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2 | Clean Energy, 2017, Vol. XX, No. XX of hydrogen [8]. However, dwindling sources of natural gas and the larger footprint of the natural gas reforming pro- cess have shifted attraction of researchers toward oxygen- ates such as methanol [9–11], ethanol [8, 12, 13], propanol [14, 15], glycerol [16, 17], acetone [18, 19], acetic acid [20, 21] and butanol [5, 22, 23] as hydrogen sources. Feasibility stud- ies on hydrogen production from renewable biomass feed- stock derived from bio-oil [24–26] and its key components [27–29] have also been reported. Butanol is a very attractive feedstock because of its high hydrogen content (13.51 wt.%), compared to methanol (12.5 wt.%) and ethanol (13.04 wt.%), greater tolerance to water content and lower vapor pres- sure [30]. Similar to ethanol, butanol can also be produced via biological routes. Butanol obtained via a biological route is called bio-butanol, which is a mixture of butanol, acetone and ethanol (~6:3:1 mass ratio) with ~60 wt.% water [30]. There have been few studies published on production of bio-butanol by fermentation of renewable biomass [31–33]. Butanol is also one of the key components of bio-oil [34]. The availability of butanol from renewable sources and its properties makes butanol an attractive research option to be explored for its hydrogen production capability. Techniques for hydrogen production can be classified in mainly four broad categories, namely (i) photobiology, (ii) photoelectrochemistry, (iii) electrochemistry and (iv) thermochemistry [35]. Photobiological technique uses natural photosynthesis activity of bacteria and algae for hydrogen production. Despite its green and renewable na- ture, this technique currently cannot be used on industrial scale for hydrogen production because of poor yield com- pared to thermochemical and electrochemical techniques [35, 36]. Photoelectrochemical technique involves water splitting using photon energy from sunlight in the pres- ence of light-absorbing materials, such as a semiconductor, for hydrogen production [35, 37]. However, development of a high-efficiency photoelectrochemical system is chal- lenging [38], and this technique is in its early development phase [35]. Hydrogen production from the electrochemical technique is a well-known technology, but lower overall ef- ficiency makes this technique suitable only where electri- city can be obtained at low cost [35]. The thermochemical technique includes catalytic conversion of hydrocarbons Table 1 Comparison between SR, OSR, DR and POX techniques Technique Nature SR Endothermic. Specialized case of SR is sorption- enhanced steam reforming (SESR), and is a worldwide-accepted technique for larger-scale hydrogen production. SR of natural gas is the most widely used thermochemical technique for hydrogen production and accounts for almost 50% of total hydrogen production [35, 39]. Pyrolysis, SR and partial oxidation (POX) are different approaches used in thermochemical technology. The cur- rent review is focused on the four most widely known and accepted approaches of thermochemical techniques: (i) SR, (ii) oxidative steam reforming (OSR), (iii) dry reforming (DR) and (iv) POX. All these techniques have their advantages and disadvantages. Table 1 compares the different techniques in nature, hydrogen production and catalyst deactivation. This article aims to review hydrogen production from bu- tanol and the effect of operating parameters such as tempera- ture, pressure, steam to carbon molar ratio (SCMR), oxygen to carbon molar ratio (OCMR), carbon dioxide to carbon molar ratio and catalysts. The definition of yield, selectivity, con- version, SCMR and OCMR differs between researchers. We adopted the following nomenclature to remove ambiguity dur- ing comparison throughout this article. Superscript after value indicates respective formula used by various researchers. A : % Selectivity = moles of hydrogen produced × 100 to hydrogen 12 × moles of butanol reacted B : % Selectivity = moles of hydrogen produced × 100 to hydrogen C : % Yield of hydrogen sum of moles of product = moles of hydrogen produced × 100 12 × moles of butanol fed D : % Carbon conversion = to gaseous products (CCGP) moles of carbon in gaseous product stream 4 × moles of butanol fed × 100 E : %Yield of hydrogen = moles of hydrogen produced × 100 12 × moles of butanol fed × fractional CCGP where CO2 is adsorbed in the reformer to shift the equilibrium of SR and water–gas shift reactions in a forward direction OSR Endothermic/exothermic depending on the operating temperature, SCMR and OCMR. Specialized case of OSR is ATR, in which overall heat reaction is zero DR Highly endothermic POX Highly exothermic Downloaded from https://academic.oup.com/ce/advance-article-abstract/doi/10.1093/ce/zkx008/4743500 by guest on 15 December 2017 Hydrogen production Highest Lesser than SR but greater than POX and DR Lower than SR and OSR Lowest Catalyst deactivation due to coking Possible Lesser than SR but greater than POX Highly possible Least possiblePDF Image | Renewable hydrogen production from butanol
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