalyst can be maintained at high temperature favoring the dehydrogenation reaction. Using several reactors in combination with a time phase lag between injections would provide the hydrogen on a continuous basis. Selection of the reactor is based on the application for which the hydrogen is required and the method used for heating the catalyst. In the case where the solar concentrators

are used for heating the catalyst, then tubular packed bed reactors are useful. Even a microchannel reactor could be a good option. Whereas when electrical heaters are used, either reactor can be employed. The catalysts on a laboratory scale have been evaluated for their hydrogen evaluation rate at various conditions. The reaction conditions were optimised for an advanced spraypulse injection reactor. The optimum temperature for the dehydrogenation of cycloalkanes is in the range of 300e350  C. In our previous study we have reported optimization of the pulse injection frequency and pulse width for feeding cycloalkanes to the reactor [18,20]. Accordingly for the catalysts referred in this study for dehydrogenation of methylcyclohexane the best feed conditions obtained were pulse injection frequency of 0.33 Hz and pulse width of 10 ms.

3.4.

Mass and energy balance on the process

The process of delivering hydrogen using LOH is described in Fig. 1. In order to establish the flow of raw materials, products, product separation and various process parameters, a detailed mass and energy balance for the process has been worked out. The basis for calculations was taken from laboratory data (our own work) on catalyst performance for generating hydrogen at 10 kg/h with continuous operation of 100 h. As depicted in Fig. 1 the mass balance has been carried out for targeted delivery of 10 kg/h of hydrogen. The delivery pressure is about 1e1.2 bar and the temperature is ambient. In order to maintain the flow through the reactor, hydrogen is used as a sweep gas. Initially an external source of hydrogen may be used to start the reaction. Once the system is able to generate the hydrogen, a part of the hydrogen is recycled back as the sweep gas. The reactor is designed to generate about 12 kg/h of hydrogen. Out of the total 12 kg/h of hydrogen generated, 10 kg/h is supplied to the vehicles after compression. The balance of 2 kg/h of hydrogen is recycled back to the reactor, after compression, at a pressure of 2.5e3 bar. Estimated requirement of MCH at the conversion efficiency of 90% is 216 kg/h. The products hydrogen and toluene are separated by using a condenser. The condensable product contains about 22 kg/h of MCH. The separation of MCH and toluene is carried out in an extractive distillation unit. An evaporative loss of 0.3% from storage of MCH and toluene has been estimated by considering the maximum ambient temperature of 40  C. Similarly, other process losses have been estimated as 0.1% and evaporative losses during transportation is estimated as 0.5%. This amounts to a total loss of MCH of about 0.9%. The energy requirement for the hydrogen delivery process consists of energy for carrying out the reaction at 320e350  C, energy required for pumping MCH to the reactor, energy for the condenser, energy for extractive distillation, energy required for compression of hydrogen, and for process equipment. When the required energy is compared with the energy that can be evolved by hydrogen combustion, an energy efficiency factor can be calculated using: Energy efficiency ¼ Energy generation potential of hydrogen supplied/Total fossil fuel energy supplied. Based on the energy balance estimates are given in the Table 2. The total energy consumption for production of hydrogen during is 5.10 kW/kg and the energy that can be

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Table 2 e Energy efficiency estimation. Sr. No. Description Quantity
3465.5 547.07 8.53 54.4 13.2 623.2 112 80 815.2 5.10

A) Calculations for energy Consumption during the process 1. Methylcyclohexane requirement (kg/day) 2. Energy requirement for dehydrogenation a) Heat of reaction @62 kJ/mol (kW) b) Energy required for pumps and instrumentation (kW) c) Energy required for chillers (kW) d) Energy required for illumination and plant accessories (kW) Sub Total (a to d) (kW) 3. Energy required for separation of unconverted methylcyclohexane and toluene afterreaction (kW) 4. Energy required for compression of hydrogen (kW) Grand total of energy consumption (kW) In terms of per kg of hydrogen the energy required (kW/kg) B) Energy production by hydrogen made available through LOH 5. Total hydrogen produced (kg/day) or In terms of (kmol/h) 6. Energy that can be released by hydrogen (kJ/mol) 7. Gross energy available by hydrogen produced (kW/h) 8. Total energy available at 60% efficiency of fuel cell stacks (kW/h) 9. Total energy available in 16 h (kW) In terms of per kg of hydrogen the energy available (kW/kg) 10. Ratio of energy generated/energy consumed a) Without considering the energy requirement for compressor b) With considering the compressor energy need

160 4.96 242 333.65 200.19 3203 20.02 4.36 3.92

made available by hydrogen is 20.02 kW/kg. This indicates a favourable energy ratio in terms of energy produced/energy consumed. The energy efficiency ratios when the compressor is not considered and when it is considered are 4.36 and 3.92 respectively. The major energy requirement out of the total energy for dehydrogenation of methylcyclohexane is for the heat of reaction. This requirement is about 67.12%. Separation of products and unreacted reactant contributes to 13.7% of the total energy requirement. This clearly indicates that the scope of energy reduction is rather marginal as most of the energy required is for heat of reaction. Energy efficient pumps and separation units could be designed for reduction in the energy requirement.

3.5. Financial feasibility analysis of the manufacturing process
Cost-effectiveness analysis was carried out for hydrogen delivery using dehydrogenation of methylcyclohexane. Assuming the cost of methylcyclohexane at the rate of 0.97 USD/kg and the selling price for toluene considered about 0.89 USD/kg the cost of hydrogen production at present estimates would be approximately 5.33 USD/kg delivered at the fuelling station. The following assumptions were considered:  10 kg/h of hydrogen production.  300 working days per year.  16 h working per day. Most importantly the cost of hydrogen delivery will not increase significantly even if the distance of delivery is increased.

Therefore the hydrogen delivery using LOH is a cost-effective process having favourable energy efficiencies. The technology, which is offered, should be based on realistic assessment of cost and benefit, keeping in view the technical and economic feasibility. Many of the potential benefits of this technology assure sufficient incentives to the manufacturers to achieve the desired goals. A key component, therefore, must be the cost-effective production of Hydrogen to ensure compliance with standards. The cost of each system component includes the cost of raw material, manufacturing, assembly and mark-up. Mark-up refers to the additional cost percentage to account for payment to workers, overhead expenses and profit. The final resulting “cost” is thus actually a projected “price” of the hydrogen generated at the fuelling station. In addition, the projected cost of hydrogen to the consumer (potentially an FCV motorist) is provided in this report, with inclusion of taxes. The detailed financial analysis is done considering the various cost components involved in the process to arrive at optimum plant capacity. As the capacity of the plant (amount of hydrogen produced) increases, the fixed capital and the operating capital both increase but evidently an increase in fixed capital is not as proportional as increase in the operating capital. With increase in the capacity of the plant, the payback period decreases. From the cost estimations, carried out on different plant capacities, it has been observed that the capacity of a plant of 10 kg/h is suitable with respect to demand and economic criteria. A total of 300 working days in a year with 16 h working per day were considered for the calculation of equipment capacities. For the above mentioned production schedule the cost of fixed capital and operating cost requirement has been estimated and reported subsequently. Tables 3e6 depict the cost involved in plant and machinery, electrical power requirement, manpower, and annual operation &

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Table 3 e Plant and machinery taking 1 USD [ 47 Rs. Equipment
Reactor Storage tanks Resistance temperature Detector (RTD) Pressure gauge Level transmitter Flow meters Control valves Frequency controller Safety interlocking Gas chromatograph Extractive distillation columns (For MCH & toluene separation) Distillation column Air compressor Water pump and Storage Fuel pumps Chiller Condenser (heat exchanger) Phase separating vessel Total

Table 5 e Manpower requirement. Category No. of People Total Salary USD/Month
255.32 340.43 212.77 808.51 9.70

Required No.
2 3 6 4 4 6 2 1 2 1 2 1 1 1 10 1 2 2

Cost (Thousand USD)
22.55 17.23 6.38 1.70 0.85 1.28 3.83 2.13 2.13 13.83 12.77 4.26 0.43 0.96 0.74 6.38 12.77 0.85 111.06

Supervisor 1 Operators (skilled) 2 Cleaners (unskilled) 2 Total 5 Annual man power cost (Thousand USD)

# Man Power calculation is based on Indian Standards. It might differ from country to country.

maintenance cost respectively. The cost of plant and machinery has been estimated on the basis of prevailing costs in the local market for fabrication of various equipments. The details of equipment are given in Table 3 and a schematic of the process flow sheet without finer details in depicted in Fig. 1. Based on the local sources the plant and machinery cost is estimated at 11106 USD. As shown in Table 4 the cost estimate for energy requirement for per day operation for 16 h is 178 USD/day. Table 5 shows manpower calculations using Indian standards. Production cost is calculated by finding annual operation and maintenance cost, utilities cost and manpower costs as shown in Table 6. Total project cost was calculated as shown in Table 7 as 327000 USD. According to the break-up of total cost of the plant about 37.36% cost is of plant and machinery. The second major component of the cost is working capital contributing 18.07%. The implication of fluctuations in the price of methylcyclohexane may affect the working capital cost. Whereas

technical know-how/engineering fees, cost of plant and machinery would remain the same for the same capacity of the plant. However cost reduction in the plant and machinery, preoperative and contingencies cost may be attempted to reduce the total cost of the project. Out of the total working capital the major cost is due to raw materials (69.5%) and utilities (22.6%). The cost of raw materials was considered as the cost of methylcyclohexane and the basic cost of hydrogen for a year. The cost of hydrogen if to be purchased from hydrogen production facility would be approximately 1.5 USD/kg. This assumption is based on the projected cost of the hydrogen from coal gasification or hydrocarbon reforming as available in the open literature. The pricing of hydrogen as projected by different reports in the literature ranges between 2 and 5 USD/kg (untaxed). The cost of CO2 sequestration in case of hydrogen production from steam reforming would generally offset the price of hydrogen. Based on the estimated cost of production of hydrogen at fuelling station using dehydrogenation of methylcyclohexane (including re-hydrogenation of toluene for subsequent cycles) a comparison has been carried out for pricing of hydrogen. The sales price of hydrogen (including taxes) to the customer was varied from 7 to 7.75 USD/kg. Effect of this variation on cumulative cash accruals is depicted in Fig. 2. In order to obtain a reasonable payback period, price of hydrogen was selected as 7.45 USD/kg. Cost benefit analysis as seen in Table 8 indicates that hydrogen if sold at 7.45 USD/kg, results in an annual profit of 58770 USD (after tax). The effective payback period was calculated based on the assumption that

Table 4 e Electric power requirement cost of electricity (per unit i.e. kW-h) [ 0.149 USD/kW-h (Indian standards). Plant Operation
Energy for dehydrogenation Energy for hydrogenation Energy for lighting and illumination Chiller and instrumentation Extractive distillation Distillation of hydrogenation products Total (kW-h/day) Power Cost (USD/day)

Table 6 e Annual operation & maintenance and cost of hydrogen production. Item Cost (in Thousand USD)

No. of Units
1 Heater & 8 Pumps 1 Heater & feed pumps Lump Sum 1 3 1

Power (kW-h/day)
502.50 500 13.2 54.72 80 48 1198.42 178.49

Raw Material/Chemicals. 164.51 Cost on Utilities. 53.55 Annual Manpower cost 9.70 Annual cost of Repairs. 5.55 Depreciation on P&M @ 10% 11.11 Depreciation on L&B @ 5% 1.06 Interest on capital 10.44 (@ 25% of total capital) @ 12% Total annual expenditure for 48,000 kg 255.92 hydrogen production. Therefore the cost of hydrogen production is 5.33 USD/kg

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Table 7 e Total project cost. Item
Land (on existing fuel pumps) Site development Building and civil work Plant and machinery: Indigenous Imported Erection/Commissioning (10% of P &M) Technical know how and engineering fee Misc. Assets: Electrical Fittings Deposits Fire fighting/Others Preliminary and preoperative Contingency provision Margin money for working capital (3 Months O&M) Total cost of Project

Table 8 e Cost benefit analysis. Costs (Thousand USD)
Nil 21.28 5.32 111.06 Nil 11.10 53.19 2.17 6.38 4.22 21.28 31.91 59.09 327

Item
Sales price of hydrogen (USD/kg) Basic cost of production Royalty on sales price @ 1% Local tax, octroi @ 5% Sales overhead Total cost of manufacturing Profit per kg of hydrogen Annual profit before tax (Thousand USD) Annual profit after tax @ 30%(Thousand USD)

Cost USD/kg
7.45 5.33 0.07 0.27 0.03 5.70 1.75 83.96 58.77

the fuelling station will operate at 50, 70, 95 and 100% capacity for the first, second, third and fourth year respectively. From the fourth year of operation 100% capacity utilization is expected. The cash inflow estimates shown in Table 9 results in a payback period of 6.41 years.

4. Comparison with hydrogen carrying pipelines
When the LOH based system is compared with a pipeline transport system for hydrogen, it can be seen that pipeline installation requires huge investments per km of pipeline. According to estimates provided by NREL, DOE, USA [21] and ANL, USA [22] the hydrogen pipeline cost may be of the order of 400000 USD per mile. This cost may be higher for the pipeline with diameter more than 3 inches (0.075 m). Although

it is argued in the literature that the variation in pressure simply can vary the hydrogen storage/delivery capacity of pipeline, compression of hydrogen is an energy intensive operation. Whereas calculations show LOH based systems with 10 kg/h hydrogen delivery had an overall installation cost of approximately 327000 USD (as shown in Table 7). This includes all preoperative as well as three months operative costs. Unlike in the case of pipelines, the costs of transportation do not vary largely depending on the distance if LOH approach is used. Use of pipelines has limitations when the distance of transport is high. For an example, in this case wherein the hydrogen transportation upto 300 km is considered the approximate cost of hydrogen pipelines could be of the order of 800 million USD. Moreover due to high flammability of hydrogen, transportation of using pipelines is risky as well.

5. Reduction in total carbon footprint emission
Estimation of total carbon footprints is an increasingly important evaluation tool for decision making. Especially applied during the planning phase, it can pinpoint process steps with a high environmental impact and thus, provide guidance towards optimising the actual technology implementation. One of the main goals of this study was the assessment of the environmental impact of hydrogen fuel transported in the form of liquid organic hydrides.

600

Cummulative cash accrual (1000 USD)

500 400 Project Cost 300

7.75 USD/kg 7.45 USD/kg 7.25 USD/kg 7.0 USD/kg
Table 9 e Pay back period Total project cost [ 327 Thousand USD. Year Percentage production capacity utilization
50 70 95 100 100 100 100 100

Net Cash Inflow (Thousand USD)
29.38 41.14 55.83 58.77 58.77 58.77 58.77 58.77

Cumulative Cash Inflow (Thousand USD)
29.38 70.52 126.36 185.13 243.90 302.68 361.45 420.23

200 100 0
1 2 3 4 5 6 7 8

0

2

4 6 Number of years

8

10

Fig. 2 e Variation in cumulative cash accruals for varying sales price of hydrogen.

Payback period ¼ 6.41 years.

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Table 10 e Annual savings in Carbon footprint assuming total distance of travel for transport once [ 300 km, mileage of a fuel cell car [ 73.6 miles/kg of hydrogen and gasoline car mileage [ 15 km/l. Sr. No.
A 1 2 3 B 4 5 6 7 C 8 9 10 D

Description
Dehydrogenation and hydrogenation processes Number of electrical units consumed (kW/day) Units per year (kW/Year) Amount of CO2 emitted in the process of dehydrogenation and hydrogenation (kg/year) Transportation of LOH Average distance travelled (km/year) Mileage (km/l) for a tanker carrying LOH Total diesel consumed (l/year) Amount of CO2 emitted in the transport (kg/year) So Total Carbon footprint of the process (kg/year) [ (3) D (7) Hydrogen produced in one year (kg/year) Distance that could be travelled by fuel cell vehicle (mile/year) CO2 being evolved by normal Gasoline vehicle to travel the same distance (kg/year) CO2 that can be saved (kg/year)

Value
1198 359,526 503,336 25,800 4 6450 17,415 520,751 48,000 353,280 866,713 345,962

The function of the product, i.e. hydrogen, is to serve as fuel for motor vehicles. This produces water when used as fuel in an FCV that lead to zero tail gas emissions. The total CO2 emissions calculated for LOH system include the CO2 emissions attributed to the energy requirement for dehydrogenation and emissions from transportation of LOH using tank lorries. Furthermore, if the distance travelled by the FCV is compared to that of a gasoline powered vehicle, the total carbon footprint reduction is remarkably high for LOH based hydrogen transport and delivery system. As detailed in Table 10, for the basis for estimation of CO2 emissions avoided a distance of 300 km for hydrogen transportation is considered. The CO2 emissions due to transportation of LOH and dehydrogenation reaction at a fuelling station have been estimated about 17,400 and 503,300 kg/year. This amounts to total carbon foot print of 520 tons/year. A gallon of gasoline equivalent (gge) of hydrogen is about 1 kg. A fuel cell driven passenger car would cover about 74 km per kg of hydrogen. It is considered that a gasoline driven car gives mileage of 15 km/l of gasoline. Using a proper emission factor for CO2 emissions from gasoline driven cars, for a total car-kms travelled of 350,000 km/year the carbon foot print would be 866 tons/year. Considering that a fuelling station with 10 kg/h of hydrogen delivery capacity would serve to fuel cells vehicles there by avoiding use of gasoline, the carbon foot print reduction of 345 tons/year can be achieved. This amounts to a 40% reduction in CO2 emissions as compared to normal gasoline driven vehicles by enabling the use of fuel cell vehicles through supply of hydrogen using LOH system.

capacity of 10 kg/h has been estimated as 7.47 USD/kg including all expenses and taxes. Although the analysis is carried out in an Indian context, it nevertheless is useful for estimating the potential for other countries. Further, estimations of carbon footprint exhibit the possibility of a large saving on carbon emissions by facilitating hydrogen supply using this option. In view of the excellent activity of our proprietary catalyst the option is highly feasible.

Acknowledgements
Financial support received from Ministry of New and Renewable Energy, New Delhi is acknowledged. The authors Ms. Anshu Shukla and Ms. Jayshri Pande would like to acknowledge CSIR for their Senior Research fellowships.

references

6.

Conclusions

Several advantages associated with liquid organic hydrides (LOH) for storage and supply of hydrogen include relatively high hydrogen storage capacity, carrying hydrogen in chemically bonded form at near ambient conditions, easy delivery of hydrogen, and purity of hydrogen for applications in fuel cell vehicles. In view of LOH as a potential hydrogen delivery option, the economic analysis carried out reveals a high feasibility. The near future cost of hydrogen for a plant of

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e9

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