DRIVING REFINING CHANGE

A look at how automotive emissions legislation and the drive for energy

sustainability are impacting the refining industry (part 1)

The European Union (EU) has designated 2013 as “The Year of Air”, with issues

around clean air taking centre stage during environmental policy discussions

throughout the year. That the European Commission is collaborating with the World

Health Organisation on this matter is a strong message that air quality is a major

concern in Europe and globally.

Both recent - and upcoming - legislation on automobile emissions has become the

major change agent within this environmental arena. As with all legislation, regulation

around emissions levels the playing field for all stakeholders in the automotive industry,

effectively ensuring a competitive business climate. All participants must adjust their

operations to comply with the latest regulations, leaving no-one at a competitive

disadvantage.

Legislation also has the purpose of setting common targets within geographic

economic zones such as the USA and the EU, aligning the many diverse organisations

involved in automotive R&D and the production supply chain through common goals

and objectives. This ensures that consistent standards are set for the industry and that

change applies across the board, with all players being measured by the same

performance yardstick.

In this industry R&D to improve the environmental performance of vehicles demands

substantial investment. A high level of technical complexity is involved, with great

reliance on first and second tier suppliers, who are among a vast number of partners in

the automotive value chain. Therefore, when all these technology partners work

towards a clear and common target, such as limiting the amount of carbon dioxide or

nitric oxide emitted from a car, the fragmented value chain aligns all its resources to

achieve this common objective.

Another common benefit of legislation is that it creates an enabling environment for

cost effective transfer of technology, by broadly communicating best practice to

achieve the required changes - for example, offering guidance on the latest analytical

measurement instrumentation.

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An excellent example of technology transfer is the Euro IV, V and VI emission

standards developed for European markets that have been adopted elsewhere in the

world, for example South Korea and China. Europe has successfully prescribed targets

and adopted relevant and useful technology to achieve targets, and this effective

approach is being replicated elsewhere.

Today there are three main global legislation groups related to automotive emissions

coming out of Europe, the USA and Japan. European legislation is already progressing

towards Euro VII, while in the USA, the Environmental Protection Agency (EPA) takes

a leading role. The USA also has federal environmental legislation, as well as certain

state-specific regulations and one of the most common terms, “ultra-low emissions

vehicle” (ULEV), in fact, derives from California state legislation. There is also a

formidable legislative movement in Japan, since a large number of automotive

producers originate in that country. China, however, which also has a substantial

automotive industry in terms of the number of production centres, tends to take its cue

from European legislation.

So, what are the common goals of all this disparate geographical legislation? Firstly,

legislation seeks to drive fuel economy by developing more economical ways to move

people and goods from A to B, in order to conserve the world’s dwindling fossil fuel

resources for future generations. There are also economic benefits associated with the

issue of fuel economy, as the more economic it is to move people and goods, the more

competitive a market will be. The other key goal of legislation is to mitigate the effects

of damaging automotive emissions, such as carbon dioxide, on climate change. This is

also closely linked to the goal of fuel economy, as the less fuel we burn, the fewer

emissions are released into the atmosphere.

Environmental impact

In terms of climate change the industry also looks at other greenhouse gases with

global warming potential (GWP). An example is nitrous oxide, which has a much higher

GWP than carbon dioxide, but because it exists in relatively low quantities in the

atmosphere, it attracts less headline press. Other issues exist around particulate matter

and soot and there is a more recent focus on minimising the emission of any substance

that has stratospheric ozone depleting potential, since stratospheric ozone’s role is to

absorb potentially harmful ultraviolet rays from the sun.

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For the first time, greenhouse gases such as carbon dioxide and nitrous oxide are

being included into US EPA protocol gases. Not that long ago, these greenhouse

gases were introduced in addition to - what was previously referred to - as the criteria

pollutants - the six most common air pollutants of concern: ozone, carbon monoxide,

nitrogen dioxide, sulphur oxides, particulate matter and lead. This is a significant step

forward that could even be described as a fundamental evolution in legislation, not only

towards controlling toxic gases, but also those which contribute to global warming.

Automotive emissions such as nitrogen dioxide and sulphur dioxide must also be

controlled to protect our physical environment. These emissions can react with

rainwater and create acid rain that damages forests and buildings, since it reacts with

limestone and concrete to corrode structures. Ground water contamination is another

concern, since the chemicals benzene and MTBE (methyl tertiary-butyl ether), added to

improve engine combustion, are also damaging when they are washed down in rainfall.

Public health

With a strong historic US EPA focus on so-called criteria pollutants, much automotive

legislation has been structured around public health issues, resulting in tightening

emission targets. It is noticeable that there has been a tangible move from purely

monitoring automotive emissions, to monitoring the ambient environment - including

detecting the presence of chemicals in the air that the public is breathing. A significant

section of legislation is moving into prescribing exactly what should be measured in the

ambient environment, how often it should be measured and in which locations. And

there is more data transparency around these findings than ever before, giving the

public real time access to this important information.

Improving public health by controlling air quality is a key focus of automotive legislation.

Air quality must be maintained at a level that ensures it does not cause disease. With

this in mind, there is a contemporary focus on minimising ground level ozone that has

the potential to damage the human respiratory tract and is produced principally by a

reaction between nitric oxide and volatile organic compounds (VOCs).

Carbon monoxide is a prevalent gas in automotive exhaust systems that, in enough

quantity, can damage the nervous system, while formaldehyde gas is categorised as a

“probable carcinogen” and, like ozone, has the potential to cause respiratory problems.

Benzene is a VOC that not only contributes to the ground level ozone problem, but is a

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toxic chemical and pollutant in its own right. It is a known carcinogen that can be

inhaled from the atmosphere or absorbed into the human body by eating contaminated

fish and crops. Nitrogen dioxide, ammonia and sulphur dioxide are other examples of

gases that can cause health problems by weakening the respiratory system and

rendering humans more susceptible to illness. Chemicals like this must be reduced or

completely eliminated from automotive emissions.

Cohesion of the issues

Any legislation framework must address these problems effectively, but how do these

issues all cohere in a matrix? On the issue of fuel economy, the USA has two sets, or

"tiers", of emission standards for light-duty vehicles, defined as a result of the Clean Air

Act Amendments of 1990. Within the Tier II ranking, there is a sub-ranking ranging

from BIN 1–10, with 1 being the cleanest (zero emission vehicle) and 10 being the

dirtiest. These standards specifically restrict emissions of carbon monoxide, oxides of

nitrogen, particulate matter, formaldehyde and non-methane organic gases (non-

methane hydrocarbons).

President Barack Obama has recently called for America’s fleet of trucks, lorries and

cars to be elevated into the next category of environmental cleanliness and fuel

economy — BIN 4. This target cascades down to automotive producers to incentivise

them to make sure that the average vehicle being sold is moving to a progressively

more fuel efficient future.

The changing legislative environment relating to fuel economy is enabling the

introduction of new generation fuel types in a safe and consumer friendly manner. In

the United States all eyes are on E15 — fuel with a 15% ethanol blend — which will

soon be commercially introduced to that market. This could herald in a new era,

enabling the production and sale of a new generation of environmentally friendly fuels.

Many years ago it was decided to transition to unleaded fuels, a decision principally

taken to protect the catalysers installed in cars for the enablement of nitric oxide,

nitrogen dioxide and carbon monoxide emissions reduction. With catalysers becoming

prevalent, legislation was needed to facilitate the introduction of unleaded. And, to limit

the sulphur dioxide emissions that react with rain to create acid rain, ultra-low sulphur

diesel was introduced.

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However, legislation always needs to look ahead holistically to possible consequences,

so that the totality and end result of changes is truly beneficial. This is because,

inevitably, as one problem is solved, there are consequences of changes and in some

cases it might even become a case of “out of the frying pan and into the fire”.

Legislation would not be effective if it had this effect on automotive producers.

Therefore in seeking to create change in a particular area, it is essential to look at any

secondary implications the change is likely to create and to simultaneously mitigate

secondary outcomes.

An example is the ambition to reduce nitrous oxide emissions from car engines by

converting oxides of nitrogen simply into nitrogen itself. One way to achieve this is to

harness a technology called selective catalytic reduction (SCR) that converts nitrogen

oxides back to harmless nitrogen gas, using ammonia in the catalysers. However, in

trying to resolve the problem of nitrogen oxide emissions, urea is being added to create

ammonia in the catalyser and this could potentially lead to the secondary negative

impact of ammonia as an automotive emission gas. Ammonia must now also be added

to the list of emissions that must be monitored.

Another secondary impact of emission legislation involves carbon monoxide. The

principle reduction of carbon monoxide is achieved through catalytic convertors to

oxidise it to carbon dioxide, which is potentially a problem in its own right in terms of

global warming, but is considered preferable to emitting carbon monoxide. These

catalytic converters in turn reduce the overall fuel economy of the engine, so there a

compensating increase in overall engine efficiency is needed to ensure that the

introduction of the catalytic converter is having an overall beneficial effect.

It is evident that this is a complex legislative area that highlights the delicate balance at

play. Well-intentioned legislation may be able to solve one problem, but could also

introduce an unanticipated secondary risk that needs to be compensated for.

Legislators must find a way to arrive at a careful balance by trading off one chemical

consequence against another.

Recent or imminent legislative changes

In addition to greenhouse gases now being included in the US EPA protocol, for the

first time protocol standards for formaldehyde and ammonia have now been

introduced. Ammonia is being included at an emissions level of 10 ppm in the Euro VI

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legislation that will come into force in 2014 in Europe, with the automotive industry

already aligning itself to those requirements, elevating the subject of ammonia

emissions from diesel engines. Another impact of Euro VI will be the reduction of

oxides of nitrogen emissions, bringing diesel oxides of nitrogen emissions more closely

in line with petrol engine emission standards.

An interesting change is the move from, in UK terminology, “miles per gallon”, to

“grams of carbon dioxide emitted per kilometre travelled” as an emissions standard.

Miles per gallon refers to the amount of fuel required to travel a certain distance,

regardless of fuel type and the amount of carbon dioxide emitted by that fuel. With the

move to grams of carbon dioxide emitted per kilometre, there is a clear signal that

carbon dioxide is becoming the ultimate goal of measurement. It also recognises that

hybrid vehicles running on electricity, and therefore emitting no carbon dioxide, can

also fit into these legislative measures.

Another significant development with regard to Euro VI legislation refers to a trend

called “speciation” that focuses on the various chemical species present in the

automotive emissions. An example of this is the split of total hydrocarbons (THC) into

methane, which is a hydrocarbon, and non-methane total hydrocarbons (NMTHC).

Historically, emissions were measured in terms of total hydrocarbons, but in future we

will increasingly see a split between methane and NMTHC and this recognises that

methane has its own issues with regard to GWP. However it is the NMTHC that relates

to public health issues and this intensified focus will allow for better control of such

emissions.

Chinese legislation is moving forward very rapidly in this major market for auto

producers and consumers alike. Here the changes include a nationwide move from

Euro IV for diesel engines in 2011 a move to Euro IV for combustion engines in 2013.

Similar to the USA, legislation in China exists both at a national level and a more

specific, geographically targeted level, and in Beijing the legislation will move to Euro V

in 2013.

Analytical techniques

Euro VI legislation specifies that ammonia must be measured at a maximum level of 10

ppm in diesel and petrol engine emissions and this effectively requires the

measurement of a new molecule in our exhaust emissions. Legislation is only as good

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as its enforcement and this enforcement relies on effectively applying analytical

techniques to measure automotive emissions. One of the hidden benefits of this

legislation is that it points the industry in the direction of the most suitable technology to

accomplish this task.

Legislative requirements to measure new emission molecules must bring with them a

requirement for reliable, repeatable technology to conduct these measurements.

Legislation also explains to the industry how to perform this measurement in a

consistent and dependable way, for example, providing two types of technology

deemed to be suitable for ammonia measurement in exhaust emissions.

Both these technologies are described in detail in Euro VI legislation. The first

technology uses laser light tuned to a certain light frequency designed to be absorbed

by ammonia and other exhaust chemicals. In other words, a laser light is shone

through an exhaust emission to measure the chemical levels present. The other type

of technology for measuring ammonia in exhaust emissions is Fourier transform

infrared (FTIR) spectroscopy, based on the principle of shining infrared light through

the exhaust gas mixture and determining at which frequencies light is being absorbed

in order to assess which chemicals are present and at what concentration they occur.

The principle is the same for both technologies - absorption of light by chemicals.

Legislation also prescribes the types, traceability and degree of accuracy of calibration

gas mixtures needed to calibrate instruments used for these measurements. This

clarifies for suppliers of calibration mixtures, such as Linde Gases Division, which

mixtures they should be developing for this particular market. Detailed specifications

for pure gases which are used for gas chromatography or to zero instruments and for

fuel and oxidant gases which are used for flame based analytical detection methods

are also prescribed in the Euro VI legislation.

The other area of legislative change is the reduction in nitrogen oxide levels, also

prescribed in Euro VI. The technology referred to in this regard is chemiluminescence,

an analytical technique based on the emission of light spectra by the chemical

molecules. The industry is now seeing the reduction of nitrogen oxide levels in diesel

to a similar level that exists for petrol engines. It could therefore be argued from an

analytical techniques perspective, that this technology shift is not all that onerous, since

it is simply bringing diesel engines in line with the measurements currently required for

petrol engines.

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The future

Against this background of robust legislative change, it is interesting to speculate what

the future might hold by examining past trends and extrapolating them to determine

future legislative direction.

For the first time in the USA, the EPA protocol has issued standards for zero air. This is

important, because when setting up an analyser, a calibration gas is needed to

calibrate at the high end of the scale, as well as a zero gas to determine the zero of

that instrument. Both these gases are equally critical in setting up the instrument. For

many years, the EPA protocol has regulated on the calibration gas mixture required for

the high end of the scale, but this is the first time that standards for zero air have been

set. At present, the requirement to use this zero air standard is voluntary, but industry

stakeholders can speculate that it will become mandatory in the near future.

On the issue of speciation, with the increasing concern about nitrogen dioxide, nitrous

oxide and nitric oxide emissions it is very likely that future legislation might mandate

measurement and control for each one, instead of for the total oxides of nitrogen that is

in place at the moment. With more speciation taking place within the total

hydrocarbons, there is likely to be further speciation within the total hydrocarbons

element, looking specifically for molecules such as ethanol and formaldehyde, the new

potential pollutants arising from the move towards biofuels and LNG. The industry

could therefore also be moving towards a requirement to measure particular chemical

species within automotive emissions going in the direction of ethanol, formaldehyde

and specific oxides of nitrogen.

Exhaust after-treatment is perhaps one of the most dynamic parts of the auto industry

right now. The companies involved in producing the catalysers and the overall after-

treatment systems are facing an enormous technological challenge to keep up with the

pace of change. Here, in addition to SCR, exhaust gas recycling (EGR) is coming to

the fore, representing two very fundamental changes in exhaust gas treatment

technology to reduce harmful emissions from the engine.

The other area of considerable change is the sophistication of engine management

systems (EMS) or on board diagnostic systems (OBD). Emissions are now being

controlled by these micro-computers which rely on multiple engine sensors responsible

for ensuring the engine is working at optimum fuel efficiency and releasing minimum

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emissions. In this regard the industry is seeing a whole new suite of regulations being

targeted to ensure these systems are stable and that they function correctly.

Finally, the increasing use within the industry of gases that comply with US EPA

protocols, or relevant ISO standards relating to the traceability and accuracy of

calibration gas mixtures, such as ISO17025 will be of great consequence to companies

like Linde, which support measurement technology with accurate and consistent

calibration gas mixtures across the EU and other legislative groups. Applicable

worldwide, these standards will make sure that international automotive producers and

environmental agencies working in this arena are working from a uniform base.

In our September issue – our Clean Energy issue – Linde will continue to examine the

impact on refinery end-products with a discussion on the effect of the sustainable

energy drive.

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DRIVING REFINING CHANGE

A look at how automotive emissions legislation and the drive for energy

sustainability are impacting the refining industry (part 2)

In the first part of their discussion on the drivers affecting change in the refining

industry, Linde’s Stephen Harrison looked at recent automotive emissions legislation.

He now continues story with the search for alternative and sustainable fuel sources.

Alternative fuels

As the demand for sustainable fuels intensifies, there has been a marked convergence

of plant science, biotechnology, crop science and petrochemical refining over the past

ten years. Fossil fuels are being progressively depleted and professionals in these

arenas are collaborating in the pursuit of sustainable alternative fuel sources that will

reduce future dependence on traditional petroleum products.

The quest to develop fuels from other sources is being driven by geopolitics as much

as it is influenced by legislation. Security of oil supply is a growing concern among

countries who import massive quantities of oil for transportation fuel. A desire to

establish a sustainable economic strategy by reducing expenditure on oil imports is

another factor in play. So while major fuel consuming countries like China will continue

to import oil from leading suppliers in Middle East, Venezuela and Brazil, there is an

unprecedented trend aimed at achieving greater geopolitical self-sufficiency through

the development of local biofuel production capabilities based on plant science. This

trend recognises that fuel sources which harness the continuous energy of the sun to

produce crops are both sustainable and cost efficient.

The current decade has heralded some dramatic changes in the fuels being used in

both the automotive and aviation sectors. These biofuels are sometimes introduced to

conventional fuels as additives or, in other applications, are wholly used as 100%

biodiesel from rapeseed oil or other biological sources.

Finnish company Neste Oil is a leading example of a refining operation that produces

biofuels and refined petroleum products derived from biological sources, notably

biodiesel. A major portion of Neste Oil's annual R&D investment goes to research into

renewable raw materials and refining technologies for processing these materials.

Neste Oil is involved in research involving completely new raw materials – such as

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microbes, algae and wood-based biomass – and existing alternatives, like waste fat

from the fish processing industry. The company selects the focus of its raw material

research based on availability, price and sustainability.

Neste produces NExBTL diesel, which is a hydrodeoxygenated (HDO) paraffinic fuel,

as opposed to traditional transesterified biodiesel. In 2007, the entire bus fleet owned

by Helsinki Region Transport switched fully to NExBTL. Experiments by Neste, VTT

Technical Research Centre of Finland and Proventia showed that local emissions were

decreased significantly, with particle emissions decreased by 30% and nitrogen oxide

emissions by 10%, with excellent winter performance and no problems with catalytic

converters. In Finland, Neste brought two renewable diesel plants, located at the

Porvoo refinery, on stream in 2007 and 2009. Together, these produce 0.525 million

tons annually, which is approximately one fifth of the diesel consumption in Finland. In

2010, Neste completed its third renewable diesel plant in Singapore. Producing

800,000 tons annually, it is the world’s largest renewable diesel plant. A fourth plant of

the same capacity was brought on stream in Rotterdam in 2011.

Thailand’s state-owned PTT oil and gas company announced last year that it planned

to develop algae biofuel in collaboration with Australia’s Commonwealth Scientific and

Industrial Research Organisation. PTT plans to transfer algae knowledge back to its

own research facilities and is also considering investing in algae biofuel production in

Australia in the near future. Though the project development is still in its first phases

PTT hopes to introduce algae biofuel into the market by 2017.

Established refineries that wish to follow the same route will need to implement

technological changes focused on feedstock handling that will enable them to process

agricultural products such as rapeseed oil instead of crude oil.

Methane

A stop/start driving profile is the most difficult cycle for any vehicle’s engine, resulting in

production of the highest level of toxic emissions when conventional petrol or fuel is

consumed. This profile is typically associated with buses and garbage collection trucks

operating in urban areas and, to mitigate emissions, an increasing volume of these

vehicles is now being run on Liquefied Natural Gas (LNG) or natural gas.

This natural gas, also known as “biogas” or methane, can be sourced from natural

underground sources or is produced as a by-product of the waste water treatment

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industry, where contaminants from wastewater and household sewage, both runoff

(effluents), domestic, commercial and institutional are removed from water. One of the

two principle technology routes harnessed by this industry to purify water is anaerobic

digestion, which is a collection of processes by which microorganisms break down

biodegradable material in the absence of oxygen. Anaerobic digestion produces

methane gas as a by-product, while the alternative purification technology — aerobic

treatment that harnesses pure oxygen or ambient air — does not produce methane.

It’s clear that as the significance and number of applications of biogas increases, the

value of natural gas will go up, prompting a shift in water treatment technology towards

the anaerobic method in order to produce a by-product that has a useful economic

value. This in turn will lead to a change in waste water treatment infrastructure in favour

of anaerobic sludge digesters.

The handling of biogas from waste water treatment works is very similar to the handling

of natural gas from other sources, since it typically remains in a gaseous form as a

compressed high pressure natural gas. The gas arising from natural resources is

generally converted to LNG so that it can be easily moved around the world in tankers.

Handling biogas as a source of methane presents a challenge to the refining industry

because, although the same chemical is involved, the handling of a high pressure

compressed gas requires different technology and different storage mechanisms in the

form of high pressure cylinders, as opposed to the cryogenic technology required for

LNG. Regardless of source, natural gas is poised to become an important fuel of the

future, rendering the correct sourcing of technology associated with handling high

pressure compressed natural gas increasingly important.

Ethanol

The properties of ethanol as a fuel for transportation are quite similar to the properties

of the regular petrol currently used in today’s vehicles. Ethanol can be derived from

crops such as sweetcorn, which is converted to ethanol by fermenting it in a similar

process to producing beer and wine. The process removes sugars from the sweetcorn

and converts them through a process of biological fermentation to produce a mixture of

water and ethanol. This mixture is then distilled to produce pure ethanol, which can be

added to petrol.

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This process creates a strong link between agricultural science and biotechnology and

brings these two worlds close to the heart of petrochemical processing and refining. In

Europe today most automotive fuels contain 10% ethanol and 90% fossil fuel petrol

derived from the distillation of crude oil from fossil fuels. In the USA recent legislation

has allowed the use of 15% ethanol in fuel and this development foreshadows higher

percentages of ethanol in fuel in the not too distant future.

Ethanol production within a refinery involves the production of the ethanol via a

fermentation process, followed by the distillation of the ethanol away from water to

produce pure ethanol, and finally the blending of the ethanol with conventional fuel.

These are relatively new process steps and time will tell if they will be progressively

incorporated into the petrochemical industry, or will lead to the establishment of

factories dedicated to producing pure ethanol which will also perform the blending

operation.

In a certain number of cases, instead of producing distilled ethanol from agricultural

crops, refineries simply create ethanol through chemical synthesis by introducing a shift

in their product mix.

Research into next generation transportation fuels incorporating as much as 85%

ethanol is gaining momentum in automotive test centres and emissions testing

laboratories around the world, particularly in major fuel consuming nations like China,

whose government and automotive sector are key sponsors of this research.

The upstream implications for the petrochemical sector as it adjusts to the production

of greener fuels are many. Where refineries were originally built to process fossil fuels,

huge changes in technology will be necessary, incurring substantial capital costs. In

many cases it will not be possible to adapt existing processing equipment to suit the

new processes and new equipment will be required.

Emissions

Combustion reactions between the new fuels and oxygen in a vehicle’s engine herald

the advent of different emissions into the atmosphere. In a perfect world, the ideal by-

products would be carbon dioxide and water, but other emissions leak through the

system as a result of engine imperfections. When using ethanol or methanol in an

internal combustion engine, or when using biogas in a liquefied natural gas (LNG)

vehicle, different molecules are being introduced into the engine. They burn in different

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ways and have a different footprint of emission molecules. Methanol in fuel, in an

internal combustion engine, produces formaldehyde as an emission. In effect, a new

pollutant has gained entry as a consequence of trying to introduce more

environmentally friendly fuels and it must be added to the list of emissions to be

monitored and regulated.

This is a challenge that lies at the doorstep of the automotive manufactures, rather than

the petrochemical refineries, and obliges vehicle producers to take a long, hard look at

the impact of this new emission molecule that will be added to the environment watch

list. Measuring this molecule in automotive emissions must be highly accurate and this

calls for accurate calibration gas mixtures. Linde Gases Division is poised to meet

increasing demand for these precise mixtures of low concentrations of formaldehyde in

nitrogen from its specialty gas range for the optimal function of analytical

instrumentation.

This being said, ethanol falls into the category of Volatile Organic Compounds (VOCs)

which are coming under intense scrutiny by environmental authorities. The release of

VOCs from industrial processes not only poses a potential hazard to human health, but

can also represent a threat of financial losses to the operator. The trend towards

biofuels means refineries will handle higher quantities of ethanol than in past decades,

calling for amplified monitoring measures in and around the plant as a required

environmental control measure.

As ethanol percentages in fuel are stepped up, methane emissions monitoring and

control will also be required in greater measure in and around urban filling stations — a

potential challenge that has not confronted towns and city managers before now.

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