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DEVELOPMENT OF A PRESSURIZED BIPOLAR ALKALINE WATER ELECTROLYZER

NEWTON PIMENTA NEVES JR. (1) ANTONIO JOS MARIN NETO (2) EDGAR A. DE GODI RODRIGUES PINTO (1) ENNIO PERES. DA SILVA (1) ANDR LUIS FURLAN (3) DANIEL GABRIEL LOPES (2) JOO CARLOS CAMARGO (2) PAULO F. P. FERREIRA (2) RBIA RAPELLI (1) CRISTIANO DA SILVA PINTO (1)
(1)

Laboratrio de Hidrognio DFA IFGW Universidade Estadual de Campinas, Campinas/SP, Brazil (2) Hytron Hydrogen Technology, Campinas/SP (3) Faculdade de Engenharia Mecnica DE Universidade Estadual de Campinas, Campinas/SP

ABSTRACT
This paper reports the actual development status of a bipolar alkaline water electrolyzer with 3 maximum production capacity of 1 m /h of hydrogen and controlled by a PLC (Programmable Logic Controller), which also interfaces the electrolytic system with operators and other equipment, such as gas storage tanks, fuel cells and photovoltaic panels. The project also includes the construction of an electrolysis test bench to record electrical parameters (cathode, anode, separator and electrolyte potentials), the amount of produced gases and gas quality determined by gas chromatography.

KEY WORDS
Bipolar Alkaline Water Electrolyzer; Pilot Plant Development; Pressurized Electrolysis.

1. INTRODUCTION
The development of water electrolysis systems for hydrogen production is considered a priority within the Program on Science, Technology and Innovation for the Hydrogen Economy of the Brazilian Ministry of Science and Technology (MCT). This development must enable the country for industrial production of electrolyzers in order to meet the domestic and foreign markets of decentralized production of hydrogen in the future Hydrogen Economy. The high cost of such equipment is also considered by fuel cell companies and experts as one of the main bottlenecks for the introduction of backup power systems based on hydrogen technologies. The Hydrogen Laboratory (LH2) at UNICAMP already has the technology to build monopolar electrolyzers, also known as tank type. This technology was used to develop equipment up to 3 3 5 m /h. Two electrolyzers of 1.5 m /h each successfully operated for almost 20 years in LH2.

Correspondence should be addressed to Newton Pimenta Neves Jr.: Phone: +55 (19) 3289-1860; e-mail: nevesjr@unicamp.br

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Bipolar electrolyzers are more compact when compared to the monopolar type. Moreover, this technology works with higher voltages and lower electrical currents, which is more convenient technically and economically. Another remarkable advantage is the ability to work at higher pressures, avoiding the use of compressors in applications requiring intermediate gas pressures (up to 30 bar, e.g.). One interesting way to use hydrogen in energy applications is producing the gas by water electrolysis in periods of low power demand, when the industrial electricity tariff is cheaper, and converting the hydrogen to electricity during the period of high power demand, when the electricity is significantly more expensive. This strategy has proven to be economically viable depending mostly on the difference between hourly tariffs [1]. Additionally, the cash flow of such a project can be largely improved by reducing the costs of major equipment, such as electrolyzers, power electronics and fuel cells. The same concept and prognostic apply to power supplies provided by renewable intermittent sources of energy such as wind and photovoltaic.

2. OBJECTIVES
The main objective of this project is to develop a bipolar alkaline water electrolyzer with nominal 3 capacity of 1 m /h of hydrogen and maximum pressure of 8 bar. Considering the needs related to the experimental evaluation of the device, another objective is to design and build a test 3 bench for electrolyzers up to 6 m /h of H2 (0.5 kg/h). The bench is intended to evaluate electrical parameters, such as cathode, anode, separator and electrolyte potentials, balance of plant, electrical efficiency, as well as the amount of produced gases and gas purity. The gas analysis is performed by gas chromatography using a methodology that allows a detection limit below 1 mol/mol (parts per million) for oxygen in hydrogen. This limit can be achieved by a HP 5890 gas chromatograph, while for micro-GCs the expect value is 2 mol/mol. Additionally, the project aims to evaluate the units performance in continuous operation in order to determine the reliability and availability factors, actual lifetime, maintenance schedule, safety aspects of the control system, as well as the necessary technological improvements in the proposed system configuration and operation.

3. METHODOLOGY
The development includes conceptual design, construction, set-up, test and operation of a 3 alkaline water electrolyzer to produce 1 m /h of H2 with purity exceeding 99%mol/mol and operating pressure up to 8 bar. The unit is composed by the electrolysis module consisting of a series of cells arranged side by side, forming a stack, characteristic of the bipolar technology. Biphasic mixtures, hydrogen or oxygen plus electrolyte, are conducted to their respective gas-electrolyte separator, responsible for water vapor and electrolyte (KOHaq 30%g/g) removal. The electrolyzer is controlled by a PLC, which also interfaces the unit with operators and other equipment. Thermal management is performed by three heat exchangers, for hydrogen, oxygen and electrolyte, all of them cooled by chilled water, a concept chosen due to its scalability.

3.1 Components of the Electrolysis Module Each unitary cell consists of two metallic electrodes, a cathode and an anode, and a membrane between them, also called diaphragm. This membrane should prevent the gas mixing between the H2 and O2 circuits, although remaining permeable to ions in solution in order to enable the ionic current in the electrolytic cell.
The following considerations were taken in account to choose the membrane: 3.1.1. Material free of asbestos: although the use of white asbestos (chrysotile) is still permitted, its mineral nature and processing make it expensive. However, the main disadvantage of this

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type of separator is related to the woven characteristic of the material. The fabric is difficult to handle and presents small holes in it that allow gas exchange between the cathode and anode sides, especially at high operating pressures. 3.1.2. Preferably non-woven: due to the reasons exposed previously, the use non-woven membranes was preferred in order to provide a better separation between the hydraulic circuits, resulting in smaller cross contamination of the produced gases. As an innovative approach, it was decided to test a specific hydrophilic Teflon membrane. 3.1.3. Thermochemical stability: the material should present chemical and mechanical stability at intermediate temperatures and long time exposure to concentrated alkaline medium. Regarding this aspect, hydrophilic Teflon also has advantages compared to other alternative material, including certain polymeric materials. 3.1.4. Commercial availability: considering the time, budget and goals of the project the work group have selected materials and components that were commercially available and with good technical and economical characteristics. Regarding the electrodes, their properties should be stable for a long time, reducing operational and maintenance costs. These components must be resistant to the high corrosive alkaline medium, as well as to high oxidant or reductive atmospheres. Additionally, the electrodes should introduce low ohmic losses related to the activation overpotentials required for the electrochemical dissociation of water into hydrogen and oxygen. As a first approach, Ni 200 (99.5%g/g nickel) was chosen as the electrode material, since it presents good chemical resistance in the required conditions. At the moment, this choice also prevents the uncertainties related to the use of electrodes produced by electrodeposition of catalysts over metallic substrates. Electrodes are supported by a frame assembly that constitutes the body of the electrolysis stack. This frame is exposed to the harsh conditions of the process and needs to ensure tightness of gaseous products between H2 and O2 circuits, as well as tightness against electrolyte leakage to the environment. A recently developed high-performance polymer was selected for frame construction, and the material designation is omitted due to a patent pending. Figure 1 shows the designs of a single cell and the electrolysis stack.

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(b) Figure 1. a) Design of the single cell; b) electrolysis stack.

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3.2 Electrolytic System After designing the electrolysis module, the work was focused on developing the system integration, which must provide stability and safety to the process, and adequate gas processing afterwards. Figure 2 shows a simplified Diagram of Process and Instrumentation of the electrolytic system.

Figure 2. Simplified Diagram of Process and Instrumentation for the electrolytic system.

3.3 Gas-Liquid Separator Tanks The separator tanks receive the biphasic mixtures coming from the electrolysis module and their main function is to promote the separation between the gases evolved during the process, and the liquid electrolyte, maintained in natural or forced circulation.
In order to avoid cross contamination between hydrogen and oxygen there are two independent circuits, as observed in Figure 2. After the gas-liquid separation takes place the electrolyte, now free of dissolved or entrained gases, returns to the electrolysis module. The two tanks communicate by the bottom in order to maintain the electrolyte level and the pressure balance between the circuits. At the same time it provides small gas contamination. Separator tanks are also connected to the process instrumentation responsible for the following operations: system inertization with nitrogen during start-up and shutting-down; continuous monitoring of the electrolyte level, temperatures of electrolyte and evolved gases; and prevention of electrolyte loss (demisters).

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Since the biphasic mixture coming from the electrolysis module provokes fluctuations in the electrolyte level inside the separator tanks, it was incorporated a wave-breaker inside each tank in order to facilitate the level control. The wave-breaker covers 90% of the internal cross section of the tank. The remaining area is equally divided: 5% at the upper side is intended for gas exit and 5% at the bottom, for liquid communication. Considering that the operating temperature is 60C, the last elements attached to the separator tanks are coalescent filters, called demisters, in order to reduce the amount of water vapor in the gas, as well as to prevent alkaline electrolyte loss. The use of such demisters also act to reduce equipment maintenance, such as heat exchangers, control valves, catalytic reactors, instrumentation, etc., that are located after the separators.

3.4 Heat Exchangers Since the gases from the electrolytic process are saturated with the electrolyte, the use of heat exchangers will decrease the dew point of the gases, facilitating the return of electrolyte to the process.
The heat exchangers used for cooling the hydrogen and oxygen produced are of the type shell and tube, with all the wettable parts constructed of AISI 316L, the same material used for the electrolyte heat exchanger. The thermal management is performed using chilled water, also responsible for cooling the power source used to energize the electrolysis module.

3.5 Metering Pumps Two metering pumps are integrated to the system to control the liquid flows into the electrolysis module. The first one is dedicated to replace the deionized water consumed in the process, and operates at low flow range. The second pump presents a wider flow range in order to circulate the electrolyte into the electrolysis module. One of the important tasks to be accomplished during the experimental tests is related to understanding how the electrolyte flow influences the electrolysis module performance.
Both pumps are positive displacement type (single-coil), driven by three-phase electric motors assisted by frequency inverters, enabling automated flow control. A detailed view of the electrolysis pilot plant is shown in Figure 3.

Figure 3. Concept of the electrolytic system.

4. RESULTS AND DISCUSSION

After deciding the material to produce the frames (engineering plastic) and the material to be used as membranes, in agreement with item 3.1.4, the dimensions of each single cell were established as well as the number of cells necessary to achieve the desired hydrogen production.

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To accomplish this task the current densities were considered to be in the same range usually 2 employed in industrial bipolar alkaline water electrolyzers, from 200 to 300 mA/cm [2]. Considering those current densities and the effective area of each electrode the direct electrical 3 currents should vary from 114 to 172 A, and the hydrogen production from 0.96 to 1.44 m /h, for 3 a specific energy consumption of 5.0 kWh/m H2 (71% efficiency, based on the Lower Heating Value of hydrogen at 25C). Considering the yield strength of the engineering plastic, the frames were designed to support a working pressure of up to 8.0 bar with a safety factor of 3.8 [3, 4].

4.1 Diaphragm Tests The electrochemical characterization of the membrane was done by a galvanostatic experiment with a potentiostat (Omnimetra Instrumental Potentiostat, Mod. PG-05) and the experimental apparatus depicted in Figure 4.

Figure 4. Experimental apparatus used to evaluate the Teflon membrane as a separator for alkaline water electrolysis. The electrochemical cell has two sides that communicate only through an orifice and the experiments were done with the membrane in place and also without the membrane. Each side has a platinum electrode and a reference electrode type Ag/AgCl. They are immersed in aqueous KOH solution (30%g/g) at ambient temperature and atmospheric pressure. When a direct current is established between the two platinum electrodes a potential difference can be measured between the reference electrodes. The membranes were received in hydrophobic condition, commonly associated with Teflon . The activation and consequent change to a hydrophilic condition occurs simply by putting it in contact with a solvent, usually methanol. However, following the dealers instructions, the hydrophilization process can also occur when the membrane is immersed into the alkaline electrolyte. Figure 5 presents four polarization curves that were taken with the membrane in place and immersed in the electrolyte, at intervals of approximately 12 min, and currents varying from 0.100 to 0.600 A. The same experiments were performed without the membrane in place to determine the electrolyte contribution to the potential, and in this case the results can be represented by the equation: i) V0 = 0,023 + 0,050. i. The membrane resistivity, ii) = V . A / i, was calculated using the parametric equations obtained for the polarization curves shown in Figure 5, with help of the following additional equations: iii) V = Vm - V0, iv) V = R . i and v) R = / A, where: Vm and V0 were obtained by the parametric equations (Figure 5) respectively with and without the membrane; V is voltage (V),

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R is resistance (), i is current (A), is resistivity in terms of area (.cm ), and A is area (cm ), 2 equal to 3.14 cm . In these calculations the current value was considered to be i = 0.500 A, approximately the maximum current in all trials.
3,5

3,5

Second measure 2th: V = 0.58 + 6.50 . i

3,0

Y = 0,57929 + 6,5 X

4th:Fourth measure . i V = 0.16 + 6.34

3,0 2,5

Y = 0,16126 + 6,33667 X

ERef1-Ref2 / V

V (V)

V (V)

2,5

ERef1-Ref2 / V

2,0 1,5 1,0 0,5

2,0

1,5

1,0 0,10 0,15 0,20 0,25 0,30 0,35 0,40

0,1

0,2

0,3

0,4

0,5

/A iI (A)

i (A)

I/A

3,0 2,5

6th:Sixth 0.26 + 5.26 . i V = measure

3,0 2,5

Y = 0,25688 + 5,26303 X

8th: Eighth measure . i V = 0.30 + 4.96

Y = 0,3008 + 4,96 X

ERef1-Ref2 / V

ERef1-Ref2 / V

V (V)

V (V)

2,0 1,5 1,0 0,5 0,1 0,2 0,3 0,4 0,5 0,6

2,0 1,5 1,0 0,5 0,1 0,2 0,3 0,4 0,5 0,6

I/A

i (A)

i (A)

I/A

Figure 5. Polarization curves obtained with hydrophilic Teflon as diaphragm in water electrolysis. Polarization curves without the membrane can be represented by: V0 = 0,023 + 0,050. i.

Figure 6. Membrane resistivity in function of time during the experiment.

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Figure 6 presents the membrane resistivity versus time. Although a significant decrease was 2 observed during the short period of test, the minimum resistivity value achieved, 17 .cm , is still high for commercial alkaline bipolar water electrolyzers. This result is probably related to the short immersion time, 45 min, implying that the hydrophilic character of the membrane was not fully developed. So, new methods of activation and longer times of immersion will be tested in 2 order to get the membrane resistivity in the range 0.1 to 1.0 .cm , as suggested in the literature [5, 6]. Increasing the operation temperature to 60 nomin al temperature of the electrolysis module, C, will also contribute to reduce the overpotential caused by the membrane, leading to smaller energy consumption to produce the same amount of hydrogen.

5. CONCLUSIONS
During the development of this pilot plant, both incremental and disruptive approaches were employed in several parts of the system. Regarding the electrolysis module for example, the use of nickel plates as electrodes can be considered incremental and focused on the reliability of the electrolysis module. It avoids electrochemical surface treatments that go beyond the normal routine of industrial processes, but on the other hand the nickel plates are resistant to the alkaline medium and constitutes an excellent substrate that could be submitted to physical treatments, such as plasma spray, sputtering or ion implantation, in order develop new electrocatalyst surfaces. Using a Teflon membrane as separator for alkaline electrolysis can be considered a disruptive approach. Although in the initial tests the membrane has shown a resistivity higher than expected, the results are promising, since a reduction of 25% was obtained after an exposition of only 45 min to the alkaline solution. Engineering plastics of high molecular weight were used to manufacture and assembly the electrolysis module. Such materials present several advantages compared to metallic materials, such as the improved chemical compatibility, lower costs, and a variety of process can be employed in order to reduce manufacturing and maintenance costs. Regarding the whole system and the test bench, the PLC routine is under development and the basic data necessary to calibrate and control all the components and the system itself are being acquired. The operation of the pilot plant will provide important experimental data which will contribute to clarify the behavior of the operational parameters and their relationship. Furthermore, the level of knowledge of the process will advance and several improvements are expected in terms of system integration, system control, energy efficiency, operation and maintenance, durability and safety. The pilot plant also presents many opportunities for cooperation with other laboratories and research institutes mainly in areas such as materials, electrochemistry, modeling and simulation.

6. ACKNOWLEDGEMENTS
The authors would like to thank the Coordenao de Aperfeioamento de Pessoal de Ensino Superior (CAPES), the Conselho Nacional de Desenvolvimento Cientfico e Tecnolgico (CNPq), the Financiadora de Estudos e Projetos (FINEP) and the Fundao de Amparo a Pesquisa do Estado de So Paulo (FAPESP) for their financial and institutional support.

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7. REFERENCES
[1] FERREIRA, P.F.P.; Anlise da Viabilidade de Sistemas de Armazenamento de Energia Eltrica na Forma de Hidrognio utilizando Clulas a Combustvel, 94p. Dissertation. FEM/UNICAMP, 2003. [2] BOCKRIS, J.O.M. et al; Comprehensive Treatise of Electrochemistry, Vol.2; Plenum-Press, New York, 1989; [3] BUFFONI, S.S.O.; Vasos de Presso. Notas de aula da Disciplina Resistncia dos Materiais; 12p; UFF, Volta Redonda. Available at: http://www.professores.uff.br/salete/res1/aula15.pdf, accessed on 30/Nov/2009. [4] REDDO, A.M., Apostila de Dimensionamento de Equipamentos I, Fundao Tcnico Educacional Souza Marques, Rio de Janeiro, 2008. Available at: http://www.scribd.com/doc/19215394/DIMENSIONAMENTO-DE-EQUIPAMENTOS-1-VASOSDE-PRESSAO, accessed on 30/Nov/2009. [5] ROY, A., WATSON, S., INFIELD, D., Comparison of electrical energy efficiency of atmospheric and high-pressure electrolysers, Int. J. Hydrogen Energy, 31, p. 1964 - 1979, Elsevier, 2006. [6] MONTONERI, E., Evaluation of asbestos composite separators in advanced water test electrolysers, J. Appl. Electrochem., 18, p. 280-287, 1988.