Nov 22, 2013 Sponge
Shell, the Netherlands based international oil company has no less than three research teams collaborating and coordinating in an effort to get biomass made into transport fuels. From Shell Global Solutions International B.V. Shell Technology Centre in Amsterdam to the Shell Global Solutions (UK), Shell Technology Centre in Thornton UK and on to Shell Global Solutions in Hamburg Germany with twelve people involved one has to think this ‘Big Oil’ firm is serious.
Using acid hydrolysis of lignocellulose to levulinic acid, followed by hydrogenation to valeric acid and its subsequent esterification the Shell team can produce valeric esters or ethyl valerate (EV). The ethyl valerate can be used as biofuels that are fully compatible for blending with gasoline or diesel, and have passed a road trial of 250,000 kilometers at fuel proportions of up to 20%. This is serious and one can be certain that an eye was kept on commercial scale during the research period.
The team has published a paper on the work in the journal Angewandte Chemie International Edition, May 5, 2010.
The key point in the process is the production of γ-valerolactone (GVL) as an intermediate chemical produced from biomass-derived carbohydrates. Using nothing more complex that acid hydrolysis the biomass is made into a product that can be made into a transport fuel supplement. As a supplement the EV also raises the octane a small amount. It looks like EV is good stuff for a petroleum fuel extender with at least 20% market potential.
Gasoline blended with 10 and 20% of ethyl valerate (EV) largely complies with the European gasoline specification (EN 228). When compared to the base gasoline, the EV blends without fuel deterioration properties such as corrosion and gum formation. EV blending also increases the gasoline density and oxygen-content, reduced its volatility (lower RVP and lower E70-E120 numbers) and lowered its content of aromatics, olefins and sulfur. EV seems to clean up the gasoline, at least to the extent that EV makes up the whole.
The authors note that non-compliant variability in volatility or density can be corrected for by minor reformulation of the base gasoline as currently done for ethanol blending. Modern cars can use the EV biofuels without any modification to their engines; similarly, the existing network of fueling stations could be used for their distribution without the stop for “splash blending” as is required for ethanol.
Testing is pretty far along. In one road test, ten current types of vehicle, new and used, were fueled exclusively with a mixture of normal gasoline mixed with 15% by volume of EV, and were sent out on the road to cover 500 km a day. After a total distance of 250,000 km, no negative impacts were found in the motor, tank, or fuel lines.
The authors point out the multistep process described in the paper provides maximum flexibility and robustness, integrating several of these steps can deliver significant process simplifications and intensification.
The authors note that a production process could be reduced to just two steps.
The levulinic acid can be converted to valeric acid in a single reactor loaded with a catalyst and operated with a large temperature gradient from 150°C at the inlet to 250°C from the middle of the reactor onwards. Or the levulinic acid can be converted to valeric acid under reactive distillation conditions, in which the bottom of the reactor is loaded with a simple Pt-based catalyst and operated under a hydrogen flow at a temperature that allows selective stripping of the GVL and water from levulinic acid. The middle part of the reactor is loaded with a catalyst to convert the GVL vapor.
Or, again, the levulinic acid can be converted to EV in a single step by co-feeding ethanol with levulinic acid as a physical or chemical mixture, in the form of ethyl levulinate, over a zeolite-based catalyst leading to the co-production of valeric acid and EV in a single step. The valeric acid intermediate over run can be recycled back to the reactor for further upgrading to EV. It seems there is no lost hydrogen or carbon in the process. Adding hydrogen rich ethanol is one kind of process choice. The economics of the biomass and the location of a facility might decide which of the three paths might be most productive and economical.
The second and last reaction handles the undesired co-production of diethyl ether. Diethyl ether can be minimized by co-feeding ethanol and levulinic acid to a reactive distillation reactor that contains a bifunctional catalyst in the bottom segment and a simple hydrogenation catalyst in the rectification segment. Levulinic acid is hydrogenated to GVL over the hydrogenation catalyst, which is subsequently converted to ethyl pentenoate upon reaction with EtOH in the presence of the acid catalyst.
The last step is to handle the volatile ethyl pentenoate, which is stripped off the solution by hydrogen and is hydrogenated to EV upon passing over a hydrogenation catalyst. Or skip the step and sell the ethyl pentenoate because it is a promising gasoline component and chemical intermediate.
The glitches are going to be all that acid to start the whole thing off and recycling it or working out a way to reuse it economically. Whether that is or will be addressed isn’t answered. Acid wastes can be awfully messy and one hopes the team has a clean and elegant solutions or the process might never get any further. All the mineral components and insoluble organics of the biomass will be in the acid waste stream and should go back to the soil.
The other glitch might be in the catalysts. From what was disclosed, no exotic or ‘expensive’ catalysts are involved, but that doesn’t preclude issues aren’t there.
On the plus side – little process heat is involved. The note of 250°C at one point is quite low by pyrolysis standards or Fischer-Tropsch. That suggests the energy input isn’t high.
This looks good with only an acid issue to deal with.
On the other hand, Dr. James Dumesic at the University of Wisconsin is exploring a different biofuel pathway involving the use of GVL. The UW process converts already aqueous solutions of GVL to liquid alkenes in the molecular weight range appropriate for drop-in replacement transportation fuels by using an integrated catalytic system that does not require an external source of hydrogen or precious metal catalysts.
The process upgrades GVL to C9 alkenes, which are then oligomerized over an acid catalyst to produce longer chain alkenes that, after hydrogenation, can be used as drop-in fuels.
If one were to guess on what path might be used at scale for biomass to fuel, at least in the higher carbon atom count molecules, Shell is likely the leader now. Dumesic is surely elegant and innovative, but the Shell researchers have commercial scale as one aspect that stood tall when the budget was set. Ability to scale will be the first criteria of any successful biomass to fuel process. Shell can see a world market for 22 million barrels per day of EV. That’s the scale.
Original post created by: New Energy and Fuel
Oct 31, 2013 Energy Talks
The researchers at the Department of Energy’s Oak Ridge National Laboratory have designed, fabricated and demonstrated a PHEV traction drive power electronics system that provides significant mobile power generation and vehicle-to-grid support capabilities. (The Oak Ridge press release isn’t specific, but here PHEV seems to mean Plugin Hybrid Electric Vehicle, not parallel hybrid EV.) The device acts as the vehicle charger.
Oak Ridge PHEV Controller. Click image for the largest view. A high resolution image is on the Oak Ridge press release page.
The effort has yielded an interesting take on the potential that an EV controller offers when there is substantial storage and some generation ability. Have a seat – this hasn’t occurred to many – the Oak Ridge controller provides more power than typical freestanding portable generators; the PHEV can be used in emergency situations such as power outages and roadside breakdowns or leisure occasions such as camping. Day-to-day, the PHEV can be used to power homes or businesses or supply power to the grid when the power load is high.
In the midst of freezing rain, ice storms and “snowmageddon” the press release seems prescient or well planned, perhaps. But the idea positioning has serious emergency value merits. It would not be much of an expense to wire one’s home charge arrangement such that emergency power would be available from the car.
Oak Ridge likes to say it as “An advancement in hybrid electric vehicle technology is providing powerful benefits beyond transportation.” That’s a little strong, but lets look at what information is available.
Gui-Jia Su of ORNL’s Power Electronics and Electric Machinery Research Center says, “The new technology eliminates the separate charging mechanism typically used in PHEVs, reducing both cost and volume under the hood. The PHEV’s traction drive system is used to charge the battery, power the vehicle and enable its mobile energy source capabilities.” Wait a minute . . . That remark would mean to this writer that wall current would be the connection to the EV, not a charger. Not a special plug. If so, that does simplify things, one would need either a 110 volt or 220 volt extension cord for the personal infrastructure investment for EV ownership.
Su also offers the charging system concept, which is market ready, could also be used to enhance the voltage stability of the grid by providing reactive power. Some clever folks out there with smart meters are thinking they might hedge the power company; take current overnight, give back current during the afternoon. Whether the pricing will make that viable isn’t a topic yet – it had better be soon.
The controller is the work of The Power Electronics and Electric Machinery Research Center, the DOE’s broad-based research center, charged and funded for helping lead the nation’s advancing shift from petroleum-powered to hybrid-electric and plug-in hybrid vehicles. The center’s efforts directly support DOE’s Vehicle Technologies Program and its goal to provide Americans with greater freedom of mobility and energy security while lowering costs and reducing impacts on the environment.
From the photo above some interesting features are visible. The controller is built on a production DSP universal controller board. It’s using a Texas Instruments chip. And it’s cooled with a fluid system seen to the right side. It’s not especially big either. As a lab unit it’s not been optimized for production, but the row of 10mm Phillips headed cap screws denote the diminutive size.
By no means is this all there is to controlling the power in an EV though. The controller Oak Ridge is proposing is more of an interface controlling device between the battery or capacitor pack and line in or grid source. There seems to be no facility to control the vehicle itself. Which is just as well. That is an area if intense engineering interest to auto manufacturers worldwide.
That suggests the Oak Ridge controller would be an option in an EV design. Should the offering actually simplify the charging at home and reduce the infrastructure cost for someone to switch over, the market should be very welcoming indeed. But that’s not to say that every EV would have one, or that every buyer would understand why or why not they’d want one.
Building the technology is one thing. Teaching consumers how it is their interest might be much harder. But I’d be game; power went down a couple days here, having the furnace run would nave been really nice.
Author: New Energy and Fuel
Oct 22, 2013 Energy Talks
The cover story at Nikkei Electronics Asia titled ‘Winning in the Gigantic New EV Market’ examines over 16 web pages the positioning of industry in lithium ion battery production. Its a long piece so I’ll condense it down, but by all means if you’re interested in a world view seen from the Japanese point of view, with still much more than half the world’s market share, the full story is very worthwhile. The story opens with “Ninety times larger in five years” an explosion in building factories for lithium ion batteries that will circle the world. It’s a very big story and writers Kouji Kariatsumari, Hideyoshi Kume, Hiroki Yomogita, and Phil Keys have done a great job is getting a mass of data worked into presentable material.
The covers story opens with a look at the Nissan Leaf EFV model; the projected production of only 200,000 will demand 4800 MWh in the second year. In comparison the 2009 world total cell phone battery demand was 3000 MWh. And Nissan isn’t the only maker. Honda in a joint venture with Yuasa hopes to boost their hybrid car sales by 50% by 2020. As the Nikkei puts it from a quote “Production can’t keep up.”
The cells now aren’t so much different, the coming years will see large size, large capacity cells.
New investment is flooding into battery production from established firms, firms that build other battery types and new entrants. The Japanese firms Sony, Sanyo and Panasonic alone are committed to $3.3 billion by 2015. Korea’s LG and Samsung are committing another $1.5 billion with Samsung also partnering with Europe’s Bosch for $600 million more. Even Japan’s Mitsubishi has started a building a $111 million pilot plant opening in the fall of 2010 with 66 MWh capacity – from a pilot plant.
The US firm A123 has agreed with Japan’s IHI to help supply Japanese needs. Dow Chemical has a joint venture with Korea’s Kokam Engineering funded to another $600 million.
The lithium ion battery market is shifting from small electronic devices to electric vehicles. Fuji Keizai researchers think the revenue for 2009 was $9.3 billion with only an added $276 million going to EVs. By 2012 the EV market is expected to grow to $17.5 billion, and $25 billion in 2014.
The cover story illustrates the demand this way. A cell phone needs 2 to 3 Wh of capacity – 1 battery. A notebook PC 70 Wh or 8.8 batteries, a hybrid car 1 kWh or 125 batteries and a full EV 20 kWh some 2500 batteries. This shows the need for larger capacity designs. Here is where the numbers get big. New cell phones in 2009 sold at about 1.1 billion handsets – about 3000 MWh for the year. Add notebooks and other gear the number grows to between 10,000 and 15,000 MWh. That puts the equivalent EV number between 500,000 to 700,000 units. Keep in mind the world makes 70 million cars annually – less than 0.1% EV penetration and the lithium battery market doubles.
If the large capacity market grows prices could fall dramatically. At over $2,200 per kWh now, the price can fall by half and another half, to $553 by 2015 when production gets fully underway. The trigger could be rail, industrial equipment and more ideas.
The trigger may have already let loose. Hitachi has taken an order for $11 billion worth of diesel hybrid rail drive units with lithium ion storage batteries going to the UK. Add buses, forklifts, guided vehicles, port cranes, construction equipment, residential solar storage, large scale solar and wind power – then the numbers sky rocket – all based on falling lithium ion battery prices. The cranes and forklifts are already on sale and economically viable. The cover story asserts this amount of scale could push pricing to $330 per kWh.
The vehicle market isn’t about just cars. Light duty trucks, delivery vehicles and bicycles use batteries too. China built and sold 20 million electrified bikes in 2009.
China, and its rapidly increasing wealth is driving the market in its own way. Some in the battery industry have concerns. China is headed for the lowest cost producer with compromises in design from the latest, most efficient, safer and simpler designs. A lithium ion battery’s most expensive part is the cathode (between 30 and 35%) and Chinese manufactures have elected to go to old technology for now although the changes coming are going to be somewhat safer and be even much less expensive single element designs that cost a tenth as much as the best materials.
At the low cost end of the business, working with the latest manufacturing equipment made in Japan, China’s BYD should get to 4000 MWh of production in 2012.
Meanwhile, the Obama administration policy is for everything to be made domestically, with money available. Korea’s LG, France’s Saft Groupe and Japan’s Toda Kogyo’s US subsidiaries have cash already in hand. Nissan plans to use another government program to build a full battery factory. The political angle in the U.S. goes further with a comprehensive cooperative agreement with China in energy including the already started promotion of EVs, renewable energy and others.
The ‘others’ include joint standards and demonstration projects and developing smart grid strategies for power distribution.
This part of the review lets a little of the apprehension that subtlety runs in the Nikkei covers story. The insular attitude and concern about the U.S. entering the business with capital for competitors is good cause. But a solid reputation, leading research, enough capital and personal connections already in place will serve the Japanese industry well.
The lithium ion battery business is in the early boom. From miners and the equipment they use, to the consumers of cars, cell phones and laptops the signal is clear – there is going to be a great variation in quality. Losing the Japanese leadership is going to force consumers to get sophistication and knowledge before committing to a large battery pack. Keep in mind, there are plans for used vehicle batteries going to mass storage for use before recycling. You wouldn’t want to miss the high trade value from a quality battery pack for choosing a cheap entry price.
Part two – tomorrow.
Author: New Energy and Fuel
Oct 3, 2013 Energy Talks
Felix Kramer, the founder of the California Cars Initiative, a Palo Alto CA based nonprofit, has an opinion or overview or criticism on the widely held views on battery technology that’s being applied to electric vehicles. It’s a long one available at GreenChipStocks.com. For you I’m going to review it, check some bits and opinionate on it myself.
First off lets keep in mind Mr. Kramer’s view or bias. Without doubt he’s intensely pro electric vehicle, and that’s fine coming in knowing that. On the other hand his perspective offers what is for this writer and likely you is to see the driving forces and the very fast moving technology progress.
Kramer’s point is to rebut the National Research Council’s (NRC) fuel cell analyst team allegation (a $30 pdf download) it would be a mistake to commit to plug-in vehicles because battery costs will remain high for over a decade. The report has gained wide attention, reported across the press and media. Then on the same day that GM opened its new Michigan battery plant, the Boston Consulting Group (BCG) released a study ( a free pdf so far) saying it would take decades for plug-ins to become competitive without subsidies. These two studies set off Kramer’s response.
Kramer is correct thinking the bureaucratic and academic studies are relevant to the pubic perspective and government process. Yet battery and auto manufacturers are spending tens of billions of dollars on factories to support over a dozen new plug-in vehicle models they see as a long-term path to low-cost, competitive components. Something is amiss, the naysaying vs. tens of billions in investment simply can’t be matched up.
The nexus is in the produced costs for EV battery costs. The NRC report says today’s EV battery packs can cost well over $1,000/kilowatt-hour. They see it taking 10 years for packs to drop from $1,000+ to the $400/kwh necessary to make unsubsidized EVs and PHEVs competitive. Even by 2030, the NRC says the battery premium for a GM Volt-like PHEV with a 40-mile range would still be over $10,000. With the obvious threat that governments will stop providing the $5-$10,000 subsidies necessary to sell cars with $15-$20,00 packs, the NRC concludes only a “battery breakthrough” or a quintupling of oil prices will motivate consumers to buy plug-ins.
This is where Kramer shines, five critical inputs are listed. The reports . . . “limit expected price reductions to the low rate expected for already-high-volume and already-cheap laptop and mobile phone battery cells. They don’t evaluate PHEVs with 10 or 20 mile ranges, which have much smaller batteries and very different economics than PHEV-40s and all-electric vehicles. They don’t count the cost savings from an all-electric vehicle not including an internal combustion engine. And they don’t factor in the likelihood of an eventual cost to emit carbon – already an assumption in much corporate long-range planning. Finally — and fundamentally — they don’t follow standard research procedures used in similar studies to document their cost assumptions, look at cost sensitivities or conduct a bottoms-up cost model. Add in all these flaws and ignore the results and reports below, and we can see why they forecast EV and PHEV sales totaling a few million by 2020 — instead of the tens of millions that automakers already plan to build and expect drivers to buy.”
The five input criticisms are valid. Leaving out an engine, transmission and the equipment to use them is a major part of the cost in building cars – one is hard pressed to imagine that those effects are not factored in. Battery choices for total storage are going to vary greatly with a vast array of inputs to decide what amount of storage to load aboard. One hopes that manufactures will leave optional space and connection facilities. The carbon cost element is going to come, cap and trade, tax or just energy pricing itself with the inevitable peaks and valleys is going to drive electric vehicle sales. The notation that not following standard research procedures don’t surprise as much as add to the disappointment closing in on the science profession led by the global warming campaign.
The fifth input criticism is the most notorious. It’s hard to get battery pack pricing data. Most batteries sell at dramatically high retail prices, but manufacturer’s pricing forecasts are for cells or packs in large volumes to potential automotive customers. Since automotive batteries are not yet mature products, price and performance continually evolve. With such competitive pressures and rapid-fire changes, researchers and even governments are often left with incomplete, inconsistent, out-of-date, or even erroneous price data.
Following on the price thread Kramer presses to get pricing data out of battery manufacturers – good luck on that – which would help disabuse the bureaucracies, media, and press of the current popular prognosis.
But the meat is in the quotes Kramer has found. One is from AutoGreenBlog speaking with GM representatives, “ . . . the study cites a current cost of $1,000-1,200 per kWh for automotive lithium ion batteries. That figure may be as much double the actual cost if General Motors is to be believed. When we spoke with Denise Grey and Jon Lauckner from GM this week they both hinted that the Volt battery was actually in the $500-600/kWh range now and they expect this number to drop.” Continuing, “ . . . GM is working closely with suppliers to cost optimize all of the pack’s components and hopes to hit the US Advanced Battery Consortium target of $300/kWh by 2015.”
The second is with Nissan’s Carlos Ghosn who expects costs to fall fast. Nissan has teamed up with Sumitomo Corp. to sell the used batteries that can no longer withstand automotive requirements but can store power for utilities, thus effectively bringing down battery prices for the consumer. In that scenario you’d lease rather than own the battery set.
Kramer adds a paragraph from the Argonne National Lab that looks to prices going down to $210/kWh. The paper is from way back in May 2009. The odd thing is the NRC report notes laptop and cell phone cells have become commodities selling at fairly stable prices as low as $200/kWh. He notes other comments from Argonne personnel, the California Air Resources Board, and the Electric Power Research Institute.
Kramer winds up calling for more information from battery manufacturers. Unless you’re a creditable buyer, no hope there. But clues remain from the prices for computers, cell phone and others that demonstrate cell prices can fall way down when standardized and smart engineering fit and connect the cells into battery packs. The auto manufacturers have huge influence on costs, both from the pre engineering and the construction choices.
Suppose the laptop computer suggestions can run true at $200 per kWhr for EVs. Two hundred dollars times forty kWh is still $8000.00. But a no engine no transmission etc EV might well price at a strong incentive to buyers. Cut the kWh to 20 or less and a manufacturer could look into fuel cells or small charging engines with the $4000 in battery savings in a straight comparison. Consider ultra capacitors and the picture gets very cloudy over a bright sun.
It’s going to be about what you want to buy. And a certainty is the manufacturers are going all out to get that for you. They’ve already spent billions by the tens and much much more is going to get spent. You’re going to get that EV – and it might be sooner than you think – one day you’ll get one whether you want one or not.
The original is here: New Energy and Fuel