Direct production of hydrogen-rich gas and/or pure-hydrogen with high-pressure from alcohol/water/metal-powder mixture at low processing temperature

https://doi.org/10.1016/j.ijhydene.2019.11.166Get rights and content

Highlights

  • Pure-hydrogen with 10.0 MPa is produced from methanol/water/Al-powder at 723 K.

  • Maximum pure-hydrogen producing rate is 24.9 LN/(dm2min).

  • Pure-hydrogen with above 15 MPa is produced from ethanol/water/Co-powder at 723 K.

  • Hydrogen-rich gas with around 8 MPa is produced from rice-wine/Co-powder at 723 K.

  • All produced hydrogen-rich gases keep a full potential in PEFC for over 24 h.

Abstract

High-pressure hydrogen-rich gas producing experiments from various alcohol/water/metal-powder mixtures at low processing temperatures from 473 to 723 K are carried out in a prototype airtight apparatus possessing a withstand pressure of 15 MPa in the aim of technologizing an incidentally emerged high-pressure hydrogen-rich gas production from a methanol/water/aluminum-powder mixture at 723 K. Methanol/water due to a proven track record and ethanol/water in order to make an allowance for replacing the reagent to commercially-available potable alcohols are selected as main hydrogen sources. As tested metal-powders, aluminum, cobalt, iron, magnesium and nickel are chosen, taking their ready-availabilities and costs into consideration.

Among tested metal-powders, aluminum and cobalt are found optimal adding metals for the high-pressure hydrogen-rich gas productions from 60.0 wt% methanol/water and ethanol/water solutions, respectively. From 60.0 wt% methanol/water and Al-powder mixture at 723 K, pure-hydrogen with 10.0 MPa is produced at a great hydrogen producing rate of 24.9 LN/(dm2min). All carbons discharged from methanol are fixed as a wide variety of solid higher hydrocarbons and organic liquid residues of benzyl alcohol and toluene. Almost all oxygens from methanol/water solution are fixed as aluminum-compounds of aluminum oxide hydroxide and aluminum hydroxide. From 60.0 wt% ethanol/water and Co-powder mixture, pure-hydrogen with pretty high pressure over 15 MPa can be produced at 723 K with simultaneous fixations of all the carbons and oxygens from the main hydrogen source as solid/liquid residues of wide variety of solid higher hydrocarbons, benzyl alcohol, toluene, cobalt oxide, cobalt hydroxide, tricobalt tetroxide and cobalt carbonate. Responding to the outcome from 60.0 wt% ethanol/water and Co-powder mixture, a certain rice-wine having an alcohol degree 60 with Co-powder at 723 K is experimented, and provides high-pressure hydrogen-rich gas with hydrogen concentration of 80 % and hydrogen partial pressure of around 8 MPa.

All the produced hydrogen-rich gases are confirmed to keep a full declared potential in polymer electrolyte fuel cell for over 24 h without any exceptions. These findings speak by themselves that this developing high-pressure hydrogen-rich gas (pure-hydrogen) direct producing method is surely approaching a self-operating dispersed hydrogen producing appliance (i.e. a part of a dispersion type power source) anywhere whole the world. And, this method still leaves unlimited room for far higher pure-hydrogen pressures and hydrogen producing rates by slight changing the operating conditions, and its applicable fields are broadening for eternity. Finally, some recommended future strategies to improve this method so as to supply complete solutions to any global-scale issues are also proposed in every part through this paper.

Introduction

The world has been facing many critical problems such as global warming and exhaustion of fossil fuels. Thus, one of the essential achievements for the current generation is to find exhaustless renewable energies alternative to fossil fuels emitting an appreciable amounts of carbon dioxide (CO2). Hydrogen is one of the most promising energies since it does not emit any CO2 when it is used, and can be used as fuel for FC (Fuel Cells), keeping anthropic activities stable and realizing energy sustainable for eternity.

During our developing investigations for new annealing processes of inorganic powders in critical water together with metal-salt [1,2], high-pressure hydrogen-rich gas could be incidentally produced from a methanol/water/aluminum-powder mixture at 723 K [3,4]. Some existing hydrogen producing methods are compared with this incidental high-pressure hydrogen-rich gas production in Table 1 [[5], [6], [7], [8], [9], [10], [11]].

Of course, all the existing hydrogen producing methods are well-investigated, reliable and have firm public acceptances. Catalytic methane steam reforming (MSR) is widely adopted since methane can be obtained for a little longer from the ground, under the sea, fermentation and so on [[5], [6], [7], [8], [9], [10]], and be easily widespread by existing gas line. Catalytic MSR is normally operated at 1023 K, or the temperature can be reduced down to about 823 K, which is still comparatively high, when a hydrogen separating membrane is applied. Hydrogen discharged as industrial by-product holds a great deal of promises because it is obtained at no charge, but huge energy consuming operations such as purification, compression and land transportation are indispensable. The international Energy Network (WE-NET) project provided significant credits on the basic policy of pure-hydrogen production by water electrolysis using electric-power generated from renewable energy sources such as hydro-power and wind-power [11], but this scenario also requires compression and sea/land transportations, consuming vast amounts of energy. There are still plenty of hydrogen producing methods such as biological conversion [[12], [13], [14], [15]], catalytic steam reforming of hydrocarbons [[5], [6], [7], [8], [9], [10],[16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29]], thermal dissociation of water and photocatalytic water splitting [[30], [31], [32], [33], [34], [35], [36], [37]], being far-out technologies and/or requiring technical breakthroughs for practical applications.

It is seen from Table 1 that our incidental hydrogen-rich gas production outclasses other hydrogen producing methods in terms of a single and simple operation, a high hydrogen partial pressure, a relative low processing temperature and independency on any lifelines. However, its drawback lies on further experimental investigations for much higher hydrogen concentration aiming for pure-hydrogen and much higher hydrogen partial pressure heading off for over 80 MPa by changing hydrogen source compositions of alcohol/water/metal-powder mixtures and processing temperatures.

In the present study, high-pressure hydrogen-rich gas producing experiments were carried out with various alcohol/water/metal-powder mixtures at different processing temperatures in the aim of technologizing our incidental high-pressure hydrogen-rich gas production. As main hydrogen sources, methanol/water and ethanol/water were selected from the actual achievement of our incidental high-pressure hydrogen-rich gas production and for antedating to pass in a direction toward commercial alcoholic beverages (i.e. ethanol) so as to improve this method up to a complete carbon-neutral process, respectively. Concerning these alcohols, catalytic steam reformings have been preceded [[19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29]]. However, most of the preceding works have been focused on improving each catalyst in terms of chemical stability, cost reduction and elevated selectivity at lower-temperatures. In contrast, our incidental high-pressure hydrogen-rich gas production occurs through chemical reactions, getting away from conventional catalyzed reactions [[5], [6], [7], [8], [9], [10],[16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29]], so as to accomplish hydrogen purity 100 %, pressure close to 15 MPa (over 80 MPa in future) and producing rate greater than 20 LN/(dm2min) simultaneously at lower processing temperatures below 723 K for practical applications. Though there are some similar hydrogen productions from various aqueous solutions together with metals [[38], [39], [40], [41], [42], [43], [44], [45], [46]], almost all the precedent works have been performed at normal pressures. Therefore, it can be said that one of the most outstanding features for the present study locates on quite high-pressure experiments close to 15 MPa, exceeding ever achieved 6.9 MPa [38]. Furthermore, ubiquitous materials (e.g. commercially-available rice-wine) were utilized as far as possible in order to make our incidental high-pressure hydrogen-rich gas producing method self-operating process (i.e. a dispersed hydrogen producing appliance or a part of a dispersion type power source) anywhere throughout the world.

Concretely, a prototype hydrogen producing apparatus possessing a withstand pressure of 15 MPa was firstly manufactured [3,4]. As tested metal-powders, aluminum (Al), cobalt (Co), iron (Fe), magnesium (Mg) and nickel (Ni) were chosen, taking their ready-availability and costs into consideration. And, alumina (Al2O3) was also experimented as blank tests. Table 2 shows approximate current costs of tested metal-powders in Japan (FUJIFILM Wako Pure Chemical Corporation, Japan).

60.0 vol% of methanol/water solution, various vol% of ethanol/water solution and/or a certain commercially-available rice-wine (alcohol degree: 60 = 60 vol%) were utilized as the main hydrogen sources. High-pressure hydrogen-rich gas producing experiments were carried out at lower processing temperatures between 473 and 723 K. Chemical compositions of produced gases were quantitatively measured by TCD and FID gas-chromatography. Solid and liquid residues were analyzed by means of TEM with EDX, XRD and pyrolysis-GC/MS [47].

Section snippets

Experimental apparatus

Fig. 1 illustrates a schematic drawing of the prototype high-pressure hydrogen-rich gas producing apparatus possessing the withstand pressure of 15 MPa manufactured [3,4]. A main reactor was made of a SUS304 pipe with ¼ inch of outer diameter and 200 mm in height. A pressure indicator (W232-111, Migishita Seiki MFG. CO., LTD. Japan) was installed to monitor the ever-changing pressure inside the apparatus, and its value could be recorded by a remote system consisted of a web-camera and a PC

Optimal metal-powder for methanol/water solution

Fig. 2 presents time trends of hydrogen partial pressures from 1.50 mL of methanol/water (0.90 mL/0.60 mL) solution together with various metal-powders at a constant processing temperature of 573 K. Since no hydrogen was produced without metal-powder, any metals composing the prototype high-pressure hydrogen producing apparatus could be confirmed to have no capabilities to react with methanol/water solution to hydrogen. And, no hydrogen was also produced from methanol/water solution with Fe and

Conclusions

High-pressure hydrogen-rich gas producing experiments from various alcohol/water/metal-powder mixtures at low processing temperatures from 473 to 723 K were carried out in the prototype airtight apparatus possessing the withstand pressure of 15 MPa in the aim of technologizing our incidental high-pressure hydrogen-rich gas production. Methanol and ethanol were selected as main hydrogen sources, and metal-powders of aluminum, cobalt, iron, magnesium and nickel were chosen as tested

Acknowledgements

The present work is supported by “Tanikawa Fund Promotion of Thermal Technology”. This financial support is gratefully acknowledged. The authors would like to thank KUROSE CHEMICAL EQUIPMENT CO., LTD. for generous providing a splendid spiral type heat exchanger (KMSA-06), which will be soon applied to this high-pressure pure-hydrogen producing method developed through this work. The authors appreciate the splendid contributions from Prof. Hajime Ohtani for quantitative and qualitative analyses

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