Future perspectives for biofuels in road transport

The promotion of biofuels is a political priority and part of the European energy-climate policy. The EC Directive 2009/28/EC on the promotion of the use of energy from renewable sources introduced a binding target of 10 % share of renewable energy in transport by 2020. For this target, biofuels will make a substantial contribution. In addition, Directive 2009/30/EC allows for the blending of ethanol into petrol up to 10 % (v/v) and for a FAME content of 7 % (v/v) in diesel.

In 2013, the European Parliament stated its intention to place a 6 % cap on first-generation biofuels and a 2.5 % incorporation threshold of advanced biofuels, produced from waste or algae, but these initial ambitions were cut down in the draft directive on the change of land use (June 2014). This agreement imposes a minimum level of 7 % of final energy consumption in transport in 2020 for first-generation biofuels and does not provide for a binding incorporation target for advanced second and third generation biofuels. The agreement is still in a draft version, a final decision is expected for 2015 (EurObserv’ER 2014).

Future expansion of biofuels in road transport up to 2020 and beyond depends on a favourable regulatory environment for advanced biofuels value chains, in particular to support:

·   availability of more diverse feedstocks including energy crops, wastes and residues

· demonstration of innovative thermochemical, biochemical and chemical conversion technologies at commercial scale

·  market development of advanced biofuels through support mechanisms at national and EC level

Global expansion of biofuels use in road transport also depends on the ongoing development of:

·   CI and DI engines able to use higher blends of ethanol and diesel

· the development of drop-in biofuels with properties 'near-identical' to their fossil fuel counterparts. Drop-in fuels can be used in standard engines at much higher blend levels than conventional biofuels, or even at 100% with similar performance.

Reverse Photosynthesis Makes Biofuel

Photosynthesis, as you are probably aware, is Kind Of A Big Deal. It’s the process by which plants, algae and other organisms convert sunlight into chemical energy.

Scientists at the University of Copenhagen figured out reverse photosynthesis — using sunlight to convert plant biomass into usable fuel. The process could radically transform the industrial production of plastics and chemicals.

A given amount of biomass – straw or wood, for instance – is combined with an enzyme called lytic polysaccharide monooxygenase, found in certain fungi and bacteria.

When chlorophyll is added and the entire mixture is exposed to sunlight, sugar molecules in the biomass naturally break down into smaller constituents. The resulting biochemicals can then be more easily converted into fuel and plastics.

The key is using the very energy of sunlight itself to drive the chemical processes. By leveraging the power of the sun, reactions that would otherwise take 24 hours or longer can be achieved in just 10 minutes, researchers say.

That means faster production, lower temperatures and enhanced energy efficiency in industrial production.

Photosynthesis by way of the sun doesn’t just allow things to grow, the same principles can be applied to break plant matter down, allowing the release of chemical substances. The immense energy in solar light can be used so that processes can take place without additional energy inputs.

Effect of Biodiesel in ignition delay and levels of NOx emitted

Biodiesels have generally been found to exhibit a shorter duration of ignition delay (the interval between fuel injection and autoignition).

An increase in the fatty acid ester alcohol moiety alkyl chain length can reduce the duration of ignition delay, while the presence of carbon chain branches in the alcohol moiety can increase the duration ignition.

However, the impact of the alcohol moiety on ignition delay is less than the fatty acid moiety, and so where a specific ignition delay of a biodiesel is required, this is best achieved through modification of the fatty acid profile.

In direct injection common rail compression ignition combustion, the primary influence of the biodiesel composition on the levels of NOx emitted is through the duration of ignition delay.

Longer ignition delays result in a larger premixed burn fraction and peak heat release rates, which increase the rates of thermal NOx production.

In mechanically actuated fuel injection, biodiesel bulk modulus, which increases with alkyl chain length and degree of unsaturation, has a significant influence on the time at which fuel injection commences and thus the residence time of in-cylinder gases at elevated temperatures at which NOx formation occurs.

Therefore, it be may be advantageous to utilize different biodiesels of compositions optimized for lower NOx emissions in common rail and mechanical fuel systems respectively.

Making biodiesel with used cooking oil and a microwave

Using a microwave and catalyst-coated beads, scientists have devised a new way to convert waste cooking oil into biodiesel that could make it more affordable. They report how they did it in ACS' journal Energy & Fuels.

Biodiesel has many advantages over traditional fuels. It is renewable, biodegradable and emits less carbon dioxide. It can also easily take the place of conventional diesel without the need for carmakers to modify engines. However, producing biodiesel at a low cost remains a challenge. Waste cooking oil is currently the most appealing source because it doesn't compete with the demand for virgin cooking oil. However, the process to convert it to fuel is complicated and expensive.

The researchers developed silica beads coated with a catalyst and added them to waste cooking oil. Then, they zapped the mixture with a modified microwave oven to spur the reaction of the beads with cooking oil. In just 10 seconds, nearly 100 percent of the oil was converted to fuel. The researchers could also easily recover the beads and reuse them at least 10 times with similar results.

MacroFuels – Third Generation Biofuels from Seaweed

In the last decade, seaweed has received increasing interest worldwide as potential source of advanced biofuels production, which has resulted in a considerable attention from research, industry and policy makers. However, no large-scale, commercial algae-to-biofuels facilities had yet been implemented by the end of 2015.  Over the next four years experts from six European countries will concert their efforts to achieve breakthroughs towards the commercially viable production of third-generation biofuels from seaweed or macro-algae. In their efforts they will be financially supported by the European Commission who funds the MacroFuels project with 6 million Euros from their Research and Innovation programme ‘Horizon 2020’.

While current biofuels compete for scarce cropland, fresh water, and fertilizers, seaweed does not need fresh water, arable land or fertilizers to grow. In addition, seaweed beds can serve as a significant CO2 sink resulting in environmental benefits of seaweed derived biofuels and high value co-products.For improved cultivation MacroFuels will use 2D substrates based on advanced textiles to facilitate open sea cultivation. These patented and award winning substrates have been developed in the previous project (funded by the European Union under FP7) with the participation of several MacroFuels partners, and yield 3-5 times more biomass than state of the art 1D rope based systems. A rotating crops technology in combination with advanced textiles will further increase the biomass per area yield.

MacroFuels will achieve the following urgently needed technological and process-oriented breakthroughs which will make it possible for seaweed-derived biofuels to eventually compete favourably with fossil or older generation equivalent fuels.

·    Improve the efficiency of the seaweed-to-biofuels conversion technologies, which are currently in their infancy.

·   Vital breakthroughs in terms of pre-treatment and bioconversion of algae sugar to ethanol and butanol as well as thermal chemical conversion to furanics based biofuels. Significant efficiency improvements will be made by reducing the water through chemical and enzyme usage in the pre-treatment steps. Water reduction of more than 50% and total elimination of process steps will be achieved.

·      Quadruple the output on the same amount of substrate while decreasing the production cost of the seaweed raw material by a factor 10.

·  Creation of about 15,000 jobs based on the EU target of 2.5% biofuels which corresponds to 5000 km of cultivated seaweed area.

Hazards associated with biodiesel production

Regardless of the scale of operation of a biodiesel plant the hazards are the same: a combination of flammable, toxic and corrosion hazards depending on the stage of the process. In particular:

Methanol

This is a highly flammable and toxic liquid. It will freely burn in the open air or explode if confined in a vessel or room and ignited. Whilst all precautions should be taken to avoid leaks of flammable vapors into the workroom, leaks and spillages may still occur and it is necessary to take further precautions to reduce the likelihood of their ignition. In areas where such materials are handled, companies are required to identify the areas where flam­mable atmospheres may exist, for example due to a leak, and determine their likely extent. Such areas are classed as hazardous and should be classified into zones, depending upon the likelihood of their occurrence. In such areas ignition sources such as naked flames should be excluded and only suitably protected electrical equipment should be used. It should be noted that the presence of metha­nol can also render the product and any waste materials flammable, depending upon the way the biodiesel is manufactured.

The catalyst

Most of the catalysts used for biodiesel production are corrosive and some of them are violently water reactive, toxic, explosive and highly corrosive.

Feedstock oil

If clean and pure it should not be a health problem. However, if the source is unknown or of doubtful quality, then it should be treated as contaminated. Oils are a serious slipping hazard if spillage or contamination outside sealed vessels occurs. Oils can seep into lagging and many can self-combust following a period of chemical degradation. All oils are combustible and will add fuel to any developing fire.

Glycerol

This material is combustible (with a flash-point of 160°C). However, it may be contaminated with methanol and caustic, with their associated hazards, including a potential reduction in flash-point. Unless the initial by-product quality is reliably monitored, then prudence dictates that it should be regarded as contaminated until it has been suitably purified.

Biodiesel

If certified to EN 14241 : 2003  it may be regarded as combustible (its flash-point is approximately 150°C). It has rather unusual solvent properties, and will attack some common engineering polymers, including polyvinyl, natural rubber, some gasket and hose materials and metals, including copper, tin and zinc5. The effect can increase with heating and ageing of the biodiesel. It is also hygroscopic, and can absorb up to 1500 ppm water from the air. If even slightly contaminated with acid or alkali, biodiesel may be hydrolyzed to fatty acids and methanol. This reaction also occurs more slowly in the absence of water, so material stored for more than a couple of weeks may show evidence of a different flash­point than anticipated (which may be significantly lower). Unless this can be reliably prevented, then the product should be used as quickly as possible after production, or reclas­sified and stored and handled accordingly.

Wash water

This may be contaminated with acid, alkali and methanol. It should be treated as corrosive, toxic and flammable unless tests determine otherwise.

Reaction hazards

The main reaction hazards identified are in the preparation of the base catalyst, which can be by one or more of the following methods:

- The direct addition of sodium or potassium to methanol: this reaction is very exothermic and should be the subject of a rigorous risk assessment, particularly as molten sodium is spontaneously combustible in air and the reaction produces hydrogen as a by-product. Fortunately this route is not generally available to smaller/domestic producers.

- The addition of dried hydroxide or methoxide to methanol which is also very exother­mic (heat of dilution)

A much gentler heat of reaction is produced if the catalyst is supplied in methanol solution (although this has to be manufactured safely elsewhere), and further diluted to the required strength on plant. This is normally the preferred option for smaller companies.

A further reaction hazard occurs when concentrated mineral acid is mixed with water. Addition of water to acids often results in violent boiling and ejection of the acid from vessels. Acids should be added slowly to water with cooling and agitation.

  

General hazards

These include:

- Corrosion of processing equipment, building fabric, and supporting structures through exposure to caustic and acids leading to premature weakening and catastrophic failure. A by-product of the corrosion process is hydrogen,

- Biodiesel can soften and dissolve a variety of polymers commonly used in safety equipment, such as plastic aprons and rubber boots, causing premature failure.

Sodium Methylate as a catalyst for biodiesel industry

Growth in the biodiesel market is spurring two small companies to invest in U.S. production of sodium methylate, a catalyst used to convert fats and oils into the renewable fuel. These Davids will be going up against two biodiesel catalyst Goliaths, the German chemical makers BASF and Evonik Industries.

New Heaven Chemicals is starting up a plant in Manly, Iowa, that will make 18,000 metric tons per year of sodium methylate for biodiesel industry customers. Prasad Devineni, the firm’s director, says the plant is being commissioned and should be running in the next few weeks.

Although New Heaven will be new to U.S. production, its parent company, India’s TSS Group, has been importing sodium methylate from Saudi Arabia since 2006, Devineni notes. New Heaven anticipates building a second, similarly sized, sodium methylate plant in Houston.

Meanwhile, Interstate Chemical is advancing plans to produce sodium methylate in Erie, Pa., to serve customers such as the nearby firm Hero BX, which calls itself the largest biodiesel maker east of the Mississippi.

Interstate says it will spend $60 million to build plants for sodium methylate and methanol, the latter of which is reacted with sodium hydroxide to make the catalyst. Interstate has been producing sodium methylate for close to 10 years using an older process that starts with sodium metal. The firm’s plan to invest in the newer route follows DuPont’s decision to close its sodium facility in Niagara Falls, N.Y.

U.S. biodiesel consumption has enjoyed a meteoric rise from less than 100 million L in 2004 to almost 8 billion L in 2015, according to the National Biodiesel Board. During those years, Evonik erected sodium methylate plants in Alabama and Argentina. BASF built in Argentina and Brazil.

However, the years ahead may not be as heady for the catalyst newcomers. U.S. imports of biodiesel are on the increase. And a growing portion of biodiesel is so-called renewable diesel, which is made via a hydrotreating process that doesn’t require sodium methylate.