WORLD PETROLEUM CONGRESS

Rio de Janeiro, 1-5 September 2002 Forum 11: The Future of Aromatics in Motor Fuels and its Impact on Refining and Petrochemistry

Aromatics in European Motor Fuels: sources, rationale and strategies to meet year 2000/2005 limits, impact on costs and CO2 emissions
Jean-Franois Lariv, Neville Thompson CONCAWE, Brussels Abstract
European motor fuel specifications have changed dramatically in recent years. This has included a reduction of the benzene content of gasolines to less than 1%, the introduction of a maximum limit for total aromatics in gasolines and polyaromatics in diesel. Total aromatics in diesel are also indirectly limited by increasing cetane and decreasing density specifications. These new limits, associated to the improvements in vehicle emissions partly enabled by the reduced sulphur content of the fuels, have already reduced the contribution of road transport to total emissions and are set to further dramatically reduce this contribution in the coming decade. As vehicle exhaust after-treatments become more efficient, the absolute level of emissions decreases and the impact of the fuel quality becomes increasingly marginal. The already implemented and foreseen changes in motor fuel specifications have had and will have major consequences for refinery operations, affecting the whole product chain. They have and will require major investment programmes and also result in an overall increase in CO2 emissions. As competition for desirable components increases, the quality of the feed to petrochemicals is likely to worsen. As long as the spark ignition engine dominates the gasoline vehicle market, aromatics will play a vital role in providing both the quantity and high-octane quality of the required fuel. Further changes in road fuel quality would not give significant improvements in air quality but could have major implications in terms of refinery investments, global CO2 emissions as well as available volumes.

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1.

Evolution of EU specifications affecting aromatics in road fuels

Aromatic hydrocarbons are an integral part of motor fuels. In gasolines they provide the bulk of the octane rating, the fundamental quality for a spark-ignited engine. In diesel they are part of the package of molecules found in the relevant virgin crude oil cuts and are also produced in catalytic and thermal cracking of heavier cuts. Over the years and particularly in the last decade, EU motor fuel specifications have been dramatically tightened. This has followed a general trend, supported mainly by concerns on the effect of road traffic on urban air quality. The USA, and more specifically California, has lead the world with regards to gasoline whereas diesel has also attracted great attention in Europe due to its much larger share of the personal car market. Table 1 summarises the main recent changes to EU specifications. Table 1: Evolution of EU gasoline and diesel specifications from the early 90s
1994 EN228 Max Max Max Max Max Max min 1000 5 500 150 1 42 18 2.7 60 46 50/10 35 10 1995 1996 2000 2005 2011
(1)

Year Gasoline Unleaded 95/85 ppm m/m Sulphur % v/v Benzene % v/v Aromatics % v/v Olefins % m/m Oxygen RVP (summer) kPa % v/v E100 Diesel (standard grade) CI CN ppm m/m Sulphur 3 kg/m Density T95 Aromatics PAH Lubricity
(1) (2)

min min Max min Max deg C Max % v/v Max % m/m Max m @ 60C Max

2.5 up to 80 40(s)/43(w) EN590 46 49 2000 820 860 370

(2)

500

51 350 845 360 11

50/10

10

460

The mandate date is still under debate and may be brought forward to 2008-9 Up to 3.7% at Member State discretion. Individual limits apply to specific coumpounds

The benzene content of European motor gasoline has been limited to 5% v/v for many years. Directive 98/70/EC reduced this limit to 1% v/v from 2000 and introduced, for the first time in Europe, limits on total aromatics in gasoline and on polyaromatics (PAH) in road diesel. This followed a similar trend in the USA where aromatics limits have also been introduced for some grades. A number of other parameters have also been changed, most notably sulphur, now due to be reduced below 10 ppm by the end of the decade. Also from 2000 the cetane number of diesel was increased from 49 to 51 while the maximum density was reduced to 845 kg/m3. These two new limits indirectly control the level of total aromatics in the fuel. It is important to realise that, in complex blends such as modern motor fuels, the different properties are not independent. Any change has a bearing on the type of processing and treating the refiners need to use and therefore on the volumes and quality of the various blending components. A new set of specifications leads to a new equilibrium and a new average quality of the actual products.

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2.

The focus on aromatics

Exposure of workers and the public at large to benzene, an acknowledged category 1 carcinogen, has caused particular concern and justified drastic reduction measures. Benzene can be released into the atmosphere through evaporative emissions from gasoline storage (fixed or mobile) or through vehicle tailpipe emissions. The former are directly related to the benzene content of the fuel while the latter are also influenced by the total aromatics content of the fuel. The reduction of the benzene content of gasoline to below 1% in 2000 essentially resolved the exhaust emissions problem while other measures including vapour recovery systems and reduction of the vapour pressure of gasolines, particularly in summer, curtailed emissions of benzene and more generally of volatile hydrocarbons from tankage. Other aromatics, such as toluene, xylenes or ethylbenzene are not recognised carcinogens, but their effect on vehicle emissions of benzene and other pollutants has been the focus of attention. Increasingly effective after-treatment systems and the introduction of lower sulphur fuels already have and are set to further dramatically reduce these effects.

3.

Effect of fuel aromatics content on vehicle emissions Gasoline

The relationship between benzene in the exhaust gases and benzene and other aromatics in gasoline has been extensively studied. In particular a literature survey was carried out by Technical Group 1 prior to the EPEFE programme [1]. Figure 1 shows the corresponding relationships for vehicles with and without a catalyst (Euro 1 standard). The catalyst predictably reduces emissions considerably. Although exhaust benzene is still notably affected by the fuel aromatics, the overall level of benzene emissions can be expected to be reduced even further as more advanced exhaust after-treatment systems are introduced to meet the more stringent Euro 3 and Euro 4 emissions standards.
120.0 Exhaust Benzene (mg/km) 100.0 80.0 60.0 40.0 20.0 0.0 0% 10% 20% 30% 40% 50% Benzene or non-benzene aromatics in fuel (%m/m) 40% non-benzene aromatics Catalyst cars 1% benzene Non-catalyst cars

Figure 1: Benzene in vehicle exhaust as a function of aromatics in the fuel In the EPEFE programme [2], diesel cars were found to have benzene emission level up to 4 mg/km, the maximum fuel quality effect being about 1 mg/km. As with gasoline, this is likely to be further reduced with the introduction of more efficient after-treatment systems required to meet Euro 3 and Euro 4 standards.

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The combination of measures taken so far in terms of vehicle emission limits, fuel quality and curbing of evaporative emissions is set to effectively solve the problem of benzene emissions from transport. Figure 2 shows actual and predicted benzene emission figures from various sources in Europe. While these measures have already resulted in a dramatic decrease of benzene emissions from road transport, their full effect will not be felt before the end of the decade in view of the rate of renewal of the vehicle population and other factors. By that time, the contribution of road transport to total benzene emissions will have dropped from around 70% in 1990 to about 15% of the total.
300 Benzene emissions (kt/a) 250 200 150 100 50 0 1990 90.0% 75.0% 60.0% 45.0% 30.0% 15.0% 0.0% 2020

Other mobile Road transport Process Combustion Agriculture Others Road % of total

1995

2000

2005

2010

2015

Figure 2: Benzene emissions from various sources in Europe

(Underlying data from EU Commission)

The EPEFE programme showed that a very large reduction of total aromatics from 50 to 20% would give a 10 to 20% reduction in hydrocarbons and CO emissions from catalyst cars but a similar increase in NOx emissions (8%). In contrast the introduction of Euro 4 vehicles with advanced after-treatment systems associated with low sulphur fuels will bring an order of magnitude reduction in all regulated emissions.

Diesel
In the case of diesel, early work in the USA suggested a link between regulated emissions and total aromatics content of the fuel. Later work, however, showed the importance of density and demonstrated that polyaromatics have more effect than monoaromatics. Polyaromatics have also come under scrutiny because of the carcinogenic nature of some of these compounds. Recent CONCAWE work has shed some light in this area [3]. Figure 3 shows the emissions of benzo(A) pyrene (B[a]P1) for light-duty vehicles for different fuels with varying content of polyaromatics. The quality of the fuel has a discernible effect for older technology vehicles (A and B) but this virtually disappears with more modern technology engines (C) and/or when an oxidation catalyst is installed (ACAT).

Benzo(a) Pyrene is a polyaromatic molecule widely used a marker for polyaromatics in the air quality debate 4

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2.0 1.8 B[a]P ( g/km) 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 5 10 15 Polyaromatics in fuel (IP391, % m/m)
Notes: The error bars show 95% confidence limits for the true mean value. The horizontal line shows the approximate contribution of blanks.

A B C ACAT Blanks

Figure 3: Effect of fuel polyaromatics content on B[a]P exhaust emissions of light-duty diesel vehicles CONCAWE recently evaluated the effects of cetane quality and total aromatics content of diesel fuels on the emissions of current Euro 3 vehicles [4]. Fuel effects were generally found to be small compared to engine technology effects and test variability. Despite the rigorous test design, statistically significant fuel effects were difficult to identify. These findings confirm that there would be no emissions benefits in reducing aromatics levels in diesel fuels. Increasingly efficient exhaust catalyst systems will become more widely used, further reducing the impact of the fuel quality. However, CONCAWE recognises that fuel effects need to be kept under review as new vehicle technologies emerge and is currently engaged in test work involving state-of-the-art engines and exhaust after-treatment systems that will provide further understanding of the interaction between fuel quality and emissions in more advanced systems. Finally it should be noted that the efforts to reduce emissions from road transport in Europe are paying off as evidenced by EU Commission projections shown in Figure 4. CO2 emissions are still expected to increase though, partly as a result of the additional processing necessary to produce the new fuels.

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140 Emissions, % of 1995 level 120 100 80 60 40 20 0 1985 CO NOx PM-diesel VOC Benzene SO2 CO2

1990

1995

2000

2005

2010

2015

Figure 4: Reduction of emissions from road transport in Europe

(Underlying data from EU Commission)

4.

Aromatics in gasoline: the quest for octane

The key property of a motor gasoline is its octane rating or its ability to resist self-ignition when compressed with air2. A high-octane fuel enables the use of a higher engine compression ratio and therefore a higher efficiency. The demand for octane has increased over the years. Levels have always been higher in Europe than in the USA or Japan, due to the quest for power from smaller engines and a higher emphasis on fuel economy. The standard EU premium grade has a rating of 95/85 RON/MON and accounts by far for the largest market share. A super grade (typically 98/88) is sold in limited quantities in most EU countries whereas a regular, typically 92/82 grade is still marketed in some countries such as Germany. Octane is related to the molecular composition of the fuel. Straight chain paraffins and naphthenes (saturated cyclic hydrocarbons) have poor octane ratings whereas aromatics, branched paraffins and olefins, have high octane values. Oxygenated compounds such as alcohols and ethers generally have very high blending octanes. The difference between RON and MON (called sensitivity) is a few points for paraffins but much higher for unsaturated molecules (10-12 points or more) and oxygenates. The refiner must therefore arrive at the correct blend of molecular species in order to produce, not only the quality, but also the volumes that the market requires. Because of the predominance of unsaturated molecules in the blend, the sensitivity of gasolines is high and MON rather than RON tends to be the constraining parameter. The molecular cocktail of virgin naphthas is such that their octane rating is generally very low, typically 65-75. The lighter fractions are improved by isomerisation, turning straight-chains into branched paraffins. The heavier fractions are reformed that is paraffins are cyclised and cyclic molecules are dehydrogenated to aromatics. The process is therefore an essential source of hydrogen (and in many refineries the only one), a commodity in increasing demand for hydrotreating of various streams. Most reformates are produced with RON values between 98 and 102 and contain between 60 and 75% aromatics. Virgin naphthas contain some benzene but also so-called benzene precursors or molecules which, during reforming, are converted into benzene. The two main precursors are cyclohexane
2

Octane rating is a performance property measured by comparison of the self-ignition tendency of a fuel with that of two standard fuels in a standard test engine. Two different sets of testing conditions are used resulting in a RON (Research Octane Number) and a MON (Motor Octane Number) rating. MON is lower than RON and is considered more representative of actual operation. The road octane number, (RON+MON)/2, is used as a single specification in the US whereas both numbers are separately specified in Europe. 6

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and methyl-cyclopentane. Benzene itself remains essentially unconverted through the reforming process. Both benzene and precursors content are strongly dependent on the crude oil origin. The extent to which the precursors are included in the reformer feed has a determining impact on the benzene content of the reformate. Large volumes of the world gasoline are produced via catalytic cracking of heavier cuts such as vacuum distillates and atmospheric residues. These cracked naphthas are strongly unsaturated, containing aromatics (including some benzene) and large amounts of olefins. Their octane rating is relatively high, typically 91-93 RON, although not high enough for the modern European premium grades especially in view of their high sensitivity. Catalytic crackers (FCC) also produce significant quantities of mixed C3 and C4 hydrocarbons. These and particularly the C4 fraction can be combined by alkylation to form C7 and C8 hydrocarbons. Addition of an organic lead compound was, in the past, an alternative way to boost the octane rating by typically 3-4 points. The elimination of lead, both on health grounds and to enable the 3-way exhaust catalyst, has removed this option. Alternative metal-based additives are available, such as MMT or Ferrocene. Their use is not widespread in Europe and there is a continued controversy on possible effects on engines and after-treatment systems. The whole of the octane requirement therefore has to stem from the molecular composition of the gasoline. Oxygenates such as alcohols or ethers also generally have favourable octane properties and have in recent years assumed an important role in gasoline manufacture, principally in the form of MTBE. Table 2 gives an overview of the typical octane values as well as availability of key blending components. Table 2: Typical octane values and aromatics content of some compounds and common blending components and relative availability in a standard refinery
RON Pure compounds Benzene Toluene Isooctane Blending components Reformate Isomerate Full-range cracked naphtha Alkylate MTBE RON-MON Aromatics %m 15 18 0 12 2 10-12 2 16 100 100 0 68-75 0 20-30 0 0 Benzene Relative availability %m % m on crude 100 0 0 2-8 0 0.5-1.5 0 0 12-20 3-5 10-15 2-3
Limited to 15% in blend by maximum oxygen specification

106 114 100 98-102 81-87 91-93 92-96 115

Only reformates and cracked naphthas have the potential to provide the bulk of the required volumes as well as octane levels. The sources of isoparaffins are limited and such components as isomerates and alkylates, although important, can only play a supporting role when it comes to producing the large volumes of gasoline required by the market.

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5.

Dealing with a reduction of gasoline aromatics content

A reduction of the aromatics content of gasolines must be compensated by an increase in other high-octane molecules. Refineries strive to achieve this through a combination of measures depending on the availability of alternative components.

Benzene
The new 1% benzene limit included in Directive 98/70/EC and introduced in 2000 in EU gasolines triggered a flourish of activity aiming at meeting that new limit with minimum octane loss and at minimum cost. The issue had to be dealt with in virtually all refinery configurations, although refineries without access to cracked naphthas had the most serious problems. Essentially two routes are available to refiners to reduce benzene: either not producing the benzene in the first place or separating it to either sell it or saturate it to cyclohexane. These options are not mutually exclusive and many practical solutions have used a combination of measures. Reformates have been the main source of benzene. Cutting the precursors out of the reformer feed has been widely used, thereby avoiding benzene make at the cost of a loss of reformate volume. This is achieved by changes in the way the naphtha splitter is operated, possibly involving a revamp to improve separation efficiency. The amount of precursors in the naphtha is very dependent on the crude origin but there is usually limited flexibility or justification to change the entire crude diet for the sake of reducing benzene. Precursor reduction combined with measures to reduce the proportion of reformate in the blend was in some cases sufficient to meet the 1% benzene limit. Such measures could include installation or debottlenecking of an isomerisation plant, installation of an alkylation plant or increased use of MTBE. In many cases this was neither sufficient nor practical and significant additional investment was required. Benzene is commonly separated through a reformate splitter. Benzene is a feedstock for the chemical industry and, in some cases, refineries concentrate it in a side-cut that is sold for recovery of benzene as a pure compound. Alternatively the isomerisation plant can be used to hydrogenate the benzene contained in light reformate. There is, however, a limit to the amount of benzene that can be allowed in the isomerisation feed in order to avoid large exotherms in the reactor when the benzene is hydrogenated. In some cases specific benzene hydrogenation plants have been installed.
Isomerisation Benzene-free isomerate Naphtha splitter (*) Full-range naphtha Reformer Option 1 Reformate splitter Low-benzene Heavy reformate Low-benzene Reformate splitter Option 2 Benzene-rich heart-cut to outside Hydrogenation Benzene-free heart-cut

(*) Elimination of benzene precursors may include changes in the cut-point and/or in the separation efficiency

Figure 5: Typical benzene reduction routes Such measures, essentially based on distillation and fractionation of existing streams, have by and large been sufficient to achieve the 1% benzene limit. Although the average benzene content of EU gasolines has effectively been reduced from about 3 to less than 1%, a large part of the benzene previously found in gasoline is not produced anymore. The dramatic increase in benzene availability that some analysts had forecast has not materialised.

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The residual benzene comes now more or less in equal parts from reformate and from cracked naphthas. Any further reduction of the benzene specification would require addressing the problem of removing benzene from both streams. At this level the options are limited. Solvent extraction of reformates, although applied for the production of BTX3 aromatics, has not been used specifically for the purpose of removing benzene from gasoline. This could be envisaged but would be very capital and energy intensive. The full-range cracked naphtha is often split into two or three cuts to provide optimum blending flexibility and, more recently, sulphur removal. Benzene can be concentrated in the heart-cut, a stream that is sometimes hydrotreated and reformed because of its comparatively low octane. In this way the bulk of the benzene can be concentrated in the reformate and dealt with accordingly. Directionally though, this entails replacing olefinic by aromatic octane and is therefore limited by the total aromatics specification.

Aromatics
In simple terms, reducing aromatics in the gasoline blend means reducing the proportion of reformate. In order to maintain octane, alternative high-octane components have to be found and the options are relatively limited especially when one considers the issue of volumes. Branched paraffins provide good octane rating both in terms of RON and MON. They are obtained by either isomerisation of light naphthas or alkylation of mixed C3 and C4 hydrocarbons. In the former case, thermodynamic limitations amongst others limit the octane to the high 80s (in RON terms) in the best cases. Alkylates can reach the mid 90s. Although a useful complement to the cocktail, these components do not provide the high RON values required for the final blend although their low sensitivity is a welcome feature in a MONconstrained environment. Stemming only from light naphthas (in the case of isomerates) and FCC light ends (for alkylates) they are also only available in limited quantities. Oxygenates generally have very high octane ratings albeit with a large sensitivity. Their use, mainly in the form of MTBE, has been widespread in Europe in the last decade. The proportion of oxygenates is limited by the maximum oxygen content of gasolines (2.7% m/m). Although groundwater contamination issues resulted in a ban on MTBE in the USA, it now appears to be accepted, at least in Europe, that the problem can be contained with appropriate measures to avoid leakages and spills. Alternatives may be iso-octane or iso-octene that can be manufactured in former MTBE plants with relatively minor modifications. Available volumes, however, would be seriously reduced as the feed becomes purely iso-butene rather than a combination of the latter with methanol in the case of MTBE. Although the branched paraffins have much lower RON than oxygenates their MON levels are comparable. It has to be noted that other quality constraints also conspire to pulling the level of octane downwards. The olefin specification limits the amount of olefinic octane while deep desulphurisation goes the same way by more or less enforcing a certain amount of olefin saturation. The above suggests that, although limited amounts of low to very low aromatics gasoline can technically be produced, this cannot be extended to the entire demand of a country or a fortiori of the whole EU. In many ways this is a matter of running out of molecules. As long as the efficiency imperatives of the spark-ignition engine impose an octane constraint, aromatics will be the only compounds that can be produced in the required quantities and provide the required level of octane. The introduction of a total aromatics specification for gasolines presented refineries without an FCC with a particularly difficult problem. Indeed the standard gasoline blend in such refineries would have consisted of reformate with just enough virgin naphtha and isomerate (when available) to meet the various distillation and volatility specifications. The resulting aromatics content would be close to or above the current 42% limit and certainly well above the 35% limit to be enforced from 2005. FCC refineries fare better as the large amounts of cracked naphtha with relatively high octane and low aromatics provide a buffer. On the other hand the concurrent drastic reduction of the maximum sulphur content essentially affects the FCC refineries.
3

Benzene, Toluene, Xylenes 9

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Desulphurisation of FCC naphthas invariably results in some loss of octane so that such refineries have a growing interest in sulphur-free, high-octane components. This creates a general incentive for components exchanges between refineries to the extent that few of them, apart from the most complex, can now afford to operate in isolation. The results for 2000 of a regular CONCAWE survey of commercial gasoline across a number of European countries are shown in Figure 6. The columns show the average of the samples while the error bars show the minimum and maximum recorded values
50 45 Total aromatics (% v/v) 40 35 30 25 20 15 10 5 0 BE FI FR DE GB GR HU IT NL PT ES CH
max. limit EN 228

Figure 6: CONCAWE gasoline winter 2000 survey. Aromatics in super 95 grade The spread of the values reflects the different circumstances of individual refineries. Although the global average is, at 33%, already within the 2005 limit of 35%, this value is still exceeded by a large proportion of the samples. Additional measures will be required for all gasolines to meet the 2005 limit. This will be rendered more difficult by the loss of some olefinic octane associated to the deep desulphurisation of FCC naphthas. At the 35% aromatics level, the combined pressure of benzene reduction, virtually complete sulphur removal and olefins limitation will stretch the octane producing capability of the refineries to the maximum. Any further reduction of the total aromatics, besides having no environmental justification, would require a complete rethink of the way gasoline is manufactured and require massive investments.

6.

The impact of gasoline specifications on the availability and quality of petrochemical feed
To a certain extent, petrochemicals compete with gasoline for a number of refinery streams. Olefin producers generally look for high olefin yields, which means light, highly paraffinic feedstocks as well as mixed C3/C4 hydrocarbons. In the past a large proportion of the light virgin naphthas have been used as petrochemicals feed. The pressure on aromatics and olefins and therefore on octane has driven refiners towards maximising the availability of non-controversial molecules such as isoparaffins. As discussed above these are essentially obtained by either isomerisation of C5-C6 straight-chain paraffins or alkylation of mixed C3/C4 olefinic and aliphatic streams. At the same time, the reduced demand for reformates releases heavier naphtha streams. As a result the average feed available to petrochemical plants is generally expected to become heavier. A CONCAWE study on the consequences of reducing total aromatics from 42 to 35% [5] suggested an increase of the density of petrochemical naphtha from 869 to 871 kg/m3. Such
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a change can have far-reaching consequences. Higher feed density generally equates to lower olefin yields and proportionally higher production of pyrolysis gasoline i.e. mainly aromatics that may not match the demand. Portions of these heavier streams also traditionally find their way back into the refinery blends where they are increasingly unwanted. The increased value of C4 olefins as alkylation feed introduces an extra front in the competition of fuels and petrochemicals for appropriate feedstocks. In order to fully capture and understand these interactions, CONCAWE in cooperation with CEFIC4 have now extended their modelling of the EU refining system to include the first line petrochemical plants i.e. steam-crackers and aromatics extraction plants.

7.

Aromatics in diesel
Although there is no total aromatics limit as such in EU diesel, the amount is effectively constrained through the combination of the density, distillation and cetane specifications. Currently at 51 in terms of cetane number, the latter limit is much higher in Europe than e.g. in the USA. In practice the current specifications preclude the use of but small amounts of simply desulphurised cracked stocks such as LCO (light cycle oil) from FCCs in diesel blends. This is even more so at the 10 ppm sulphur level as ultra deep desulphurisation of LCO is difficult to achieve in standard or modified hydrodesulphurisation plants. Turning LCOs into suitable diesel components requires deep hydrogenation either in a purpose-built plant or as part of the feed stream to a hydrocracker. EU diesel already is, and is set to become even more, based on virgin and deeply hydrogenated streams. Tightening of tail-end distillation limits (T95) as well as the need for ultra deep desulphurisation, also pushes refiners towards selecting lighter fractions for the diesel pool. As a consequence these relatively light, low aromatic fractions, favoured as petrochemical feed, are likely to become more desirable to the refiners for their fuel business. In Europe, these additional quality requirements occur in a context of increasing demand for diesel and jet fuel. As refiners margins are unlikely to be sufficient to justify massive yield shift investments, the development of a sizeable distillate deficit is likely. While this will be partly filled from sources outside Europe such as Russia and the Middle East, this will also give European refiners a strong incentive to maximise diesel and jet production from their existing facilities. This may include maximising middle distillate yields from hydrocrackers and therefore may also affect the availability of heavy hydrocracked feeds (commonly known as hydrowax) to steamcrackers. The extent of the switch will be dictated by technical considerations (e.g. degree of flexibility in the design of existing hydrocrackers) as well as economics. The polyaromatics limit is so far specific to Europe. The polyaromatics content of a virgin gasoil is highly dependent on the origin of the crude. Cracked stocks generally have high levels of polyaromatics but this is also very variable. Upon hydrotreatment a proportion of the polyaromatics is partially saturated to mono-aromatics. Although the total aromatics are little affected, the polyaromatics content is reduced. The rate of reduction depends, however, on a number of parameters. The reaction being exothermic, the rate of conversion is higher at lower temperatures. As a result, more modern, higher-pressure hydrotreaters using more active catalysts tend to achieve higher conversion rates. Conversion, however, decreases as the catalyst deactivates and higher operating temperatures are required to maintain desulphurisation levels. For this reason there is great diversity of polyaromatics content of finished diesels. The results of a recent CONCAWE survey of commercial fuels across Europe are shown in Figure 7.

Conseil Europen des Fdrations de Industrie Chimique (European Chemical Industry Council) 11

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12
max. limit EN 590

Polyaromatics (% m/m)

10 8 6 4 2 0 AT BE DK FI FR DE GB GR HU IT NL NO PT ES SE

Figure 7: CONCAWE diesel winter 2000 survey. Polyaromatics in road diesel The average of some 5% m/m for the survey population hides a great disparity of individual situations in terms of crude diet, processing schemes etc5. This average figure is fairly typical of what can be achieved through deep desulphurisation of virgin gasoils. Significantly lower figures would require more severe hydrogenation conditions and in most cases additional processing facilities.

8.

Costs and CO2 emissions associated to the reduction of aromatics in motor fuels
A significant reduction of the aromatics content of motor fuels generally requires in-depth changes in the way streams are processed and selected in the refinery. Any additional constraint invariably generates extra processing steps, which translate into extra costs and extra energy use i.e. extra CO2 emissions from the refinery. Aromatics limits are of course not specified in isolation but as part of a package of specifications, most of which are interrelated to a certain extent. The actual cost and/or CO2 effect of a single change is therefore somewhat difficult to calculate. Any reduction of the aromatics content of gasoline must involve rebalancing the octane that is finding alternative high-octane components. In practice refiners have a limited number of options, essentially isoparaffins (isomerates and alkylates) or oxygenates. Which component is deemed to be used can significantly affect the predicted overall CO2 balance. MTBE for instance is mainly produced from natural gas so that its introduction in the gasoline pool effectively results in a substitution of crude oil by natural gas, and a corresponding reduction of CO2 emissions, even when taking the production energy into account. Whereas this is perfectly legitimate for a specific refinery, the actual realism of such a substitution on a global scale can be a matter of debate. As the main source of aromatics is reformate, a reduction of the reformer input and/or severity is required. This results in turns in a lower hydrogen production in the refinery that has to be compensated by other means (usually a dedicated hydrogen manufacturing plant), generating investment and operating costs as well as additional CO2 emissions. Of course the reduced aromatics content of the finished fuel results in a lower carbon/hydrogen ratio and therefore relatively lower CO2 emissions when the fuel is burned. Limited studies
5

The so-called Swedish class 1 grade, which accounts for virtually 100% of the Swedish market, is a special low sulphur, low aromatics grade that is almost completely dearomatised. It is also much lighter than a standard diesel. 12

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carried out by CONCAWE on the subject suggest that the reduction of aromatics in gasoline is globally about CO2 neutral, at least within the range of European specifications. The costs are high though. CONCAWE estimated the cost of reducing aromatics from 42% to 35% at about 3 billion euros in terms of net present value [5]. Although the global CO2 effect is small, there is a definite increase in emissions from the refineries, an important point in the context of CO2 allocation and trading, which is bound to translate into yet an extra cost to refiners. Even in the case of benzene, the removal of which has relatively limited implications for other properties, there are many solutions to reach a new target value and no generic scheme can be proposed. Actual costs are strongly refinery-specific, depending on the local situation in terms a/o of crude diet, existing reformer feed preparation system, opportunity of exporting a benzene-rich fraction, existing isomerisation unit with spare capacity etc. It is clear though that, a few years back, very few if any EU refinery was in a position to produce 100% of its gasoline with less than 1% benzene. All have had to invest to a certain extent so that the cost to the industry has been significant. As an example, a typical size reformate splitter (700 kt/a) costs in the region of 10 million US dollars. Aromatics reduction in diesel (either total or polyaromatics) is a comparatively simpler question of hydrogenation of existing molecules. Costs are relatively easy to calculate and can be very high. In reference [5] we calculated an net present value cost of 9 billion euros for a cetane number increase from 51 to 55 across Europe. Apart from the air quality arguments, vehicle CO2 emissions reduction is also a key driver for vehicle technology development. Reducing aromatics can, through reducing the carbon to hydrogen ratio of the fuel, slightly reduce the vehicle CO2 emissions. However, emissions of CO2 (and of other greenhouse gases) need to be considered on a well-to-wheels basis. In a recent article [6], we have shown that the global process of hydrogenating an existing molecule before burning it, always generates extra CO2 compared to the base case, even when taking into account the lower emissions from burning the fuel. Hydrogenation means extra processing and the laws of thermodynamic apply to limit the efficiency of the process.

9.

Conclusions
Major improvements in both vehicle and fuel technologies will result in a dramatic reduction of the impact of road traffic on European air quality. Benzene emissions in particular will be reduced to a level at which road traffic will only contribute a small fraction of total emissions. The drastic reduction of sulphur in road fuels enables advanced exhaust after-treatment technologies on both gasoline and diesel engines thereby contributing to a further reduction of emissions of all pollutants. As such treatment systems become more efficient the contribution of the other fuel properties to the level of emissions becomes negligible. The European refining industry has achieved great improvements in the quality of road fuels and is actively working towards meeting the 2005 specifications as well as the virtual elimination of sulphur by the end of the decade. This has and will call for large investments and result in additional CO2 emissions. Changes affect the whole product chain. As competition for desirable components increases the quality of the feed to petrochemicals is likely to worsen. As long as the spark ignition engine dominates the gasoline vehicle market, aromatics will play a vital role in providing both the quantity and high-octane quality of the required fuel. Further changes in road fuel quality would not give significant improvements in air quality but could have major implications in terms of refinery investments, global CO2 emissions as well as available volumes.

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References
1. 2. 3. 4. 5. 6. Effect of fuel qualities and related vehicle technologies on European vehicle emissions. An evaluation of existing literature and proprietary data. Working group European Commission Industry. Technical Group 1. July 1995. European Programme on Emissions, Fuels and Engine Technologies. 1995. CONCAWE Review. Volume 10.1, April 2001. Evaluation of diesel fuel cetane and aromatics effects on emissions from Euro 3 engines. CONCAWE report to be published. EU oil refining industry costs of changing gasoline and diesel fuel characteristics. CONCAWE report 99/56. CONCAWE Review. Volume 10.2, October 2001.

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