The Hunt for hydrogen and hydro-riches

March 6, 2014 |

the-sunOK, you have a carbon strategy, and that’s good.

But how’s your hydrogen strategy coming along?

In our “100 Fortune Cookies,” we put it as plainly as we could: “You will never have enough affordable hydrogen.”

Perhaps that is the attractor in the news from little-known Solarvest Bioenergy, when they announced  third party confirmation of their bio-hydrogen expression system following the successful completion of a six month NSERC Engage project at the Université de Montréal, a world leader in bio-hydrogen production and proteomics.

For those following the Solarvest story — it’s a microalgae company aiming to produce hydrogen as well as omega-3 fatty acids.

The study indicated that the Solarvest modified strain of microalgae produced six times more hydrogen per cell as compared to the industry standard wild-type strain. In addition the Solarvest strain demonstrated continuous hydrogen production, producing hydrogen ten times longer when compared to the industry standard wild-type microalgae even though the laboratory growth conditions were less than optimal.

Why hydrogen?

Here’s some biobased math, shall we? Let’s say you start with a basic glucose — the type we have fermented into alcohol for eons. C6H12C6, right?

Now, let’s make an alkane, your basic combustion fuel molecule. Take hexane, to use a simple example. That’s C6H14. So, you’re short hydrogen. Just about every biomass conversion to hydrocarbon fuel — or even alcohol fuel — is short a little hydrogen.

So we got to get it from somewhere, or we lose yield — even more than we do blowing off the oxygen. Traditionally, we obtain it through petrochemical operations. But, that’s not very renewable, is it?

So, what’s happening in the world of making biobased hydrogen — either as an energy carrier, a feedstock for fuel production of for green chemistry?

Hydrogen as a material

But wait, there’s more. Hydrogen gas is a dependency in a number of processes that make renewable fuels — most notably, those that have a hydrotreating step to remove excess oxygen. That includes the upgrade of pyrolysis oils, and even the production of aviation biofuels from renewable oils (the HEFA pathway that is currently powering most of the current flight activity).

When the bioeconomy runs short on hydrogen

Back in 2012, Syntroleum had to stop its biofuel production at the Dynamic Fuels facility in Geismar for four weeks as a result of hydrogen supply interruptions. The company took advantage of the shut down to switch out catalysts and undertake other maintenance that is required every seven years — but it went a-huntin’ for different hydrogen suppliers to avoid future supply disruptions — without finding, as we heard, economically viable options.

The market?

Last month, we reported that  growth in the utilization of hydrogen outside of petroleum refining and chemical manufacturing is expected to accelerate sharply over the next 16 years. According to a recent report from Navigant Research, hydrogen consumption for non-traditional applications (i.e., outside the petroleum and chemical sectors) will grow from 168 million kilograms (kg) in 2013 to nearly 3.5 billion kg in 2030.

What’s the R&D leadership doing about it?

In November 2012, the US Energy Department issued a request for information to garner input from researchers in industry, academia, and other interested biofuels stakeholders to identify key technical barriers in converting biomass via thermochemical direct liquefaction pathways to transportation fuels in the gasoline, diesel, and jet fuel ranges. For the purpose of this RFI, thermochemical direct liquefaction pathways include fast pyrolysis, in-situ and ex-situ catalytic pyrolysis, hydropyrolysis, hydrothermal (or solvent) liquefaction, followed by various combinations of bio-oil stabilization and upgrading processes.  For more information, view the full RFI (DE-FOA-0000796) on the EERE Exchange website.

5 ways to make hydrogen, renewably

1. Electrolysis

The process? Hydrogen can be produced from water, and routinely is, using an electrolytic process that you can demonstrate in a high school lab.

The problem? The process will chew up some 35-50 kilowatt hours of electricity per kilo of hydrogen. There being roughly a kilo of hydrogen in a gallon of hydrocarbon fuel — at $0.10 for lowest cost renewable electricity (e.g. wind), there’s $1.70-$2.50 cost per gallon just to provide the hydrogen feedstock, and you still have to pay for the process and whatever cost of aggregating CO2.

Solution? Advocates routinely talk about producing hydrogen using excess (and thereby, nominally priced) renewable power — at times when the grid is loaded, rather than shunting biomass steam energy to cooling towers (as opposed to the turbines) or using large scale battery storage of the type that Duke Energy put in place at its Notrees wind farm in North Carolina.

Another solution. ORNL has developed a low-cost process – yet to be demonstrated at scale.

2. Anaerobic digesters.

The process? Here, microbes chew waste materials and produce biogas, rich in methane.

The problem? Costs have been the issue. But systems have been getting bigger, and options for producing hydrogen from them are there, using essentially the same processes by which hydrogen is produced from natural gas.

Solution? As an example of progression in system size, Western Plains Energy announced plans to build a $40 million anaerobic digester to produce enough biogas to replace 90% of the fossil fuel used in the manufacturing process at the company’s 50-million-gallon Oakley ethanol plant. When completed, the digester is expected to provide 15 jobs converting manure, grain dust and food waste to power. The project received a $5 million grant in April from the U.S. Dept. of Agriculture, and $15.9 million one year ago when Kansas Gov. Sam Brownback redirected unspent American Recovery and Reinvestment Act funding to the project.

3. Steam reformation or other catalytic processes from biogas or biooil

The process? Cracking hydrogen from biomass using heat and catalysis.

The problem? Cost, again. Steam reformation itself has struggled with high costs associated with the high temperatures at which the system operates. But it has been a technology worth chasing, for in the development of F-T plants it eliminates both the need for expensive oxygen plants and larger footprints needed to deal with nitrogen dilution from air, lowering capex and space requirements.

Solution? In 2010, we reported on a team from East China University of Science and Technology and Guangxi University  has conducted a study of hydrogen production via catalytic steam reforming of bio-oil in a fluidized-bed reactor. They note that “hydrogen production from renewable biomass is particularly adapted to sustainable development concerns. Biomass, a kind of renewable resource that adsorbs CO2 during its growth, contributes net zero carbon emissions when used to produce hydrogen.”

A system that has been attracting the most attention in this area is the ClearFuels gasifier, the star gasifier at Rentech’s Product Demonstration Unit in Colorado. Unlike other gasifiers or pyrolysis processes, ClearFuels HEHTR is a one-step rapid steam reforming process that converts all the biomass to syngas with no char, no liquid intermediates, no ash slagging/fouling and low tar content.

The technology has operational controls for a tunable hydrogen to syngas ratio of 1:1 up to 3.5 to 1, while also interchangeably running on syngas, tailgas, biogas or natural gas.

4. Syngas as a source of hydrogen — and renewable fuels, all at once.

You may recall that LanzaTech can use hydrogen-free gases for the production of ethanol. That is because their proprietary microbe can produce hydrogen from carbon and water as required. Which, of course, raises the possibility of combining a LanzaTech-type process with a process that needs hydrogen — and obtaining both feedstocks at the same time from synthesis gas (a combination of hydrogen and carbon monoxide), produced by gasifying biomass. Just a matter of membrane separation of the hydrogen gas. Voila, renewable hydrogen, ready to be fed to a second system that uses CO2 and hydrogen to make fuels.

But it might well come from MSW. In terms of the power value, you have something like the potential to make 500 pounds of syngas from the annual US household garbage pail, roughly enough to run a 12 KW generator. That wouldn’t exactly power an electricity-hungry Western lifestyle, but it’s enough to keep the lights, heat, AC, fridge, freezer and sump pump running in a 1500 ft home. And no 2 gallons of diesel fuel per hour to run the generator.

Now, you’re not going to see household-size conversion systems any time soon on the horizon on a cost feasible basis, but Sierra’s Pathfinder system appears to be making some waves with a skid-mounted, 10 ton-per-day system that it originally developed as a small demo unit to prove the viability of its technology.

5. Mimicking photosynthesis.

In California recently, HyperSolar announced its plan to build renewable hydrogen generators for commercial use. Named the H2Generator, the company’s first commercial product is expected to sell at a substantially lower price than other renewable hydrogen systems that rely on expensive and energy intensive electrolyzers to split water.

By optimizing the science of water electrolysis, the low cost device mimics photosynthesis to efficiently use sunlight to separate hydrogen from water, to produce environmentally friendly renewable hydrogen. The HyperSolar H2Generator will be designed to be a linearly scalable and self-contained renewable hydrogen production system. As a result, it is intended to be installed almost anywhere to produce hydrogen fuel for local use. This distributed model of hydrogen production will address one of the greatest challenges of using clean hydrogen fuel on a large scale – the need to transport hydrogen in large quantities.

5 technologies to watch

1. Last October, a research team at the University of Santa Cruz developed a solar-microbial device and reported their results in a paper published in the American Chemical Society journal ACS Nano. The hybrid device combines a microbial fuel cell and a type of solar cell called a photoelectrochemical cell that can use sunlight and wastewater to produce hydrogen gas.

The researchers are optimistic about the commercial potential for their invention. Currently they are planning to scale up the small laboratory device to make a larger 40-liter prototype continuously fed with municipal wastewater. If results from the 40-liter prototype are promising, they will test the device on site at the wastewater treatment plant.

2. Last April, researchers at the U.S. Department of Energy’s Brookhaven National Laboratory developed an effective catalyst could replace costly platinum in the production of hydrogen. The catalyst, made from renewable soybeans and abundant molybdenum metal, produces hydrogen, cost-effective manner, potentially increasing the use of this clean energy source.

Assisting in the research were Shilpa and Shweta Iyer, twin-sister high school students who contributed to the research as part of an internship under the guidance of Brookhaven chemist Wei-Fu Chen, supported by projects led by James Muckerman, Etsuko Fujita, and Kotaro Sasaki.

3. Also last April, researchers at Virginia Tech related that they had made a major breakthrough by using xylose to produce a large quantity of hydrogen that previously was only theoretically possible. The method can be applied to any kind of biomass to produce hydrogen, a process which could find its way to the market in as quick as three years.

4. In January 2013, the Ecotechnologies fund, managed by CDC Entreprises, made a second investment in the company McPhy Energy. This €5M equity investment aims at supporting the commercial development of the company following the acquisition of an electrolysis equipments production unit. This investment is part of a 10M€ capital increase completed by the company’s historical investors: Emertec Gestion, Sofinnova Partners, Gimv, Arevadelfi and Clipperton Finance.

At the technological level, the hydrogen storage solution brought by McPhy Energy is a disruptive discovery compared with the conventional hydrogen storage solutions (high pressure gaseous storage or liquefied storage at extremely low temperature), with significant advantages such as an improved security thanks to low pressure storage, a lower energy consumption and a greater ease of use.

5. In July 2012, Korea Ocean Research and Development Institute (KORDI) said that it had developed technology that uses single-celled microorganisms from deep under the seabed in the Pacific Ocean to transform carbon monoxide emissions from steel manufacturing into hydrogen for biofuel use.

Innovation in the petrochemical world

It may not be green, but doing things better with traditional process is green-er.

Case in point. Last July, Air Products extended its PRISM Hydrogen Generator product line for on-site gas production to supply requirements greater than 4,500 normal cubic meters per hour (4.1 million standard cubic feet per day). By combining the company’s proprietary reformer technology with its hydrogen pressure swing adsorption capabilities, Air Products’ PRISM Hydrogen Generators can now offer lower cost hydrogen in this production range. The company has contracted more than 30 PRISM Hydrogen Generators, and more than 20 have been installed and are currently operating around the world.

The PRISM Hydrogen Generator is an on-site hydrogen generation technology that allows for easy field installation and a fast start-up. Air Products’ focus on safety is embedded in the product design, and the units have the capability for full local and remote control.


The bottom line.

There are more paths to hydrogen than routes to a candy store — but none of them have proven out just yet. No one is head and shoulders above the rest. Long-term, mimicking photosynthesis might well be the ticket — but in the short term, we may see digesters rule the day.

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