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Materials of Construction for Electrolyzer Systems

Are there recommended resources that cover material stability for both PEM and alkaline electrolyzers at high pressures?

The answers are in context of PEM and alkaline electrolysis operating at or below 30 bar and below 85 deg C°. A general suggestion: Ask component suppliers about material compatibility, but do an independent investigation to confirm. As a general resource,  safety data sheets (SDSs) sometimes provide material compatibility information. Specific recommendations follow. 

  • Hydrogen: Hydrogen material compatibility information can be found at Material Compatibility Hydrogen Tools (h2tools.org), including the very detailed technical reference developed by Sandia National Laboratories.
  • Alkaline Water Electrolysis Systems: Cell stack electrolytes are typically potassium hydroxide, sodium hydroxide, or sodium chloride solutions. The pumps, piping, gas/liquid separators, and other components must be compatible. An example of an MSDS that provides information about material compatibility can be found at ERCO Worldwide: Potassium Hydroxide Solution.  Other resources include publications by the National Association of Corrosion Engineers and the Materials Technology Institute.
  • Oxygen: Oxygen compatibility is a big concern, especially at pressure. ASTM subcommittee G04.02 affords no-cost access to apt standards and cleaning practices for oxygen. Start here: ASTM International Jurisdiction of G04.02. Other resources include CGA G-4.4, Oxygen Pipeline and Piping Systems. Only certain materials are rated for pressurized oxygen. Cleaning to remove particles and oils is very important to reduce fire hazards - remember, almost anything can be fuel in oxygen. 
  • Water: Pure water feed to electrolyzers is important. A good approach is to consult with the water purification equipment supplier for recommended materials for the feed water supply components. High purity water corrosion products can contaminate PEM membranes and degrade electrolyte. 
  • The use of plastic tubing in H2 and O2 pressure applications is usually precluded. See the AICHE CHS H2 Laboratory Safety course, which discusses a PNNL laboratory incident. Metal tubing is preferred. While plastic tubing may be desirable for non-conductivity and flexibility, one should only consider plastic tubing after a full hazard analysis to assure there are effective protective safeguards (e.g., ventilation, flow limits, protective enclosures, active leak detection, isolation/depressurization) in place. 
  • H2 and O2 gases dissolve in significant quantities in liquids at 30 bar. Materials in these services will need to be compatible with the gas as well as the fluid. Note that these gases will readily come out of solution when pressure is reduced and directed to a drain. Open drains in well-ventilated areas are strongly recommended.

Pay particular attention to material compatibility of safety devices, such as pressure relief valves and pressure sensors. It is important to follow the guidance for proper design of vent systems given in CGA G 5.5 for H2 and EIGA Doc 154 for O2. These standards cover topics such as where back pressure is to be avoided and safe vent locations.
 

FAQ Category
Submission Year
2023
Month
08

Explosions - Electrolysis

Is there a list of earlier references to water alkaline H2 electrolysis explosions like the one at https://h2tools.org/lessons/water-electrolysis-system-explosion?

The lesson learned (LL) article referenced in the question cites an incident that occurred in December 1969. While there may have been other accidents, the HSP does not have any other LL articles on alkaline water electrolysis explosions. In the LL article that was updated in 2017, the technology described employs a potassium hydroxide (KOH) electrolyte solution. The KOH electrolyte is held by surface tension within a fibrous mat used as a cell separator. A 30 weight % KOH solution is typically circulated through each of many electrolysis cells internally manifolded together within a bipolar electrolysis cell stack. Product hydrogen with KOH solution rises into an overhead degassing tank (drum in the LL article); product oxygen with KOH solution rises into a separate overhead degassing tank. 

The article describes a breakdown of the separator allowing H2 and O2 gases to mix. Slight differences in pressure between the oxygen and hydrogen sides of the cell are enough to permit crossover of gases. A recent Gangwon electrolysis incident involved a semipermeable alkaline membrane technology instead of a fibrous cell separator. Conditions at near idle current may have allowed sufficient cross cell diffusion to occur, permitting an explosive mixture to collect in the storage tanks with the result reported. This event has not yet been published in our Hydrogen Tools LL database.

FAQ Category
Submission Year
2024
Month
04
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