Renewable and Sustainable Energy Reviews 16 (2012) 67826792

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Renewable and Sustainable Energy Reviews

An overview of hydrogen gas production from solar energy

Department of Thermal Engineering and Energy, Douala University Institute of Technology, PO Box 8698 Douala, Cameroon Environmental Energy Technologies Laboratory (EETL), University of Yaounde I, PO Box 812 Yaounde, Cameroon

a r t i c l e i n f o
Article history: Received 22 February 2012 Received in revised form 13 July 2012 Accepted 16 July 2012 Keywords: Hydrogen production Renewable energy Solar energy Electrochemical processes Photochemical processes Thermochemical processes

a b s t r a c t
Hydrogen production plays a very important role in the development of hydrogen economy. Hydrogen gas production through solar energy which is abundant, clean and renewable is one of the promising hydrogen production approaches. This article overviews the available technologies for hydrogen generation using solar energy as main source. Photochemical, electrochemical and thermochemical processes for producing hydrogen with solar energy are analyzed from a technological environmental and economical point of view. It is concluded that developments of improved processes for hydrogen production via solar resource are likely to continue in order to reach competitive hydrogen production costs. Hybrid thermochemical processes where hydrocarbons are exclusively used as chemical reactants for the production of syngas and the concentrated solar radiation is used as a heat source represent one of the most promising alternatives: they combine conventional and renewable energy representing a proper transition towards a solar hydrogen economy. & 2012 Elsevier Ltd. All rights reserved .

nts 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hydrogen production from new energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hydrogen production from solar energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Photochemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1. Bio-production of hydrogen from photosynthetic microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.2. Photo-electrolysis of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Thermochemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1. Solar cracking of hydrocarbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.2. The steam reforming of hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.3. Thermochemical transformation of biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Electrochemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Comparison and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Exergy efficiency of the different processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6782 6783 6784 6784 6784 6785 6786 6786 6787 6788 6789 6790 6790

4.

5.

4.2. Economic comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . ..................................................................................................

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1. Introduction

crisis. The growing energy demand coupled with the depletion of fossil resources, the accentuation of climate change, the fragility and dangers of nuclear The critical energy situation of the world raises serious con-cerns and projects on the horizon, energy and power recently witnessed at Chernobyl and environmental Fukushima, raised an obvious question; what alternative is there in our society to come out of this energy slump? n Corresponding author at: Department of Thermal Engineering and Energy, After the era of fossil fuel, renewable energy Douala University Institute of Technology, PO Box 8698 Douala, Cameroon. Tel.: (notably solar) appears as a strong driving force 237 961 23 570. capable of maintaining the availability of energy with E-mail address: s1_koumi@yahoo.fr (S. Koumi Ngoh) hydrogen as energy carrier. Hydrogen with its properties listed in Table 1 is presented as one of 1364-0321/$ - see front matter & 2012 Elsevier Ltd. All rights the
reserved. http://dx.doi.org/10.1016/j.rser.2012.07.027

S. Koumi Ngoh, D. Njomo / Renewable and Sustainable Energy Reviews 16 (2012) 67826792 Table 1 Physico-chemical characteristics hydrogen [1]. Properties ICP (inferior calorific power) SCP (superior calorific power) Gaseous density 20.3 K and 273 K Liquid density 20.3 K Specific heat capacities Cp/Cv Heat capacity of vaporization Numerical values 10,800 kJ/Nm or 33.33 kWh/kg 3 12,770 kJ/Nm or 39.41 kWh/kg 3 3 1.34 kg/m /0.08988 kg/m 3 70.79 kg/m 14,266/10,300 J/kg K 445.4 kJ/kg
3

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energy mixed up in order to satisfy both the needs of the local population and the industries.

Oil 30% Natural gas 48%

Water 4% Coal 18%

Fig. 1. Distribution of the modes of hydrogen production [2].

alternative energy carrier [1]. What is it really? Is hydrogen the actual solution to all future energy provision problems? In order to answer the existing question about hydrogen as an alternative energy carrier and hydrogen as a future energy survival, many different techniques have been exploited. Cur-rently hydrogen production through advanced technologies using fossils [2] ( Fig. 1) is realized at 95% in particular by steam reforming of natural gas (48%) [3]. Hydrogen production from other fossil resources (Hydrocarbon 30% and Coal 18%) is princi-pally obtained by the process of partial oxidation. The last advanced process of hydrogen production is by the electrolysis of pure alkaline water as a function of the raw material which permits an answer to 4% of the worlds demand [2, 3]. This recourse of fossil resources which is not only a raw material for hydrogen but also an energy source for the processes posed two major problems namely: the depletion of resources and the increase of the concentrations of carbon dioxide and Methane; main greenhouse gases in the atmosphere, as they contributes respectively 63% and 19% of the peak [4]. As an illustration, the average of only carbon dioxide emitted to the atmosphere with respect to the amount of methane gas being consumed as analyzed by the process of steam reforming stands at 9 kg/kg of hydrogen [5].

The scarcity of fossil resources and the consequent emission of CO2 and CH4 into the environment drive us to revise means for this

thermochemical and electrochemical technologies that offer a promising Renewables are an emissions-free way to produce hydrogen, alternative for the storage of solar energy. and, conversely, hydrogen offers a way for renewables to generate transportation fuel and reliable power. The versatility of renew-able The objective of this work is to make a technologies allows them to be adapted to meet diverse energy large inventory of fixtures of these needs. Though costs for some renewable technologies are higher technologies of hydrogen production than traditional generated sources, technological advance-ments and through solar energy which brings out the increased in demand in the energy market has lead to reduction necessary elements responding to a prices. Additionally, the environmental benefits help to compensate number of questions and even the for the higher costs. When taken as a whole, the future conjunction problems earlier men-tioned. The of hydrogen and renewable energy technology is a promising one. methodology of the study made below is at first technological. The environmental and Solar energy is potentially the most abundant renewable energy economical stakes relative to an economic resource available to us and hydrogen production from solar energy development of hydrogen through solar is considered to be the ultimate solution for sustain-able energy. means will be approached. This will ensure Many researchers have been involved in analyzing the different solar some degree of reflection on the viability hydrogen production methods based on energy and exergy analysis. and future perspectives on the production Wang et al. [6] have examined the solar-to-hydrogen reaction and use of solar hydrogen as an energy mechanisms including thermochemical cycles that utilize heat to split vector especially for regions endowed with water molecules, electrolysis that utilizes electric potential to split sufficient solar radiation. water molecules, and photochemical processes that utilize photonactivated electrons of auxiliary reagents (sensitizer and catalyst) to activate and split water molecules. An overview of theory and current technological status of hydrogen from Solar Energy was done by 2. Hydrogen production from new energy Erickson and Goswami [7]. The Exergetic assessment of solar hydrogen produc-tion methods was investigated by Joshi et al. [8]. The recourse on exhaustible fossils They have classified the solar hydrogen production system based on sources for hydrogen production the energy input and solar thermal, type of chemical reactants and contributes greatly to the increase in the for different hydrogen production processes involved for example, greenhouse effect. This is what would have electrolysis, reforming, gasification, cracking etc. For a case study been taken care of technically and they have analyzed the sustainability of a solar PV based hydro-gen system through exergy efficiency and sustainability index. Laterfinancially (harnessing CO2 or ecotax), Joshi et al. [9] have made the comparison of sustainability index forcapable of modifying the thresholds of solar thermal and photovoltaic (PV) hydrogen produc-tion systems. alternative competitive economic solutions particu-larly renewable energy [10]. The development of the methods of hydrogen Among the many techniques of solar hydrogen productionproduction based on renewable energy sources takes place as much as possible identified, some have reached a stage of industrial and commer-cial without releasing the greenhouse gas [11]. maturity, and others are the subject of research. These technologies These methods represent alternative ways beyond their diversity are grouped into three families: photochemical, for hydrogen

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Pyrolisis cell Sun Solar cell Thermal collector Thermal engine

Termochemical cycle of water

Craquing of hydrocarbon

Geothermal

splitting Gasificatio n

Thermochemical Organic Waste combustor decompositio

Solar reforming of hydrocarbon Solar electricity + electrolysis

Wind

Wind turbine combustor

Solar Hydrogen

Photosynthetica l

Hydrogen
Gasogene

plant

Fig. 3. An outline of the techniques of hydrogen production from solar energy.

Fig. 2. Techniques of hydrogen production from renewable energies.

Photochemical processes use solar light to produce the hydrolysis of water. production through fossils combustibles. Hydrogen provides theNowadays two procedures are known: the connecting point between renewable electricity production andphotobiological and the transportation, stationary and portable energy needs. When thephotoelectrochemical. electricity from solar photovoltaics, wind, geothermal, ocean and hydro technologies is used to produce and store hydrogen, the renewable source becomes more valuable and can meet a variety of needs. In transportation applications, hydrogen provides a way to convert renewable resources to fuel for vehicles. Renewably produced hydrogen for transportation fuel is one of the most popular hydrogen economy goals, as it can be domestically produced and emissions-free. Recently, Koroneos and Dimitrios [12] have worked on the comparison of hydrogen production processes based on the exergy efficiency using various renewable energy sources. The Green methods for hydrogen production were also presented by Dincer [13] while Prospects and chal-lenges of renewable hydrogen were discussed by Mazloomi and Gomes [14] and Abbasi [15]. In all the techniques involved in hydrogen production three things must be taken into considera-tion: The raw material, the energy necessary for the production and the process of production. For most of the processes, there exist relatively many important variants [16]. Fig. 2 below summarizes the different methods of hydrogen production from renewable energy sources such as wind, hydroelectricity and geothermal.

3. Hydrogen production from solar energy. The techniques involved for the production of hydrogen from solar origin have attained a state of effectiveness and maturity thanks to the upcoming of new technological concepts and the creation of new solar thermodynamic stations [17]. These tech-nologies enable the transformation of solar radiations into heat up to a temperature ranging between 200 1C and 2000 1C with a maximum efficiency of 70%. This primary heat will later be converted to an energy vector of hydrogen. Many different works have been realized for the promotion of solar energy as a primary source of energy production [18, 19]. The techniques of hydrogen production through solar energy are summarized in Fig. 3. 3.1. Photochemical processes

tages, as well as problematic issues [20]. The H2 metabolism of green algae was first discovered in the early 1940s by Hans Gaffron. He observed that green algae (under anaerobic conditions) can either use H2 as an electron donor in the CO2fixation process or evolve H2 in both dark and the light [21]. Although physiological significance of the H2

metabolism in algae is still a matter of basic research, the process of photohydrogen production by green algae is of interest because it generates H2 gas from the most abundant resources, light and water as shown on Fig. 4 [22 Fig. 4 24]. Cystis pyrifera is the most convenient species because it has the highest growth rate of (50 t VS/ha yr) and can be harvested many times per year.

Fig. 4. Bio-production of hydrogen.

3.1.1. Bio-production of hydrogen from photosynthetic All microbial conversions can be microorganisms carried out at ambient conditions, however Photobiological processes are based on the capacity of some organisms, such as green algae, cyanobacteria, and photosyn-theticlower rate of H2 production and low yield bacteria, to act as biological catalysts in the production of hydrogen are the main drawbacks. All processes are from water and different enzymes, such as hydrogenase andcontrolled by the hydrogen-producing nitrogenase. Diversity in microbial physiology and metabo-lismenzymes, such as hydrogenase and nitromeans that there are a variety of different ways in which genase. Hydrogenases exist in most of the microorganisms can produce H2, each one with seeming advan-photosynthetic micro-organisms and they can be classified into two categories:

S. Koumi Ngoh, D. Njomo / Renewable and Sustainable Energy Reviews 16 (2012) 67826792 Table 2 Comparison of important biological H production processes [25, 26].
2

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Process Direct biophotolysis

General reaction 2H Ohigh-2H O

Advantages Can produce H directly from water and sunlight Solar conversion energy increased by ten folds as compared to trees, crops
2

Disadvantages Required high intensity of light. Simultaneous production of O and H

Hydrogenase is highly sensitive to even moderately low concentration of O 2 Lower photochemical efficiency Indirect biophotolysis (a) 6H O6CO light2 2

Cyanobacteria can produce H from water

C H O 6O 6 12 6 2 (b) C H O 2H O6 12 6 2 4H 2CH COOH2CO 2 3 2 (c) 2CH COOH4H Olight3 2 8H 4CO 2 2 Overall reaction 12H Olight-12H 6O
2 2 2

Has the ability to fix N from atmosphere

Uptake hydrogenase enzymes are to be removed to stop degradation of H 2 About 30% O present in gas mixture
2

Photofermentation

CH COOH2H Olight3 2

4H 2CO
2

A wide spectral light energy can be used by these bacteria Can use different organic wastes High substrate conversion efficiencies Degrade a wide range of substrates

Production rate of H is slow O has an inhibitory effect on 2 2 nitrogenase Light conversion efficiency is very low, only 15% Pre-treatment may be needed due to either the toxic nature of the substrate (effluent), or its color/opaqueness. Large reactor surface areas requirementExpensive equipment

H2O

(i) uptake hydrogenases and (ii) reversible hydrogenases. Uptake hydrogenases, such as NiFe hydrogenases and NiFeSe hydrogenases, act as important catalysts for hydrogen consump-tion. Reversible hydrogenases, as indicated by its name, have the ability to produce H2 as well as

O2

Fig. consume hydrogen depending on the reaction condition. The major components of nitrogenase are 5. Principle diagram for the photochemical decomposition of MoFe protein and Fe protein. Nitrogenase has the ability to use magnesium adenosine triphosphate (MgATP) and electrons to reduce a variety of substrates (including protons). This chemical reaction yields hydrogen production by a nitrogenase-based system where ADP and Pi 3.1.2. Photo-electrolysis of water refer to adenosine diphosphate and inorganic phosphate, respectively Photo-electrolysis of water is the dissociation of a semicon-ducting photocatalyser by an electric current through 2e 2H 4ATP-H2 4ADP4Pi (1) lighting ( Fig. 5). The photoelectrochemical cells (PEC) (photoactive elec-trodes) is The processes of biological H2 production using solar energy can be broadly classified into submerged in an aqueous electrolyte or in following distinct approaches which includes: Direct biophotolysis, indirect biophotolysis andwater and is illuminated by solar light which can photofermentation. decompose water into hydrogen and oxygen. The thermodynamic cycles constitute a method The comparison of important biological H2 production pro-cesses is summarized in Table 2of hydrogen production without the intervention [25 Table 2 , 26]. From an engineering perspective, they all potentially offer the advantages ofof carbonized fossils by means of exhaustion lower cost catalysts (microbial cells) and less energy intensive reactor operation (mesophilic) thanand susceptible for the production of large

the present industrial process for making hydrogen.

amount of CO2 responsible for the green-house

effect. The decomposition process of water However, several biological and engineering challenges must be overcome before thisconsists of realizing a thermal decomposition or promising technology becomes a prac-tical reality. Foremost, the cellular metabolism and basica thermoelectrochemical decomposition of bio-chemistry that support this process must be well understood and much fundamental researchwater with the supply (hence stocking) of solar on the mechanism of H2 production by S-deprivation remains to be done. energy thanks to a succession of reactions The diffusive nature of solar energy and the consequent low energy density places severe whose sum is equiva-lent to: economic restrictions on potential light-driven processes for biological conversion of solar energy to hydrogen [20]. H2O-H1/2O DH284 kJ/mole H Other barriers to microbial based, large-scale production of H2 include [27] [101] [27] (a) inherent properties of the microbes that preclude continuity and efficiency of H2 production; (b) underlying limitations of photosynthetic efficiency; and (c) limitations of the hydrogenase catalytic function. (2) The advancement of the direct decomposition is not significant (10%) for a temperature of 2800 K with DG0 at about 4700 K. taking into account the action of the intermediate stages enables the reduction of the reaction temperature. This answers the question on the decarbonization of the sources providing energy.

4esun

The cycles have been an active research objective during the decades 7080, in particular withatomic energy (JAERI and GA) have developed the aim of valorizing heat in nuclear reactors of type HTGR [28, 29]. The research institutes forworks from the

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Fig. 6. Elements of the monolithic reactor for the dissociation of water [37].

basis of data obtained from cycles in order to select the most appropriate cycles and presenting superior level of temperature compatible with a heat source of nuclear origin (about 900 1C). The cycles generally retained are I-S and UT-3 [30]. The works of Research and Development on these cycles have been taken (in particular I-S) by the CEA recently in the framework of research on nuclear traces of the 4th generation. The cycles with two or three stages and at temperatures greater than 900 1C constitute the most promising research channels for the solar path because it is very easy to be set up. The studied cycles in the setting of solar primary energy are principally cycles with basic oxides (2 stages) or the UT-3 and the I-S [31]. Concerning cycles with basic oxides like CdO/Cd and ZnO/Zn in the earlier 80 at IMP Odeillo [32], and most recently at Paul Sherrer Institute (PSI) in Switzerland [33] in collaboration with LSGC in Nancy [34] and the ferrite cycle [35]. These cycles involved a temperature of the order of 2000 1C using O2 mixture (typical example: manganeseferrite or nickelferrite cycle in Tokyo Institute of Technology permitting the step down of the cycle temperature [36].

Energy

Hydro carbo n

Solar Cracking

H2
Fig. 7. Schematic of solar cracking process.

The cycles with high temperature for instance sulphate or oxide3.2. Thermochemical processes present an important advantage of being very much easy but also necessitate an endothermic stage temperature of more than 850 1C. Thermochemical methods for the Meanwhile the taking into consideration criteria such as the nonproduction of hydrogen from solar energy toxicity of the products and the simplicity of realization of the cycleincludes: direct thermolysis of water, are primordial for the success in terms of such production path;thermochemi-cal cycles and cracking, certainly more than the efficiency criterion within the framework ofreforming and gasification of hydrocarthe use of a solar primary energy source. Agrafiotis et al. [37] hadbons. These processes use concentrated elaborated on a monolithic reactor for the solar dissociation of water solar radiation as high temperature heat with the aim of producing hydro-gen. The different components ofsource to carry out the endothermic the system are represented in Fig. 6. Andrade et al. [38] havereaction. Different devices are used to made proposition of a phenom-enological modeling ofreach high solar concentration ratios: photoelectrochemical cells with applica-tions on non doped hematiteparabolic disks, tower systems and solar electrodes for the production of hydrogen by thermal dissociation offurnaces. water. Photoelectrochemical processes are still under the stage of3.2.1. Solar cracking of hydrocarbon The cracking of hydrocarbons consists investigation. Their implementation is expected only in the long term. in the realization of the co-synthesis of

hydrogen and black carbon as shown in Fig. 7. The advantages of this method include [39]: 0 The confinement and valorization of carbon contained in a natural gas in solid state;

0An

economic emission of 14 kg CO2/kg H2 and energy

from fossil origin of 277 MJ/kg of H2. This is with respect to the other conventional methods of hydrogen production like steam reforming and charcoal (black carbon) [40].

S. Koumi Ngoh, D. Njomo / Renewable and Sustainable Energy Reviews 16 (2012) 67826792

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P=25 bars, T=850 C

The decomposition of methane for the production of hydrogen was proposed by Matovitch [41] in 1978. The developed reactor

CH

Reformage Desulfuration

permitted the complete dissociation of CH4

into fraction of

High Temperature Shift

seconds at a temperature of 2100 K. This method was later encouraged by Steinberg [42] and Muradov [43] in 1993. Thermodynamic studies of this reaction have elsewhere been proposed by Hirsch et al. [44] and Dahl et al. [45]. The endothermic reaction is presented below;
H pur
2

Low Temperature Shift

Wate r

Pressure Swing

CH4-C(s)2H2 (DH75 kJ mole1) (190 kJ mole1 at 2000 K)

(3)

99,999%

Adsorption

Thermodynamically, the decomposition of methane is theore-tically complete within the neighborhood of 1300 K. Realistically, methane is very stable and the kinetic decomposition is not favorable whereas the properties of black carbonhave equally landed depend as well on the temperature of decomposition. These two factors have given preference to the reaction temperature to on the modeling and be much greater than 1500 K. simulation of heat transfer within Two types of solar reactors have been put in place for the cracking of methane namely; direct [46 48] and indirectsuspended particles reactors [40 49]. Works have been engaged in Switzerland in PSI by Steinfeld et al. [35], then by Hirsch and Steinfeld [46],in an irradiated in USA by the National Renewable Energy Laboratory (NREL) [49], and in Israel by Kogan and Kogan [47, 48] on thereactor. Rodat et al. thermal and or catalytic decomposition of Hydrocarbons by solar channel, this is in order to decarbonize future combustibles. [56] have the For example Dahl et al. [50] obtained a maximum conversion of 90% of methane at 2133 K from a mixture of Ar/CH4 in aexperimented of reactor of suspended particles ()Aerosol Reactor*). At very low temperature Hirsch and Steinfeld [46] carried outproduction experimental studies on the cracking of methane in a reactor directly irradiated with a power of 5 KW under a solar fluxhydrogen and black carbon in a intensity of 2.8 MW/m2. prototype solar reactor with the The out flow of methane was loaded with Carbon particles which also served in the absorption of radiations and a reacting experimental surface for the cracking process. In domains where the tempera-ture ranges between 1510 and 1680 K, they arrived at the diagram ( Fig. 8) conversion of 44 to 66% of methane and measured a conversion of 67% in a solar reactor of vortex type. Study on the kinetic described earlier decomposition of methane in a solar reactor was realized by Rodat et al. [51]. This study was preceded by numerical simula[57]. tion of the tubular solar reactor [52]. Many other authors [53 55] The cracking of methane as the afore works reveal is the most exploited channel for the production of hydrogen using the solar method in recent times. Unfortunately, this means of production consumes non renewable fossil resources and gives Fig. 8. Diagram of a solar reactor of capacity 10 kW and an Odeillo filter [50]. off polluting wastes. 3.2.2. The steam reforming of hydrocarbons Steam reforming ( Figs. 9 and 10) consists of the slow trans-formation of hydrocarbons into a synthesized gas by reacting them with

sun H C nH m
2

Reactor
H2O
Fig. 9. Principle diagram for solar reformation.

C O

water vapor in the presence of Nickel as catalyst [58, 59]. This takes place at very high temperature range of 840 950 1Cof soot. These can and at moderate pressure of the order of 2030 bars. The pure hydrogen necessary for other use is put into action in thereactions be production chain which is relatively complex. In all cases of production, the composition within the steam reforming unit can behowever by natural gas, methane, propane and even Napthaline. Natural gas essentially consists of methane which generally has to becontrolled adjusting the rate of desulphurized before being directed into the steam reform-ing unit. The two principal chemical reactions put in place are the vapor injected into production of synthesized gas and the conversion of CO: the reactor which permits the elimination of soot CH production. The H2O-CO3H2 (DH206 kJ/mol) (4) 4 following two stages consist of separating COH2O-CO2 H2 (DH 41 kJ/mol) (5) CO2 and hydrogen CH and to eliminate the 2H2O-CO2 4H (DH165 kJ/mol) (6) 4 remaining traces of impurities principally Reaction (4) is the steam reforming stage. It is an endothermic reaction and is characterized by an H2/CO2 stoechiometricmethane and sub rela-tion of order 3. CO contained in the gas being dangerous is eliminated by the second reaction which permits restitution of products of CO . 2 hydrogen. Several works and projects have been This second reaction corresponds to the conversion of CO into CO2 (a process called water gas shift). It is slightlyrealized on steam exothermic and more or less complete according to its realization in stage 1 or 2. These stages involve high and lowreform-ing the temperature shifts reactions respectively gearing towards 400 and 200 1C. We thus obtained a gas essentially made up of H2,throughout world. CO2 (1620% in volume), H2O, a little of CO and CH4 [59, 60]. Generally, the result of the two preceding reactions is endothermic. The parasitic reactions for the decomposition of Hydrocarbons can equally take place and generally end with the formation

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Marty [61] carried out a study on non catalytic steam reform-ing Just like the cracking process in the of Propane at high temperature in a solar reactor. Langnickel et al. solar method, this technology consumes a [62] also carried out an experimental study on catalytic steamlot of hydrocarbons and remains to be a reforming of methane in a solar reactor that is directly irradiated anddebatable issue due to the exhaustive obtained a rate of hydrogen gas production oscillating betweennature of fossils. 45.8% and 53.1%. Rainer Tamme et al. [63] under the same conditions obtained a methane conversion rate of 87% with 49.3% of molar fraction of hydrogen in the output products from the reactor. 3.2.3. Thermochemical transformation of biomass Biomass consists of all the plants The CSIRO energy technology team [64] in Australia worked on growing on the earth surface. It is obtained the catalytic steam reforming of methane in a 46 KW capacity reactor of the same standard. Associated with a concentrator of typefrom the photosynthesis of CO2, H2O and

dish engine the reactor was capable of producing hydrogen for thesunlight leading to the production of supply of a fuel cell of type PEMFC of 10 kW. Buck et al. [65]molecules, cellulose, Lignocellulose and lignin having the same composition as simulated the catalytic reformation of methane with CO2 in the same C H O It can then be possible to regain type of reactor. They did among others a simulation for the 6 9 4. stored energy in the combustible form [68, performances of the reactor according to the thermodynamic results 69] by more or less effective transformation (balanced) obtained and further predicted a methane conversion ofon the energetic and economic platform. 79.8% for an output gas temperature of 753 1C. The total thermalThis is done through combustion, power absorbed was 322 KW for which 81% was for the chemical methanation, alcoholic fermentation and reaction and 14% for an increased in the sensitive enthalpy of thethermochemical transformations [70, 71]. gas and a total gas flow of 0.102 kg/s. Levitan et al. [66] from This method is particularly convenient Weismann Institute of Science equally studied experi-mentally thefor the valorization of lignocellulosic reformation of methane with CO2 by the catalytic channel in aproducts such as wood or straw. This reactor that is indirectly irradiated. This reactor constitutes abranch which leads to the gasification of cylindrical aluminum with interior diameter of 16 cm, 45 cm of lengthorganic substances [72], constitutes a and partition thickness 1 cm. They characterized the reaction successive chain of operations that necessitate the simultaneous transfer of kinetics, the temperature level attained and they also led parametric physical quantities and the control of the survey. Menigault [67] used a porous medium (indirectly irradiated proportion and times of reaction contacts at reactor) with its surface exposed to concentrated solar radiation for a given instant. Fig. 11 sum-marizes the the heating of air. According to the nature of the porous surface different steps of operation. The processes used, he showed that higher temperatures can be attained. of gasifica-tion currently represent a capacity of 430 million Nm3 of the worlds hydrogen daily production [73]. Generally, this can be translated through the following reaction: C6H9O4 2H2O-6CO6,5H2 (7) In case where we want to favor the production of hydrogen, supplementary hydrogen is obtained by the gas shift reaction as shown below: (8) 2e
-

O
2

H2

Electrolyt

Table 3 Characteristics of Varnamo, Sweden unit [64]. Power/heat generation Fuel input (wood chips) Net electrical efficiency Total net efficiency Gasification pessure/temperature Lower calorific value of product gas Product gas steam pressure/temperature Fig. 11. Processes involved in the thermochemical transformation of biomass. 6 MW /9 MW
e th

Anode Diaphragme

Cathode
Fig. 12. Alkaline water electrolysis process.

18 MW 32% 83% 18 bar/950 1C 3 5 MJ/Nm 40 bars/455 1C

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6789

Amongst the 12.5 molecules of hydrogen finally obtained, onlyelectrolyzers PEM (Proton Exchange 4.5 comes from biomass and 8 are brought by water which is onlyMembrane) are very practical for the used as a reactive agent. We can also consider that the 6 moleculesproduction of high quality hydrogen. A of CO2 gas which is liberated does not contribute to the produc-tionreview of the PEM technology electrolyzers has been done by Grigoriev et al. [84]. of the greenhouse effect because they are the same molecules that Agbli et al. [85] have developed a the process of photosynthesis captures from the atmosphere for the graphical model of the electrolyzer from growth of plants and which are recycled. Devi et al. [74], Maniatis [75] raised an inventory of fixtures of research link in the domain ofmacroscopic energetic representations. phenomenological models of gasification. The principal parameters to be considered are; theOther temperature of the process, pressure and type of gas chosen forelectrically supplied electrolyzers by renewable energy particularly solar origin gasification (air, vapor, oxygen, etc) ( Fig. 12). have been an objective of many works [86, The first step of gasification is the pyrolysis of biomass. This 87]. Vanhanen et al. [88], Galli and stage has as a specific research objective the development of rapid pyrolysis [76 78] or torrefaction [79]. Another way of research is ofStefanoni [89] succeeded in a small scale course the optimization of the conception of the process [74] whichproduction of electrolytic hydro-gen from photovoltaic solar energy. This prowess will eventually allow improving the efficiency of the process. has equally been realized at an industrial Table 3 below presents the principal characteristics of unit of scale by Szyska in [90, 91] for fixed and Varnamo (Sweden) which started in 1993. This unit is the heart of mobile applications. At Forschungszentrum European project CHRISGAS, whose aim was production of fuel Julich in Ger-many, a technological unit of through the synthesis of hydrocarbon by gasification. demonstration, PHOEBUS (Photo-voltaik, Biomass is potentially a reliable energy resource for hydrogen Elektrolyseur,Brennstoffzelle Und production. Biomass is renewable, abundant and easy to use. Over Systemtechnik) has been installed for the the life cycle, net CO2 emission is nearly zero due to theproduction of electrolytic hydrogen from a photosynthesis of green plants. The thermochemical pyrolysis andvoltaic fields of 43 kW [92]. gasification of hydrogen production methods are economic-ally Negrou et al. [93] have equally studied viable and will become competitive with the conventional natural gasthe development of hydrogen production by reforming method. Biological dark fermentation is also a promisingelectrolysis in Algeria. They focused on the hydrogen production method for commercial use in the future. With economic aspects and they also showed further development of these technologies, biomass will play a role in that the higher the quantity of hydrogen the development of sustainable hydrogen economy. gas produced the lower is the cost of production of a kg of hydrogen. For an annual production higher than 4 106, the 3.3. Electrochemical processes electrolytic hydrogen becomes more competi-tive than hydrogen produced by Apart from gas reformation, the electrolysis of water [80] is theconventional sources (see Table 4). This most developed and useful method in industries for the produc-tionresult can be generalized to all other of hydrogen. Water electrolysis ( Fig. 12) is an electrochemicaltropical country with strong solar potential process permitting the decomposition of water into its constitu-entand in which the electrolytic technology can elements of hydrogen and oxygen thanks to electrical energy [81],be carried out for the production of according to the two chemical reactions separately taking place athydrogen in high quantity. the anode and the cathode: At the anode: High temperature electrolysis of steam (HTE) is expected to consume less electrical energy as compared to H2Oelectricity-2H (1/2)O2 2e (9) electrolysis at low At the cathode: 2H 2e-H2 The general electrolysis reaction is H2Oelectricity-H2 (1/2)O2 (10) Comparison on hydrogen production cost: case study
Algeria [84]. 10 Production capacity (kg/year) (11) Conventional source (h/kg H2) Solar tower (h/kg H )
2 6

Table 4

2 10

The process of electrolysis can occur at both ambient temperature and at high temperature. The electrodes are separated by an electrolytic conductor made up of ions which permit the easy transfer of ionic particles between the electrodes. In the course of the process, electrical energy provided to the system is then transformed into chemical energy in the form of hydrogen. The electrolysis of water is well known but not cost-effective on the economic base unlike the case where electricity was to come from a renewable source. The most important technologies in the electrolysis of water process are the alkaline electrolytes, the polymer membranes and the oxide electrolytes of ceramic, the electrolysis of steam [80, 82, 83] in which the efficiencies currently obtained from the electrolytic process are of order 6585%. Among these technologies the

3.41 11.45

4 10 3.35 7.54

Fig. 13. Energy demand for water and steam electrolysis.

6790

S. Koumi Ngoh, D. Njomo / Renewable and Sustainable Energy Reviews 16 (2012) 67826792

temperature ( Fig. 13) as a consequence of the more favorableTable 5 thermodynamic and electrochemical kinetic conditions for theProjected costs (long term) of hydrogen production (h/t of H ) [89]. 2 reaction [94]. Thermodynamic conditions are more favorable in the sense that Cost (h/ton of H ) Current process designs and small scale pilot plants 2 the molar Gibbs energy of the reaction (DG) drops from 1.23 eV Solar hybrid sulphur cycle 1900 1 (237 kJ mol ) at ambient temperature to 0.95 eV at 900 1C (183 Solar sulphuriodine cycle 2000 kJ mol1), while the molar enthalpy of the reaction (DH) remains Solar metal/metal oxide cycle 3500 1 4667 essentially unchanged (DH 1.3 eV or 249 kJ mol at 900 1C) Solar high temperature electrolysis 1767 [95]. A significant part of the energy required for an ideal (loss free) Solar methane cracking Solar methane steam reforming 1633 HTE can thus be provided by heat. Solid oxide steam electrolysis Cost (h/ton of H ) 2 (SOSE), is a promising technology if used in conjunction with Other future renewable options Biomass gasification 1067 renewable energy [96, 97]. Alkaline electrolysis using photovoltaic power 6667 The main commercial advantages of hydrogen production by Alkaline electrolysis using solar thermal power 2667 electrolysis are its scalability and the emission-free production of Alkaline electrolysis using wind power 2333 hydrogen (when produced via renewable energy). There are challenges to setting up mainstream electrolyzer use for hydro-gen production, primarily high capital costs and the cost of electricity. For example, PV electricity today costs approxi-mately $ 30/kw-hr,index which tells how sustainable a system perhaps ten times what is needed to make electrolysis cost is in actual practice. The exergy efficiency competitive, and the cost of electrolyzers themselves must beand corresponding sustainability index for significantly reduced to enable large-scale implementation. the different process of solar hydrogen production are shown in Figs. 14 and 15. The sustainability index for the electrolysis process of Ni et al. [98] is 2.7 respectively and for Balta et al. [99] it varies from a 4. Comparison and outlook minimum of 4.76 and a maximum of 7.14 with respect to the minimum (473 K) and 4.1. Exergy efficiency of the different processes maximum (1173 K) operating The comparison of the various processes associated with thetemperatures. The reason for Balta et al. solar hydrogen production can be done through exergy efficiencyelectrolysis possess higher sustainability which gives an idea of the amount and the quality of useful energyindex is that the unit has higher exergy efficiency as they have used high that can be completely utilized in useful work and the sustainable temperature electrolysis. The corresponding sustainability index for solar Exergy efficiency decomposition of Natural gas, for solar 86% steam reforming of Natural gas and for 79% solar steam gasification of coal are 1.47, 1.85 and 1.85, respectively [100]. It should 63% be noted here that despite of the higher 46% 46% exergy efficiency of the electrolyzer, charge regulator and inverter units, the system 32% exergy efficiency is still low. It is mainly because of the low PV exergy efficiency. There is a need to improve the PV array efficiency in order to have better Decom sustainability index and hence better Electrolysis Electrolysis Electrolysis Gasification Reforming [100] sustainability. (at 473K)[99] (at 1173K) (at 353K) [100] [100]
[99] Fig. 14. Exergy efficiency of the different processes of solar hydrogen production.

4.2. Economic comparison Table 5 shows the projected costs (in the long term) of hydrogen production (h/t

7.14

Sustainability Index

of H2) using the commercial available

technologies presented in this paper. Costs values of hydrogen production from other 4.76 future renewable options and actual largescale commercial plants consuming fossil fuels are also presented in Table 5 for 2.70 comparison purposes. 1.85 1.85 Steam methane reforming is nowadays 1.47 the more competitive available technology for the production of hydrogen from an economical point of view. Table 4 shows Decom Electrolysis Electrolysis Electrolysis Gasification Reforming [100] how the conventional SMR has production (at 473K)[99] (at 1173K) (at 353K) [100] [100] costs of 1200 h/t of hydrogen. With carbon [99] capture and storage technologies (CCS), Fig. 15. Sustainability index of the different processes of solar hydrogen production. SMR become more expensive.

Water electrolysis is considered a However the development and implementation of CCS sys-temspromising hydrogen produc-tion method is a pre-requirement for the hydrogen scenario in order to meet thealthough the hydrogen cost by electrolysis ambitious goals of the world environmental policy. would be very high as compared to the Among related technologies for the hydrogen production throughother mature technologies such as steam solar energy, only solar methane steam reforming could becomemethane reforming. But taking into account cost competitive. Nevertheless, the costs of this technol-ogy dependthe environ-mental benefits help and the on natural gas availability and prices. Same consid-erationeffective utilization of by-product oxygen of corresponds to solar methane cracking. It is expected that their high electrolysis for a medical or industrial use hydrogen production cost will noticeably decrease as prices ofthe process efficiency and cost can be improved. methane and carbon decreases.

S. Koumi Ngoh, D. Njomo / Renewable and Sustainable Energy Reviews 16 (2012) 67826792

Biomass gasification can also be competitive despite the fact that biomass is mainly used in the production of biofuels, for cooking and other residential use (in poor countries). Therefore, a limited potential of this type of hydrogen production technology is expected. Within this scenario, an opportunity for those regions with high solar potential appears. The tropical regions of the world in general, the Middle East, the large majority of African countries, some European and American region have the possibility to become world powers in solar hydrogen generation. A proper policy could help not only the production of hydrogen for internal consumption, but also, in the long term, the export of interconti-nental energy to other hydrogen markets.

6791 an overview of theory and current technological status. In: Proceedings of the

5. Conclusion The various methods for utilizing solar energy for hydrogen production were examined and both their advantages and disadvantages are compared in terms of exergy efficiency, sustainability factor and economic efficiency. If perhaps the cracking and steam reforming of hydrocarbons have additional attributes, yet they remain limited by their non renewable fossil energy char-acter and their environmental impacts. Electrolysis of water for tropical countries with strong solar radiations potential is an interesting option which assumes much development with high temperature electrolyzers commercialization. The solar-to-electricity conversion efficiency is the main lim-itation in the improvement of the overall hydrogen production efficiency. By comparison, solar powered electrolysis, photoelec-trochemical and photochemical technologies can be more advan-tageous for hydrogen fueling stations because fewer processes are needed, external power sources can be avoided, and extra hydro-gen distribution systems can be avoided as well. High temperature processes need further materials develop-ment which focuses on high temperature membranes and heat exchangers for solar thermal processes. Therefore the worlds solar hydrogen utilization systems consist mainly of photovoltaic hydrogen systems for transportation and stationary applications. Ecofriendly hydrogen production via solar is very important to save environment as it does not emit any greenhouse gases during operation. At present it is a challenging task for research-ers and scientists as the exergy efficiency of the PV array is low and hence, the overall exergy efficiency of a solar hydrogen system. Many of the renewables have sitting, social, or environmental concerns which also must be overcome. However, all these barriers are being addressed aggressively by government and industry, and it is worth considering whether the benefits warrant greater investment today. References
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