text:
Properties of n-butanol and ethanol with gasoline .
Worldwide demand for liquid fuels will increase steadily, but not in the form of CO2-emitting scheme, rather in a renewable and sustainable way. Keywords for the future energy direction must be clean, renewable, and sustainable. Alcohol fuels are again becoming a frequent keyword for clean fuel utilization in connection with mitigation of climate change and clean fuel technology suitable for less-used local energy sources. There are a lot of interests in widening the raw feedstock to lignocellulosic biomass and algae from grain-based raw materials. Using the locally available, underutilized feedstock becomes important for local energy security as well as an option for distributed energy infrastructure.
- alcohol fuel
- low-grade feedstock
- alternative fuel
High strategic risk of dependence on imported energy sources is attracting profoundly alarming concerns as indicated by recent international trend and past experience. Self-sufficient energy supply system is at least needed to maintain a certain minimum living standard in a nation in general and the society in particular so that easy access to domestic and neighboring energy sources is a key factor to maintain. Alcohol fuels are very promising alternative energy sources from this point of view.
Worldwide demand for liquid fuels will increase steadily at least through the mid-twenty-first century, but not in the form of CO2-emitting scheme, rather in a renewable and sustainable way. Actually, there had been many options that can use locally plentiful energy resources, typically in a biomass type.
The major energy source nowadays is most certainly (hydrocarbon) gas, electricity, and liquid fuel, which is almost unanimously agreed upon. Current energy infrastructure has already been solidly established with (hydrocarbon-based) gas, electricity, and liquid fuel as convenient energy sources and such energy infrastructure appear to get more and more solidly implemented. Inconvenience related to the utilization of solid fuels is no longer tolerable, and rapid commercialization of electric vehicle is also foreseen in the near future. Liquid fuel gets replaced to the ultra-clean fuel that meets the ever-stringent environmental regulations. Electricity is produced from atomic energy, coal, natural gas, and petroleum oil products, but safety, environmental friendliness, and global warming issues must also be comprehensibly considered. Many Asian countries almost exclusively depend on imported liquid natural gas for energy source. This raises dual issues on the feasibilities of steady supply in energy sources and of reasonably affordable cost. In fact, natural gas that emits 40–55% level of reduced CO2 evolution compared to coal is surely a promising source of energy. Ethanol produced from sugarcane is one of the most carbon-efficient biofuels available globally, with life cycle greenhouse gas emissions around 70% lower than conventional hydrocarbon transport fuels . Current worldwide trend of shifting to alternative clean, sometimes ultra-clean, gas/liquid fuel from more conventional liquid fuel of gasoline/light oil necessitated a new definition of role and position of alcohol fuels in the emerging picture.
Alcohol fuels were originally regarded as an alternative energy sources for petroleum oil to realize energy independence during oil crisis of the 1970s. A brief look into the history of bio-ethanol shows Ford Motor Company’s development of ethanol-fueled car in 1899, which was terminated by low-priced gasoline then. Oil crisis of the 1970s revived similar interest in the form of gasohol by mixing ethanol, which was developed and commercialized mainly in Brazil.
The first starting point on alcohol fuels in the 1970s tells the basic background at that time. It is prompted by concerns about reliance on foreign sources of oil and a desire to support domestic agriculture. In the United States, in particular, E10 gasohol was implemented during the oil crisis of 1970s to reduce petroleum oil dependence and simultaneously to utilize surplus farm crops. At present, E15 product with 15% ethanol content is distributed for consumer market.
In the twenty-first century, alcohol fuels are again becoming a frequent keyword for clean fuel utilization in connection with mitigation of climate change and clean fuel technology suitable for less-used local energy sources. As a matter of fact, demand for alcohol fuels is mainly derived from socioeconomic and political motivations rather than from consumer conscious reasons and economic viability.
The centralized energy system that emphasizes cost-effectiveness had diminished the key driving force for technological advances in alcohol fuels. Petroleum-based liquid fuel has dominated the transportation area till now. Also, low petroleum oil cost lessened the motivation for further technology development for alcohol fuels. Global oil shock of the 1970s are not expected to break out again within the foreseeable future, and the prospect for alcohol fuel as a remedy to soaring petroleum price is not a plausible picture either. On the other hand, clean energy generation policy by utilization of locally acquired biomass or sea algae will be emphasized to replace local consumption of liquid fuel and to produce electricity or pure alcohols for fuel cells or other means, as a rather cleaner way.
For the future energy sources, renewable-based energy society must be the final goal to reach, but unfortunately it takes a long time to reach the economics and technological easiness to be a common practice, which appears to take at least one or two decades. In order to bring the technology in earlier time, there exist many hurdles and require efforts in scientific and societal side.
All in all, future energy generation direction had been solidly established as “to be clean, renewable, and sustainable,” but low petroleum cost lessened the necessity of alternative clean energy source development, e.g., alcohol fuels.
Recently, global warming is becoming a central social issue attracting worldwide attention and provides a kind of consensus that society should be changed to deal with alleviating the prime causes of CO2 evolution in addition to pollution-related issues such as fine dust. The utilization of alcohol fuels reduces carbon dioxide contents in the atmosphere, thus significantly alleviating global warming potential.
Alcohol fuels have been known as a good replacement of fossil-based liquid fuels . Brazil and the United States consume alcohol fuels in the most significant proportions, and such trend will not easily change. In particular, bio-ethanol are well known for its use in Brazil as a gasoline supplement (Figure 1).
When we say alcohol fuels, they comprise of methanol, ethanol, ethers (MTBE, ETBE, TAME, TAEE, and DME and DEE), and esters (biodiesels: methyl and ethyl esters of fatty acids derived from vegetable oils and animal fat), in a broad sense. Most widely used alcohol fuels typically include methanol, ethanol, and bio-butanol. Ethanol that is produced through yeast-based fermentation using corn or sugarcane is the most well-known. Bio-butanol is capable of overcoming technological limitations surrounding bio-ethanol, and it is currently becoming another promising focal issue of clean energy.
The chapter deals with the current status of alcohol fuels and tries to elaborate the future direction for more wider utilization and the possible roles of alcohol fuels in attaining the far-reaching goal of low-carbon economy using sustainable energy resources.
2. Properties of alcohol fuels
Alcohols and ethers can replace gasoline and oil. Table 1 exhibits properties of n-butanol, ethanol, and gasoline for comparison. In Table 1, RON, MON, and RVP values for butanol and ethanol are meant for gasoline blend fuels.
|Specific gravity @ 60°F||0.814||0.794||0.720–0.775|
|Heating value, MJ/L||26.9–27.0||21.1–21.7||32.2–32.9|
|Research octane number (RON)||94||106–130||95|
|Motor octane number (MON)||80–81||89–103||85|
|Reid vapor pressure (RVP) of 5 and 10% Alcohol/gasoline blends, psi||6.4/6.4||31/20||<7.8/15 (summer/winter)|
|Water solubility at 25°C, %||9.1||100.0||<0.01|
Table 2 contains a more wide range of properties of alcohols and ethers compared to gasoline and fusel oil. Fusel oil or fusel alcohol is defined as a mixture of several alcohols produced as a by-product of alcoholic fermentation.
|Boiling temperature, °C||27–225||117.25||78||78.25||52.2||−25.1||53.4–54.4|
|Reid vapor pressure, Kpa||53–60||18.6||32.4||17||54.47||—||—|
|Research octane no.||90–100||98||108.7||108.6–110||118||—||106.85|
|Motor octane no.||82–90||78||86.6||92||102||—||103.72|
|Low heating value, MJ/kg||44.0||33.2||20.1||26.9||34.9||28.8||29.536|
|Freezing point, °C||−40||—||−97.5||−114||−108||—||−52|
|Flash point, °C||−45 to −13||—||11||12–20||−25.5||—||—|
|Autoignition temperature, °C||257||385||423||425||435||253||41.6|
|Alcohol name||Chemical formula||Water solubility|
In general, alcohols contain higher values than gasoline in oxygen content, octane number, and autoignition/flash point temperatures, while freezing point temperature is lower.
Tetraethyllead has been banned for use as an additive to improve octane number of gasoline fuel. Methyl tertiary-butyl ether (MTBE) and alcohols are thus used as alternative additives to gasoline, but MTBE has also been banned after the 2000s, and alcohols have become useful additives to increase octane number of gasoline.
Water solubility of alcohols is an important property when alcohols are being used as fuel. Gasoline has a water solubility value of less than 0.01, whereas ethanol exhibits a full miscibility as 100. When alcohols contain a high solubility in water, spill or leakage of the mixed alcohol fuels can cause polluting the underground water.
Methanol, ethanol, and propanol are completely miscible in water, which means that they dissolve in water in any amount. Both methanol and ethanol dissolve readily in water, are fortunately biodegradable, and do not bioaccumulate. They are not rated as toxic to aquatic organisms .
Starting with the four-carbon alcohol (butanol), solubility is starting to decrease, and from the seven-carbon length heptanol, alcohols are practically immiscible in water (Table 3) . This is one of the backgrounds for the development of butanol as another alcohol fuel.
Other important properties of alcohol fuels reside in its inherent swelling of plastics and corroding power for metals. These properties ask modification in the existing infrastructure of automobiles and other appliances.
Ethanol is a clear, colorless, toxic liquid and has a characteristic odor. Ethanol is not classified as toxic to humans. Ethanol has a higher octane number than gasoline, providing premium blending properties as a liquid fuel. Ethanol contains less energy per volume than gasoline, and denatured ethanol (98% ethanol) contains about 30% less energy than gasoline per volume . Since ethanol contains oxygen, using it as a gasoline additive results in up to 25% fewer carbon monoxide emissions than conventional gasoline .
Ethanol is soluble in polar and nonpolar solvents and has a clearly higher vapor pressure than gasoline and an oxygen content of approximately 35%. Ethanol itself is a good solvent and can be mixed with water in unlimited quantities. Because ethanol is a short-lived compound in surface water and subsurface aquifer, substantially limiting the risk to aquatic organisms, environmental problem is minimal even when it is spilled. Ethanol degrades quickly in the natural environment, and the biodegradation is rapid in soil, groundwater, and surface water, with predicted half-lives ranging from several hours to 10 days .
Methanol, or wood alcohol, is a colorless, odorless, toxic liquid and is the simplest form (CH3OH) among alcohols . Methanol is corrosive to some materials. Methanol can be produced from several sources: synthetic gas (syngas), formic acid, formaldehyde, and methane. Methanol is classed as toxic so it requires additional considerations during usage to limit inhalation exposure and skin contact.
Methanol is hygroscopic, meaning that it will absorb water vapor directly from the atmosphere. Because absorbed water dilutes the fuel value of the methanol and may cause phase separation of methanol-gasoline blends, containers of methanol fuels must be kept tightly sealed .
Butanol has higher energy densities and could be distributed in the existing infrastructure . The use of ethanol as an additive to gasoline to increase octane number has downside effects such as corrosion of metal component and vapor lock. Such troubleshooting can be remedied by modification of engine and fuel system, but addition of alcohols with high carbon number such as bio-butanol enables utilization in existing system without rendering any change.
Alcohols with high carbon contents such as butanol can be synthesized from syngas through catalytic reaction that employs modified catalysts used in Fischer-Tropsch or methanol synthesis.
3. Feedstock for alcohol fuels
Alcohols fuels can be made from all available organic materials. Natural gas, coal, biomass, and organic wastes are good sources. Alcohol fuels have been synthesized from corn and sugar cane as major raw materials, but focal issues nowadays are synthesis and production of alcohol fuels from non-food crops and agricultural residues. Non-food lignocellulosic biomass includes energy crops, cellulosic residues, and wastes.
Grain-based ethanol as a first generation has been tried to change to the second-generation cellulosic ethanol and other advanced cellulosic biofuels. Cellulosic ethanol has identified as a key biochemical route of converting biomass to fuels after the 2000s . Algae-based third-generation feedstock for alcohol fuels emerged as a candidate that can provide a vast raw material for future alcohol fuel industry. Figure 2 illustrates the generations of raw feedstock for the alcohol fuel production and also shows the most apparent material that is being utilized in different countries.
Definitely there exists a clear difference between developing countries and developed countries in the priority choice, but basic understanding should be identical: use the locally available, underutilized feedstock, and choose the feedstock that tipping fee is available to treat the feedstock like municipal/industrial wastes. However, when wastes are involved as feedstock, it should be noted that not-in-my-backyard (NIMBY) problem occurs as a norm in almost every countries nowadays.
The European Commission has recently resolved by voting against utilization of biofuels synthesized from biomass of food crop sources by the year 2030. Intensive interdisciplinary efforts are anticipated for timely commercialization of cellulosic bio-ethanol, which is the second-generation bio-alcohol.
Agricultural waste typically contains a relatively high content of alkali metals (potassium and sodium) and other inorganic elements including calcium, magnesium, and sometimes chlorine and sulfur. When applying thermal methods in converting these wastes to alcohol fuels, alkali metal components act to produce low-melting salts that will cause plugging and other ash-related problems during the process. In contrast, fermenting method can reduce the tendency of ash problems, which is a beneficial aspect in actual manufacturing process.
In particular, rice husk contains ash content of over 90%, and rice straw consists of more than 30% as silica, although there is a variation with rice stock, climate, and geographical environment. Such inorganic contents work as a barrier to thermal conversion process, and fermenting can be a more appropriate way in converting this biomass feedstock.
3.1 First generation: grain feedstock
Starch and carbohydrates have been used as a first-generation raw material to produce ethanol. During the year 2013, more than 90% of bio-ethanol had been produced from the starch and carbohydrates. Corn, grain, and cassava are major such crops. Downside issues are the destruction of environment during the crop cultivation and ethanol production as well as the use of valuable food resources as fuel production. Therefore, at current situation, large agricultural countries like the United States, Brazil, and China are major production places of biofuels including alcohol fuels. In the United States, 95% of ethanol has been produced from the starch in corn grain .
3.2 Second generation: lignocellulosic biomass
Recently, the production of bio-ethanol from grain-based raw materials is gradually becoming limited, and the second-generation bio-ethanol production from non-grain-based biomass is now receiving a gradually increasing priority.
Bio-ethanol is currently becoming a solid option as automobile fuel, and it has been usually produced from starch of corn and cassava or sugary contents of sugar cane and sugar turnip. Bio-ethanol is also produced from lignin cellulose-based material of crop wastes. Sugar and starch are readily convertible to bio-ethanol but their availability is limited and they are costly. Therefore, work is underway to investigate into various processes to produce bio-ethanol from lignocellulose-based raw materials to utilize their abundant amount in nature and to meet the economic viability in the market . Wood chips or crop residues are common lignocellulosic feedstock (Figure 3).
Non-edible xylem parts that constitute most of the botanical stocks or cellulose are used to produce ethanol. Rice straws, weeds, and other shrubbery are good examples as raw material for alcohol production, and valuable food resources are not wasted in this case. However, a large-scale forest or farmland is still used and the low-production efficiency is a problem. Also, economically, viability is not satisfactory yet and is not applied at measurable proportion .
The main obstacle of using lignocellulosic biomass resides in the difficulty in extracting the essential parts from the hard-binding components of lignin, hemicellulose, and cellulose in plants as shown in Figure 3.
High-growth productivity of lignocellulosic crops compared to corn and sugarcane is one of the key factors that bio-alcohols can be produced economically in the future. Figure 4 clearly shows the high growth rates in lignocellulosic crops like sorghum, energy cane, and water hyacinth.
3.3 Third generation: algae species
Sea algae grow relatively faster than most of the land-based plants as shown in Table 4, and they are good source of raw material to produce alcohol fuels. They do not require large-scale farmland to cultivate, and non-edible algae are also a good source of bio-ethanol. Due to their fast growth rate, large-scale farming for 4–6 times cropping per year is possible and their carbon dioxide sequestration is 3–7 times more effective than that of grains. However, large-scale acquisition of the raw sea algae and its economic viability remains to be overcome before commercialization. Most of algae-related efforts are still under R&D probing stage.
Fundamental background to try algae species for biofuel production relies on their higher efficiency in converting solar energy than higher plant biomass. However, actual cultivation of microalgal biomass is not easy, rather quite challenging and still expensive than growing crops. It is a similar situation as comparing the product that has been updated for several decades and the one that is starting to experience initial trial and errors.
Figure 5 illustrates the typical biofuel production procedures in which the basic process is identical with the hydrolysis/fermentation/separation parts of bio-ethanol production, except the feedstock cultivation and harvesting parts.
4. Manufacturing processes
Ethanol can be produced in various ways: syngas from coal and biomass, synthesized from petroleum-based ethylene, or by fermentation of sugary contents. Bio-ethanol is produced through the procedures of fermentation of regenerative biomass, distillation, and purification.
Sugar canes and corns are mainly used to produce bio-ethanol in Brazil and the United States, respectively. Overall manufacturing process for bio-ethanol composes the following key parts: pretreatment, saccharification (hydrolysis), fermentation, and purification as shown in Figures 6 and 7.
Ethanol is mainly made by fermenting the sugars found in grains, such as corn and wheat, as well as potato wastes, cheese whey, corn fiber, rice straw, urban wastes, and yard clippings. There are several processes that can produce alcohol (ethanol) from biomass. The most commonly used processes today use yeast to ferment the sugars and starch in the feedstock to produce ethanol. Another process uses enzymes to break down the cellulose in woody fibers, making it possible to produce ethanol from trees, grasses, and crop residues .
Synthesis of ethanol as a sustainable source of energy, especially related to more high-end product form of alcohol with high carbon contents, requires the accumulation of technical know-how in preparation for future depletion of petroleum oil resources. The bio-alcohol production process is shown in schematic flow diagram for bio-butanol manufacturing in Figure 8.
Recently, the conversion of valuable food resources into alcohol fuel is facing very negative criticism worldwide, and work is underway to switch the raw material for bio-ethanol to non-edible biomass. However, the production of bio-alcohol from non-edible cellulosic biomass requires solving the problem of breaking the hard biomass structure before converting into alcohol fuels. Pretreatment step is important. The pretreatment process is costly since it involves several process steps and costs for enzymes. It is very important to develop the low-energy/energy-saving process scheme and the suitable enzyme to overcome such technical/cost barriers.
The first challenge in the conversion of biomass to alcohol fuels starts with the difficulty in breaking down the recalcitrant structure of biomass cell walls and further breaking down the cellulose to 5–6 carbon sugars that can be fermented by microorganisms . Size reduction and uniformization in density/size are the first preparation step. Pretreatment by steam, hot water, or slight carbonization is a common procedure.
Various ways of pretreatment are used in biomass conversion to alcohols as illustrated in Table 5. Recent types include steam explosion auto-hydrolysis, wet oxidation, organosolv, and rapid steam hydrolysis (RASH) . Organosolv is a pulping technique that uses an organic solvent to solubilize lignin and hemicellulose. The principal purpose of most pretreatment is to increase the susceptibility of cellulose and lignocellulose parts of biomass at the next process in which acid and enzymatic hydrolysis occur. Cellulose enzyme systems react very slowly with un-pretreated biomass, whereas the rates of enzymatic hydrolysis enhance dramatically when the lignin barrier around the plant cell is partially disrupted .
4.2 Saccharification (hydrolysis)
Saccharification is basically a step of breaking down the cellulose/hemicellulose through hydrolysis to make sugars such as glucose and xylose. The overall hydrolysis is based on the synergistic action of three distinct cellulase enzymes depending on the concentration ratio and the adsorption ratio of the component enzymes (endo-beta-gluconases, exo-beta-gluconases, and beta-glucosidases) .
Two main procedures exist in hydrolysis: acid hydrolysis and enzymatic hydrolysis. Most commonly employed procedure is the enzymatic one because it has a better environmental and economic performance. Acid hydrolysis operates under severe conditions of high temperature and low pH, which results in corrosive conditions and requires a special construction material .
Fermentation is the biological process using microorganisms to convert sugar and starch into ethanol. The production of bio-ethanol from starch-containing cereals typically includes the following five steps :
Milling, which is the mechanical crushing of the cereal grains to release the starch components
Heating and addition of water and enzymes for conversion into fermentable sugar
Fermentation of the mash using yeast, whereby the sugar is converted into bio-ethanol and CO2
Distillation and rectification, which is a step of concentrating and cleaning the ethanol produced by distillation
Drying (dehydration) of bio-ethanol
In Brazil, bio-ethanol is produced from sugar cane. Sugar cane is a sugar-bearing crop, and it is readily converted into ethanol by fermentation with yeast. Harvested sugar cane is thoroughly washed and crushed into pieces, the juice is extracted, and finally it is converted into sugary juice, which is further fermented by yeast. During the process, hydrous alcohol is produced by non-dehydration process and anhydrous one by dehydration process. Anhydrous ethanol is mixed with gasoline for the prevention of phase separation, and hydrous alcohol is used as fuel for all kinds of vehicles. The process wastes during the washing and crushing are again utilized as a boiler fuel to generate steam and electricity for subsequent ethanol production. In addition, for each ton of bio-ethanol, 1 ton of GMO-free, high-protein animal feed can be produced.
4.4 Comparison between SSF and SHF processes
Cellulose hydrolysis and fermentation can be achieved through two different process schemes, depending on where the fermentation occurs: separate hydrolysis and fermentation (SHF) and simultaneous saccharification and fermentation (SSF) .
In SHF, hydrolysis is performed in one reactor and the hydrolysates are fermented in the next second reactor. In SHF, feedstock and utility costs are high due to the cellulosic conversion that shows only about 73% to ethanol in 48 hours, while the remainders are burned. In SSF, hydrolysis and fermentation are carried out in a single reactor, and the operating cost is in general lower than the SHF case. In SSF, yeast ferments the glucose into ethanol as soon as the glucose is produced, which results in preventing the sugars from accumulating/inhibiting the final product.
The SSF system offers a large advantage over SHF processes, because of their reduction of final product inhibition of the cellulase enzyme complex . The SSF process shows a higher yield (88 vs. 73%) and greatly increases product concentrations (equivalent glucose concentration, 10 vs. 4.4%). The most significant advantage is that enzyme loading can be reduced from 33 to 7 IU/g-cellulose, which results in lowering the ethanol cost significantly.
A hybrid hydrolysis and fermentation (HHF) process is also proposed in converting lignocellulosic biomass into ethanol. This process configuration begins with a separate hydrolysis step which involves a higher temperature enzymatic cellular saccharification and ends with SSF step which involves a simultaneous step of mesophilic enzymatic hydrolysis and sugar fermentation.
5. Utilization of alcohol fuels
About 66% of worldwide ethanol products are used for transportation purpose and 21% goes to industrial use. Most widely used area is gasohol in that alcohols are mixed to replace a portion of gasoline. In the near future, alcohol-using fuel cells and alcohol-mixed jet fuels are promising area of application.
Figure 9 shows the ethanol consumption trend for mixing to gasoline in the United States during the period of 1980–2020. During the years 2005–2010, ethanol use has drastically increased and remains as ca. 10% of the total gasoline consumed amount.
5.1 Fuel for automobiles
The most abundant application of alcohol fuels is related to internal combustion engine of automobiles. Mixing alcohol fuels into gasoline has also a purpose of reducing pollutants by oxygenating the fuel. Since methanol is less expensive to produce than ethanol, although methanol is generally more toxic and has lower energy density than ethanol, it has been used with ethanol as automobile fuels. Compared to gasoline, methanol and ethanol have characteristics of burning at lower temperatures and lower volatility, which results in difficulty in starting the automobile engine in cold weather.
Current alcohol mixing status of ethanol-based fuel utilization in different countries is tabulated in Table 6.
|Brazil||Mandatory of bio-ethanol proportion as mixture of 24 ± 2%|
|United States||10% target for bio-ethanol proportion among primary energy sources (2010)|
|EU||Biofuel proportion increase to 2% in 2005, to 5.75% in 2010|
|Canada||Mandatory of bio-ethanol proportion in fuel set at 10%|
|China||Mandatory mixing of bio-ethanol at regional government level|
|India||Current mandatory 5% mixing of bio-ethanol and to be increased to 20%|
|Columbia||10% bio-ethanol to be mandatory at metropolitan area|
|Thailand||10% mandatory mixing of bio-ethanol to be enforced within Bangkok area|
|Argentina||5% bio-ethanol to be mandatory|
Currently, flexible fuel vehicle (FFV) with dual fuel supply system for ethanol and gasoline is commercialized and widely distributed. In the case of methanol blending to gasoline, it is limitedly used in China from the 2000s. In China, M15 (15% methanol/85% gasoline) is the most familiar type .
Low-molecular weight alcohols such as ethanol have replaced conventional octane boosting additives like MTBE in automobile fuels. Alcohols that are added to gasoline make the mixed fuel to combust more completely by acting of higher oxygen content by alcohols and provide the ensuing effects of higher combustion efficiency and lower air pollution emissions .
In the United States, bio-ethanol is mandatorily mixed with transportation fuels. It has been reported that the bio-ethanol policy reduced crude oil reliance to 25% from 60%, and simultaneously creating 400,000 jobs, reducing 43% in greenhouse gas generation and cost-saving effect of $1.5/gallon-gasoline to the consumer .
Small amounts of methanol and higher alcohols are also allowed to be blended into gasoline within EN228 limits. E85 is used in FFVs in certain areas within the EU (such as Sweden, France, and Germany) . There was a trial to use a near-neat fuel as M85 which contains 85% methanol/15% gasoline.
Racing cars used methanol for a long time, mainly by not producing black smoke which otherwise will block the view of ensuing other racing cars. Other than this application to racing cars, methanol fuel has not applied widespread other than some experience in China, methanol programs in California during the 1980–1990s, and a trial in Sweden as a marine fuel.
More than 98% of US gasoline contains typically 10% ethanol as E10 (10% ethanol/90% gasoline) . Flexible fuel automobiles that can use E85 (85% ethanol/15% gasoline) exist in the United States and Brazil.
In Brazil, 95% of automobiles are using fuel-flex engine system. Around 70% of automobiles in Brazil are able to run on ethanol, and the Brazil’s demand for ethanol is estimated to increase by around 70% by 2030 (Figure 10) [1, 22].
As for bio-butanol, the commercial scale production facility has not been constructed in sufficient numbers. In the United States, bio-butanol can be mixed up to 12.5%, and the 16% mixture is reported to be equivalently effective to existing E10 .
Ethers such as dimethyl ether (DME) contain oxygen in chemical structure which acts as an oxidant in minimizing soot formation. Other exhaust emissions such as unburned hydrocarbons, NOx, and particulate matter are also reduced . DME is an ultra-clean fuel that has similar properties to LPG.
5.2 Fuel cells
Alcohol fuel cell is an energy conversion device to generate electricity via electrochemical reactions on the catalytically active electrodes without direct combustion of alcohol fuel. Direct alcohol fuel cell (DAFC) is named for its direct supply of alcohol to fuel electrode and is called with specific terminologies as direct methanol fuel cell or direct ethanol fuel cell depending on the alcohol fuel source.
The mechanism of electricity generation is based on the oxidation of methanol fuel at the anode (fuel electrode) and conduction of electron(s) to the cathode (air or oxygen electrode) via external conducting circuit and simultaneous electrolytic conduction of proton (H+) via polymer electrolyte to the cathode.
DAFC can provide portable energy source to electronic devices such as cellular phones and notebook computers . DAFC that uses alcohol can have several advantages in terms of storage, transportation, safety, etc. over fuel cell systems like proton exchange membrane fuel cell (PEMFC) that use hydrogen.
5.3 Jet fuel
Alternative jet fuel typically contains a complex mixture of primarily n/iso-paraffins, cycloparaffins, and alkylbenzenes with a carbon number range of 9–15 . Carbon tax accelerates the development of jet fuel from renewable resources. Lowering emissions of particles and greenhouse gases during the flight are the fundamental reason of trying alcohol fuels as a jet fuel option.
Using a 50/50 (v/v) blend of petroleum-based and lipid-based jet fuels for flight was already approved by the American Society for Testing and Materials (ASTM) committee. However, the lack of raw materials and relatively low jet fuel yield of this process limit its application .
6. Environmental aspects
Global recognition regarding the significant long-term impact due to climate change provides a key foundation for utilizing alcohol fuels, which means that alcohol fuels should be able to accommodate chances in reducing climate change gases(CO2, methane, N2O, etc.). Bio-ethanol is highly effective in reducing greenhouse gas evolution. Corn-based bio-ethanol is reported to generate 43% less greenhouse gases compared to pure gasoline.
From purely theoretical point of view, ethanol can be finally produced from the biomass that is made based on the CO2 absorbed by plants during photosynthesis, and thus it can be called carbon neutral. Unlike hydrocarbons which evolve voluminous amount of CO2 from their internal carbon atoms during combustion, ethanol can be regarded as carbon neutral without generating as much CO2 from internal carbon atoms. In practice, however, significant amount of greenhouse gas evolution is directly and indirectly caused by cultivation of biomass crops and synthesis of alcohol fuels.
The range of CO2 reduction potential is large when alcohol fuels are used. Values range between 0.5 kg CO2-equivalent/liter of ethanol for ethanol produced from wheat and up to 2.24 kg CO2-equivalent/liter of ethanol for ethanol manufactured from sugar cane (Figure 11) .
According to the result shown in Figure 11, among alternative liquid fuels, only cellulosic ethanol, biomass to liquid (BTL), and CCS-involved processes (BTL-CCS, CBFT-CCS, CBMTG-CCS) exhibit the CO2-negative performance in life cycle analysis (LCA) perspective. Carbon capture and storage (CCS) process is not fully economically feasible and technically proven till now; moreover, considering public objection on CCS, connecting the process to CCS is not practical for the time being. In CO2 reduction aspect, cellulosic ethanol is the most reasonable choice as a renewable alternative fuel.
Adding ethanol to gasoline fuel of automobile, oxygen contents of fuel mixture increases and yielding the effect of reducing pollutants evolution. As alcohol fuels are inherently sulfur-free, it suits for cleaner environment. Besides, since ethanol is produced by fermentation with crops that contains starch, its purity is high, and no hazardous combustion by-products such as SO2 or metal oxides are generated during the combustion when compared to the petroleum-based fuel. But, high solubility into water by short carbon chain alcohols such as ethanol and methanol can cause an underground water pollution, although short carbon chain alcohols are well degradable in few days under normal circumstances. This problem can be minimized with the use of higher carbon chain alcohols like bio-butanol.
Forest clearing and chemical fertilizer are involved to grow corn and other grains for the first-generation bio-ethanol, which eventually ends up with CO2 production and countervailing the CO2 reduction amount by bio-ethanol use, sometimes more than the reduced amount. In this regard, the second-generation lignin-based or third-generation algae-based raw material is a better candidate for bio-alcohols.
It is especially noteworthy that the definition of (environment friendly) bio-energy is rather more stringently defined in the EU and United States: more than 35% reduction of greenhouse gas is required to qualify compared to fossil fuels of the same calorific value .
The issue of required water amount asks the approach of water-energy nexus in that technology development will follow for the process of better environment-friendliness and sustainability . As an example, recent water shortage encountered in Chennai, India, might be attributable to global warming, and the water quantity consumed for the production of alcohol fuels is emerging as an important issue. Chennai region went without rain for 200 days in 2018.
The process consuming the largest amount of water is the cultivation of biomass crops. Among the production processes for alcohol fuels, refinery step consumes the largest amount of water. The water quantity consumed for US corn-based ethanol production is approximately equivalent to the water requirement that can sustain 5000 people for 1 year.
Moreover, the refinery process that is going to be extended for the second-generation cellulosic ethanol is expected to consume 2.9 times more water needed for corn-based ethanol refinery process. At present, cellulosic ethanol production process consumes about 9.8 L/L-ethanol , which is unduly high.
7. Incentive system: renewable fuel standard (RFS)
To a great extent, expanding the distribution of bio-alcohol depends on the RFS system currently implemented in many countries. Basically, biomass ethanol cannot compete in normal market situation with petroleum-based fuels. As shown in Figure 12, liquid fuel cost of corn ethanol and cellulosic ethanol is similar to the level of crude oil price around $90–110/barrel. Considering the crude oil price during the 2000s, this high level of biomass-based ethanol price cannot compete in normal market situation. To make a room to enter the fuel market, incentive system of renewable fuel standard (RFS) was introduced.
Important aspect in Figure 12 is that bio-ethanol route (corn ethanol, cellulosic ethanol) is cheaper than the biomass to diesel/gasoline (BTL) route and comparable to the coal/biomass to diesel/gasoline (CBFT) route.
Mandatory addition of renewable energy sources in regulated proportions for transportation fuel is underway in 64 countries worldwide in connection with greenhouse reduction effects. Most such countries employ ethanol-based mixing program, while a few countries including Korea implement mandatory mixing of biodiesel only .
In the EU, 27 countries operate the mandatory mixing policy for bio-alcohol. Many countries in different continents implement similar policy: 13 nations in North and South America, 12 nations in Asia-Pacific, 11 nations in Africa and contiguous nations along Indian Ocean, and 2 nations in non-EU sphere . All in all, current trend regarding bio-ethanol mixing in major countries is summarized as follows: mandatory mixing ratios are 27% in Brazil since 2015, while nine provincial governments of China mandate 10% mixing and, it will be expanded to the entire China by 2020. RFS program was newly initiated in Vietnam since 2018 for 5% ethanol mixing. Canadian E5 mandates 5% mixing and E8.5 program is implemented in five Canadian states. Columbia implemented E8 since 2008, but E5 was targeted in Chile but not mandatorily regulated. Costa Rica mandatorily implement E7 while E10 and E2 are regulated in Jamaica and Mexico, respectively. The EU currently mandates 5.75% mixing with 10% objective for 2020 and recommends EU member nations to accomplish target 10% ratios of 2020 .
In the United States, MTBE additive to transportation fuel was gradually becoming prohibited since 2002 to prevent the groundwater pollution, and 25 US states had banned the use of MTBE by 2007. Bio-ethanol has thus become a replacement for MTBE. Mandatory mixing of bio-ethanol in transportation fuel has been implemented for dual purposes of using US surplus corn products as raw material for bio-ethanol and simultaneously safeguarding US farm economy, which prompted legislation and implementation of mandatory mixing of bio-ethanol in transportation fuel.
More specifically, Energy Policy Act of 2005 paved a way for RFS program which led to more concrete implementation plan in 2007 via Energy Independence and Security Act. The US Environmental Protection Agency (EPA) announced Regulatory Impact Assessment (RIA) in 2010, and RFS2 program was thus made available to the public, where LCA was required for the greenhouse gas evolution during the bio-ethanol production.
In many countries, government-level subsidies are being curtailed for bio-alcohols with no significant contribution to the greenhouse gas reduction. For example, cellulosic bio-ethanol is given higher Renewable Identification Number (RIN) credit in the United States for its efficient greenhouse gas reduction and non-edible nature of raw material. RIN credit ratio is 0.85:2.85 for corn-based ethanol/cellulosic bio-ethanol, which sets a higher ratio for the cellulosic ethanol.
8. Methanol economy
Methanol economy had been touted as a possible replacement for fossil fuel society. Now, hydrogen economy is starting to replace the momentum of methanol economy. Methanol has quite versatile usages in many sectors of modern industries for energy source and chemical raw material, which is a very good point when selling the product. Compared to the recent unmatched supply-demand issue in bio-ethanol, the point that there are many selling market can be a major advantage.
Related technologies to methanol are mostly mature such that there are only economic uncertainties, not major technical difficulties. Its related utility can expand as an energy media for society if cost is appropriate with eventual goal of replacing fossil fuels with methanol.
Methanol is produced from various raw materials including biomass or wastes which has not been fully utilized till now. Methanol-based energy can be quite useful especially for developing countries to cope with global climate change issue and related environmental issues while simultaneously securing some portion of national energy security. But, the issue of slipping into underground water stream when it is not properly regulated might be an issue that is to be solved. Underground water contamination shall be much smaller than the case by petroleum-based liquid fuels, but it needs to be comparable eventually to hydrogen and clean gas energy sources.
9. Relationship with hydrogen society
Hydrogen economy that is being a focal point in several developed countries can be a chance as well as danger to alcohol fuels. It is a chance because hydrogen can be manufactured with easily distributable alcohols but can be a danger when all liquid fuel-based infrastructure might be changed to the fully gas-based or hydrogen system in the long run.
Due to the concerns on climate change that requires CO2 reduction and the concerns on environmental pollutants like fine particulate and NOx, hydrogen has been hoped eventually to replace all other energy mainstream options. During the last few years, hydrogen economy has reborn as a cure for CO2 and environmental issues like an ultra-fine particles and PM2.5. But due to its high cost in hydrogen production as well as in application tools such as fuel cell and still-unstable infrastructure, hydrogen era might come after few decades of development and trial and errors. In contrast, alcohol fuels have been viewed as a cheap and reliable option in replacing fossil fuels. Especially, the possibility of utilizing abundant biomass prompts to try many ways in technology development and commercialization.
Hydrogen is the most abundantly available element in the universe with immense possibility as essential energy source sometime in the future. At present, however, technologically and economically viable means of its utilization as an affordable energy source are not ready and many countries opt to pursue the hydrogen economy path as a mean for dealing with climate change and pollution problems in their major cities.
Hydrogen economy involves the generation of renewable electricity from photovoltaic cell or wind turbine, and the so-called water-to-gas (PtG or P2G) which involves water electrolysis using the excess electricity to produce hydrogen. Green hydrogen energy generation and utilization is the ultimate goal in hydrogen economy in which society of no CO2 evolution and no fossil fuels will eventually be accomplished. On the other hand, methanol society focuses on the production of CO2-free energy source from renewable biomass or sea algae which grow by photosynthesis in nature. Green hydrogen energy will be further refined to maturity, at least by the 2030s, in such countries that can afford to bear the related high costs.
More specifically, introduction of fuel cell vehicle using hydrogen will initiate and further expand in those countries which suffer from persistent air pollution (China, Korea, Japan, large metropolis areas of the EU and United States). In contrast, alcohol-based energy source such as ethanol and methanol is most suitably applicable in tropical or semitropical countries where biomass resources are abundantly available, while domestic energy sources are not plentiful.
For realization of such alcohol-based energy generation from raw material of (very low) calorific value per unit volume, the current high-cost situation related to the pretreatment and production processes should be solved.
10. Ways for wider utilization
Changing the basic liquid fuel infrastructure that can accommodate alcohol fuels in a global scale will be slow like maneuvering a massive ship and very competitive even with right environmental slogans such as renewable, clean, and sustainable for the society. It is a well-known hidden fact that major local oil companies as well as auto manufacturers do not want to change their market unless certain compulsory regulation applies or proper incentives are given.
A report in July 2019  on the US ethanol industry nearing breaking point succinctly shows the problem related to enlarged supply and dwindling demand. Report says that US ethanol production in early June 2019 reached almost 1.1 million barrel/day, the highest seasonally on record, but the economic margins to produce ethanol are at the lowest seasonally since 2015. Infrastructure for E85 gasoline as well as government policy like US Small Refinery Exemptions (SREs) plays key roles in demand side of alcohol fuels. This situation illustrates the weak point of alcohol fuel industry. Technical endeavor only cannot make a way for wider utilization. Policy and infrastructure should follow in parallel.
Food vs. fuel controversy is the main topic in utilization of alcohol fuels, which pushed the feedstock from corn to non-food lignocellulosic biomass. Technical breakthroughs in solving the difficulties in non-uniform/hard-to-break lignocellulosic biomass and in lowering the process cost are key factors, although it would not be an easy task, considering the already established relatively cheaper bio-ethanol industry from corn.
There are clear directions, especially in developing countries in Africa and Southeast Asian countries, where environmentally benign liquid fuel supply is in great need and the centralized energy supply infrastructure might be too costly. When alcohol fuels can be supplied in enough quantity with reasonable cost, securing energy security and installing the distributed energy infrastructure can be a socially acceptable justification.
10.1 Securing energy security
When a large volatility exists in oil and gas prices, a niche market of alternative fuels like alcohols can act a role. In the time of large availability of shale gas and shale oil in addition to a remarkably fast-advancing market share by renewable electricity, the probability in global energy price jump might be low. When the energy market situation goes down to local scale, however, there are many volatility in liquid fuel supply chain.
Countries with scant energy resources are expected to be more actively searching for a way to utilize pre-existing affordable energy source and raw materials for chemical industries instead of solely relying on imported natural gas and petroleum oil. It is necessary to diversify energy sources to satisfy domestic demand even for a small proportion at the start. Alcohol fuel could take some of such small proportion.
Since most countries prefer to use gas as a basic energy source, resulting in more demand for clean and easy-to-use gas resources, even Southeast countries which are currently gas-exporting countries are going to be net importer from the 2030s, as shown in Figure 13 . Energy diversification through alcohol fuels must be a practical option to ease the burden in transportation and energy utilities in these countries.
Because the demand for natural gas is large and the accommodating space is limited in urban areas, the centralized gas supply by pipeline appears to be essential. On the other hand, local villages and smaller township can satisfy their energy needs in a distributive way by alcohol fuels produced from locally available biomass and wastes. At present level, relevant technologies are not fully ripe, which necessitates international cooperation for comprehensive and interdisciplinary R&D.
10.2 Distributed energy applications
Future trend of energy utilization is in the type of distributed application. There are many limitations for making the system that will be competitive to the centralized big-scale system that has a huge advantage in the economics of scale.
Nevertheless, the preference for the distributed energy system that is more suitable in effectively responding to the local energy demand is on the increase worldwide recently over centralized energy distribution systems. Distributed energy system market is expected to steadily expand, and this trend is most significant in the field of less than 50 MW output, where the gas turbine is taking large proportion of market share. Alcohol fuel is also expected to play a significantly important role in the distributed energy system market (Figure 14).
Locally produced biomass, wastes, and agricultural by-products are converted to alcohol fuels for energy sources, and they are locally distributable and consumed. Such system is cost-competitive by minimizing the transportation distance and is important as the basic infrastructure in securing the clean energy source as well as in proceeding to the sustainable society. However, the distributed energy application system costs more than the centralized energy distribution system, in general. It can be accomplished only by meeting the pre-conditions that cost should be down significantly and proper commercialization with reliable technologies should be available for greenhouse gas reduction and for alleviation of environmental pollution.
11. Future direction
There emerged several candidates that compete with alcohol fuels in the twenty-first century liquid fuel field. Green hydrogen and green electricity are the most prominent players. Whether alcohol fuels can compete with these two players will depend on the future progress in dealing with key required target: CO2 reduction, environmental cleanness, convenience in existing infrastructure, and price competitiveness. Moreover, energy-related focal points nowadays are sustainability, suitability for carbon-free (green energy) status, and alleviation of polluting materials such as fine dust, which are primarily emerging and ecologically important topics.
Replacement of fossil fuels with alternative clean fuel will eventually lead to green energy-based sustainable society. However, currently available technology is not up to the level of commercially viable standard for social acceptance in terms of CO2 evolution and fine dust, etc., which must be comprehensively overcome.
Currently available elementary and applied technology can be utilized to synthesize liquid fuel in various forms. Although synthesis of liquid fuel is more costly than direct mining of petroleum, the application of currently available technology to alcohol fuel synthesis should be tried to make ways that can be economically feasible and lucrative when commercialized. In a sense, it is rather a problem-solving for cost-effective technology rather than the technology itself. Mass production of lignocellulosic ethanol necessitates economically competitive technology rather than the barely profitable or only technically feasible technologies.
Actually, bio-alcohol such as bio-ethanol is an industry of low unit cost. Without installing a proper scale of plant size, cost competitiveness with other liquid fuels must be quite low . Actual plant construction cost remains high because of the inherent limitation of using low-energy density raw feedstock and of complex nature involved in converting into alcohol fuels. Among these, pretreatment/detoxification and hydrolysate conditioning processes are especially costly. Such auxiliary processes have to be developed in such a way that overall process cost can be dramatically reduced through the introduction of more energy-efficient and process simplification .
Another important aspect is that soils and climates in much of Africa have similar characteristics to those in Brazil . Africa and South America have a great potential in increasing bio-energy products including alcohol fuels.
In short, alcohol fuels should work as an energy source that can minimize the environmental impact as lower than natural gas at all applications while opening more applicable places as well as manufacturing a cheaper liquid fuel that can be used in big scales also in developing countries where plentiful but low-grade raw materials exist in plenty.
Alcohol fuel is one of the most important source of energy in view of its renewable nature and the abundance of feedstock on earth. Even when many bright prospects of alcohol fuels shed light on possible options for the environmental conscious society, still cost dictates and it will be that way. Carbon taxation might help, but the market might lead to a totally different direction such as hydrogen or green electricity from renewable energy, instead of choosing alcohol fuels. Abundant shale natural gas might play a replacing act of cheap oil that had prevented most of other energy source developments from the 1950s till the 1970s. All these situation point that the future of alcohol fuels depends upon the technological advances in cost and convenience in use.
As discussed in this chapter, the direction of future energy is simple and clear. It is the low-carbon economy using sustainable energy resources but with affordable cost. Alcohol fuels can act as connecting threads between current conventional oil/gas society and the future hydrogen society in attaining this far-reaching goal.
Current status regarding alcohol fuels can be summarized as stagnant in scale and also in utilizing market. Since bio-ethanol dominates the alcohol fuel market, the system has an inherently sensitive structure to changes in supply-demand and government’s policies. More wide application ranges of alcohol fuels should be sought in areas such as fuel cells, marine ships, and jet fuels. Alcohol fuels must remain as an essential component for the realization of sustainable low-carbon society, and continuous research on key bottlenecks should be pursued systematically.

domain: chemistry


text:
James Ulrich, the most successful coach in the history of the New York State Collegiate Conference and winner of twenty straight State University of New York Athletic Conference championships, shares the secrets of his success.
This book contains a wealth of knowledge that will enhance your ability to coach effectively and successfully.
Specific areas include:
- Coaching for speed
- Relationships with your athletes
- Psychology in coaching
- Preparing and organizing practices
- Teaching techniques of your sport
- Conditioning and physical training
- Injury prevention, care, and rehabilitation

domain: library


text:
133 Magnolia AveDaytona Beach, FL 32114
From Business: No matter the severity or type of hair loss, we have many non-surgical solutions. Today a new wave of technology and sophistication is here. Here at Carl Walters …
Very nice and clean salon. Valerie Kirkland has been doing my hair for 10 years and does an awesome job!
511 N Clyde Morris BlvdDaytona Beach, FL 32114
From Business: Welcome! Since 1992, Heller Dermatology Center has been working with patients to provide the best dermatological care for patients in the Daytona Beach area. Jeff…
155 N Nova RdOrmond Beach, FL 32174
From Business: John C. Long, Jr., M.D., your board-certified dermatologist, is dedicated to helping patients with all their skin care and dermatological needs. He is an expert a…

domain: medical


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Maf, organization that deals with vocational training, will participate at RiminiWellness 2018 this year too. We’ll coordinate an awesome stage enhanced by so many sporting disciplines.
Our stage will be in outdoor pool area. Our master trainers will alternate with high level masterclasses. Our planning will be made up of 18 masterclasses a day during 30 min.
Our training activities: Functional Training, Lambaerobica, Fit Boxing, Jumple by Aerower, Freestyler.
Competence and knowledge for a discipline that unify martial arts technique (kick boxing, boxe, muay thai, etc.) with music and fitness. This year too, Fit Boxing Master Fit will be at Rimini Wellness 2018.
Functional Training is a global workout. It works on axis and plane of the body, training strength in its different aspects (speed-strength, speed-resistant, peak force, explosive power).
Functional Training workout is considered highly preventive, it submits the body always looking stability, balance and coordination. Core streightening is the basis of the functional workout.
It’s a workout method that used very important concepts, like as proprioception, trough the activation of many deep muscles in order to maintain positions during exercises execution.
The activation of this muscles increase the potential of a specific phisique, motor and athletic attitude.
It’s a training program borned by a professionals decades-long work experience that deals with fitness world and rebound shoe.
This funny training program makes you live an experience that will allow you to train correctly and in safety with your rebound shoe, based on the participant experience, by applying the difference between rebound technique and the propulsion and training session intensity. The participant can train correctly reaching high professional level.
Jumple by Aerower is a training program studied for professional in fitness world.
Is a toning system that combines a training device and an extensive spectrum of workout programs & support.
It works the whole body at once ... as oppose to products or exercises who work only one muscle group producing imbalance in body and creating potential for injuries. Freestyler on the other hand provides simultaneous attachment of the tubes to all four limbs at the same time, so your body is under safe & efficient elastic resistance throughout the workout (on the Freestyler every move counts). This facilitates better efficiency and a workout which gives you a good looking body (lean tone muscles, no bulk) and at the same time a functional body (injury prevention, improvement in sport activities since it promotes whole body coordination with amazing "core" training).
Lambaerobica is a Brazilian dance-fitness program with animated choreographies, using a different type of rhythms like as Axé, Pagode Baiano, Arrocha, Forro, Sertanejo, Funk Carioca, ecc.
Lambaerobica is intended to infuse joy, brightness and relaxing, it’s a good way to eliminate sadness and to release all negative energy. During a Lambaerobica lesson you can lose 500-950 calories, you can strengthen your hips, waist and legs, reducing cholesterol.
There’s no need to know how to dance, you can just follow your heart and your trainer. Every lesson last from 45 min. to 1h. Lambaerobica is the only dance-fitness program 100% Brazilian.

domain: sports


I gave a talk recently at the Commonwealth Club in San Francisco about science publishing and PLoS. For the first time in my life, I actually gave the talk (largely) from prepared remarks, so I thought I’d post it here. (An audio recording of the talk with Q&A is available here.)
On January 6, 2011, 24 year old hacker and activist Aaron Swartz was arrested by police at the Massachusetts Institute of Technology for downloading several million articles from an online archive of research journals called JSTOR.
After Swartz committed suicide earlier this year in the face of legal troubles arising from this incident, questions were raised about why MIT, whose access to JSTOR he exploited, chose to pursue charges, and what motivated the US Department of Justice to demand jail time for his transgression.
But the question that should have been asked is why downloading scholarly research articles was a crime in the first place. Why, twenty years after the birth of the modern Internet, is it a felony to download works that academics chose to share with the world?
The Internet, after all, was invented so that scientists could communicate their research results with each other. But while you can now get immediate, free access to 675 million videos of cats (I checked this number today), the scholarly literature – one of greatest public works projects of all time – remains locked behind expensive pay walls.
Every year universities, governments and other organizations spend in excess of $10 billion dollars to buy back access to papers their researchers gave to journals for free, while most teachers, students, health care providers and members of the public are left out in the cold.
Even worse, the stranglehold existing journals have on academic publishing has stifled efforts to improve the ways scholars communicate with each other and the public. In an era when anyone can share anything with the entire world at the click of a button, the fact that it takes a typical paper nine months to be published should be a scandal. These delays matter – they slow down progress and in many cases literally cost lives.
Tonight, I will describe how we got to this ridiculous place. How twenty years of avarice from publishers, conservatism from researchers, fecklessness from universities and funders, and a basic lack of common sense from everyone has made the research community and public miss the manifest opportunities created by the Internet to transform how scholars communicate their ideas and discoveries.
I will also talk about what some of us have been doing to liberate the scholarly literature – where we have succeeded and where there is more work to be done. And finally, with these efforts gaining traction, I will describe where we are going next. ...
This post originally appeared on Michael Eisen's blog "it is not junk." Read the rest of his speech here.


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Where to buy First Calgary Financial in Canada?
4.4/5 (88 %), 10 votes
Total number of First Calgary Financial stores in Canada: 6
The biggest shopping centre/mall in Canada with First Calgary Financial store: The Core Shopping Centre
List of First Calgary Financial stores locations in Canada. Find the First Calgary Financial store near you in Canada Cities, Provinces and Territories.
You will get following information:
Click on the map to see all states with First Calgary Financial stores.
70 Shawville Boulevard S.E., Calgary, AB T2Y 2Z3
333 – 7th Avenue SW, Calgary, Alberta T2P 2Z2, Canada
130 Country Village Rd NE #623, Calgary, AB T3K 6B8
3630 Brentwood Road, Northwest Calgary, Alberta, AB T2L 1K8
5696 Signal Hill Center Southwest, Calgary, Alberta, AB T3H 3P8
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1661 Duranleau Street, Vancouver,BC V6H 3S3205 stores
17600 Yonge St, Newmarket, ON, Canada, L3Y 4Z1195 stores
401, boulevard Labelle, Rosemère, Québec, J7A 3T2217 stores
7205 Goreway Dr(goreway drive and morningstar,), Mississauga, On L4t 2t9242 stores
220 Yonge Street, Toronto, ON M5B 2H1
1 Bass Pro Mills Drive, Vaughan, Ontario - ON L4K 5W4, Canada425 stores
4300 Steeles Ave. E. (NE corner of Steeles & Kennedy), Markham, Ontario - ON L3R 0Y5, Canada552 stores
1200 Bay Street, Suite 310, Toronto, ON M5R 2A5, Canada231 stores
419 King Street West, Oshawa, ON L1J 2K5, Canada309 stores
25 Peel Centre Drive, Brampton, ON L6T 3R5

domain: geography


The 42nd anniversary of the liberation of Warsaw and an exhibition entitled ‘Fighting Warsaw’ that takes place in the building of the former gas plant in Wola. The Poniatowski Bridge is being renovated for too long. There is a progress in constructing the Warsaw metro. Opera artists give a charity concert. Toys for children that are not made from plastic. It’s time to skate since the winter has come.


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However, a recent giant, placebo-controlled, randomized study failed to point out any benefit from vitamin E on coronary heart disease. Although antioxidant dietary supplements are not beneficial, antioxidant meals sources –particularly plant-derived foods similar to fruits, vegetables, whole-grain meals and vegetable oils –are really helpful. Moreover, vitamin or mineral dietary supplements aren’t a substitute for a balanced, nutritious diet that limits extra calories, saturated fat, trans fat, sodium and dietary cholesterol. This dietary approach has been proven to cut back coronary coronary heart disease threat in each healthy individuals and those with coronary illness.
As a result, you could be getting more of those elements than you assume, and extra may not be higher. Taking more than you need is always dearer and can also raise your risk of experiencing side effects. For example, getting an excessive amount of vitamin A may cause complications and liver injury, cut back bone power, and cause start defects.
Best supplements for cholesterol: Taking this complement could help maintain levels wholesome
If too much vitamin D builds up in the blood, it could possibly turn out to be toxic, inflicting nausea, weak point, and constipation. And even after these probably dangerous medicine hit the market, the FDA lacks the capability to keep up with all of the merchandise and well being claims to be able to flush out dangerous actors. It’s exhausting accountable them. Doctors, too, have trouble maintaining with the 90,000 plus products.
If the FDA receives stories of potential problems with a supplement, it will concern warnings about products which are clearly unsafe. The FDA may also take these dietary supplements off the market.
The investigators warned that the implications of their findings were worrisome given that greater than half of individuals 60 or older take supplements containing vitamin E. Moreover, 23 percent of them take at least four hundred IU per day despite a really helpful day by day dietary allowance of only 22 IU for adult men. Antioxidants. Far from reducing most cancers risk, as lots of people consider, high doses of some antioxidant dietary supplements may actually improve it, evidence suggests. Omega-3 fish oil.
If lab tests present that a lady’s iron status is low throughout pregnancy, her healthcare supplier will recommend an iron supplement. The American Academy of Pediatrics, in addition to the Centers for Disease Control and Prevention, advocate that breastfed infants get vitamin D dietary supplements. The AAP also recommends iron dietary supplements for breastfed infants. Breast milk simply doesn’t include sufficient of these nutrients for babies.

domain: biology


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Some owners may try their hand at selling their renovations in the retail market due to low carrying costs (i.e. no or low mortgage). The upper bracket buyers are custom gut rehabbing existing buildings or building luxury new construction "in-fill" single family homes.
The existing two flat building at 2242 W Leland shown here was in great shape and sold for $580,000 in October of 2009. It looks like the current owners are "gut rehabbing" the building, although I could not tell from my quick look from the sidewalk if they are maintaining any wood trim etc... In any event, this is another example we are seeing in Lincoln Square of taking advantage of low mortgage interest rates and favorable loan terms to create a custom home in a wonderful location.
Read more of our posts on new construction around the area here!
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domain: economics


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One could speculate that, like my other recent Mac N’ Cheese recipe, this recipe is also the result of a pregnancy craving but the truth of the matter is that I love jalapeno poppers. I loved them before I was pregnant, I love them now that I am pregnant, and I’ll probably continue to love them after I am pregnant. The fact that I crave them at 10am is probably because I am pregnant but that is besides the point. It is this love affair with jalapeno poppers that prompted me to try my hand at jalapeno popper mac n’ cheese. And as it turns out jalapeno poppers and macaroni and cheese make a beautiful combination.
To get the true taste of jalapeno poppers two ingredients were obvious: jalapenos and cream cheese. Getting the crunch right was a bit more of a challenge. Should I try bread crumbs? Croutons? Ultimately I decided on panko because I tend to like jalapeno poppers that are coated in panko. In this dish, the panko bread crumbs added the perfect bit of crunch to the creaminess of the mac n’ cheese.
While I really enjoyed the baked version, if you are short on time and looking for a stove-top variation, I’d recommend cooking the pasta according to package directions, then follow the instructions up until 4. Instead of baking, place the mac and cheese in a bowl and top with crumbled potato chips. It sounds weird but trust me, it’s quiet delicious as well.
A juicy cheese burger topped with whiskey caramelized mushrooms, onions and soft and creamy Dubliner cheese.
Everyone’s favorite theme park treat gets turned into a popcorn snack with this churro popcorn loaded with cinnamon, sugar and white chocolate.
These quick and spicy pickled onions are all kinds of easy and all kinds of delicious. I love putting them on tacos, nachos, taco salads and I’ve even been known to just snack on them. They are super yummy, friends, but then again you know I love anything spicy. And speaking of all things spicy, […]
If you like peanut butter and chocolate you are going to love this Nutter Butter Fudge Swirl Ice Cream.
Flat iron steak is marinated with fresh oregano, olive oil, vinegar and garlic and then grilled to perfection.
Tomatoes, garlic, olive and salt are all that top this bruschetta and it is divine.
My name is Des. I’m a Mom to Kellan and Preston. Wife to Ryan. Dog mom to Pumpkin and lover of all things food. Whether it is cooking it, eating it, shopping for it or watching TV about it, food is one of my favorite things. Read more »
Have new recipes emailed to you.

domain: food


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By Debayan Mukherjee
Kolkata– Talismanic skipper Sunil Chhetri and goalkeeper Gurpreet Singh Sandhu will have to play leading roles on and off the pitch, if India are to do well in the upcoming Asian Cup football tournament, feels former captain Bhaichung Bhutia.
India, who qualified for the Asian Football Confederation’s flagship tournament after a gap of eight years, have in their ranks a lot of youngsters, complemented by the experience of Gurpreet and Chhetri. Both of them were part of the Doha Asian Cup back in 2011.
India, who lost all their matches back then and bowed out of the group stages, take on Thailand on January 6, before facing hosts United Arab Emirates (UAE) on January 10, and Bahrain on January 14.
“Two persons will be very crucial — Sunil Chhetri and Gurpreet Singh (Sandhu). Both have the experience of playing AFC. India have a young team and their guidance will be the key on and off the field,” Bhutia told IANS over phone.
The 42-year old Sikkimese icon, who was the captain of the side in 2011, maintained that his former teammate Chhetri will have to take up the mantle of looking after not only his game but also his lesser experienced colleagues who might get overawed by the stage.
“Especially for Sunil, it’s not about his own game but also guiding the players, keeping their focus off the ground and giving them confidence. He has to be the leader off the ground and see that they don’t get carried away,” Bhutia said.
Asked about India’s chances in the competition, Bhutia pointed out that their first assignment against lower-ranked Thailand will make or break them.
“The first match is going to be very crucial. The match against Thailand is the most crucial game because if we can get three points (from that game), I genuinely feel we can go through to the second round. But if there is a defeat in the first match, then it looks difficult,” he said.
“The morale and confidence will also be built from the first match. That’s why the Thailand match will be crucial for them.”
India coach Stephen Constantine had rued that his boys could not play more preparatory games leading up to the big ticket tournament. India have played China, Jordan and Oman in preparatory friendlies.
Bhutia, though, said India’s build-up has been just fine and these are players who are raring to go at the big stage.
“Preparation has been good. This is a good bunch of players who have done well together and are raring to go. There should be fire in the belly to do well and I strongly feel the Thailand game is the key. We need to beat them at any cost,” he said.
Meanwhile, The Baichung Bhutia Football School (BBFS) with its 50th centre recently announced an angel investment by the promoters of the CarWale & Chalo and Zomato.
“We got some people to come on board and take up the school in a bigger way and expand it in a bigger scale. In future, we also need to raise some more money to come into the company. We are looking to expand BBS pan India,” Bhutia said on the association. (IANS)

domain: news


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If you feel overwhelmed and anxious about what to do after a Toronto car accident, you aren’t alone. Many injury victims have countless questions about what to expect moving forward. Below are some of the most common questions our law firm receives from accident survivors just like you.
If you have a question that was not answered on this page, you can discuss your case in further detail during a free consultation.
Going to court may not sound enjoyable, but it could be necessary depending on a number of factors, including how successful negotiations with the insurance company go and how considerable your losses are.
Before accepting an offer from the insurance company, it’s important to review the offer with your lawyer. Insurance companies aren’t known for putting their claimant’s needs first, and they will like try to settle your claim for less than you deserve.
The basic limitation period for car accident lawsuits across Ontario is two years. This gives you a maximum of two years from the date of the accident to file a claim. If your lawsuit is not filed within the basic limitation period, also known as the statute of limitations, then you will lose the opportunity to be awarded compensation for your losses.
There are many reasons car accidents occur, and if you were involved in a single-car accident, you may still be entitled to compensation. Your lawyer will need to investigate the cause of your accident. If another party is to blame for the injuries you sustained, suing may still be an option.
If you are interested in discussing the individual details of your case in greater detail with an experienced Toronto car accident lawyer at Jasmine Daya & Co., you can do so by scheduling a free, no-obligation consultation. You can do so by filling out the quick contact form at the bottom of this page or by giving our office a call at 416-967-9100.

domain: law


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- Begins in:
- CÓRdoba, AN, Spain
- Created By:
- Alberto Rivas Best Time: 10:16
- This is a 5.77 mi Other in CÓRdoba, AN, Spain. The Other has a total ascent of 205.51 ft and has a maximum elevation of 445.77 ft. This route was created by soyalberto on 09/21/2011. View other Others that soyalberto has done or find similar maps in Cordoba.


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With over 20 years in the game the Lox still continues to shake the streets with that hard and gutter sound. The Lox have blessed fans with two projects for the month of November. The Trinity: 2nd Sermon, a five track EP and now The Trinity 3rd Sermon. This is something fans have been definitely waiting for. With producers starting from Chris Stylez to Roc Nations artist Jhalil Beats , they strike us with their classic D-block sound with a slap of knowledge on a few tracks. While both projects are still hyping up the streets, The Lox has more to come . Stream after the jump.
Each member in 2015 will release solo projects, but keep your ears cleans are eyes alert for the long-time intense We are the streets 2 album.

domain: artistic


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Fuji first pressing or reissue. Complete your Out Of The Blue (3) collection. Deutsch English Español Français Italiano 日本語.
Fuji is a hard bop music live album recording by OUT OF THE BLUE released in 1987 on CD, LP/Vinyl and/or cassette. Recorded live at the Mt. Fuji Blue Note Festival on August 31, 1986. Thanks to snobb for the addition. No release results found : showing artist results instead.
Download Out Of The Blue - Live At Mt. Fuji (Full Album). Download Mt Fuji Blues. Download 【HD・720p】Mt FUJI JAZZ FESTIVAL '86 with BLUE NOTE 1986,08,29 31 1986,09,07 OA. Download Paul Gilbert - Mt Fuji Xmas (live paris 2007). Download Mt Fuji 1989. Daily Movies Hub. Daily Movies Hub is an online movies download platform where you can get all kinds of movies ranging from action movies, indian movies, chinese movies, nollywood movies,hollywood movies, gallywood movies etc. For Advert placement and enquiries, mail us at contactymovieshub.
Singer: Out Of The Blue Album's name: Live At Mt. Fuji Label: Blue Note – PRP-8297 Type: Vinyl, LP, Album Country: Japan Date of released: 1987 Category: Jazz Style: Contemporary Jazz, Cool Jazz.
The second half of the program has three group originals, all previously recorded but here stretched out a bit, performed by the same rhythm section plus trumpeter Michael Mossman, altoist Kenny Garrett and Ralph Bowen on tenor. Fine straight-ahead music.
MT FUJI IN BLUE by withershins, released 12 August 2014 1. Aquamarine 2. An Amateur Chemist 3. Mt Fuji in Blue 4. Chronic 5. Moss God 6. All You Need 7. Eternal Return 8. Coward's Clothes 9. STFU or GTFO 10. How Not To Be Seen 11. Leaving Ground 12. A Patient Bo. Jeoffrey Owen I can only hope to see this band play live one day. I found this a little late after its release. It doesn't stick to one genre but excels at all of them. It effortlessly transitions and flows between styles melding them making each song uniquely their own. There in no weak songs and this release is solid from top to bottom. Two 12" vinyl records of the full-length album. Pressed on blue-white haze, 150-gram vinyl with gatefold jacket. Includes unlimited streaming of MT FUJI IN BLUE via the free Bandcamp app, plus high-quality download in MP3, FLAC and more.
Live at Mt. Fuji (audiophile). LP. Blue NoteBT 85141. 1987, Europeaudiophile. 19,24 €. view record. The image is a scan of the item which is for sale. Live at Mt. Cover, Media grading.
On this page you can listen to mp3 music free or download album or mp3 track to your PC, phone or tablet. Fuji A Live Transmission album. And you can download the album in one file to your computer or tablet or phone. Attention! All audio material is presented solely for information. ru All rights are reserved by their respective owners, authors, composers, performers. On this site you can find any kind of music except for MP3 download.
|BT85141, BT-85-141||Out Of The Blue||Live At Mt. Fuji (LP, Album)||Blue Note, Blue Note||BT85141, BT-85-141||US||1987|
|BTC 85141||Out Of The Blue||Live At Mt. Fuji (LP, Album)||Blue Note||BTC 85141||Canada||1987|
|CDP 7 46784 2||Out Of The Blue||Live At Mt. Fuji (CD, Album)||Blue Note||CDP 7 46784 2||US||1987|
|PRP-8297||Out Of The Blue||Live At Mt. Fuji (LP, Album)||Blue Note||PRP-8297||Japan||1987|
|068240808||Out Of The Blue||Live At Mt. Fuji (LP, Album)||Blue Note||068240808||Brazil||1987|

domain: entertainment


Some Florida residents started returning to their homes Tuesday in the aftermath of the widespread destruction spawned by Hurricane Irma, but officials warned the recovery would be frustrating and lengthy.
Damage was still being assessed in the Florida Keys: the island chain remained somewhat cut off from communication after highways into the area were rendered impassable by the storm.
Damaged sail boats are shown in the aftermath of Hurricane Irma in the Florida Keys.
After the Keys, Irma crossed over warm waters and hit the USA mainland near the beach town of Marco Island. The ocean storm had been the strongest kind of hurricane - a Category 5 - as it moved through the Caribbean area last week.
A man was found dead in Winter Garden, Florida, after being electrocuted by a downed power line, local police said.
More than two million people were also left without power across the state, which is home to President Trump's famous resort, Mar-a-Lago, located in Palm Beach on the east side of the state. Chatham County, which includes Savannah, sustained massive flooding due to the storm, a surge of 4.7 feet and a high tide, known locally as a king tide.
While the projected track showed Irma raking the state's Gulf Coast, forecasters warned that the entire Florida peninsula - including the Miami metropolitan area of 6 million people - was in extreme danger from the monstrous storm, nearly 400 miles (640 kilometers) wide. "This is an extremely unsafe and life-threatening situation".
"It's going to take some time to let people back into their homes, particularly in the Florida Keys", said Brock Long, administrator of the Federal Emergency Management Agency.
The National Hurricane Center in Miami said the storm made landfall at 3:35 p.m.
Parts of Georgia lost power on Monday as Irma passed.
South Carolina Governor Henry McMaster on Sunday night issued a mandatory evacuation for some barrier islands, CNN reported. It gradually weakened to a tropical storm by Monday morning. Schools in the state planned to close Monday. The previous flood record was 4 feet.
Irma comes just days after Hurricane Harvey dumped record-setting rain in Texas, causing unprecedented flooding, killing at least 60 people and leaving an estimated $180-billion in property damage in its wake.
The reproduction of the story/photograph in any form will be liable for legal action. We'll be digging out of Irma damage for years, too.


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The Elwins have shared a video for their new track “Take Me All The Way” off of their forthcoming LP, which is set for release later this year.
The new track “fits in that zone I love, where it’s an upbeat sounding song with sad/introspective lyrics,” bassist Francesco Figliomeni explains. “Very excited for this to be the first taste of what people hear from the new album, I feel like this is one of the songs that helps us dial in where we wanted to head vibe ways. Guitarist and vocalist Matthew Sweeney went on to explain that “Take Me All The Way” is about wanting more from life and “wondering if someone can help fill the void.”
The accompanying black-and-white video comes with layers of clips of the band performing along to the energetic tune, eventually taking on a Queen-style harmony formation toward the end.
Lead photo courtesy of Becca Hamel.


- Posts 3
Last Activity:09-05-2011 11:24 AM
Posted in thread: Attic exhaust fan repair on 09-05-2011 at 05:17 AM
though it is a fact home owners do not care about the attic fans has been installed for no of
years they need service for further work...
Posted in thread: Cleaning plastic shower. on 08-26-2011 at 12:17 AM
yes it is nice advice you have given...along with vinegar you can also use it with petrol...
Posted in thread: How to repair the leaking roof on 08-26-2011 at 12:14 AM
although many reson could be there ..one main reason is that u have installed improper sky
light...or it may contain water marks through leakage..


India's booming digital payments market, which is expected to mushroom from less than $200 billion currently to $1 trillion over the next five years, had lured several global players, including Facebook-owned WhatsApp and Google. But the country's new thrust on data localisation seems to have started scaring them away.
Apple Inc has shelved plans to introduce Apple Pay, a Unified Payments Interface-based payments platform, in India, according to The Economic Times. This development comes at a time when WhatApp Payments and Amazon's plans to launch its own UPI payment service in the country have run into regulatory trouble.
"Apple will not launch payments in India yet. They are waiting to see how the regulatory landscape shapes up," a source told the daily. That's a U-turn from the company's stance less than a year ago. "What Apple Pay does is make that process easy, integrated and safe. We absolutely want to bring Apple Pay to the market here," Eddy Cue, Apple's senior vice-president for internet software and services, had told the daily last October. Apple Pay is currently available in Australia, Canada, Mainland China, France, Hong Kong, Ireland, Italy, Japan, New Zealand, Russia, Singapore, Spain, Switzerland, the UK, the US, and Taiwan.
People in the know told the daily that although Apple had held discussions with a few leading banks and the National Payments Corporation of India, which manages the UPI platform, the Silicon Valley giant's main worry is the RBI's recent data localisation rule.
In April, the apex bank had released a 'Statement on Developmental and Regulatory Policies', which announced that "all payment system operators will ensure that data related to payment systems operated by them are stored only inside the country within a period of 6 months". The idea, it said, was "to have unfettered access to all payment data for supervisory purposes".
Subsequently, the Justice Srikrishna Committee report on Personal Data Protection also recommended that every data fiduciary has to store one live, serving copy of personal data in India. The draft personal data protection bill is currently open for public feedback, which the government yesterday extended the deadline for comments till the end of this month.
The RBI's diktat has not only put the brakes on Apple's plans, but also landed several other foreign companies in a regulatory grey zone, including Mastercard, Visa, Amazon, WhatsApp and PayPal. Even Google, which recently rebranded its India payment app from Tez to Google Pay, has said that it is assessing the evolving situation around data localisation, its aggressive plans for a bigger share of the market notwithstanding.
Apart from regulatory hiccups, Apple had also run into technical and design hurdles related to the flow of payments on UPI. Citing a banker, the daily added that Apple wanted to include fingerprints as a mode of authentication for UPI payments, instead of the typical six- or four-digit number used for the purpose, but NPCI had refused. "NPCI has prescribed that transactions can be authenticated by biometrics only when they get validated by UIDAI [the Aadhaar-issuing body]," said the banker, adding, "NPCI does not allow biometrics collected by devices as a mode of authentication."
Apple, in fact, has been facing headwinds in the country on other fronts too, be it churn in its India leadership team or running into an impasse with the telecom regulator over supporting its do-not-disturb (DND) app. The iPhone maker finally agreed to include about 75% of the features of the DND app in its new operating system last month.


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At Path Coffee Roasters, we want you to know that our coffee is important to us. We are a small family company, and our primary focus is on providing exceptional customer support.
Specialty coffee isn’t just one thing. It’s the culmination of a few essential processes that all have to work in unison. In many cases, the term specialty coffee is pinned solely on green coffee and how it is grown and processed. However, if you only focus on green coffee, you’re missing many other important aspects of the production process.
As a coffee roaster, sourcing green coffee is one of the most important aspects of what we do. To make sure we get the best coffee for our retail, wholesale, and drop shipping customers, we work with a selected group of farmers and exporter/importers that we have deep relationships with. These connections allow us to […]


New Bedford Trading Parking Lot for Paradise
They're tearing up a parking lot to put in paradise.
Construction on the new urban park where the Custom House Square parking lot now sits is scheduled to begin Friday. City crews will begin setting up fencing around the site, in preparation for the green space designed by New Bedford native Christopher Reed of Stoss Landscape Urbanism.
The new park, being funded by a $300,000 grant, should be finished by late summer.
Mayor Jon Mitchell says the goal of the project is to transform the underutilized parking lot into a central green space.


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JULIAN'S HOT WHEELS BLOG
My name is Julian and this is my blog for those who love Hot Wheels!
Check back regularly for new posts! Thanks for visiting, keep collecting!
Wednesday, March 16, 2016
Surf Crate (2015 Walmart Exclusive Zamac #16)
After all these years, the Surf Crate is still all metal! Though it did lose its removable surfboard feature, oh well. Still looks good as a Zamac car though!
Julian's Hot Wheels Blog
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domain: hobby