Bio Diesel leader Valero Energy Corp has been joined by other big oil firms Marathon Petroleum Corp., Phillips 66 and HollyFrontier in developing new projects designed to produce what’s been dubbed bio diesel or “renewable diesel,” a second-generation fuel made from animal fat that’s almost chemically identical to the petroleum form and offers the same performance.

The efforts are based using vegetable oils and animal fat, which is gaining new prominence among the top U.S. petroleum refiners, who see it as a potential growth engine in a climate change-driven future.

Early forms of biodiesel have been available for decades, but were said to lack the punch of the petroleum-based fuel, particularly in cold weather. The newest products, processed at much higher temperatures in specialized equipment, solves that issue.

Valero’s existing joint venture in the renewable diesel field could generate $1.4 billion in earnings by 2024, according to a report by the research firm Piper Jaffray & Co. That has seized the attention of the oil industry.

Patrick Flam, a Piper Jaffray analyst who has been following the emergence of renewable diesel noted, “Valero is the only one that’s broken it out on its own and shown how good this thing is. Others are looking at this and they’re saying, ‘Oh man those returns are actually pretty compelling.’”

The green social push toward the renewable fuel, which cuts back the emissions of petroleum-based diesel, comes at a time when gasoline use by drivers is flagging as vehicles get more fuel efficient. Drivers are becoming more concerned about climate change and state governments are intensifying their environmental regulations.

Flam added, “There is a pretty good drive from the shareholder side that we need to be growing this business somehow or another. Traditional refining is probably not the best way to do it at the moment.”

For now in the midst of a petroleum glut, the renewable fuel is more costly than the petroleum-based version on a wholesale basis, but the pump price is competitive thanks to tax credits designed to promote use of the environmentally friendly alternative.

Bio diesel first got rolling about 20 years ago. One form uses the same feedstock as the original biofuel, the scraps and fat left over when food companies process their products for the market, as well as leftover grease from restaurants, according to the Washington-based National Biodiesel Board. The other is using vegetable oils. Valero is the second-biggest maker of renewable diesel, trailing only Helsinki-based Neste Oyj. The San Antonio-based refiner, which owns a 50% stake in Diamond Green Diesel, has invested about $1 billion in developing and producing the fuel.

Valero Chief Executive Officer Joe Gorder told analysts and investors in October on a conference call, “We just think it’s a really good business. When we look at the opportunities to produce products where there is going to be growth in the market, and they’re going to have sustainably high margins, we look to renewable diesel.”

In the face of considerable market resistance, the combination of renewable diesel and biodiesel has been chipping away at traditional diesel’s dominance to a small single digit share.

About 2.6 billion gallons of both biodiesels were produced last year, according to the biodiesel board. The industry group forecasts production of the fuels to grow roughly 5% a year in the U.S. for the near future. By contrast, the petroleum diesel market for vehicle use stands at more than 40 billion gallons.

In the face of an ocean of vegetable oils and animal fats available, the plans include HollyFrontier announcing last week it will expand its Artesia, New Mexico, plant with new equipment to make as much as 125 million gallons a year, using soybean oil and other renewable feedstocks. It expects an internal rate of return of as much as 30% on the initiative. Phillips 66 plans several projects stretching from the U.K. to Washington state, including two plants built in Nevada in the next year with Ryze Renewables, its joint venture partner. Marathon is in the process of working to convert an existing refinery in North Dakota into a renewable diesel plant.

By no means are biodiesel or renewable diesel going to annihilate the petroleum diesel market, there isn’t enough grown and food grade products are even more profitable. For now and the expectation is, that these raw materials need a bigger and better market to support the increase in food production.

A technology developed at the U.S. Department of Energy’s Oak Ridge National Laboratory and scaled up by Vertimass LLC to convert ethanol into fuels suitable for aviation, shipping and other heavy-duty applications can be price-competitive with conventional fuels while retaining the sustainability benefits of bio-based ethanol, according to a new analysis.

Block flow diagram illustrating 1) water removal from wet ethanol vapor above the feed tray to produce pure fuel grade ethanol or 2) CADO of the same wet ethanol to fungible blendstocks. HE, heat exchangers. Image Credit: Oak Ridge National Laboratory. Click image for the largest view. More details at the study link below.

ORNL worked with technology licensee Vertimass and researchers at 10 other institutions on a technoeconomic and a life cycle sustainability analysis of the process – single-step catalytic conversion of ethanol into hydrocarbon blendstocks that can be added to jet, diesel, or gasoline fuels to lower their greenhouse gas emissions. This new technology is called Consolidated Dehydration and Oligomerization, or CADO.

The analysis, published in Proceedings of the National Academy of Sciences, showed that this single-step process for converting wet ethanol vapor could produce blendstocks at $2/gigajoule (GJ) today and $1.44/GJ in the future as the process is refined, including operating and annualized capital costs. Thus, the blendstock would be competitive with conventional jet fuel produced from oil at historically high prices of about $100/barrel. At $60/barrel oil, the use of existing renewable fuel incentives result in price parity, the analysis found.

The conversion makes use of a type of catalyst called a zeolite, which directly produces longer hydrocarbon chains from the original alcohol, in this case ethanol, replacing a traditional multi-step process with one that uses less energy and is highly efficient.

Zhenglong Li, staff scientist for biomass catalysis at ORNL and a collaborator on the project said, “The robustness of the catalyst enables direct conversion of wet ethanol, which greatly simplifies the process, reduces the cost of ethanol purification and makes hydrocarbon blendstock production costs competitive based on the analysis.”

While this single-step catalysis was effective at laboratory scale, further testing and improvements by Vertimass resulted in even higher product yields when scaled up 300 times using commercial catalyst formulations. The conversion operation could be integrated into new biofuels plants or installed as bolt-on technology to existing ethanol plants with minimal new capital investment, the researchers noted.

Advanced biofuels hold promise as clean-burning, carbon-neutral renewable energy sources. The goal is to create advanced liquid biofuels that can take advantage of existing pipeline delivery infrastructure and can be used in existing or advanced engines without loss of performance. The fuels are particularly attractive to help reduce net carbon emissions in heavy-duty engines such as those in aircraft, ships and large commercial vehicles where electrification is challenging.

Given current standards, the advanced biofuel could be blended at 20% with petroleum-derived jet fuel and somewhat higher for gasoline, subject to certification and verification.

Meanwhile, a life-cycle analysis of the conversion process found that its greenhouse gas emissions profile is similar to that for the ethanol fed to the process.

Brian Davison, chief science officer for DOE’s Center for Bioenergy Innovation (CBI) at ORNL and a collaborator on the project said, “The sustainability of bio-derived ethanol, now mostly produced from corn in the United States but with some now being made from corn stover and eventually dedicated biomass feedstocks like switchgrass, carries through with the catalytic process.” CBI is pursuing specific research targets for a thriving bioeconomy: sustainable biomass feedstock crops; advanced processes to break down and convert plants into specialty biofuels; and valuable bioproducts, including chemical feedstocks, made from the lignin residue after bioprocessing.

Refinements by Vertimass to the original, lab-scale process include the development of cheaper forms of the catalyst, as well as more than doubling the liquid fuel yield, the paper noted.

The paper details the refinements as well as results from analyses by Argonne National Laboratory, the National Renewable Energy Laboratory, Vertimass, and ORNL in collaboration with Dartmouth, the Federal Aviation Administration, Boeing, Pennsylvania State University, University of California-Riverside, Imperial College of London, the Brazilian Bioethanol Science and Technology Laboratory, and the Brazilian Center for Research in Energy and Materials.

Professor Lee Lynd of Dartmouth College, who collaborated on the research and is the corresponding author said, “This research shows how ethanol, in addition to being a valuable fuel for cars, can be an effective intermediate for sustainable production of low-cost fuels for air travel and heavy-duty vehicles. The integration of biological and catalytic technologies shown here reflects the power of such hybrid systems.”

Now that folks have gotten used to better automotive fuels with ethanol added, it will come as no surprise that technological progress is going to take this fuel source to new markets. More better cheaper!

Research from the University of Illinois, the University of California, Davis and contributions from the Oregon Health and Science University has chemists one step closer to recreating nature’s most efficient machinery for generating hydrogen gas. This new development may help clear the path for the hydrogen fuel industry to move into a larger role in the global push toward more environmentally friendly energy sources.

The researchers reported their findings in the Proceedings of the National Academy of Sciences.

Currently, hydrogen gas is produced using a very complex industrial process that limits its attractiveness to the green fuel market, the researchers said. In response, scientists are looking toward biologically synthesized hydrogen, which is far more efficient than the current human-made process, said chemistry professor and study co-author Thomas Rauchfuss.

Biological enzymes, called hydrogenases, are nature’s machinery for making and burning hydrogen gas. These enzymes come in two varieties, iron-iron and nickel-iron – named for the elements responsible for driving the chemical reactions. The new study focuses on the iron-iron variety because it does the job faster, the researchers said.

The team came into the study with a general understanding of the chemical composition of the active sites within the enzyme. They hypothesized that the sites were assembled using 10 parts: four carbon monoxide molecules, two cyanide ions, two iron ions and two groups of a sulfur-containing amino acid called cysteine.

The team discovered that it was instead more likely that the enzyme’s engine was composed of two identical groups containing five chemicals: two carbon monoxide molecules, one cyanide ion, one iron ion and one cysteine group. The groups form one tightly bonded unit, and the two units combine to give the engine a total of 10 parts.

But the laboratory analysis of the lab-synthesized enzyme revealed a final surprise, Rauchfuss said. “Our recipe is incomplete. We now know that 11 bits are required to make the active site engine, not 10, and we are in the hunt for that one final bit.”

Team members say they are not sure what type of applications this new understanding of the iron-iron hydrogenase enzyme will lead to, but the research could provide an assembly kit that will be instructive to other catalyst design projects.

“The take-away from this study is that it is one thing to envision using the real enzyme to produce hydrogen gas, but it is far more powerful to understand its makeup well enough to able to reproduce it for use in the lab,” Rauchfuss said.

Getting close. The hydrogen storage research has simply got to make more significant progress, or the potential for a hydrogen economy at scale will never get going.

University of Houston researchers have reported a significant breakthrough with a new oxygen evolution reaction catalyst that, combined with a hydrogen evolution reaction catalyst, achieved current densities capable of supporting industrial demands while requiring relatively low voltage to start seawater electrolysis.

Seawater is one of the most abundant resources on earth, offering promise both as a source of hydrogen – desirable as a source of clean energy – and of drinking water in arid climates. But even as water-splitting technologies capable of producing hydrogen from freshwater have become more effective, seawater has remained a challenge.

Schematic illustration of the synthesis procedures for the self-supported 3D core-shell NiMoN@NiFeN catalyst. Image Credit: University of Houston. Click image for the largest view.  More photos at the study link below.

Researchers say the device, composed of inexpensive non-noble metal nitrides, manages to avoid many of the obstacles that have limited earlier attempts to inexpensively produce hydrogen or safe drinking water from seawater.

The work is described in Nature Communications.

Zhifeng Ren, director of the Texas Center for Superconductivity at UH and a corresponding author for the paper, said a major obstacle has been the lack of a catalyst that can effectively split seawater to produce hydrogen without also setting free ions of sodium, chlorine, calcium and other components of seawater, which once freed can settle on the catalyst and render it inactive. Chlorine ions are especially problematic, in part because chlorine requires just slightly higher voltage to free than is needed to free hydrogen.

The researchers tested the catalysts with seawater drawn from Galveston Bay on the Texas coast. Ren, M.D. Anderson Chair Professor of physics at UH, said it also would work with wastewater, providing another source of hydrogen from water that is otherwise unusable without costly treatment.

Anderson pointed out, “Most people use clean freshwater to produce hydrogen by water splitting,” he said. “But the availability of clean freshwater is limited.”

To address the challenges, the researchers designed and synthesized a three-dimensional core-shell oxygen evolution reaction catalyst using transition metal-nitride, with nanoparticles made of a nickel-iron-nitride compound and nickel-molybdenum-nitride nanorods on porous nickel foam.

First author Luo Yu, a postdoctoral researcher at UH who is also affiliated with Central China Normal University, said the new oxygen evolution reaction catalyst was paired with a previously reported hydrogen evolution reaction catalyst of nickel-molybdenum-nitride nanorods.

The catalysts were integrated into a two-electrode alkaline electrolyzer, which can be powered by waste heat via a thermoelectric device or by an AA battery.

Cell voltages required to produce a current density of 100 milliamperes per square centimeter (a measure of current density, or mA cm-2) ranged from 1.564 V to 1.581 V.

The voltage is significant, Yu said, because while a voltage of at least 1.23 V is required to produce hydrogen, chlorine is produced at a voltage of 1.73 V, meaning the device had to be able to produce meaningful levels of current density with a voltage between the two levels.

In addition to Ren and Yu, researchers on the paper include Qing Zhu, Shaowei Song, Brian McElhennyy, Dezhi Wang, Chunzheng Wu, Zhaojun Qin, Jiming Bao and Shuo Chen, all of UH; and Ying Yu of Central China Normal University.

This is more significant than one might first think as water clean enough to enter into the usual electrolysis process isn’t low cost. Then there is the value of the concentrated chemicals that the new catalyst may make in the process that could offer an offsetting value. Even more interesting is the catalyst components are all not noble rare earth elements or highly priced ones. There is lots more experimentation to be done, but for the hydrogen community this is immensely good news.

An International Institute for Applied Systems Analysis (IIASA) researcher has proposed using a combination of Mountain Gravity Energy Storage (MGES) and hydropower as a solution for long term energy storage. The background for these work is the storage of energy for long periods of time is subject to special challenges.

Batteries are rapidly becoming less expensive and might soon offer a cheap short-term solution to store energy for daily energy needs. However, the long-term storage capabilities of batteries, in a yearly cycle for example, will not be economically viable.

Although pumped-hydro storage (PHS) technologies are an economically feasible choice for long-term energy storage with large capacities – higher than 50 megawatts (MW) – it becomes expensive for locations where the demand for energy storage is often smaller than 20 MW with monthly or seasonal requirements, such as small islands and remote locations.

Mountain Gravity Energy Storage Visualized. Image Credit: International Institute for Applied Systems Analysis. Click image for the largest view.

In a study published in the journal Energy, IIASA researcher Julian Hunt and his colleagues propose MGES to close the gap between existing short- and long-term storage technologies. MGES constitutes of building cranes on the edge of a steep mountain with enough reach to transport sand (or gravel) from a storage site located at the bottom to a storage site at the top. A motor/generator moves storage vessels filled with sand from the bottom to the top, similar to a ski lift.

During this process, potential energy is stored. Electricity is generated by lowering sand from the upper storage site back to the bottom. If there are river streams on the mountain, the MGES system can be combined with hydropower, where the water would be used to fill the storage vessels in periods of high availability instead of the sand or gravel, thus generating energy. MGES systems have the benefit that the water could be added at any height of the system, thereby increasing the possibility of catching water from different heights in the mountain, which is not possible in conventional hydropower.

Hunt notes, “One of the benefits of this system is that sand is cheap and, unlike water, it does not evaporate – so you never lose potential energy and sand can be reused innumerable times. This makes it particularly interesting for dry regions. Additionally, PHS plants are limited to a height difference of 1,200 meters, due to very high hydraulic pressures. MGES plants could have height differences of more than 5,000 meters. Regions with high mountains, for example, the Himalayas, Alps, and Rocky Mountains, could therefore become important long-term energy storage hubs. Other interesting locations for MGES are islands, such as Hawaii, Cape Verde, Madeira, and the Pacific Islands with steep mountainous terrain.”

In the paper, the authors propose a future energy matrix for the Molokai Island in Hawaii, using only wind, solar, batteries, and MGES to supply the island’s energy demand. Hunt emphasizes that the MGES technology should not be used for peak generation or storing energy in daily cycles – instead it fills a gap in the market for locations with long-term storage. MGES systems can, for instance, store energy continuously for months and then generate power continuously for months or when there is water available for hydropower, while batteries deal with the daily storage cycles.

Hunt concluded saying, “It is important to note that the MGES technology does not replace any current energy storage options but rather opens up new ways of storing energy and harnessing untapped hydropower potential in regions with high mountains.”

Presumably this plan considers the energy required to load the sand for the trip up, the topside storage and loading for the trip down. In the quick view this sounds really good, how it works when in practice is yet to be experienced. Perhaps someone will try it. if the environmentalists can stand the inevitable visual impact this would have on the landscape.


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