Revolutions in Catalyst Development

The development of more efficient and more economical catalysts is key to a cleaner and more abundant future of fuels and chemicals. Important advances are being made in the substitution of cheaper catalysts in place of expensive platinum. And entire new classes of catalysts are being developed:

Catalysts are used to initiate virtually every industrial manufacturing process that involves chemistry. Metal catalysts have been the traditional workhorses, but in recent years nano-sized catalysts have surged in importance.... The key to the success of this latest research was the encapsulation of metal nanoparticles inside dendrimers. The term "dendrimer" comes from the Greek word for "tree," an apt description for branching polymer molecules that resemble a worm's eye view of a tree's root system. Somorjai, Toste and their co-authors used gold nanoclusters and polyamidoamine (PAMAM), a common class of dendrimers suitable for numerous applications in materials and biotechnology. _RDMag

This new class of nano dendrimer catalysts is likely to find wide application in industry.

Replacing expensive platinum with less expensive materials is one of the key drivers in current industrial catalysis research:

Promising research at Brown University in the use of cobalt and graphene as substitutes for platinum

Princeton University research promises to substitute cheap iron particles in place of platinum

Organic catalysts -- including nitrogen doped carbon nanotubules -- may help to replace platinum in hydrogen fuel cells

Finally, plasma arc furnaces may allow for better recycling of platinum group metals, so that current supplies of these valuable catalysts can be extended much further into the future.

Revolutions in catalysts are rarely discussed outside of specialised fields of chemistry and engineering. And yet, catalysts play an extremely important role in the well being and prosperity of advanced societies.

Dangerous children learn to understand the technological underpinnings of modern societies. It is never too late to have a dangerous childhood.

Energy Briefs

One-step closer: Biofuel from Biomass

New research from scientists at the University of Georgia who are members of Department of Energy's BioEnergy Science Center (BESC) provides a genetic method for manipulating a group of organisms, called Caldicellulosiruptor, that have the ability to use biomass directly at temperatures over 160 Fahrenheit. The ability to modify the microbes to make the needed fuel products is a required first step for modern industrial fermentations. This allows researchers to combine the natural ability to consume renewable plant materials with an altered improved ability to make what is needed. _PO

Tough industrial-strength microbes that can be programmed to produce the fuels or chemicals desired, should take biofuels and bio-chemicals production to a higher level.

Unlimited high-value chemicals from engineered microbes: Freeing up petroleum can provide a 25% boost to global petro-production!

Although the major products of crude oil refineries are fuels such as gasoline and jet fuel, approximately 20 percent of crude oil is refined, in several complicated, energy-intensive steps, into petrochemicals. These chemicals permeate our daily lives in products ranging from candles and perfume to disposable diapers, toys, tires and plastic packaging, among many others.

As an alternative to crude oil, researchers around the world are studying ways to produce fuels and chemicals from renewable sources, including plant biomass and algae. Current production processes are energy-intensive and generate sugars or oils, which are "intermediate" products. "Then you would take those intermediates and do traditional processing, whether it's biological or chemical," says Pfleger. _PO

So, if we take that 20% of crude oil production that is used for chemicals, and put it back into global oil markets, we achieve what is in essence a 20% boost 25% boost in oil production, in terms of fuels etc...

Sure, it is more complicated than that, since some fractions of petroleum are more suitable for one use than for others, but you can get a vague idea as to why substitution of unlimited renewable chemicals and feedstocks can have a powerful effect on global oil markets.

Why Iowa finds itself at the center of the ongoing revolution in next generation biofuels

New nano-composite material for fuel cells achieves a 5X increase in electric current per milligram of platinum

IBN's new nanocomposite material can produce at least 0.571 amperes of electric current per milligram of platinum, compared to 0.109 amperes per milligram of platinum for commercial platinum catalysts. This is also the first time that a catalyst has been shown to enhance both the stability and activity for the fuel cell reaction with a significantly reduced platinum content. _PO

This is a low level, nuts and bolts type advance in fuel cell mechanics and economics. But with the coming global bonanza of tight gas, we are likely to see increasing use of methane fuel cells for both primary production in residences and small business, and as critical power backup for commercial, municipal, and industrial enterprises.

None of these stories are particularly earth-shaking in themselves, but over time such innovations tend to accumulate, combine, rearrange, and evolve into significant advances.

Breakthrough in Battery Electrodes and Fuel Cell Catalysts?

For catalysts in fuel cells and electrodes in batteries, engineers would like to manufacture metal films that are porous, to make more surface area available for chemical reactions, and highly conductive, to carry off the electricity. The latter has been a frustrating challenge.

But Cornell chemists have now developed a way to make porous metal films with up to 1,000 times the electrical conductivity offered by previous methods. Their technique also opens the door to creating a wide variety of metal nanostructures for engineering and biomedical applications, the researchers said.

The results of several years of experimentation are described March 18 online edition of the journal Nature Materials.

"We have reached unprecedented levels of control on composition, nanostructure and functionality -- for example, conductivity -- of the resulting materials, all with a simple 'one-pot' mix-and-heat approach," said senior author Ulrich Wiesner, the Spencer T. Olin Professor of Engineering.

...The researchers report a wide range of experiments showing that their process can be used to make "a library of materials with a high degree of control over composition and structure." They have built structures of almost every metal in the periodic table, and with additional chemistry can "tune" the dimensions of the pores in a range from 10 to 500 nanometers. They have also made metal-filled silica nanoparticles small enough to be ingested and secreted by humans, with possible biomedical applications. _RDMag

This is another example of the "dull revolutions" taking place in research labs around the world every day. It is the breakthroughs in materials, catalysts, electrodes, solvents, and basic processes, which will build the bridges to a more prosperous, clean, and abundant future.

The biggest threat to such a transition to a cleaner, more abundant future, is the threat from well intentioned political and faux environmental movements, which have pure feelings but feeble minds.

More on Inexpensive Catalyst Substitutes for Precious Metals

Developing new catalysts derived from inexpensive minerals, instead of increasingly costly (and rare) precious metals, is an important area of research that involves several groups around the world. The next steps for the Cambridge researchers will be to investigate the activity of pyrite surfaces for strategically important industrial reactions, such as the manufacture of ammonia for fertilisers, the production of synthetic hydrocarbon fuels from renewable biomass, and the extraction of hydrogen for use in future fuel cell electric vehicles.

Dr [Marco] Sacchi added: "The necessity of finding reliable alternatives to overexploited catalytic materials - such as platinum, rhodium and gold - will soon become unavoidable. Experimental work is currently underway in our group, and we hope that our work will ultimately allow us to test the potential for catalytic application of a wide range of sulphidic and carbidic materials. In future, we aim to develop fruitful scientific collaborations with chemical engineering groups and with industrial partners." _Physorg

There is quite a long list of industrial and energy processes which are in need of cheaper and better catalysts.

The ability to cheaply and skillfully manipulate matter on the molecular scale is important to the transition to a more advanced and clean level of industrial operations. Catalysts are crude and early forms of nanoassemblers.

The goal of catalytic researchers - cum - nanotechnologists is to be able to use cheap and abundant inorganic materials to mimic the efficiency and selectivity of biological catalysts -- peptide enzymes. The inorganic mimics of peptide enzymes should be more robust, with a much wider range of temperature and pressure activities.

At this point, progress is extremely slow, since researchers are limited to a "trial and error" approach. As computational models improve, it is hoped that the process of developing cheap, efficient, and robust catalysts will become streaamlined.

Evolution! Cheap New Catalysts to Replace Expensive Platinum

Chang and his UC Berkeley colleagues worked with a common catalyst, molybdenite, that is less expensive than platinum and of increasing interest as a fuel cell catalyst. Composed of molybdenum and sulfur (MoS2), the material catalyzes reactions like the splitting of water into hydrogen and oxygen only at the edges, where triangles of molybdenum and two sulfur atoms stick out like pennants.

“These edge sites look like little MoSS triangles, and the triangular area does the business,” Chang said.

Using complex organic synthesis techniques, Chang said he and his colleagues created a small carbon framework to hold the MoSS triangle so that “every molecule has a discrete edge site that is a catalytically active unit.”

When lots of these single-molecule catalysts were dumped into acidic water and even seawater, they generated hydrogen for several days without letup.

In future research, Chang hopes to assemble billions of these molecules on a thin, ridged wafer, maximizing the number of catalytic sites for a given volume and boosting ultimate efficiency. _Berkeley

Substitution of less expensive materials and feedstocks in place of more expensive or scarce materials, is the way profits are made in industry and business. Human chemical engineers are reaching more deeply into the structure of molecules, becoming ever more deft at shaping matter in more useful and valued forms. To do this profitably, they need highly effective catalysts in very large quantities. Platinum is a very effective catalyst, but it is a precious metal -- extremely expensive, and hard on a profit line.

Chemists at UC Berkeley have achieved a breakthrough in the design of a new class of cheaper catalysts that promise to replace more expensive platinum.

Catalysts are materials ‑ typically metals ‑ that speed up chemical reactions and are widely used in the synthesis of chemicals and drugs. They also are employed in automobile catalytic converters to change combustion chemicals into less-polluting emissions and in fuel cells to convert water into hydrogen.

The problem with catalysts, however, is that chemical reactions occur only at edges of or defects in the material, while the bulk of the metal – often expensive platinum – is inactive and wasted.

In an article appearing this week in the journal Science, UC Berkeley chemists show how to construct a catalyst composed only of edges and demonstrate that it can catalyze the production of hydrogen from water as readily as the edges and defects in regular catalysts.

“This is a conceptual advance in the way we think about generating hydrogen, a clean burning fuel, from water, a sustainable source,” said Christopher Chang, associate professor of chemistry and Howard Hughes Medical Institute Investigator at UC Berkeley. “Our new catalyst is just first generation, but the research gives us and the community a path forward to thinking about how to increase the density of functional active sites so that molecules and materials can be more effective catalysts.”

At the moment, creating these catalysts in the lab is not cheaper than using traditional catalysts, but efforts by Chang and others to simplify the process and create materials with billions of active sites on a ridged wafer much like a Ruffles potato chip could allow cheaper, commercially viable fuel cell catalysts. _Berkeley

The scientists in the link above discuss producing hydrogen from water, using sunlight and advanced catalysts. Other, perhaps more common uses for new types of catalysts probably include use in conversion of natural gas, coal, and biomass into liquid hydrocarbons and industrial chemicals.

The "clean green" meme has taken over much of politics, academia, and the media, but those who must actually work for a living and get the things done that allow society to continue functioning, understand that "clean green" is just a feel-good meme. For societies to prosper, they must utilise dense forms of energy such as hydrocarbons, nuclear, and pre-densified biomass.

The popular green delusion is destroying Germany and other parts of Europe at this time, and if the Obama energy starvationist regime gets its way, it will try to destroy the US as well. This would be a good time for US and European voters to wake up.

Turning Methane into "Gold"; Siluria's Viral Nanowire Catalyst Gets More Funding from Venture Fund

Viral Template for Nanocatalyst
Wellcome Trust is giving San Francisco startup Siluria another $20 million in funding in order to advance its methane-to-ethylene advanced viral templated nano-catalytic technology. Ethylene is a $160 billion a year commodity chemical, used for the creation of a wide range of high-value products. The ability to cheaply convert abundant methane into high-value ethylene would be the chemical equivalent of the Midas touch.

More on Siluria's underlying viral-template-to-nanowire-catalyst technology:

Creating a better catalyst may be as simple as letting a virus do the construction for you. Angela Belcher and coworkers at MIT have used the M13 bacteriophage as a template for growing nanoparticles and nanowires of rhodium and nickel on ceria...“The virus is relatively stiff and has a high aspect ratio, so it forms stunning open and porous nanostructures which increase the surface area and shift the pore size distribution,” explains Brian Neltner, the report’s first author. “Surface area and pore size distribution are critical aspects of catalysts, and can improve the reaction rates and selectivity.”

The researchers also found they could eliminate expensive rhodium from the biotemplated material, creating a catalyst with just nickel on ceria. This material can catalytically reform ethanol at temperatures around 400 °C, “offering an alternative, inexpensive catalyst when higher temperatures are acceptable,” they write.

“This new approach to catalyst synthesis clearly provides desirable alternative possibilities for catalytic process applications,” comments Galen Stucky, a chemistry professor at the University of California, Santa Barbara. _ACSNews

Siluria received $13.3 million in funding last year from venture funds to develop this technology, and the additional $20 million this year reflects the progress that the startup company has made.

The chemistry for directly making ethylene from methane had eluded researchers in part because of the difficulty of getting the reaction to stop at ethylene, and not produce carbon dioxide. Siluria believes it can overcome the challenge because of the availability of new chemical discovery-and-synthesis tools. Top among these is the use of virus-based templates, a technology developed by Angela Belcher, a professor at MIT and member of Siluria's board of directors, that guides the growth of nanowire catalysts made of inorganic crystals. After the template is burned away, the researchers are left with structure of the inorganic material with a high surface area—perfect candidates for high catalytic activity. They then use high-throughput screening methods to rapidly try and find any of the nanowire structures with the desirable catalytic activities.

Siluria says it has received the additional investment because it now has multiple catalysts that work in a "commercially viable realm" of relatively low temperatures and pressures. Erik Scher, Siluria's vice president of R&D, says the company's candidate catalysts will work with conventional types of reactors and reactor designs, providing manufacturers "with a minimal risk of scale-up. They won't have to invent new types of reactors." _TechnologyReview

This approach is particularly promising due to its largely off-the-shelf high-throughput approach to selecting the most efficient catalysts. The nanowire catalysts "mimic" the structure of the viral scaffolding, which combined with genetic engineering techniques could produce an almost infinite variety of nano-configurations.

In other words, the virus-to-nanowire method of producing catalysts is extremely prolific. And off-the-shelf high throughput screening methods allow the rapid selection of the most promising catalysts.

The metallic nanowire catalysts are far more robust than their biological models, and are capable of surviving conditions of high pressure and temperature, as well as a toxic chemical environment.

Al Fin energy technologists have been predicting similar technology as the ultimate basis for high yield biofuels production. But at this point in time, abundant unconventional methane provides an economically more advantageous feedstock, due to price, existing infrastructure, and the minimal pre-processing required.

OxfordCatalysts' Microchannel Technology Wins 2011 Chemical Engineering Award

Microchannel technology developed by the Oxford Catalysts Group was named as the winner of the Kirkpatrick Chemical Engineering Achievement Award at the ChemInnovations conference and exhibition in Houston, Texas on 12 Sept.


The UK group’s modular synthetic fuel technology - which enables the small scale and economic production of synthetic fuels via gas-to-liquids (GTL), biomass-to-liquids (BTL) and coal-to-liquids (CTL) via the Fischer-Tropsch (FT) reaction - includes microchannel FT combined with a new highly active FT catalyst and steam methane reforming (SMR) reactors.

_The Engineer
The Velocys / Oxford Catalyst microchannel technology for scalable GTL, BTL, and CTL, has won previous engineering awards, and is likely to win more in the future. By bringing Fischer-Tropsch technology down to a size and cost which can be implemented for offshore and stranded GTL, the microchannel devices are likely to have a slowly building evolutionary impact on liquid fuels production from an unexpected source.

The fact that the devices can also convert biomass and coal to liquid fuels is an added advantage, which will eventually bring the cost of F-T plants down from the $billion range into the $ hundreds of thousands range.

It is designed for use in the smallscale distributed production of biofuels, and as practical way to transform associated and stranded gas via GTL into high quality synthetic crude. This opens up the possibility of carrying out GTL offshore.

According to Oxford Catalysts, the technology could also make it possible to use the GTL process to convert North America’s abundant shale gas resources into diesel and jet fuels.

The Kirkpatrick Chemical Engineering Achievement Award recognises noteworthy chemical-engineering technology commercialised anywhere in the world during the two years prior to a given award year.

Jeff McDaniel, commercial director at the Oxford Catalysts Group said the award recognised “the environmental and commercial significance of our activities in GTL and BTL. _The Engineer

Ethanol to Isobutene Direct Conversion from PNNL

With increased availability and reduced cost of bio-ethanol, conversion of this particular bio-based feedstock to highly valuable fuels and chemicals has been an especially important research goal. Currently, research on bio-ethanol conversion to value-added chemicals focuses mainly on ethanol dehydration to ethylene, or ethanol dehydrogenation to acetaldehyde and then to acetone via Aldol-condensations pathways...

Research on direct bio-ethanol transformations to other types of highly valuable fuels and chemicals has not been carried out. In large part, this is due to the fact that such a process requires catalysts with multiple functions in order to yield more valuable chemicals such as isobutene. Isobutene is of special interest because it is widely used as an intermediate for the production of a variety of industrially important products. _GCC

Ethanol to Isobutene_via_ACS
The biofuels market could become overloaded with ethanol as more producers worldwide jump into the game, and as more bio-feedstocks -- including cellulosic biomass -- can be efficiently converted to ethanol. But ethanol may well be more valuable as a chemical feedstock than as a fuel. A growing substitution of bio-ethanol for petroleum in the production of chemicals, plastics, fuels, lubricants, etc. will only extend the world's supply of petroleum that much further.

Researchers at the Department of Energy’s Pacific Northwest National Laboratory (PNNL) and Washington State University (WSU) have developed a new nanosized ZnxZryOz mixed oxide catalyst for the direct and high-yield (83%) conversion of bio-ethanol to isobutene, a widely used intermediate chemical used for the production of fuel additives, rubber and solvents.

...The PNNL and WSU researchers had been trying to make hydrogen from ethanol. To improve on a conventional catalyst, they had taken zinc oxide and zirconium oxide and combined both into a mixed oxide—the zinc and the zirconium atoms woven through a crystal of oxygen atoms. Testing the new material, PNNL postdoctoral researcher Junming Sun found not only hydrogen, but unexpectedly quite a bit of isobutene.

Investigating the catalyst in greater depth, the researchers found that a catalyst made from just zinc oxide converted the ethanol mostly to acetone; if the catalyst only contained zirconium oxide, it converted ethanol mostly to ethylene. Isobutene only arose in useful amounts when the catalyst contained both zinc and zirconium.

Zirconium oxide is capable of converting acetone into isobutene; for the isobutene yield found, however, something would have to prevent zirconium oxide from turning ethanol into ethylene.

The team reasoned the isobutene probably arose from zinc oxide turning ethanol into acetone, then zirconium oxide—influenced by the nearby zinc oxide—turning acetone into isobutene. At the same time, the zinc oxide’s influence prevented the ethanol-to-ethylene conversion by zirconium oxide. Although that’s two reaction steps for the catalyst, it’s only one for the chemists, since they only had to put the catalyst in with ethanol and water once.

To get an idea of how close the reactions had to happen to each other for isobutene to show up, the team combined powdered zinc oxide and powdered zirconium oxide. This differed from the mixed oxide in that the zinc and zirconium atoms were not incorporated into the same catalyst particles. These mixed powders turned ethanol primarily into acetone and ethylene, with some amounts of other molecules and less than 3% isobutene, indicating the high isobutene selectivity of their catalyst came from the microstructure of the mixed oxide material.

The researchers explored the microstructure using instruments and expertise at EMSL, DOE’s Environmental Molecular Sciences Laboratory on the PNNL campus. Using transmission electron microscopes, the team saw that the mixed oxide catalyst was made up of nanometer-sized crystalline particles.

A closer look at the best-performing catalysts revealed zinc oxide distributed evenly over regions of zirconium oxide. The worst performing catalyst—with a 1:1 zinc to zirconium ratio—revealed regions of zinc oxide and regions of zirconium oxide. This suggested to the team that the two metals had to be close to each other to quickly flip the acetone into isobutene. _GCC

If PNNLs catalyst can provide high enough yields at economic prices, commercial producers should be willing to license the technology.

Did you notice from the excerpt above, that the researchers were initially working on a grant to turn ethanol into hydrogen, when they unexpectedly discovered the isobutene by-product? Only then did they proceed to fine-tune the catalyst to maximise isobutene production. "Accidental science" is one of the most prolific producers of new tools, technologies, and scientific theories in existence. That is one reason it is so difficult to predict future discoveries and breakthroughs.

Methane to Methanol to Gasoline at Competitive Prices

GCC
Methane to methanol to gasoline for $2.85 a gallon, including a healthy $1.45 margin? That is what is being claimed for a combined "Gigamethanol" and MTG (methanol to gasoline) plant proposed for Alaska. Converting all the North Slope gas to gasoline could produce almost 500,000 barrels per day.

... a plant would produce methanol from natural gas on the North Slope using the proposed GigaMethanol technology. The resulting methanol would be blended with crude and transported via the trans-Alaska oil pipeline to Valdez, where it would be extracted from the oil and processed via Methanol-to-Gasoline technology into gasoline.

In January, ICIS reported that Eastman Chemical reached an agreement to sell a mothballed Texas methanol and ammonia plant to Pandora Methanol, a subsidiary of Janus Methanol.

The plant will have a capacity of 850,000 tonnes/year of methanol and 250,000 tonnes/year of ammonia, according to van Wijk. ...Van Wijk at the time said the new plant might consider the methanol-to-gasoline MTG process pioneered by ExxonMobil.
Eastman originally bought the plant in 2007 for a $1.6-billion coal-gasification project, but called off the project in late 2009 due to high capital requirements, the narrow difference between petroleum and natural gas prices and uncertain US energy policy....

Costs for a 63,000 barrel (of gasoline) per day system would be approximately $5.2 billion, he said. Gasoline could be delivered from Valdez at $2.65 to $2.85 per gallon, including a $1.45 margin.

In addition to providing a market for North Slope gas, the mix of methanol in the pipeline flow would help prevent problems with ice forming in the line, van Wijk, a former Methanex executive, suggested. If the entire daily output of North Slope gas (4.5 billion cubic feet, bcf) were converted to gasoline, it would produce 450,000 barrels per day, he suggested. _GCC

This is a different approach from the Oxford Catalysts and Sasol approaches. But the claims for efficiency and economic viability are difficult to beat, if true.

While the proposal is meant to take advantage of Alaskan natural gas, the same approach could conceivably be taken with shale gas or any other large gas deposits located anywhere.

Catalysts and Solvents: Making Everything Possible

While we like to dwell on more exotic technologies and scientific theories, it is the nuts and bolts of modern industry and industrial scale agriculture which keeps you safe, warm, dry, and well fed. Almost no one likes to think about catalysts and solvents, but the quality of those arcane, mundane, nitty-gritty ingredients of your hidden underworld, determines much of what you can do with yourself.

Some interesting developments in catalysts:

New, cheaper nickel-based catalysts may spark a fuels and chemicals revolution

Newer, cheaper, platinum-free catalysts may open the door to cheap fuel cells, and fuel cell automobiles

Cheap molybdenum catalysts may make electrolysis of water to hydrogen / oxygen cheap and practical

Nanotechnology advances add an extra dimension to progress in catalysts

Solvents are even more easily ignored in everyday discussion than catalysts -- except in the context of a faux environmental armageddon. But they are no less important to everyday life for all of that.

New ionic solvents likely to revolutionise oil sands industry -- making oil sands and heavy oils environmentally friendly and setting back peak oil decades.

Supercritical CO2 and steam are proving to be effective solvents for more and more processes.

The movement toward cleaner, cheaper, more sustainable and effective solvents is accelerating, just like the movement toward better catalysts. And those are just two of the basic foundations of modern life where marginal improvements can pay huge dividents in quality of life.

Paying attention to such things can provide amazing investment opportunities as well.

Cutting the Cost of Fuel Cell Catalysts by a Factor of 650?

Platinum, which represents at least a quarter of the cost of fuel cells, currently sells for about $65,000 per kilogram. These researchers say their activated carbon nanotubes cost about $100 per kilogram. _Physorg

That sounds like a significant reduction in the costs of fuel cells if the new catalysts work as advertised. Engineers from Case Western Reserve University have got a lot of tricks up their sleeve, which may change the face of the global fuel cell market.

In testing, the fuel cell produced as much power as an identical cell using a platinum catalyst.

But the activated nanotubes last longer and are more stable, the researchers said. Unlike platinum, the carbon-based catalyst: doesn't lose catalytic activity and, therefore, efficiency, over time; isn't fouled by carbon monooxide poising; and is free from the crossover effect with methanol. Methanol, a liquid fuel that's easier to store and transport than hydrogen, reduces activity of a platinum catalyst when the fuel crosses over from the anode to the cathode in a fuel cell. _Physorg

The engineer-researchers have plans that may actually increase efficiency of the nanotube catalysts over that of platinum. That would be quite an accomplishment -- but actually just a trifle of an early hint of the possibilities for the new age of nano. Catalysis is a particularly promising area for nanotechnology, but there are quite a few other radical changes which are certainly on the way.

Buckle up.

New Nano-Wire Catalysts Convert Methane to Ethylene

The oxidative coupling of methane converts methane into ethane and ethylene (C2 hydrocarbons). The basic OCM reaction (which is exothermic) is:

2CH4 + O2 → C2H4 + 2H2O


In the OCM reaction, methane (CH4) is activated on the catalyst surface, forming methyl free radicals (CH3) which then couple in the gas phase to form ethane (C2H6). The ethane subsequently undergoes dehydrogenation to form ethylene and water. _GCC

We are seeing the early stages of a trend which has been long predicted by Al Fin energy analysts: The creation of robust non-biological nano-catalysts which are modeled on a biological template. These newer and tougher catalysts are only possible due to advances in nanotechnological fabrication processes, and they will eventually change the way that synthetic fuels are made -- avoiding the expensive Fischer-Tropsch pathways.

The Siluria advance described in the article below, involves the catalytic production of ethylene from methane -- currently in quite abundant supply due to the ongoing unconventional natural gas bonanza. Ethylene can then be converted catalytically to long chain, high value hydrocarbons.

The catalyst materials are proprietary, doped metal oxides of early transition metals that are designed for compatibility with existing petrochemical industry infrastructure. Siluria has developed a library of compounds with a range of crystal structures, and has tested their behavior in catalyzing the OCM reaction.

The first step is creating the library of organic templates—that’s the phage. Second, you do synthetic prep, so inorganic synthetic chemistry on each of those phages, and you create a diversity of catalyst nanowires: the same composition, but a different active site. Then we take these individual compositions, we combine them with high-throughput screening to screen not some incidental or ancillary property that you then infer; we actually run every single one in the reaction of interest. We get a direct measurement on each one of those little dots [256 per wafer] which is a different catalyst.
—Erik Scher

...

The excitement and the promise is where we will be 5 years from now. The non-reducible advantages of OCM versus FT and a syngas-based route is threefold. One, [OCM] is a simpler chemistry, in terms of the number of steps required to get to the end product. With OCM, its two steps: methane to ethylene, oligomerize to liquids. In FT, there are three steps: steam methane reforming to syngas, syngas to a mixture, hydrocracking to clean it up. Non-reducible.

Two, [OCM] is a chemistry that is easier to control. Ethylene is a versatile and flexible molecule that is easy through existing technologies to convert to longer chains: detergents, lubricants, fuels. And three, it has a better energy balance. The first step in FT is endothermic; the first in OCM is exothermic.
—Alex Tkachenko

_GCC

In other alternative liquid fuels news, UCLA researchers are aiming to develop microbes which create advanced biofuels from biomass proteins. Proteins are often found in greater quantity in biomass than either carbohydrates or lipids. By creating microbes to ferment the protein component into fuels, technologists will be able to convert biomass to fuels more completely and efficiently.

Thermochemical conversion of biomass takes a lot of energy -- although it is available now, rather than 10 years from now. But in 10 years, microbes which convert biomass to fuels more efficiently will begin taking over from the less efficient thermochemical processes. And in 20 to 30 years, non-biological nano-catalysts will begin taking over liquid fuels synthesis from many of the microbial fuels approaches -- and from the more efficient thermochemical approaches.

As long as government interference can be kept to a minimum, marketplace incentives should drive synthetic liquid fuels to a high level of replacement for petrol fuels over the next 30 years.

Austrian Microchannel BTL Plant to be Upgraded to Pilot Plant

GCC
The "microchannel" approach to Fischer-Tropsch BTL developed by the Oxford Catalysts Group and Velocys, will be upgraded from a demonstration plant to a new pilot plant in Gussing, Austria. The same technology can be used in small operations such as offshore oil rigs, for GTL conversion -- to enhance the economic value of natural gas production.

The pilot plant, designed for the small scale distributed production of biofuels via the Fischer-Tropsch (FT) reaction, will be operated jointly by SGCE and Velocys, Inc., the US-based member of the Oxford Catalysts Group.

PDF White Paper on microchannel F-T

The existing demonstration plant—which is jointly operated by the Oxford Catalysts Group and SGCE—incorporates an FT microchannel reactor comprising more than 900 full-length microchannels. This reactor has been performing effectively at Güssing since July 2010. The demonstration plant produces more than 0.75 kg of high quality synthetic FT liquids per liter of catalyst per hour and exhibits productivities 4 to 8 times greater than conventional systems. _GCC

Earlier AFE article providing more links and images

Biomass to liquids (BTL) is an extremely promising technology for remote locations, due to the ability to grow biomass virtually anywhere on land or at sea. Even on lunar or Martian colonies, biomass can be grown for production of chemicals, plastics, and other valuable products.

For larger scale synthetic fuels production on-planet, natural gas to liquids (GTL) and coal to liquids (CTL) is more economically productive than BTL.

When Bacteria Share Enzymes -- Road to Microbial Fuels

Harry Beller, an environmental microbiologist who directs the Biofuels Pathways department for JBEI’s Fuels Synthesis Division, led a study in which a three-gene cluster from the bacterium Micrococcus luteus was introduced into the bacterium Escherichia coli. The enzymes produced by this trio of genes enabled the E. coli to synthesize from glucose long-chain alkene hydrocarbons, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). _GCC

Learning to mix and match genes from different species of bacteria (and other life forms) will allow humans to custom manufacture a wide range of high value chemicals, plastics, fuels, feeds, and most other things that people need for daily living. But don't tell anyone in the government -- they'll find a way to outlaw the practise. No doubt at the instigation of their faux environmentalist comrades.

These long-chain alkenes can then be cracked—reduced in size—to obtain shorter hydrocarbons that are compatible with today’s engines and favored for the production of advanced lignocellulosic biofuels.

In order to engineer microorganisms to make biofuels efficiently, we need to know the applicable gene sequences and specific metabolic steps involved in the biosynthesis pathway. We have now identified three genes encoding enzymes that are essential for the bacterial synthesis of alkenes. With this information we were able to convert an E. coli strain that normally cannot make long-chain alkenes into an alkene producer.

—Harry Beller

It has long been known that certain types of bacteria are able to synthesize aliphatic hydrocarbons, which makes them promising sources of the enzymes needed to convert lignocellulose into advanced biofuels. However, until recently, little was known about the bacterial biosynthesis of non-isoprenoid hydrocarbons beyond a hypothesis that fatty acids are precursors.

We chose to work with M. luteus because a close bacterial relative was well-documented to synthesize alkenes and because a draft genome sequence of M. luteus was available. The first thing we did was to confirm that M. luteus also produces alkenes.

—Harry Beller

Beller and his colleagues worked from a hypothesis that known enzymes capable of catalyzing both decarboxylation and condensation should be good models for the kind of enzymes that might catalyze alkene synthesis from fatty acids. Using condensing enzymes as models, the scientists identified several candidate genes inM. luteus, including Mlut_13230. When expressed in E. coli together with the two adjacent genes —Mlut_13240 and 13250—this trio of enzymes catalyzed the synthesis of alkenes from glucose. Observations were made both in vivo and in vitro.

This group of enzymes can be used to make aliphatic hydrocarbons in an appropriate microbial host but the resulting alkenes are too long to be used directly as liquid fuels. However, these long-chain alkenes can be cracked—a technique routinely used in oil refineries—to create hydrocarbons of an appropriate length for diesel fuel.

—Harry Beller

The next step in the research is to learn more about how these three enzymes work, particularly Mlut_13230 (also called OleA), which catalyzes the key step in the alkene biosynthesis pathway—the condensation of fatty acids.

We’re also studying other pathways that can produce aliphatic hydrocarbons of an appropriate length for diesel fuels without the need for cracking. Nature has devised a number of biocatalysts to produce hydrocarbons, and our goal is to learn more about them for the production of green transportation fuels.

—Harry Beller

Working with Beller on this study were Ee-Been Goh and Jay Keasling. The three were the co-authors of a paper that appeared earlier this year in the journalApplied and Environmental Microbiology, titled “Genes Involved in Long-Chain Alkene Biosynthesis in Micrococcus luteus.”

_GCC

The faux environmentalists are attacking nuclear power, biomass, coal, oil sands, oil shales, bio-ethanol, shale gas, and any other form of potentially clean and abundant energy.

These faux environmentalists promote dead-end wind and solar, huge rat holes of resource waste that will leave us gasping for energy and dying from lack of industrial, transportation, agricultural infrastructure.

The zombie apocalypse is on, and a large portion of the zombies currently reside in Washington DC -- living it up on the taxpayer's dime. Destroying the future, and writing IOU's that even your great-great-great-great grandchildren will not be able to pay.

Catalysed Pyrolysis Yields a Faster Biofuel

Pyrolysis involves the rapid heating of a feedstock under pressure, in the absence of oxygen. When you add the proper catalysts to the right feedstocks, you can create valuable fuels and chemicals amazingly quickly.

KiOR’s President Fred Cannon described KiOR’s technology as being able to crunch into seconds the millions of years that it takes to carbonize biomass (turn it into fossil fuels) in nature.

Cannon said the company’s catalyst — a fine white powder that he showed to me in a tiny see-through vial after his talk — can turn any feedstock, including non-food cellulose, into a biocrude that has 92 percent lower carbon emissions footprint than fossil-fuel based crude. It can also act as a dr0p-in replacement for fossil-fuel based crude, said Cannon, and KiOR is already making it in volumes of 15 barrels per day at KiOR’s plant in Houston.

“We scaled over the last year from a few liters a day to a few barrels a day. Even on the more expensive feedstocks we use, we’re already competitive on oil prices at this scale,” said Cannon on a panel of execs of Khosla Ventures portfolio companies in response to a question from Tony Blair about how expensive the KiOR process is.

...KiOR was formed in 2007 as a joint venture between Khosla Ventures and Netherlands-based biofuel startup BIOeCON. While I won’t pretend to fully understand KiOR’s technology, the company calls it a “biomass catalytic cracking process” — a thermochemical process that produces biocrude from grass, wood and plant waste that can then be refined. The process was derived from the traditional oil industry, by Bioecon’s founder, Paul O’Connor, who started BIOeCON in early 2006 after developing catalysts for the petroleum industry, according to MIT’s Technology Review. _Earth2Tech

Another recent pyrolysis venture

The key to the economical production of biofuels using pyrolysis (or gasification) is to combine as many steps as possible into one step. The key to doing that, is the right catalyst.

The product of pyrolysis is typically a pyrolysis oil, black carbon char, and pyrolysis gas. The product of gasification (which involves higher heat and pressure, with low oxygen levels) is syngas -- a mixture of hydrogen, CO, CO2, and small levels of CH4 etc. The products of both processes require further processing to become useful fuels -- which can be very expensive.

But throw the right catalyst into the initial pyrolysis or gasification step, and you end up with valuable fuels or chemicals off the bat.

Realistically, thermochemical processes for making biofuels should not be competitive with microbial approaches to biofuels in the long run. But thermochemical processes should be more easily and quickly arrived at -- giving them between a 5 and 10 year headstart on microbial fuels.

Biological feedstocks are problematic in that they are not typically energy-dense, and can be expensive to gather, dry, densify, and pre-process. But cane bagasse and corn stalks may be collected as part of other processes, reducing the cost of collection. Once such a feedstock is in hand, it can be dried and densified using the waste heat energy from gasification or pyrolysis.

Robotic collection of forestry and agricultural waste will also become much more common in the future, as a means of reducing costs of densifying biomass.

In the long run, microbial biomass such as algae can provide higher yields than virtually any other form of plant.

Biofuels have a great future ahead -- particularly if they are viewed appropriately as a local and regional solution.

Biomass to Diesel and Dimethylhydrotetrafuran

GCC
University of Wisconsin at Madison researchers have enlarged on earlier work where they produced gasoline from gamma valerolactone -- a biomass derived substance. They have now demonstrated the ability to make longer chain alkanes for diesel

In February, Dr. James Dumesic and colleagues at the University of Wisconsin-Madison published a paper in the journal Science describing a process to convert aqueous solutions of GVL, an intermediate produced from biomass-derived carbohydrates, to liquid alkenes suitable for transportation by using an integrated catalytic system that does not require an external source of hydrogen or precious metal catalysts.

In a new paper, published in the RSC journal Green Chemistry, Dumesic and colleagues focused on the production of alkenes in the range of C18–C27 from the oligomerization of C9 alkenes produced from biomass-derived GVL.

...The basic approach described by Dumesic and his colleagues is to hydrogenate levulinic acid—a product of biomass hydrolysis—to GVL (which is also used as a substitute for blending of ethanol in gasoline). The GVL is upgraded to C9 alkenes, which they then oligomerize over an acid catalyst to produce longer chain alkenes that, after hydrogenation, can be used as drop-in fuels. _GCC

This process is notable for not requiring an external source of hydrogen, and not needing platinum or other expensive catalysts.

Meanwhile at the University of Pennsylvania, a research team has devised a means of converting biomass and biomass derived sugars into dimethylhydrotetrafuran (DMTHF).

A team at the University of Pennsylvania has developed a one-step process for converting hexose from a wide range of biomass-derived carbohydrates, cellulose and even raw lignocellulose (e.g., corn stover) into 2,5-dimethyltetrahydrofuran (DMTHF) in good yields and under mild conditions in water. A paper on the work by Weiran Yang and Ayusman Sen was published online 30 April in the journal ChemSusChem.

...A one-step process generally requires less energy than processes that involve multiple steps, and the use of water as reaction medium is attractive, the authors note. In addition, a variety of feedstocks, including raw lignocellulosic biomass such as corn stover, can be directly used without any chemical pretreatment. _GCC

DMTHF is superior in some ways to DMF -- dimethylfuran -- which is itself significantly superior to ethanol. In other words, if DMTHF can be made from biomass efficiently, it stands to displace other less efficient biofuels such as ethanol.

Better Catalysts, Better BioDiesel from Jatropha

Conventional bio-diesels suffer from poor cold weather performance. Better means of converting unsaturated vegetable oil triglycerides to straight chain alkanes (without glycerine and without double bonds). Jatropha oil is seen as having potential for high oil yield, with minimal environmental disruption.

Researchers at Japan’s National Institute of Advanced Industrial Science and Technology (AIST) have devised rhenium-modified catalysts that significantly increase the yield of diesel-type alkanes (C15-C18) from the hydrotreatment of jatropha oil under conditions of higher jatropha-to-catalyst weight ratios. A paper on their work was published online 10 March in the ACS journal Energy & Fuels.....

... Pt-Re-based catalysts are known to be effective for naptha reforming and other processes. At 20 wt % Re, the conversion into hydrocarbons was found to be constant at ~80% at any jat/cat ratio employed, with high selectivity for C18. They also found that Pd-modified Re/H-ZSM-5 catalysts are excellent candidates for triglyceride conversion as well.

Rhenium-modified Pt/H-ZSM-5 catalysts were found to be much more effective for hydrotreating jatropha oil even at a high jat/cat ratio of 10, and 80% conversion and 70% C18 selectivity were achieved. The reaction pathway involves hydrogenation of the C=C bonds of the these triglycerides followed by mainly C15-C18 alkane production through hydrodeoxygenation with decarbonylation and decarboxylation. _GCC

Renewable green diesel-type alkanes can be produced by hydrotreating jatropha oil and vegetable oils at standard hydrotreating conditions (i.e., 543−573 K) with Pt/H-ZSM-5 catalysts, which are active under the weight ratio of jatropha or vegetable oil/catalyst of 1. The carbon molar yield of straight chain C15−C18 alkanes was 80% for hydrotreating pure jatropha oil. However, under the jatropha oil/catalyst weight ratio of 10, being important from a practical point of view, the alkanes yield falls to only 2.3%. Under a high jatropha oil/catalyst ratio of 10, rhenium-modified Pt/H-ZSM-5 catalyst is found to be effective for raising the C15−C18 alkanes yield. The yield of C15−C18 alkanes is 67% at an optimun Re/Al molar ratio of 0.8. Investigation of catalyst natures indicates that metallic Pt and Re are independently present on the surface, but synergism of these two metals could play an important role in the hydrotreating reaction, even at a high ratio of jatropha oil/catalyst of 10. The reaction pathway involves hydrogenation of the C═C bonds of the jatropha oils followed by mainly hydrodeoxygenation with decarbonylation and decarboxylation to form C15−C18 straight chain alkane mixtures. _ACS

South and Southeast Asia can become new global energy superpowers, if palm, jatropha, pongamia, moringa, and other tropical seed oil crops live up to their potential -- and if these vegetable oils can be converted into pure hydrocarbon fuels economically.

These Asian operations will be largely administered by either Chinese or Indian companies. Other tropical regions -- such as parts of South America and Africa -- also present significant potential for production of high yield tropical oilseed crops. Chinese biofuel ventures in Africa are likely to grow more numerous, as the operations in Southeast Asia begin to become more profitable.

Advances in the refinement of bio-oil fuels, such as described in the Japanese research above, should expedite the global impact of these tropical oilseed derived fuels.

Turning CO2 Into Methanol: Mitsui Plant Opens

Last summer, Brian Westenhaus reported on a Mitsui process for turning CO2 into methanol. Now a Mitsui Chemicals pilot plant for producing methanol from CO2 has begun operations.

Mitsui Chemicals (MCI) has begun operating its pilot plant for synthesizing methanol from CO2. (Earlier post.) The pilot plant will produce approximately 100 tonnes of methanol per year as a base material for plastics from the CO2 released during ethylene production at the Osaka Works petrochemical complex.....

The process relies on hydrogen obtained from water photolysis and ultra-high activity electrocatalysts consisting of zinc oxide and copper. _GCC

In truth, we do not have enough CO2 to do all the things we could be doing with it. Plants need it to grow and fruit. Single cell algae and other microbes thrive on CO2. But there is very little of it in the atmosphere -- it is only a trace gas constituting less than 0.4 % of all atmospheric gases. Mitsui chemists are tapping into industrial processes that produce CO2 as a waste product.

The Quest for Bioenergy Enzymes: Novozymes

Danish company Novozymes is investing $200 million in a Nebraska enzyme plant. That is a significant investment for the company -- particularly in an economic downturn. But the best way to be ready for higher prices for a commodity like oil is to be first in line with an economical substitute.

...Novozymes is the world's biggest enzyme maker, and its products account for about 60 percent of the market in the biofuel industry.

Enzymes are strings of protein that can serve as catalysts in many natural and manmade processes. Those include breaking down starch in corn - a vital step in ethanol production.

Novozymes is also a player in the emerging cellulosic ethanol business, and it is working with the nation's largest ethanol company, Poet LLC, on a pilot cellulosic ethanol plant in Emmetsburg, Iowa, that is expected to begin operating in 2011.

Cellulose is the woody material in branches and stems that makes plants hard, and the ethanol industry is developing ways to produce fuel from cellulose economically. Once the costs of cellulosic ethanol are similar to corn-based ethanol, companies will be able to produce ethanol from straw, corn stalks, wood pulp and other inedible agricultural leftovers.

Hansen said Novozymes has 150 researchers working to improve the enzymes it produces to break down cellulose and reduce their cost. Novozymes has reduced the cost of cellulosic ethanol enzymes to about $1 per gallon, and the company expects to cut that cost to about 50 cents per gallon next year.

Hansen predicted the technology will be ready to produce cellulosic ethanol by the end of 2010... _Bioeneryg

Enzymes can turn cellulose into more than just ethanol. But since the US government is currently backing ethanol as a gasoline additive, it makes sense to invest in EtOH -- for a start. Long term, butanol and other fuels and valuable chemicals makes more sense.

What is the advantage of the enzyme approach over the gasification / pyrolysis / torrefaction approach? Potentially higher efficiencies and profits. It is always about efficiency and profit.

Gang of 15 Fungal Cellulases Open the Bio-Gate

The bio-gateway to abundant energy and wealth was just opened a crack. Cellulose is one of nature's favourite ways of storing solar energy. But human machines and power systems do not run well on cellulose. Naturally, a conversion from cellulose to high density liquid, solid, and gaseous forms of energy storage is vital. But, how to do it? Using clever and efficient enzymes can be a good way, but single enzymes lack the power and versatility to do everything necessary. Hence, the "gang of 15 enzymes" working together.

Researchers at the California Institute of Technology (Caltech) led by Frances H. Arnold, the Dick and Barbara Dickinson Professor of Chemical Engineering and Biochemistry at Caltech, and gene-synthesis company DNA2.0 have developed a new group of 15 highly stable fungal enzyme catalysts that efficiently break down cellulose into sugars at high temperatures for conversion into a variety of renewable fuels and chemicals.

Previously, fewer than 10 such fungal cellobiohydrolase II (CBH II) enzymes were known. In addition to their remarkable stabilities, Arnold’s enzymes degrade cellulose over a wide range of conditions. A paper on the work was published 23 March in the early edition of the Proceedings of the National Academy of Sciences.

This is a really nice demonstration of the power of synthetic biology. You can rapidly generate novel, interesting biological materials in the laboratory, and you don’t have to rely on what you find in nature. We just emailed DNA2.0 sequences based on what we pulled out of a database and our recombination design, and they synthesized the DNA. We never had to go to any organism to get them. We never touched a fungus.
—Dr. Frances Arnold

...Arnold and Caltech postdoctoral scholar Pete Heinzelman created the 15 new enzymes using a process called structure-guided recombination. Using a computer program to design where the genes recombine, the Caltech researchers mated the sequences of three known fungal cellulases to make more than 6,000 progeny sequences that were different from any of the parents, yet encoded proteins with the same structure and cellulose-degradation ability.

By analyzing the enzymes encoded by a small subset of those sequences, the Caltech and DNA2.0 researchers were able to predict which of the more than 6,000 possible new enzymes would be the most stable, especially under higher temperatures (a characteristic called thermostability). _GCC

Very clever. And this is just the beginning.

We are living in a biological world. When we start working with biology to get more of the things we want, we can begin building a veritable cornucopia of riches.