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An ambitious new project is underway at Stanford University, as a team of scientists are hoping to replace the Haber-Bosch process for the manufacture of fertilizer.

With the energy consumed in the Haber-Bosch process contributing to climate change, if the research is successful then they may help solve two of mankind’s most pressing problems:
• How to feed a growing population
• How to use less fossil fuels

The team is based at the SUNCAT Center for Interface Science and Catalysis, a partnership between researchers from Stanford Engineering and the SLAC National Accelerator Laboratory. Where the team, “… is developing a fertilizer production process that can feed the world in an environmentally sustainable way,” says chemical engineer and SUNCAT director, Jens Norskov.

The SUNCAT project is being funded by a $7 million grant from the Villum Foundation, an international scientific and environmental philanthropy, which is focused on sustainable industrial chemicals, including a sustainable nitrogen-based fertilizer.

“One common thread across these projects is the need to identify catalysts that can promote chemical processes powered by sunlight, instead of relying on the fossil fuels now commonly used as energy sources and, often, as feedstock for reactions,” says Norskov. “We know of no manmade catalysts that can do what we require, [so] we will have to design them.”

Tom Jaramillo, deputy director of the SUNCAT Center and a member of the nitrogen synthesis project, put annual fertilizer production into perspective when he said, “Each year we produce more than 20 kilograms of ammonia per person for every person on the planet, and most of that ammonia is used for fertilizer.”

“We literally feed the world on fertilizers derived from the Haber-Bosch process,” adds Norskov. But the process is far from efficient, with the online scientific journal Phys.org, even stating that, “Due to the heat and pressure required by the Haber-Bosch process, ammonia catalysis accounts for approximately 1% of all global energy use. On top of that, between 3% and 5% of the world’s natural gas is used as a feedstock to provide the hydrogen for ammonia synthesis.”

Typically this process is carried out in large chemical plants, which adds cost to the fertilizer when fuel for transportation to the farm is factored in. To avoid this, the team is taking a different approach.

“We will harness solar energy in the presence of properly designed catalysts to create ammonia right in the agricultural fields. Think of it as a drip irrigation method of synthesizing ammonia, where it percolates into the roots of the crops.”

The theory behind the research is almost utopian; removing the need for fossil fuels as both a fertilizer feedstock and as an energy source, and with all processes working in the field, transportation costs will be miniscule.

As Norskovs explains, “You won’t need tremendous quantities of fossil fuels as an ammonia feedstock, or to drive the trucks that deliver the fertilizers or the tractors that apply it. And you won’t have a problem with excess application and fertilizer runoff, because virtually all the fertilizer that is produced will be consumed completely by the crops.”

Reporting on the SUNCAT team, the Phys.org report adds that, “The researchers aim to provide the benefits of fertilization without any of these [fossil fuel, transportation, application, feedstock] costs. The idea is to replace the centralized, fossil-fuel based Haber-Bosch process with a distributed network of ammonia-on-demand production modules run off renewable energy. These modules would use solar power to pull nitrogen from the atmosphere and also to catalyze the splitting of water molecules to get hydrogen and oxygen. The catalytic processes would then unite one nitrogen atom to three hydrogen atoms to produce ammonia, with oxygen as a waste product.”

However, finding the catalyst that can perform the function required will be far from easy. A point highlighted by Stacey Bent, a professor of chemical engineering at Stanford and a key member of the SUNCAT team, when she said, “While the catalyst must bind strongly enough to the target molecule to do the work required, it also has to release the end product.”

Jaramillo agrees, highlighting the complex chemical process that will need to be engineered. He said, “We have to design a series of reactions to cleave the nitrogen molecule from air, separate the hydrogen from water and combine them to form ammonia, with the only input energy coming from solar power.”

At the same time, there are other factors to consider in finding a catalyst, as the research team is aware that their end product must have a practical application. As Bent notes, “We have to design catalysts that can make and break bonds with atomic precision, and we have to ensure these materials can be mass produced at the necessary scales and price points, and are durable and simple to use in the fields.”

The challenge is clearly immense, but then so is the prize.

“Sustainable nitrogen production will only become possible with the cross-disciplinary collaboration of people working in fields such as materials science, chemical engineering and computer science,” Bent says. “It could literally change the world.”

And it seems that the researchers have the tools to make the dream a reality. “We are part of a very strong team, attacking some of the biggest challenges in chemistry, chemical engineering and sustainability,” says Jaramillo. Before adding, “We’re really just at the beginning.”

As they say, every journey begins with a single step, so being at the start of something holds no shame. How much scepticism Haber and Bosch received on beginning their journey is not known, but they must both have held large amounts of self-belief to achieve their goals; something that is clearly not missing from the SUNCAT team.

“Essentially we are attempting to restore the balance in the Earth’s carbon and nitrogen cycles that has been lost through the exponential increase in the demand for food and fossil fuels,” says Norskov. “The time to act is now.”

Like all great plans, it has strength in its simplicity. The challenge will come in working out the details, and in finding the exact catalysts that will work in harmony to provide solar-powered, in-field manufactured fertilizer. Whether they can complete their task and find a much needed replacement for the Haber-Bosch process, only time will tell.

Credit: iStock/yupiyan

In general, there is plenty of cooperation between livestock farmers and animal feed manufacturers; both aiming for healthier animals. But there are also many secrets between agribusiness traders and feed manufacturers.

Much of this confidentiality revolves around raw materials, with many animal feed producers looking for competitive advantage from secret ingredients. As an industry which has seen a move from guano (as a source of phosphate) to mining rock phosphate, knows a thing or two about the power of information when it comes to sourcing raw materials.

The development of monocalcium phosphate as an animal feed additive, or the use of insect meal as a more sustainable protein source than fishmeal have all been (or likely will be) feed industry game-changers.
With this in mind, it is worthwhile for animal feed suppliers to stay up-to-date with the raw material research. Here therefore, are two of the latest ideas being trialled and tested in the (sometimes) crazy word of animal feed R&D.

Hemp as an Animal Feed Additive

While America’s legislators are busy removing prohibitions on the smoking of cannabis, some are also trialling the use of hemp as a raw material for animal feed.

At least this is the case in Colorado, where Governor John Hickenlooper recently signed a law to allow for a feasibility study for the use of hemp in feed products. At present, while hemp can be used as a raw material for human food, the US FDA prohibits its use in animal feed, seeing it as an ‘adulterating substance’.

As the industry journal WattAgNet reports, “The group that will lead the feasibility study will include a hemp producer, a hemp processor, a legal expert, a person from an institution of higher education who has studied hemp policy, a veterinarian and a livestock producer. The group is expected to reach its conclusions and make its recommendations by the end of 2017.”

In an interview, Hollis Glenn, technical services section chief for the Colorado Department of Agriculture, explained how, “The hemp industry understands the complexities of putting hemp into the food chain,” adding that, “[The study will] provide a resource to industry and consumers to understand the complexity of this issue.”

While agreeably the issue is complex, there are many who see the natural benefits of using a plant as a feed additive. Many ‘free the weed’ campaigners fought for the decriminalisation of cannabis based on numerous advantages, but not many would have suspected at the time that it would also lower animal feed prices.

Skittles as an Animal Feed Additive

The next secret ingredient for animal feed could be the fruity, coloured sweet Skittles; a registered trademark of Wrigley. Whilst the nutritional value of the sugary snack is uncertain, it seems that some farmers have already been feeding them to their livestock.

As the Independent newspaper reports, “The discovery was made public after a truck deposited hundreds of thousands of Skittles onto a rural road. All of them were in one colour and without the trademark ‘S’ on them.”
Following an investigation, the police found out that farmers had been feeding the Skittles to their livestock to avoid high corn prices.

As the report states, “Unknown to many, the practice has been going on for years, according to experts. Not only are Skittles cheaper than corn – especially when bought for a lower price because they are defective – they could even provide other benefits over traditional feed.”

While there was some outrage online at the unusual practice, feed experts have since come forward in defence of the feed raw material.

Joseph Watson, owner of United Livestock Commodities, told LiveScience in 2012 that feeding cows sweets “actually has a higher ratio of fat [than] actually feeding them straight corn”, and that it has “all the right nutrition”.
Similarly, John Waller, a professor of animal nutrition at the University of Tennessee, told the site that it was likely to be more environmentally friendly because it keeps “fat material” from simply going into landfill.

The practice of buying in defective or unneeded food to feed to animals goes back for decades. But it is thought to have picked up around 2012, when corn prices rocketed up and farmers needed a cheaper way of feeding their animals. But whether or not the practice will continue, when corn prices return to normal, remains to be seen.

Photo credit: the bull
Photo credit: Modern Farmer

Researchers from MiT have discovered a coating that could help prevent blockages in oil drilling pipes, potentially protecting the environment from oil leaks, as well as saving millions of dollars in lost oil.

The team was inspired by the events that led to the Deepwater Horizon oil spill in the Gulf of Mexico. Following a deadly explosion and blow out in April 2010, BP engineers were confident that they would be able to stop the flow by placing a 125-ton dome over the broken wellhead.

However, the recovery operation failed because of a blockage caused by ‘an icy mixture of frozen water and methane, called a methane clathrate’. As the MiT website reports, “Because of the low temperatures and high pressure near the seafloor, the slushy mix [of methane clathrate] built up inside the containment dome and blocked the outlet pipe, preventing it from redirecting the flow. If it hadn’t been for that methane clathrate, the containment might have worked, and four months of unabated leakage and widespread ecological devastation might have been prevented.”

Publishing the results of tests on their new coating in the journal Applied Materials & Interfaces, the research team outlined that problem, stating, “Clathrate hydrates are icelike solid substances that can form inside oil and gas pipelines and are responsible for flow blockages, sometimes leading to catastrophic failures. Minimizing hydrate formation and adhesion on pipeline surfaces can effectively address this problem.”

The solution they devised is a new coating, whose design was based upon earlier research from 2011. As the online scientific journal Phys.org reported at the time, “The study produced several significant results: First, by using a simple coating, [the researchers] were able to reduce hydrate adhesion in the pipe to one-quarter of the amount on untreated surfaces. Second, the test system they devised provides a simple and inexpensive way of searching for even more effective inhibitors. Finally, the researchers also found a strong correlation between the ‘hydrate-phobic’ properties of a surface and its wettability — a measure of how well liquid spreads on the surface.”

The report continued by noting that, “The basic findings also apply to other adhesive solids, — for example, solder adhering to a circuit board, or calcite deposits inside plumbing lines — so the same testing methods could be used to screen coatings for a wide variety of commercial and industrial processes.”

Famously, one of these was a non-stick coating for shampoo, mayonnaise, or similar containers. As the industry journal Packaging Gateway reported, “Researchers at the Massachusetts Institute of Technology (MIT) have developed a non-sticking coating for food packaging, which will allow substances such as ketchup to pour from containers easier.”

Converting this idea to the challenging environment of oil extraction has not been simple, but the new pipeline coating is not dissimilar to that used in ketchup bottles. As Kripa Varanasi, professor of mechanical engineering and one of the research team members explains, in this case, “we are using the liquid that’s in the environment itself rather than applying a lubricant to the surface. The key characteristic in clathrate formation is the presence of water, so as long as the water can be kept away from the pipe wall, clathrate buildup can be stopped. And the liquid hydrocarbons present in the petroleum, as long as they cling to the wall thanks to a chemical affinity of the surface coating, can effectively keep that water away. If the oil [in the pipeline] is made to spread more readily on the surface, then it forms a barrier film between the water and the wall.”

You can watch the MiT produced video explanation of the coating discovery on this YouTube link here.

Given the extreme temperatures and pressures involved in deep water drilling, it is difficult to reproduce the exact conditions experienced at a wellhead, but lab tests conducted have shown that the coating was able to keep pipes clear of a proxy chemical [used in place of actual methane clathrate] very effectively. As Varanasi said, “We didn’t see any hydrates adhering to the substrates.”

This is a ground-breaking development for the oil drilling and oil pipeline lubricant industry. Current prevention measures, known as flow assurance measures, have existed for a long time, but as Varanasi explains, “they are expensive or environmentally unfriendly.” Current use is estimated as costing the industry “hundreds of millions of dollars” every year. But they are essential, as they prevent hydrate build up that can cause blockages that lower flow rate, or cause accidents that can cost billions. As Varanasi states, “Clogging can lead to catastrophic failures.” Adding that, “Hydrates are a major problem for the industry, for both safety and reliability.”

The challenge could become even greater, says Arindam Das, the paper’s lead author, because methane hydrates themselves, which are abundant in numerous locations such as continental shelves, are a potential fuel source. The impact of capturing and processing methane hydrates as a power source could be huge, if an economic method of extraction could be developed. “The reserves themselves substantially overshadow all known reserves [of oil and natural gas] on land and in deep water,” he says.

But as the MiT website notes, “Such deposits would be even more vulnerable to freezing and plug formation than existing oil and gas wells. Preventing these icy buildups depends critically on stopping the very first particles of clathrate from adhering to the pipe.

“Once they attach, they attract other particles” of clathrate, and the buildup takes off rapidly, said research co-worker Taylor Farnham. “We wanted to see how we could minimize the initial adhesion on the pipe walls.”

While this discovery does bring the possibility of tapping methane hydrates as a resource a little closer, for now the team’s goal is to promote their discovery as a solution to a current problem in the petroleum industry.

In fact, the breakthrough coating is already gathering significant attention from both drilling experts and coating manufacturers. An oil pipeline coating that prevents clogging will save money on a daily basis by replacing current methods and lowering maintenance costs is a popular coating product.

The Deepwater Horizon tragedy will be remembered for years to come, with the oil extraction industry still reeling from its effects. But if this new product is able to prevent just one similar incident then the coating will be more than worth its weight in gold, or even black gold.

Photo credit: newsapi.au & creditwritedowns.com