Unusual forms of carbon: Growing Commercial Uses

Scan Richard Smalley’s team’s discovery of Buckyballs( Fullerene) at Rice University in 1985 was a breakthrough in the knowledge of so-called allotropic forms of carbon. Thirty years have now gone by, but commercial applications of these interesting shapes of carbon are still hard to find. Not so for carbon nanotubes, a cylindrical form of fullerenes and for graphene, arguably the most important form of allotropic carbon other than diamonds.

Carbon nanotubes are cylinders of one or more layers of graphene. This is an extreme thin transparent sheet of carbon which is 100 times stronger than steel and an excellent conductor of heat and electricity, first produced in 2004. Graphene is a honeycomb lattice of carbon atoms. images Because of its atomic structure, graphene is the most reactive form of carbon.  It generally needs to be bonded to another material (nickel, copper, iridium) to make it usable. Graphene is a superb conductor of electricity, supporting current densities 1,000,000 times that of copper.  Graphene’s large surface area and other properties make it an ideal candidate for manufacture of medical devices, electronics, ultrafiltration, structural materials, battery energy systems and photovoltaics (displays). Batteries, in particular, could benefit hugely if certain problems can be overcome: Graphene-based batteries could be charged much faster than current lithium ion batteries (minutes instead of hours) and with greater storage capacities.While the current market for graphene uses is only around $9 million, estimates of billions of dollars have been forecast if graphene’s promise for electronics and batteries is realized (!).

Carbon nanotubes, which have been exploited for some time now, are used as electrically conductive fillers in plastics, for various painting applications in automobiles, in composite wind turbine blades, in inks, as a filtering medium (e.g. for desalination plants), in anti-fouling paints for boats, as transparent conductors and in anti-ballistic vests. With similar but enhanced properties as carbon fiber, carbon nanotubes are now used in composites for bicycle bodies and tennis rackets.Current world capacity for carbon nanotube applications reached five thousand tons in 2011. But graphene is considered a much greater technological breakthrough, in part based on the much larger number of graphene patents issued.

Graphene-based storage of electricity could be the “holy grail”. Previous posts on this blog have discussed the growing need and use of different types of electricity storage to smooth out the intermittent production of power by wind and solar energy. Could graphene provide a useful answer?






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NAFTA can work both ways: Mexico starts to privatize energy


The North American Free Trade Agreement, now over twenty years old,  has been very good for Canada and, even more, for Mexico with both countries’ enjoying highly favorable balances of trade with the U.S.  Mexico is increasingly replacing China as a source of our imports, since the cost of Chinese labor keeps increasing and the proximity of Mexico provides the advantage of lower freight costs and quicker delivery. But a very recent development in Mexico will now become a boon to U.S. energy and related companies, which are already transporting and selling huge amounts of natural gas to our neighbor South of the border. This may help to quiet some of the people here who have been opposed to NAFTA from the start.

After almost eighty years of inept management of Mexico’s vast hydrocarbon resources, the country’s senate last month voted to allow outside companies to participate in the exploration and production of natural gas and crude oil. Readers may know that President Cardenas in 1938 expropriated Standard Oil and other U.S. oil companies’ assets and denied outside oil companies the right to operate in Mexico. Petroleos Mexicanos (Pemex), the country’s national oil company, at that time received the monopoly to explore for, produce, refine and distribute hydrocarbons. A combination of lack of expertise and corruption has seen Mexico’s output of oil and natural gas fall sharply, with oil output decreasing almost a third over the last ten years and refining capacity unable to meet refined fuel demand, causing Mexico to import gasoline.

A particularly dire situation on natural gas may have speeded the process of liberalization. While doubling its spending to $ 20 billion on trying to increase crude oil production, Pemex chose to neglect investment to enhance production of natural gas from the world’s sixth largest natural gas reserve (545 Tcf).  With its economy booming, in part due to steadily increasing exports to the U.S. and elsewhere, natural gas demand rose rapidly, leading to huge imports of gas from the United States. When these flows of gas reached the limit of pipeline capacities, Pemex started buying LNG at $ 19.45 per million Btu (!)

The new privatization directives  Pemex will partner with private foreign companies, with profit-sharing agreements, production sharing agreements and licenses. Ownership of the resources will stay with Pemex. The reform will also liberalize production of electricity in Mexico. Both Pemex and Mexico’s Federal Electricity Commission will be transformed into “productive state companies” with control over their budgets.  This will allow them to act more like corporations and become more competitive. The private sector will now also be allowed to build, operate and finance electrical transmission and distribution facilities.

With Mexico now anxious to greatly increase its oil and gas production, U.S, companies i9nvolved in exploration, drilling, production and transmission will soon start to export various kinds of equipment to Mexico, creating jobs on both sides of the border.



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3D Printing comes of age


This blog is about chemical and energy developments of interest to me and, I trust, also to readers following these posts. Since I have wondered for some time about how 3D printing works, I decided to investigate and this is the result. (Full disclosure: this post is largely taken from an article about the same subject I recently wrote for the Scarsdale Inquirer, my hometown newspaper.)

The most important thing to know is that 3D Printing is an “additive” technology used to produce a very large variety of objects that are currently made in a traditional manner from many different materials. Thus, objects now made from metals like steel, brass, or aluminum or from wood or marble start as a block and are cut, machined or chiseled to form the desired shape .This is termed  a “subtractive” technology, where material not wanted is removed to create the desired object. Other items may be made using a mold, but the mold itself is made using “subtractive” technology. The 3D printer (which really isn’t a “printer” at all)  is a machine controlled by specialized software that is coded to lay down successive, additive microscopically thin layers of rapidly solidified or solid material that represent “slices” of the object that is being produced in an “additive” manner.  The software is created with a computer-aided design package or with a 3D scanner. The material used to feed the printer is called the “filament”.

Imagine making a tapered vase with base using a 3D printer. Thinking in two  dimensions, you would see (if you could look into the machine) that the first material laid down by instantly solidifying polymer is a small circle (the base) that rapidly rises to a quarter inch or so in height as successive hypothetical horizontal “slices” are added to form the base of the vase. Then, even smaller hollow rows of circles start to build, expanding as the object rises a number of inches to form the tapered vase. This, of course happens with great speed. Voilà, a vase made by 3D printing!

Such a vase could have easily been made with a mold, but as shapes become more complex, molds become more difficult to design and 3D printing overcomes this problem.  Change the example to a pitcher with handle. The software will faithfully copy the two-dimensional image and build up the handle as part of the pitcher as it directs the “printer” to add the successive layers of the handle part now part of the “slice”. That is how 3D printing can be used to make complex objects.  3D printing can produce an extremely complicated metal part that is almost impossible to make with subtractive technology, which would usually include some welding.

A great variety of 3D printing processes have been and are being developed, using a large variety of materials.  Stereolithography is a laser-based process that works with photopolymers, laser-sintering and laser melting works with powdered materials, (including metals), fused deposition modeling uses extrusion of thermoplastic materials and material jetting is a technology somewhat similar to the way ink jet printers work. That technology allows simultaneous deposition of a range of different materials. An important point is that for most of these technologies, materials, and applications some post-processing steps are required, including curing, sanding, polishing, and painting. Plastic resins such as ABS, polylactic acid and nylon are currently the most common materials used.  But they also include titanium and cobalt chrome alloys, aluminum, metal and ceramic powders, etc.

An important advantage of 3D printing versus subtractive manufacturing processes  is that in the additive process no material is wasted, while in the subtractiv process up to 90 percent of the original block of material may be wasted.

3D printing is an “enabling technology that drives innovation while being a tool-less process that reduces costs and lead times”. More and more applications are being developed for various industries. Examples include hip and knee implants, hearing aids, orthotic insoles for shoes, surgical guides for specific operations and jewellery(e.g. glass fiber-filled nylon), food and the fashion industry(mannequins, face models, shoes, hats, bags). The aerospace industry has been an early user of the technology with GE  (turbine parts), Airbus, Rolls Royce and Boeing  high profile users to make first-of-a-kind parts. Car companies are also early adopters of 3D printing technologies. A drivable prototype of an electric car has been 3D printed(!). Another excellent application is making spare parts for cars, appliances, and other consumer items that are old and out of stock.

Mass customization and competition will make the cost of 3D printers, filaments and software come down fairly rapidly. At a reasonable cost, it will be a fun thing to have around the house.

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GW/Climate Change: Why methane is so important

imagesFor some time now, it has become obvious that natural gas and crude oil production from shale deposits results in significant emissions of methane, a much more potent greenhouse gas than carbon dioxide. Efforts by drillers and gas distributors to reduce the amount of leakage during production, processing, transmission and distribution are being undertaken, as well as regulatory actions. But the problem will be difficult to solve. It is of interest to note that the recent report “Pathways to Deep Decarbonization” issued by the Sustainable Development Solutions Network does not even consider the methane “problem”, focussing entirely on carbon dioxide abatement or capture and changes in energy sources supply (major switch to renewables) and lifestyle changes. So, it is important to put this matter in perspective.

Because of its structural characteristics in terms molecular bonds, methane has a much greater global warming potential (GWP)than carbon dioxide, though its effects last over much less time. A recent article in Chemical and Engineering News the 20-year GWP of methane is 86 times greater than the GWP of CO2. (That figure shrinks rapidly as time progresses.)  This is significant because scientists, including those conducting the Decarbonization study, believe it is essential to limit the increase in mean global surface temperature from rising more than 2 degrees Centigrade, with even that much increase posing a threat to human wellbeing. Their calculations and others (e.g. the Potsdam Institute for Climate Impact Research) project an increase of 2.5 to 7.8 degrees C by the end of the century if nothing is done to limit GHG emissions.

This puts the spotlight directly on methane, because the short term harmful effects of methane emissions may be more important than those of carbon dioxide. Still, there is a great controversy as to how much methane is actually being emitted or burned to carbon dioxide as a result of oil and gas drilling and natural gas transportation and distribution. Current estimates vary from 1-2% of natural gas production (EPA estimate) to as high as 6-12%, based on samples taken from aircraft over natural gas fields. At the higher levels, using natural gas instead of coal would result in a more harmful GHG situation! And the picture is made worse by the fact that in some areas (e.g.the Bakken field) where only oil is produced, the associated gas is burned and flared. Also, since natural gas is now relatively cheap, there is less incentive for drillers to reduce gas leakage at the well (short of tighter regulations). And then there are the hundreds of thousands of old, existing wells many of which still emit methane. Still, if the EPA’s estimates of methane leakage are in the right ballpark, this source of methane emissions still ranks below that of worldwide emissions from livestock(!).

All of this does not even consider the release of methane from Arctic permafrost and methane hydrates in the ocean waters as global warming proceeds.

Methane concentrations in the atmosphere  started rising sharply around 1900 and have more than doubled since that time. From all of the above, it can certainly be argued that both methane and CO2 must be considered if serious steps are to be taken to limit global temperature rise, with methane apparently a more serious short term problem, but one that can be tackled more easily by reducing leakage. There is a tremendous economic incentive, as well. A leakage of even 1.2% of production is worth about $2 billion in lost revenue.

I am particularly interested in readers’ comments on this issue.


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Flue gas carbon removal: Skyonic’s approach

imagesCALD2L5JA new EPA ruling, just validated by the U.S. Supreme Court, is aimed at substantially reducing carbon dioxide emission in the flue gas from coal-fired power plants and other large coal-burning plants. In previous posts on this blog I have discussed different technologies designed to achieve this goal, including carbon capture. These include scrubbing flue gas with amines or other alkalis, using oxygen instead of air to burn the coal (both possible for retrofits) or gasifying (instead of burning) the coal to produce a “synthesis” gas for combined cycle operation, again with carbon dioxide recovery. In all cases, carbon dioxide is either sold (valuable for tertiary recovery of crude oil) or stored underground. The first was tested in a U.S. plant without great success and may shortly be tested in China, the second is starting to be used in  two (250KW and 100KW, respectively) power plants in Germany and Korea, and the last will be employed in a very costly government supported combined cycle-based plant fueled with lignite in Missouri. The “bottom line” is that no technology is currently available and economically justified to deal with carbon emission and capture.

This brings me to Skyonic, a private company, which is developing an entirely new technology with both private and public support. Its unique approach involves capturing the carbon dioxide with caustic soda (sodium hydroxide) and turning it into sodium bicarbonate, an article of commerce. The caustic soda is produced in a conventional adjacent chlor-alkali plant where the chlorine co-product is reacted with hydrogen co-product to make hydrochloric acid, another article of commerce, now needed in large quantities for the hydraulic fracturing “fracking” process, as well as for other industrial uses.

Skyonic’s so-called SkyMine process has been piloted and is now about to be demonstrated in a commercial-sized facility at a cement plant in San Antonio Texas, with startup slated for October 2014. A chlor-alkali plant was constructed adjacent to the cement plant and a substantial percentage of the flue gas will be fed into the SkyMine facility that also sits next to the plant. The economics for the technology look good, with offtakers for both the sodium bicarbonate and the hydrochloric acid.Skymine

The obvious drawback to the process is the need to sell the very substantial amounts of sodium bicarbonate produced. While there are a series of markets for this chemical ( baking soda, toothpaste, animal feed, etc) the amount of bicarbonate produced by several SkyMine plants would soon flood the market. Large-coal-based power plants would therefore not be a prime target. However, steel plants, which emit much less carbon dioxide and need hydrochloric acid for steel “pickling” would be a more logical place for the process. Other types of plants that will need to remove carbon dioxide from their flue gas would also evaluate SkyMine.

The company has two answers for the bicarbonate market issue. It plans to sell the technology in other countries where large bicarbonate markets exist and it is also looking at adapting the process to make sodium carbonate (a much larger market : glass, soap, paper) and calcium carbonate instead of bicarbonate.



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Westlake MLP opens new chapter

ScanEthyleneWow! How the U.S. petrochemical world has changed! The shale gas “revolution” has made the production of ethylene from ethane so profitable that a downstream integrated ethylene producer can now “donate”( well, actually sell, but under favorable conditions) some of his profits to investors in a new Master Limited Partnership(MLP) that will own the olefin production facilities and will sell the ethylene to the owner of the downstream facilities (polyethylene, PVC), on a cost plus basis.  Westlake MLP has just filed a registration statement that people familiar with the industry may want to read.

Profits from production of ethylene used to be highly cyclical, depending on the state of the industry: High margins (though nothing like today’s) when there was a shortage and little or no profit at other times.  Ethylene prices are set by supply-demand considerations and the cash cost of the marginal(highest cost) producer.. With naphtha the dominant global feedstock and high U.S. natural gas costs, the U.S., before the fracking era, had little competitive advantage. The above graphic shows how things have changed. The U.S. and the Middle East are now the lowest cost ethylene producers and the world ethylene price is set by Europe and Asia, the marginal producers, which continue to use naphtha feedstocks. Under current conditions, U.S. ethylene producers have a profit margin of around 40 cents per pound at relatively stable year/year ethylene prices around 55 cents per pound, based on naphtha feedstock from  $ 100 per barrel crude oil.  The proposed Westlake MLP will sell its ethylene to Westlake Chemical at cost plus a fixed margin of 10 cents per pound, allowing the chemical company to retain most of the margin. Nevertheless, investors in the MLP should enjoy a good return with relatively little risk. And the principal Westlake Chemical owners will, no doubt, be substantial investors as well as general partners in the MLP (as was the case in another highly successful MLP in the fertilizer area created a few years ago when Terra Nitrogen MLP was spun off from Terra Chemicals after a merger).

An article in the June 2nd edition of Chemical and Engineering News discusses the recent rapid growth of MLP’s (see graphic) which offer substantial tax advantages as they avoid the double taxation (to corporations and investors) inherent in corporate dividends and because some or most of the dividends are treated as return of capital.They have been used for energy assets used by firms that generate 90% of their income from extracting, transporting, processing or selling natural resources, mainly natural gas and oil. Recently, ethylene plants were added to the list of eligible assets for MLP’s.

Time was, as they say, when petrochemical producers thought about (but didn’t) spin their (high investment/uncertain profitability) ethylene plants off as  “utilities” that would guarantee investors a small (taxable) profit for delivering and selling ethylene to their downstream operations. That way, the uncertain financial performance of their ethylene plants would come off the company’s books. With successful MLP’s paying dividends substantiall higher than those offered by large utilities and tax free to boot, this idea has been realized in a manner that seems like a win-win situation for everybody.

A number of other petrochemicals producers (e.g. Methanex, Dow, Lyondell) are studying the possibility of creating MLP’s. As a long-time investor in successful  MLP’s (not all are doing well for various reasons), I will be taking a close look at the Westlake MLP when it comes out. It’s true that other countries will sooner or later have shale gas, but short of an economic collapse of the petrochemical industry it will be a long time before the global price for ethylene (i.e. with crude oil-based plants as marginal producers) will change, making the Westlake MLP an interesting proposition if the dividend is attractive.






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LPG for Fracking gaining ground

imagesWhile hydraulic fracturing of shale continues to be a great success in the United States, with tens of thousands of new wells drilled every year for oil and natural gas production, popular resistance to this technology is gaining ground, according to surveys.  The opposition, primarily environmentalists and people in areas where incidents of drinking water contamination have occurred, has, to its credit, succeeded in bringing about more regulations and better enforcement, but public opinion on this technology is still very mixed.  One very cogent argument against fracking, with its relatively heavy use of water, is that water availability for fracking is coming in question in some areas where climate change is arguably responsible for severe drought and serious water shortages. Companies have therefore explored other fracturing fluids, primarily propane, and it appears that this technology will be increasingly used, in part to eliminate problems associated with water-based fracking, such as ground water contamination due to spills and difficulties in removing impurities from and treating fracking waste water that is released to streams. Widespread implementation of LPG-based fracking should help in dealing with the technology’s critics.

When small amounts of ferric sulfate are added to propane, gelling is promoted, and the fluid is then mixed with sand or other proppant to fracture the shale formation. Fewer chemical additives (e.g. biocides, corrosion prevention) are needed than with water-based fracking and the propane simply becomes part of the hydrocarbons being recovered. Gasfrac Energy Services, a Canadian company, has also used butane and pentane.  About 2100 wells have been drilled using this technique. According to the company, the lower surface tension of LPG allows higher yields of hydrocarbons from the well, up to 30 percent higher, according to the company. However, the initial cost of using LPG instead of water is somewhat higher.

ECorp, a Texas-based company, is also using propane for hydraulic fracturing. Its CEO has been talking to European governments about drilling a few demonstration wells in France and Poland, both of which have substantial shale deposits. Western Europe desperately needs indigenous natural gas to lift the stranglehold that Russia’s Gazprom currently exerts, but opposition to fracking is exceptionally strong in France, for example. But the advantages of propane over water may allow developers to eventually overcome strong local resistance.

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