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Hydrogen Production Technologies

The choice of production methods will vary depending on the availability of feedstock or resource, the quantity of hydrogen required, and the required purity of hydrogen. Researchers are developing a wide range of processes for producing hydrogen economically and in an environmentally friendly way. These processes can be divided into three major research areas:

bulletThermochemical Production Technologies
bulletElectrolytic Production Technologies
bulletPhotolytic Production Technologies

Thermochemical Production Technologies

Natural Gas Steam Reforming

Photo of Petroleum Refinery
Although today most hydrogen is produced from fossil materials, such as from natural gas at this oil refinery, the Program is exploring a variety of ways to produce hydrogen from renewable resources.

The production of hydrogen from natural gas is an integral part of the strategy to introduce hydrogen into the transportation and utility energy sectors, by reducing the cost of conventional and developing innovative hydrogen production processes that rely on cheap fossil feedstocks. Today, nearly all hydrogen production is based on fossil raw materials. Worldwide, 48% of hydrogen is produced from natural gas, 30% from oil (mostly consumed in refineries), 18% from coal, and the remaining (4%) via water electrolysis.

Modification of the conventional steam methane reforming (SMR) process to incorporate an adsorbent in the reformer to remove CO2 from the product stream may offer a number of advantages over conventional processes. Upsetting the reaction equilibrium in this way drives the reaction to produce additional hydrogen at lower temperatures than conventional SMR reactors. Although still in the research stage, the cost of hydrogen from this modified process is expected to be 25%-30% lower, primarily because of reduced capital and operating costs. In addition, the adsorption of the CO2 in the reforming stage results in a high-purity CO2 stream from the adsorbent regeneration step. This has interesting implications in a carbon-constrained world.

Partial Oxidation/Ceramic Membrane Reactor

Scientists are developing a ceramic membrane reactor for the simultaneous separation of oxygen from air and the partial oxidation of methane. If successful, this process could result in improved production of hydrogen and/or synthesis gas compared to conventional reformers.

Biomass Gasification and Pyrolysis

Photo of switchgrass being swathed
The Program is exploring ways in which to produce hydrogen from biomass, such as this switchgrass, via pyrolysis and gasification.

The thermal processing techniques for plant material (biomass) and fossil fuels are similar, with a number of the downstream unit operations being essentially the same for both feedstocks. Using agricultural residues and wastes, or biomass specifically grown for energy uses, hydrogen can be produced via pyrolysis or gasification.

Biomass pyrolysis produces a liquid product (bio-oil) that, like petroleum, contains a wide spectrum of components that can be separated into valuable chemicals and fuels.

Unlike petroleum, bio-oil contains a significant number of highly reactive oxygenated components derived mainly from constitutive carbohydrates and lignin. These components can be transformed into products, including hydrogen. Coproduct strategies are designed to produce high value chemicals, such as phenolic resins, in conjunction with hydrogen.

Photo of hydrogen production at the Schatz Energy Research Center in Arcata, California
A promising option for hydrogen production from renewable resources is electrolysis, in which electricity is used to disassociate water into hydrogen and oxygen.
Photo courtesy of the Schatz Energy Research Center, Humboldt State University

Electrolytic Production Technologies

Water Electrolysis

Until the 1950s, water electrolyzers were in widespread use for hydrogen (or oxygen) production. Currently, electrolysis provides only a small percentage of the world's hydrogen, most of which is supplied to applications requiring small volumes of high purity hydrogen (or oxygen, such as for breathing atmospheres for submarines). There is significant renewed interest in the use of electrolyzers to produce hydrogen as a fuel for automotive applications, with a number of refueling stations installed around the world. In addition, research continues in the integration of intermittent renewable resources (PV and wind) with electrolyzers, for producing hydrogen to be used as a fuel or for energy storage.

Reversible Fuel Cells/Electrolyzers

Operating the proton exchange membrane (PEM) fuel cell "in reverse" as an electrolyzer is possible, but optimum operating conditions for the power production mode and for the hydrogen production mode are significantly different. Design issues for the reversible fuel cell system include thermal management, humidification, and catalyst type and loading.

 

Photolytic Production Technologies

Photobiological

Photo of system for photobiological algal hydrogen production
A set of bio-reactors use can use light (sunlight or artificial light) and the natural activities of enzymes in green algae to produce hydrogen from water. Photobiological production of hydrogen is a promising renewable option for the long term.

Certain photosynthetic microbes produce hydrogen in their metabolic activities using light energy. By employing catalysts and engineered systems, hydrogen production efficiency could reach 24%. Photobiological technology holds great promise but because oxygen is produced along with the hydrogen, the technology must overcome the limitation of oxygen sensitivity of the hydrogen-evolving enzyme systems. Researchers are addressing this issue by screening for naturally occurring organisms that are more tolerant of oxygen, and by creating new genetic forms of the organisms that can sustain hydrogen production in the presence of oxygen. A new system is also being developed that uses a metabolic switch (sulfur deprivation) to cycle algal cells between a photosynthetic growth phase and a hydrogen production phase.

Unlike cyanobacteria or algae, photosynthetic bacteria do not oxidize water. They do, however, evolve hydrogen from biomass (previously generated from sunlight, water, and carbon dioxide). These bacteria use several different enzymatic mechanisms with near-term commercial potential for biological hydrogen production from biomass. One mechanism in particular looks promising for applications as a biological conditioning agent for upgrading thermally generated fuel gases to a level where they can be directly injected into hydrogen fuel cells. This same system has potential to subsequently evolve into a second-generation photobiological method to produce hydrogen from water.

 

Photoelectrolysis

Photo of hydrogen beam generated from PV cell
Another promising option for the long term is photoelectrolysis. Here, light shining on a photoelectrochemical cell immersed in water produces bubbles of hydrogen and oxygen.

Multijunction cell technology developed by the PV industry is being used for photoelectrochemical (PEC) light harvesting systems that generate sufficient voltage to split water and are stable in a water/electrolyte environment. Theoretical efficiency for tandem junction systems is 42%; practical systems could achieve 18%-24% efficiency; low-cost multi-junction amorphous silicon (a-Si) systems could achieve 7%-12% efficiency. This is one of the advantages of a direct conversion hydrogen generation system. Not only does it eliminate most of the costs of the electrolyzer, but it also has the possibility of increasing the overall efficiency of the process. Research results for the development of PEC water splitting systems have shown a solar-to-hydrogen efficiency of 12.4% lower heating value (LHV) using concentrated light. Low-cost a-Si tandem designs with appropriate stability and performance are also being developed. An outdoor test of the a-Si cells resulted in a solar-to-hydrogen efficiency of 7.8% LHV under natural sunlight.