Bruce Hamilton's Gasoline FAQ

4.12 Are brands different? Yes. The above specifications are intended to ensure minimal quality standards are maintained, however as well as the fuel hydrocarbons, the manufacturers add their own special ingredients to provide additional benefits. A quality gasoline additive package would include:- * octane-enhancing additives ( improve octane ratings ) * anti-oxidants ( inhibit gum formation, improve stability ) * metal deactivators ( inhibit gum formation, improve stability ) * deposit modifiers ( reduce deposits, spark-plug fouling and preignition ) * surfactants ( prevent icing, improve vaporisation, inhibit deposits, reduce NOx emissions ) * freezing point depressants ( prevent icing ) * corrosion inhibitors ( prevent gasoline corroding storage tanks ) * dyes ( product colour for safety or regulatory purposes ). During the 1980s significant problems with deposits accumulating on intake valve surfaces occurred as new fuel injection systems were introduced. These intake valve deposits (IVD) were different than the injector deposits, in part because the valve can reach 300C. Engine design changes that prevent deposits usually consist of ensuring the valve is flushed with liquid gasoline, and provision of adequate valve rotation. Gasoline factors that cause deposits are the presence of alcohols or olefins [46]. Gasoline manufacturers now routinely use additives that prevent IVD and also maintain the cleanliness of injectors. These usually include a surfactant and light oil to maintain the wetting of important surfaces. Intake valve deposits have also been shown to have significant adverse effects on emissions [47], and deposit control additives will be required to both reduce emissions and provide clean engine operation [48]. A slighty more detailed description of additives is provided in Section 9.1. Texaco demonstrated that a well-formulated package could improve fuel economy, reduce NOx emissions, and restore engine performance because, as well as the traditional liquid-phase deposit removal, some additives can work in the vapour phase to remove existing engine deposits without adversely affecting performance ( as happens when water is poured into a running engine to remove carbon deposits :-) )[49]. Chevron have also published data on the effectiveness of their additives [50], and successfully litigated to get Texaco to modify some of their claims [51]. Most suppliers of quality gasolines will formulate similar additives into their products, and cheaper product lines are less likely to have such additives added. As different brands of gasoline use different additives and oxygenates, it is probable that important fuel parameters, such as octane distribution, are slightly different, even though the pump octane ratings are the same. So, if you know your car is well-tuned, and in good condition, but the driveability is pathetic on the correct octane, try another brand. Remember that the composition will change with the season, so if you lose driveability, try yet another brand. As various Clean Air Act changes are introduced over the next few years, gasoline will continue to change. 4.13 What is a typical composition? There seems to be a perception that all gasolines of one octane grade are chemically similar, and thus general rules can be promulgated about "energy content ", "flame speed", "combustion temperature" etc. etc.. Nothing is further from the truth. The behaviour of manufactured gasolines in octane rating engines can be predicted, using previous octane ratings of special blends intended to determine how a particular refinery stream responds to an octane-enhancing additive. Refiners can design and reconfigure refineries to efficiently produce a wide range of gasolines feedstocks, depending on market and regulatory requirements. There is a worldwide trend to move to unleaded gasolines, followed by the introduction of exhaust catalysts and sophisticated engine management systems. It is important to note that "oxygenated gasolines" have a hydrocarbon fraction that is not too different to traditional gasolines, but that the hydrocarbon fraction of "reformulated gasolines" ( which also contain oxygenates ) are significantly different to traditional gasolines. The last 10 years of various compositional changes to gasolines for environmental and health reasons have resulted in fuels that do not follow historical rules, and the regulations mapped out for the next decade also ensure the composition will remain in a state of flux. The reformulated gasoline specifications, especially the 1/Jan/1998 Complex model, will probably introduce major reductions in the distillation range, as well as changing the various limits on composition and emissions. I'm not going to list all 500+ HCs in gasolines, but the following are representative of the various classes typically present in a gasoline. The numbers after each chemical are:- Research Blending Octane : Motor Blending Octane : Boiling Point (C): Density (g/ml @ 15C) : Minimum Autoignition Temperature (C). It is important to realise that the Blending Octanes are derived from a 20% mix of the HC with a 60:40 iC8:nC7 ( 60 Octane Number ) base fuel, and the extrapolation of this 20% to 100%. These numbers result from API Project 45, and are readily available. As modern refinery streams have higher base octanes, these Blending Octanes are higher than those typically used in modern refineries. For example, modern Blending Octane ratings can be much lower ( toluene = 111RON and 94MON, 2-methyl-2-butene = 113RON and 81MON ), but detailed compilations are difficult to obtain. The technique for obtaining Blending Octanes is different from rating the pure fuel, which often requires adjustment of the test engine conditions outside the acceptable limits of the rating methods. Generally, the actual octanes of the pure fuel are similar for the alkanes, but are up to 30 octane numbers lower than the API Project 45 Blending Octanes for the aromatics and olefins [52]. A traditional composition I have dreamed up would be like the following, whereas newer oxygenated fuels reduce the aromatics and olefins, narrow the boiling range, and add oxygenates up to about 12-15% to provide the octane. The amount of aromatics in super unleaded fuels will vary greatly from country to country, depending on the configuration of the oil refineries and the use of oxygenates as octane enhancers. The US is reducing the levels of aromatics to 25% or lower for environmental and human health reasons. Some countries are increasing the level of aromatics to 50% or higher in super unleaded grades, usually to avoid refinery reconfiguration costs or the introduction of oxygenates as they phase out the toxic lead octane enhancers. An upper limit is usually placed on the amount of benzene permitted, as it is known human carcinogen. 15% n-paraffins RON MON BP d AIT n-butane 113 : 114 : -0.5: gas : 370 n-pentane 62 : 66 : 35 : 0.626 : 260 n-hexane 19 : 22 : 69 : 0.659 : 225 n-heptane (0:0 by definition) 0 : 0 : 98 : 0.684 : 225 n-octane -18 : -16 : 126 : 0.703 : 220 ( you would not want to have the following alkanes in gasoline, so you would never blend kerosine with gasoline ) n-decane -41 : -38 : 174 : 0.730 : 210 n-dodecane -88 : -90 : 216 : 0.750 : 204 n-tetradecane -90 : -99 : 253 : 0.763 : 200 30% iso-paraffins 2-methylpropane 122 : 120 : -12 : gas : 460 2-methylbutane 100 : 104 : 28 : 0.620 : 420 2-methylpentane 82 : 78 : 62 : 0.653 : 306 3-methylpentane 86 : 80 : 64 : 0.664 : - 2-methylhexane 40 : 42 : 90 : 0.679 : 3-methylhexane 56 : 57 : 91 : 0.687 : 2,2-dimethylpentane 89 : 93 : 79 : 0.674 : 2,2,3-trimethylbutane 112 : 112 : 81 : 0.690 : 420 2,2,4-trimethylpentane 100 : 100 : 98 : 0.692 : 415 ( 100:100 by definition ) 12% cycloparaffins cyclopentane 141 : 141 : 50 : 0.751 : 380 methylcyclopentane 107 : 99 : 72 : 0.749 : cyclohexane 110 : 97 : 81 : 0.779 : 245 methylcyclohexane 104 : 84 : 101 : 0.770 : 250 35% aromatics benzene 98 : 91 : 80 : 0.874 : 560 toluene 124 : 112 : 111 : 0.867 : 480 ethyl benzene 124 : 107 : 136 : 0.867 : 430 meta-xylene 162 : 124 : 138 : 0.868 : 463 para-xylene 155 : 126 : 138 : 0.866 : 530 ortho-xylene 126 : 102 : 144 : 0.870 : 530 3-ethyltoluene 162 : 138 : 158 : 0.865 : 1,3,5-trimethylbenzene 170 : 136 : 163 : 0.864 : 1,2,4-trimethylbenzene 148 : 124 : 168 : 0.889 : 8% olefins 2-pentene 154 : 138 : 37 : 0.649 : 2-methylbutene-2 176 : 140 : 36 : 0.662 : 2-methylpentene-2 159 : 148 : 67 : 0.690 : cyclopentene 171 : 126 : 44 : 0.774 : ( the following olefins are not present in significant amounts in gasoline, but have some of the highest blending octanes ) 1-methylcyclopentene 184 : 146 : 75 : 0.780 : 1,3 cyclopentadiene 218 : 149 : 42 : 0.805 : dicyclopentadiene 229 : 167 : 170 : 1.071 : Oxygenates Published octane values vary a lot because the rating conditions are significantly different to standard conditions, for example the API Project 45 numbers used above for the hydrocarbons, reported in 1957, gave MTBE blending RON as 148 and MON as 146, however that was partly based on the lead response, whereas today we use MTBE in place of lead. methanol 133 : 105 : 65 : 0.796 : 385 ethanol 129 : 102 : 78 : 0.794 : 365 iso propyl alcohol 118 : 98 : 82 : 0.790 : 399 methyl tertiary butyl ether 116 : 103 : 55 : 0.745 : ethyl tertiary butyl ether 118 : 102 : 72 : 0.745 : tertiary amyl methyl ether 111 : 98 : 86 : 0.776 : There are some other properties of oxygenates that have to be considered when they are going to be used as fuels, particularly their ability to form very volatile azeotropes that cause the fuel's vapour pressure to increase, the chemical nature of the emissions, and their tendency to separate into a separate water-oxygenate phase when water is present. The reformulated gasolines address these problems more successfully than the original oxygenated gasolines. Before you rush out to make a highly aromatic or olefinic gasoline to produce a high octane fuel, remember they have other adverse properties, eg the aromatics attack elastomers, may generate smoke, and result in increased emissions of toxic benzene. The olefins are unstable ( besides smelling foul ) and form gums. The art of correctly formulating a gasoline that does not cause engines to knock apart, does not cause vapour lock in summer - but is easy to start in winter, does not form gums and deposits, burns cleanly without soot or residues, and does not dissolve or poison the car catalyst or owner, is based on knowledge of the gasoline composition. 4.14 Is gasoline toxic or carcinogenic? There are several known toxins in gasoline, some of which are confirmed human carcinogens. The most famous of these toxins are lead and benzene, and both are regulated. The other aromatics and some toxic olefins are also controlled. Lead alkyls also require ethylene dibromide and/or ethylene dichloride scavengers to be added to the gasoline, both of which are suspected human carcinogens. In 1993 an International Symposium on the Health Effects of Gasoline was held [53]. Major review papers on the carcinogenic, neurotoxic, reproductive and developmental toxicity of gasoline, additives, and oxygenates were presented, and interested readers should obtain the proceedings. The oxygenates are also being evaluated for carcinogenicity, and even ethanol and ETBE may be carcinogens. The introduction of oxygenated gasoline to Alaska and some other areas of the USA resulted in a range of complaints. Recent research has been unable to identify additional toxicity, but has detected increased levels of offensive smell [54]. It should be noted that the oxygenated gasolines were not initially intended to reduce the toxicity of emissions. The reformulated gasolines will produce different emissions, and specific toxins must initially be reduced by 15% all year. The removal of alkyl lead compounds certainly reduces the toxicity of exhaust gas emissions when used on engines with modern engine management systems and 3-way exhaust catalysts. If unleaded gasolines are not accompanied by the introduction of catalysts, some other toxic emissions may increase. Engines without catalysts will produce increased levels of toxic carbonyls such as formaldehyde and acrolein when using oxygenated fuels, and increased levels of toxic benzene when using highly aromatic fuels. There is little doubt that gasoline is full of toxic chemicals, and should therefore be treated with respect. However the biggest danger remains the flammability, and the relative hazards should always be kept in perspective. The major toxic risk from gasolines comes from breathing the tailpipe, evaporative, and refuelling emissions, rather than occasional skin contact from spills. Breathing vapours and skin contact should always be minimised. 4.15 Is unleaded gasoline more toxic than leaded? The short answer is no. However that answer is not global, as some countries have replaced the lead compound octane-improvers with aromatic or olefin octane-improvers without introducing exhaust catalysts. The aromatics contents may increase to around 40%, with high octane unleaded fuels reaching 50% in countries where oxygenates are not being used, and the producers have not reconfigured refineries to produce high octane paraffins. In general, aromatics are significantly more toxic than paraffins. Exhaust catalysts have a limited operational life, and will be immediately poisoned if misfuelled with leaded fuel. Catalyst failure can result in higher levels of toxic emissions if catalysts or engine management systems are not replaced or repaired when defective. Maximum benefit of the switch to unleaded are obtained when the introduction of unleaded is accompanied by the introduction of exhaust catalysts and sophisticated engine management systems. Unfortunately, the manufacturers of alkyl lead compounds have embarked on a worldwide misinformation campaign in countries considering emulating the lead-free US. The use of lead precludes the use of exhaust catalysts, thus the emissions of aromatics are only slightly diminished, as leaded fuels typically contain around 30-40% aromatics. Other toxins and pollutants that are usually reduced by exhaust catalysts will be emitted at significantly higher levels if leaded fuels are used [55]. The use of unleaded on modern vehicles with engine management systems and catalysts can reduce aromatic emissions to 10% of the level of vehicles without catalysts [55]. Alkyl lead additives can only substitute for some of the aromatics in gasoline, consequently they do not eliminate aromatics, which will produce benzene emissions [56]. Alkyl lead additives also require toxic organohalogen scavengers, which also react in the engine to form and emit other organohalogens, including highly toxic dioxin [57]. Leaded fuels emit lead, organohalogens, and much higher levels of regulated toxins because they preclude the use of exhaust catalysts. In the USA the gasoline composition is being changed to reduce fuel toxins ( olefins, aromatics ) as well as emissions of specific toxins. 4.16 Is reformulated gasoline more toxic than unleaded? The evidence so far indicates that the components of reformulated gasolines ( RFGs ) are more benign than unleaded, and that the tailpipe emissions of hydrocarbons are significantly reduced for cars without catalysts, and slightly reduced for cars with catalysts and engine management systems. The emissions of toxic carbonyls such as formaldehyde, acetaldehyde and acrolein are increased slightly on all vehicles, and the emission of MTBE is increased about 10x on cars without catalysts and 4x on cars with catalysts [55]. When all the emissions ( evaporative and tailpipe ) are considered, RFGs significantly reduce emissions of hydrocarbons, however the emissions of carbonyls and MTBE may increase [55]. There has been an extensive series of reports on the emissions from RFGs, produced by the Auto/Oil Air Quality Improvement Research Program, who measured and calculated the likely effects of RFG [18,19,20,58,59,60,61]. More research is required before a definitive answer on toxicity is available. The major question about RFGs is not the toxicity of the emissions, but whether they actually meet their objective of reducing urban pollution. This is a more complex issue, and most experts agree the benefits will only be modest [18,19,20,61,62]. 4.17 Are all oxygenated gasolines also reformulated gasolines? No. Oxygenates were initially introduced as alternative octane-enhancers in the 1930s, and are still used in some countries for that purpose. In the US the original "oxygenated gasolines" usually had a slightly- modified gasoline as the hydrocarbon fraction. The US EPA also mandated their use to reduce pollution, mainly via the "enleanment" effect on engines without sophisticated management systems, but also because of the "aromatics substitution" effect. As vehicles with fuel injection and sophisticated engine management systems became pervasive, reformulated gasolines could be introduced to further reduce pollution. The hydrocarbon component of RFGs is significantly different to the hydrocarbon fraction in earlier oxygenated gasolines, having lower aromatics contents, reduced vapour pressure, and a narrower boiling range. RFGs do contain oxygenates as the octane-enhancer, but have different hydrocarbon composition profiles [34,41,42,43,44].

Subject: 5. Why is Gasoline Composition Changing? 5.1 Why pick on cars and gasoline? Cars emit several pollutants as combustion products out the tailpipe, (tailpipe emissions), and as losses due to evaporation (evaporative emissions, refuelling emissions). The volatile organic carbon (VOC) emissions from these sources, along with nitrogen oxides (NOx) emissions from the tailpipe, will react in the presence of ultraviolet (UV) light (wavelengths of less than 430nm) to form ground-level (tropospheric) ozone, which is one of the major components of photochemical smog [63]. Smog has been a major pollution problem ever since coal-fired power stations were developed in urban areas, but their emissions are being cleaned up. Now it's the turn of the automobile. Cars currently use gasoline that is derived from fossil fuels, thus when gasoline is burned to completion, it produces additional CO2 that is added to the atmospheric burden. The effect of the additional CO2 on the global environment is not known, but the quantity of man-made emissions of fossil fuels must cause the system to move to a new equilibrium. Even if current research doubles the efficiency of the IC engine-gasoline combination, and reduces HC, CO, NOx, SOx, VOCs, particulates, and carbonyls, the amount of carbon dioxide from the use of fossil fuels may still cause global warming. More and more scientific evidence is accumulating that warming is occurring [64,65]. The issue is whether it is natural, or induced by human activities and and a large panel of scientific experts continues to review scientific data and models. Interested reader should seek out the various publications of the Intergovernmental Panel on Climate Change (IPCC). There are international agreements to limit CO2 emissions to 1990 levels, a target that will require more efficient, lighter, or appropriately-sized vehicles, - if we are to maintain the current usage. One option is to use "renewable" fuels in place of fossil fuels. Consider the amount of energy-related CO2 emissions for selected countries in 1990 [66]. CO2 Emissions ( tonnes/year/person ) USA 20.0 Canada 16.4 Australia 15.9 Germany 10.4 United Kingdom 8.6 Japan 7.7 New Zealand 7.6 The number of new vehicles provides an indication of the magnitude of the problem. Although vehicle engines are becoming more efficient, the distance travelled is increasing, resulting in a gradual increase of gasoline consumption. The world production of vehicles (in thousands) over the last few years was [67];- Cars Region 1990 1991 1992 1993 1994 Africa 222 213 194 201 209 Asia-Pacific 12,064 12,112 11,869 11,463 11,020 Central & South America 800 888 1,158 1,523 1,727 Eastern Europe 2,466 984 1,726 1,837 1,547 Middle East 35 24 300 390 274 North America 7,762 7,230 7,470 8,172 8,661 Western Europe 13,688 13,286 13,097 11,141 12,851 Total World 37,039 34,739 35,815 34,721 36,289 Trucks ( including heavy trucks and buses ) Region 1990 1991 1992 1993 1994 Africa 133 123 108 101 116 Asia-Pacific 5,101 5,074 5,117 5,057 5,407 Central & South America 312 327 351 431 457 Eastern Europe 980 776 710 600 244 Middle East 36 28 100 128 76 North America 4,851 4,554 5,371 6,037 7,040 Western Europe 1,924 1,818 1,869 1,718 2,116 Total World 13,336 12,701 13,627 14,073 15,457 To fuel all operating vehicles, considerable quantities of gasoline and diesel have to be consumed. Major consumption in 1994 of gasoline and middle distillates ( which may include some heating fuels, but not fuel oils ) in million tonnes. Gasoline Middle Distillates USA 338.6 246.3 Canada 26.8 26.1 Western Europe 163.2 266.8 Japan 60.2 92.2 Total World 820.4 1029.0 The USA consumption of gasoline increased from 294.4 (1982) to 335.6 (1989) then dipped to 324.2 (1991), and has continued to rise since then to reach 338.6 million tonnes in 1994. In 1994 the total world production of crude oil was 3209.1 million tonnes, of which the USA consumed 807.9 million tonnes [68]. Transport is a very significant user of crude oil products, thus improving the efficiency of utilisation, and minimising pollution from vehicles, can produce immediate reductions in emissions of CO2, HCs, VOCs, CO, NOx, carbonyls, and other chemicals. 5.2 Why are there seasonal changes? Only gaseous hydrocarbons burn, consequently if the air is cold, then the fuel has to be very volatile. But when summer comes, a volatile fuel can boil and cause vapour lock, as well as producing high levels of evaporative emissions. The solution was to adjust the volatility of the fuel according to altitude and ambient temperature. This volatility change has been automatically performed for decades by the oil companies without informing the public of the changes. It is one reason why storage of gasoline through seasons is not a good idea. Gasoline volatility is being reduced as modern engines, with their fuel injection and management systems, can automatically compensate for some of the changes in ambient conditions - such as altitude and air temperature, resulting in acceptable driveability using less volatile fuel. 5.3 Why were alkyl lead compounds removed? " With the exception of one premium gasoline marketed on the east coast and southern areas of the US, all automotive gasolines from the mid-1920s until 1970 contained lead antiknock compounds to increase antiknock quality. Because lead antiknock compounds were found to be detrimental to the performance of catalytic emission control system then under development, U.S. passenger car manufacturers in 1971 began to build engines designed to operate satisfactorily on gasolines of nominal 91 Research Octane Number. Some of these engines were designed to operate on unleaded fuel while others required leaded fuel or the occasional use of leaded fuel. The 91 RON was chosen in the belief that unleaded gasoline at this level could be made available in quantities required using then current refinery processing equipment. Accordingly, unleaded and low-lead gasolines were introduced during 1970 to supplement the conventional gasolines already available. Beginning with the 1975 model year, most new car models were equipped with catalytic exhaust treatment devices as one means of compliance with the 1975 legal restrictions in the U.S. on automobile emissions. The need for gasolines that would not adversely affect such catalytic devices has led to the large scale availability and growing use of unleaded gasolines, with all late-model cars requiring unleaded gasoline."[69]. There was a further reason why alkyl lead compounds were subsequently reduced, and that was the growing recognition of the highly toxic nature of the emissions from a leaded-gasoline fuelled engine. Not only were toxic lead emissions produced, but the added toxic lead scavengers ( ethylene dibromide and ethylene dichloride ) could react with hydrocarbons to produce highly toxic organohalogen emissions such as dioxin. Even if catalysts were removed, or lead-tolerant catalysts discovered, alkyl lead compounds would remain banned because of their toxicity and toxic emissions [70,71]. 5.4 Why are evaporative emissions a problem? As tailpipe emissions are reduced due to improved exhaust emission control systems, the hydrocarbons produced by evaporation of the gasoline during distribution, vehicle refuelling, and from the vehicle, become more and more significant. A recent European study found that 40% of man-made volatile organic compounds came from vehicles [72]. Many of the problem hydrocarbons are the aromatics and olefins that have relatively high octane values. Any sensible strategy to reduce smog and toxic emissions will also attack evaporative and tailpipe emissions. The health risks to service station workers, who are continuously exposed to refuelling emissions remain a concern [73]. Vehicles will soon be required to trap the refuelling emissions in larger carbon canisters, as well as the normal evaporative emissions that they already capture. This recent decision went in favour of the oil companies, who were opposed by the auto companies. The automobile manufacturers felt the service station should trap the emissions. The activated carbon canisters adsorb organic vapours, and these are subsequently desorbed from the canister and burnt in the engine during normal operation, once certain vehicle speeds and coolant temperatures are reached. A few activated carbons used in older vehicles do not function efficiently with oxygenates, but carbon cannister systems can reduce evaporative emissions by 95% from uncontrolled levels. 5.5 Why control tailpipe emissions? Tailpipe emissions were responsible for the majority of pollutants in the late 1960s after the crankcase emissions had been controlled. Ozone levels in the Los Angeles basin reached 450-500ppb in the early 1970s, well above the typical background of 30-50ppb [74]. Tuning a carburetted engine can only have a marginal effect on pollutant levels, and there still had to be some frequent, but long-term, assessment of the state of tuning. Exhaust catalysts offered a post-engine solution that could ensure pollutants were converted to more benign compounds. As engine management systems and fuel injection systems have developed, the volatility properties of the gasoline have been tuned to minimise evaporative emissions, and yet maintain low exhaust emissions. The design of the engine can have very significant effects on the type and quantity of pollutants, eg unburned hydrocarbons in the exhaust originate mainly from combustion chamber crevices, such as the gap between the piston and cylinder wall, where the combustion flame can not completely use the HCs. The type and amount of unburnt hydrocarbon emissions are related to the fuel composition (volatility, olefins, aromatics, final boiling point), as well as state of tune, engine condition, and condition of the engine lubricating oil [75]. Particulate emissions, especially the size fraction smaller than ten micrometres, are a serious health concern. The current major source is from compression ignition ( diesel ) engines, and the modern SI engine system has no problem meeting regulatory requirements. The ability of reformulated gasolines to actually reduce smog has not yet been confirmed. The composition changes will reduce some compounds, and increase others, making predictions of environmental consequences extremely difficult. Planned future changes, such as the CAA 1/1/1998 Complex model specifications, that are based on several major ongoing government/industry gasoline and emission research programmes, are more likely to provide unambiguous environmental improvements. One of the major problems is the nature of the ozone-forming reactions, which require several components ( VOC, NOx, UV ) to be present. Vehicles can produce the first two, but the their ratio is important, and can be affected by production from other natural ( VOC = terpenes from conifers ) or manmade ( NOx from power stations ) sources [62,63]. The regulations for tailpipe emissions will continue to become more stringent as countries try to minimise local problems ( smog, toxins etc.) and global problems ( CO2 ). Reformulation does not always lower all emissions, as evidenced by the following aldehydes from an engine with an adaptive learning management system [55]. FTP-weighted emission rates (mg/mi) Gasoline Reformulated Formaldehyde 4.87 8.43 Acetaldehyde 3.07 4.71 The type of exhaust catalyst and management system can have significant effects on the emissions [55]. FTP-weighted emission rates. (mg/mi) Total Aromatics Total Carbonyls Gasoline Reformulated Gasoline Reformulated Noncatalyst 1292.45 1141.82 174.50 198.73 Oxidation Catalyst 168.60 150.79 67.08 76.94 3-way Catalyst 132.70 93.37 23.93 23.07 Adaptive Learning 111.69 105.96 17.31 22.35 If we take some compounds listed as toxics under the Clean Air Act, then the beneficial effects of catalysts are obvious. Note that hexane and iso-octane are the only alkanes listed as toxics, but benzene, toluene, ethyl benzene, o-xylene, m-xylene, and p-xylene are aromatics that are listed. The latter four are combined as C8 Aromatics below [55]. Aromatics FTP-weighted emission rates. (mg/mi) Benzene Toluene C8 Aromatics Gas Reform Gas Reform Gas Reform Noncatalyst 156.18 138.48 338.36 314.14 425.84 380.44 Oxidation Cat. 27.57 25.01 51.00 44.13 52.27 47.07 3-way Catalyst 19.39 15.69 36.62 26.14 42.38 29.03 Adaptive Learn. 19.77 20.39 29.98 29.67 35.01 32.40 Aldehydes FTP-weighted emission rates. (mg/mi) Formaldehyde Acrolein Acetaldehyde Gas Reform Gas Reform Gas Reform Noncatalyst 73.25 85.24 11.62 13.20 19.74 21.72 Oxidation Cat. 28.50 35.83 3.74 3.75 11.15 11.76 3-way Catalyst 7.27 7.61 1.11 0.74 4.43 3.64 Adaptive Learn. 4.87 8.43 0.81 1.16 3.07 4.71 Others 1,3 Butadiene MTBE Gas Reform Gas Reform Noncatalyst 2.96 1.81 10.50 130.30 Oxidation Cat. 0.02 0.33 2.43 11.83 3-way Catalyst 0.07 0.05 1.42 4.59 Adaptive Learn. 0.00 0.14 0.84 3.16 The author reports analytical problems with the 1,3 Butadiene, and only Noncatalyst values are considered reliable. Other studies from the Auto/Oil research program indicate that lowering aromatics and olefins reduce benzene but increase formaldehyde and acetaldehyde [20] Emission Standards There are several bodies responsible for establishing standards, and they promulgate test cycles, analysis procedures, and the % of new vehicles that must comply each year. The test cycles and procedures do change ( usually indicated by an anomalous increase in the numbers in the table ), and I have not listed the percentages of the vehicle fleet that are required to comply. This table is only intended to convey where we have been, and where we are going. It does not cover any regulation in detail - readers are advised to refer to the relevant regulations. Additional limits for other pollutants, such as formaldehyde (0.015g/mi.) and particulates (0.08g/mi), are omitted. The 1994 tests signal the federal transition from 50,000 to 100,000 mile compliance testing, and I have not listed the subsequent 50,000 mile limits [28,76,77]. Year Federal California HCs CO NOx Evap HCs CO NOx Evap g/mi g/mi g/mi g/test g/mi g/mi g/mi g/test Before regs 10.6 84.0 4.1 47 10.6 84.0 4.1 47 add crankcase +4.1 +4.1 1966 6.3 51.0 6.0 1968 6.3 51.0 6.0 1970 4.1 34.0 4.1 34.0 6 1971 4.1 34.0 6(CC) 4.1 34.0 4.0 6 1972 3.0 28.0 2 2.9 34.0 3.0 2 1973 3.0 28.0 3.0 2.9 34.0 3.0 2 1974 3.0 28.0 3.0 2.9 34.0 2.0 2 1975 1.5 15.0 3.1 2 0.90 9.0 2.0 2 1977 1.5 15.0 2.0 2 0.41 9.0 1.5 2 1980 0.41 7.0 2.0 6(SHED) 0.41 9.0 1.0 2 1981 0.41 3.4 1.0 2 0.39 7.0 0.7 2 1993 0.41 3.4 1.0 2 0.25 3.4 0.4 2 1994 50,000 0.26 3.4 0.3 2 TLEV 0.13 3.4 0.4 2 1994 100,000 0.31 4.2 0.6 2 1997 LEV 0.08 3.4 0.2 1997 ULEV 0.04 1.7 0.2 1998 ZEV 0.0 0.0 0.0 0 2004 0.125 1.8 0.16 2 It's also worth noting that exhaust catalysts also emit platinum, and the soluble platinum salts are some of the most potent sensitizers known. Early research [78] reported the presence of 10% water-soluble platinum in the emissions, however later work on monolithic catalysts has determined the quantities of water soluble platinum emissions are negligible [79]. The particle size of the emissions has also been determined, and the emissions have been correlated with increasing vehicle speed. Increasing speed also increases the exhaust gas temperature and velocity, indicating the emissions are probably a consequence of physical attrition. Estimated Fuel Median Aerodynamic Speed Consumption Emissions Particle Diameter km/h l/100km ng/m-3 um 60 7 3.3 5.1 100 8 11.9 4.2 140 10 39.0 5.6 US Cycle-75 6.4 8.5 Using the estimated fuel consumption, and about 10m3 of exhaust gas per litre of gasoline, the emissions are 2-40 ng/km. These are 2-3 orders of magnitude lower than earlier reported work on pelletised catalysts. These emissions may be controlled directly in the future. They are currently indirectly controlled by the cost of platinum, and the new requirement for the catalyst to have an operational life of at least 100,000 miles. 5.6 Why do exhaust catalysts influence fuel composition? Modern adaptive learning engine management systems control the combustion stoichiometry by monitoring various ambient and engine parameters, including exhaust gas recirculation rates, the air flow sensor, and exhaust oxygen sensor outputs. This closed loop system using the oxygen sensor can compensate for changes in fuel content and air density. The oxygen sensor is also known as the lambda sensor because the actual air-fuel mass ratio divided by the stoichiometric air-fuel mass ratio is known as lambda or the air-fuel equivalence ratio. The preferred technique for describing mixture strength is the fuel-air equivalence ratio ( phi ), which is the actual fuel-air mass ratio divided by the stoichiometric fuel-air mass ratio, however most enthusiasts use air-fuel ratio and lambda. Lambda is the inverse of the fuel-air equivalence ratio. The oxygen sensor effectively measures lambda around the stoichiometric mixture point. Typical stoichiometric air-fuel ratios are [80]:- 6.4 methanol 9.0 ethanol 11.7 MTBE 12.1 ETBE, TAME 14.6 gasoline without oxygenates The engine management system rapidly switches the stoichiometry between slightly rich and slightly lean, except under wide open throttle conditions - when the system runs open loop. The response of the oxygen sensor to composition changes is about 3 ms, and closed loop switching is typically 1-3 times a second, going between 50mV ( lambda = 1.05 (Lean)) to 900mV (lambda = 0.99 ( Rich)). The catalyst oxidises about 80% of the H2, CO, and HCs, and reduces the NOx [76]. Typical reactions that occur in a modern 3-way catalyst are:- 2H2 + O2 -> 2H2O 2CO + O2 -> 2CO2 CxHy + (x + (y/4))O2 -> xCO2 + (y/2)H2O 2CO + 2NO -> N2 + 2CO2 CxHy + 2(x + (y/4))NO -> (x + (y/4))N2 + (y/2)H2O + xCO2 2H2 + 2NO -> N2 + 2H2O CO + H20 -> CO2 + H2 CxHy + xH2O -> xCO + (x + (y/2))H2 The use of exhaust catalysts have resulted in reaction pathways that can accidentally be responsible for increased pollution. An example is the CARB-mandated reduction of fuel sulfur. A change from 450ppm to 50ppm, which will reduce HC & CO emissions by 20%, was shown to increase formaldehyde by 45%, but testing in later model cars did not exhibit the same effect [32,58, 59]. This demonstrates that continuing changes to engine management systems can also change the response to fuel composition changes. The requirement that the exhaust catalysts must now endure for 10 years or 100,000 miles will also encourage automakers to push for lower levels of elements that affect exhaust catalyst performance, such as sulfur and phosphorus, in both the gasoline and lubricant. Modern catalysts are unable to reduce the relatively high levels of NOx that are produced during lean operation down to approved levels, thus preventing the application of lean-burn engine technology. Recently Mazda has announced they have developed a "lean burn" catalyst, which may enable automakers to move the fuel combustion towards the lean side, and different gasoline properties may be required to optimise the combustion and reduce pollution [81]. Mazda claim that fuel efficiency is improved by 5-8%, while meeting all emission regulations, and some Japanese manufacturers have evaluated lean-burn catalysts in limited numbers of 1995 production models. Catalysts also inhibit the selection of gasoline octane-improving and cleanliness additives ( such as MMT and phosphorus-containing additives ) that may result in refractory compounds known to physically coat the catalyst, reducing available catalyst and thus increasing pollution. 5.7 Why are "cold start" emissions so important? The catalyst requires heat to reach the temperature ( >300-350C ) where it functions most efficiently, and the delay until it reaches operating temperature can produce more hydrocarbons than would be produced during the remainder of many typical urban short trips. It has been estimated that 70-80% of the non-methane HCs that escape conversion by the catalysts are emitted during the first two minutes after a cold start. As exhaust emissions have been reduced, the significance of the evaporative emissions increases. Several engineering techniques are being developed, including the Ford Exhaust Gas Igniter ( uses a flame to heat the catalyst - lots of potential problems ), zeolite hydrocarbon traps, and relocation of the catalyst closer to the engine [76]. Reduced gasoline volatility and composition changes, along with cleanliness additives and engine management systems, can help minimise cold start emissions, but currently the most effective technique appears to be rapid, deliberate heating of the catalyst, and the new generation of low thermal inertia "fast light-up" catalysts reduce the problem, but further research is necessary [76,82]. As the evaporative emissions are also starting to be reduced, the emphasis has shifted to the refuelling emissions. These will be mainly controlled on the vehicle, and larger canisters may be used to trap the vapours emitted during refuelling. 5.8 When will the emissions be "clean enough"? The California ZEV regulations effectively preclude IC vehicles, because they stipulate zero emissions. However, the concept of regulatory forcing of alternative vehicle propulsion technology may have to be modified to include hybrid or fuel-cell vehicles, as the major failing of EVs remains the lack of a cheap, light, safe, and easily-rechargeable electrical storage device [83,84]. There are several major projects intending to further reduce emissions from automobiles, mainly focusing on vehicle mass and engine fuel efficiency, but gasoline specifications and alternative fuels are also being investigated. It may be that changes to IC engines and gasolines will enable the IC engine to continue well into the 21st century as the prime motive force for personal transportation [77,85]. There have also been calls to use market forces to reduce pollution from automobiles [86], however most such suggestions ( increased gasoline taxes, congestion tolls, and emission-based registration fees ) are currently considered politically unacceptable. The issue of how to target the specific "gross polluters" is being considered, and is described in Section 5.14. 5.9 Why are only some gasoline compounds restricted? The less volatile hydrocarbons in gasoline are not released in significant quantities during normal use, and the more volatile alkanes are considerably less toxic than many other chemicals encountered daily. The newer gasoline additives also have potentially undesirable properties before they are even combusted. Most hydrocarbons are very insoluble in water, with the lower aromatics being the most soluble, however the addition of oxygen to hydrocarbons significantly increases the mutual solubility with water. Compound in Water Water in Compound % mass/mass @ C % mass/mass @ C normal decane 0.0000052 25 0.0072 25 iso-octane 0.00024 25 0.0055 20 normal hexane 0.00125 25 0.0111 20 cyclohexane 0.0055 25 0.010 20 1-hexene 0.00697 25 0.0477 30 toluene 0.0515 25 0.0334 25 benzene 0.1791 25 0.0635 25 methanol complete 25 complete 25 ethanol complete 25 complete 25 MTBE 4.8 20 1.4 20 TAME - 0.6 20 The concentrations and ratios of benzene, toluene, ethyl benzene, and xylenes ( BTEX ) in water are often used to monitor groundwater contamination from gasoline storage tanks or pipelines. The oxygenates and other new additives may increase the extent of water and soil pollution by acting as co-solvents for HCs. Various government bodies ( EPA, OSHA, NIOSH ) are charged with ensuring people are not exposed to unacceptable chemical hazards, and maintain ongoing research into the toxicity of liquid gasoline contact, water and soil pollution, evaporative emissions, and tailpipe emissions [87]. As toxicity is found, the quantities in gasoline of the specific chemical ( benzene ), or family of chemicals ( alkyl leads, aromatics, olefins ) are regulated. The recent dramatic changes caused by the need to reduce alkyl leads, halogens, olefins, and aromatics has resulted in whole new families of compounds ( ethers, alcohols ) being introduced into fuels without prior detailed toxicity studies being completed. If adverse results appear, these compounds are also likely to be regulated to protect people and the environment. Also, as the chemistry of emissions is unravelled, the chemical precursors to toxic tailpipe emissions ( such as higher aromatics that produce benzene emissions ) are also controlled, even if they are not themselves toxic. 5.10 What does "renewable" fuel or oxygenate mean? The general definition of "renewable" is that the carbon originates from recent biomass, and thus does not contribute to the increased CO2 emissions. A truly "long-term" view could claim that fossil fuels are "renewable" on a 100 million year timescale :-). There was a major battle between the ethanol/ETBE lobby ( agricultural, corn growing ), and the methanol/MTBE lobby ( oil company, petrochemical ) over an EPA mandate demanding that a specific percentage of the oxygenates in gasoline are produced from "renewable" sources [88]. On 28 April 1995 a Federal appeals court permanently voided the EPA ruling requiring "renewable" oxygenates, thus fossil-fuel derived oxygenates such as MTBE are acceptable oxygenates [89]. Unfortunately, "renewable" ethanol is not cost competitive when crude oil is $18/bbl, so a federal subsidy ( $0.54/US Gallon ) and additional state subsidies ( 11 states - from $0.08(Michigan) to $0.66(Tenn.)/US Gal.) are provided. Ethanol, and ETBE derived from ethanol, are still likely to be used in states where subsidies make them competitive with other oxygenates. 5.11 Will oxygenated gasoline damage my vehicle? The following comments assume that your vehicle was designed to operate on unleaded, if not, then damage such as exhaust valve seat recession may occur. Damage should not occur if the gasoline is correctly formulated, and you select the appropriate octane, but oxygenated gasoline will hurt your pocket. In the first year of mandated oxygenates, it appears some refiners did not carefully formulate their oxygenated gasoline, and driveability and emissions problems occurred. Most reputable brands are now carefully formulated. Some older activated carbon canisters may not function efficiently with oxygenated gasolines, but this is a function of the type of carbon used. How your vehicle responds to oxygenated gasoline depends on the engine management system and state of tune. A modern system will automatically compensate for all of the currently-permitted oxygenate levels, thus your fuel consumption will increase. Older, poorly-maintained, engines may require a tune up to maintain acceptable driveability. Be prepared to try several different brands of oxygenated or reformulated gasolines to identify the most suitable brand for your vehicle, and be prepared to change again with the seasons. This is because the refiners can choose the oxygenate they use to meet the regulations, and may choose to set some fuel properties, such as volatility, differently to their competitors. Most stories of corrosion etc, are derived from anhydrous methanol corrosion of light metals (aluminum, magnesium), however the addition of either 0.5% water to pure methanol, or corrosion inhibitors to methanol-gasoline blends will prevent this. If you observe corrosion, talk to your gasoline supplier. Oxygenated fuels may either swell or shrink some elastomers on older cars, depending on the aromatic and olefin content of the fuels. Cars later than 1990 should not experience compatibility problems, and cars later than 1994 should not experience driveability problems, but they will experience increased fuel consumption, depending on the state of tune and engine management system. 5.12 What does "reactivity" of emissions mean? The traditional method of exhaust regulations was to specify the actual HC, CO, NOx, and particulate contents. With the introduction of oxygenates and reformulated gasolines, the volatile organic carbon (VOC) species in the exhaust also changed. The "reactivity" refers to the ozone-forming potential of the VOC emissions when they react with NOx, and is being introduced as a regulatory means of ensuring that automobile emissions do actually reduce smog formation. The ozone-forming potential of chemicals is defined as the number of molecules of ozone formed per VOC carbon atom, and this is called the Incremental Reactivity. Typical values ( big is bad :-) ) are [74]: Maximum Incremental Reactivities as mg Ozone / mg VOC carbon monoxide 0.054 alkanes methane 0.0148 ethane 0.25 propane 0.48 n-butane 1.02 olefins ethylene 7.29 propylene 9.40 1,3 butadiene 10.89 aromatics benzene 0.42 toluene 2.73 meta-xylene 8.15 1,3,5-trimethyl benzene 10.12 oxygenates methanol 0.56 ethanol 1.34 MTBE 0.62 ETBE 1.98 5.13 What are "carbonyl" compounds? Carbonyls are produced in large amounts under lean operating conditions, especially when oxygenated fuels are used. Most carbonyls are toxic, and the carboxylic acids can corrode metals. The emission of carbonyls can be controlled by combustion stoichiometry and exhaust catalysts, refer to section 5.5 for typical reductions for aldehydes. Typical carbonyls are:- * aldehydes ( containing -CHO ), - formaldehyde (HCHO) - which is formed in large amounts during lean combustion of methanol [90]. - acetaldehyde (CH2CHO) - which is formed during ethanol combustion. - acrolein (CH2=CHCHO) - a very potent irritant and toxin. * ketones ( containing C=0 ), - acetone (CH3COCH3) * carboxylic acids ( containing -COOH ), - formic acid (HCOOH) - formed during lean methanol combustion. - acetic acid (CH3COOH). 5.14 What are "gross polluters"? It has always been known that the EPA emissions tests do not reflect real world conditions. There have been several attempts to identify vehicles on the road that do not comply with emissions standards. Recent remote sensing surveys have demonstrated that the highest 10% of CO emitters produce over 50% of the pollution, and the same ratio applies for the HC emitters - which may not be the same vehicles [91-102]. 20% of the CO emitters are responsible for 80% of the CO emissions, consequently modifying gasoline composition is only one aspect of pollution reduction. The new additives can help maintain engine condition, but they can not compensate for out-of-tune, worn, or tampered-with engines. There has recently been some unpublished studies that demonstrate that the current generation of remote sensing systems can not provide sufficient discrimination of gross polluters without also producing false positives for some acception vehicles - more work is required, and in some states I&M emissions testing using dynamometers is being introduced to identify gross polluters. The most famous of the remote sensing systems is the FEAT ( Fuel Efficiency Automobile Test ) team from the University of Denver [99]. This team is probably the world leader in remote sensing of auto emissions to identify grossly polluting vehicles. The system measures CO/CO2 ratio, and the HC/CO2 ratio in the exhaust of vehicles passing through an infra-red light beam crossing the road 25cm above the surface. The system also includes a video system that records the licence plate, date, time, calculated exhaust CO, CO2, and HC. The system is effective for traffic lanes up to 18 metres wide, however rain, snow, and water spray can cause scattering of the beam. Reference signals monitor such effects and, if possible, compensate. The system has been comprehensively validated, including using vehicles with on-board emissions monitoring instruments. They can monitor up to 1000 vehicles an hour and, as an example,they were invited to Provo, Utah to monitor vehicles, and gross polluters would be offered free repairs [100]. They monitored over 10,000 vehicles and mailed 114 letters to owners of vehicles newer than 1965 that had demonstrated high CO levels. They received 52 responses and repairs started in Dec. 1991, and continued to Mar 1992. The entire monitored fleet at Provo (Utah) during Winter 1991:1992 Model year Grams CO/gallon Number of (Median value) (mean value) Vehicles 92 40 80 247 91 55 1222 90 75 1467 89 80 1512 88 85 1651 87 90 1439 86 100 300 1563 85 120 1575 84 125 1206 83 145 719 82 170 639 81 230 612 80 220 500 551 79 350 667 78 420 584 77 430 430 76 770 317 75 760 950 163 Pre 75 920 1060 878 As observed elsewhere, over half the CO was emitted by about 10% of the vehicles. If the 47 worst polluting vehicles were removed, that achieves more than removing the 2,500 lowest emitting vehicles from the total tested fleet. Surveys of vehicle populations have demonstrated that emissions systems had been tampered with on over 40% of the gross polluters, and an additional 20% had defective emission control equipment [101]. No matter what changes are made to gasoline, if owners "tune" their engines for power, then the majority of such "tuned" vehicle will become gross polluters. Professional repairs to gross polluters usually improves fuel consumption, resulting in a low cost to owners ( $32/pa/Ton CO year ). The removal of CO in the Provo example above was costed at $200/Ton CO, compared to Inspection and Maintenance programs ($780/Ton CO ), and oxygenates ( $1034-$1264/Ton CO in Colorado 1991-2 ), and UNOCALs vehicle scrapping programme ( $1025/Ton of all pollutants ). Thus, identifying and repairing or removing gross polluters can be far more cost-effective than playing around with reformulated gasolines and oxygenates. A recent study has confirmed that gross polluters are not always older vehicles, and that vehicles have been scrapped that passed the 1993 new vehicle emission standards [102]. The study also confirmed that if estimated costs and benefits of various emission reduction strategies were applied to the tested fleet, the identification and repair techniques are the most cost-effective means of reducing HC and CO. It should be noted that some strategies ( such as the use of oxygenates to replace aromatics and alkyl lead compounds ) have other environmental benefits. Action Vehicles Estimated % reduction % reduction Affected Cost per $billion (millions) ($billion) HC CO HC CO Reformulated Fuels 20 1.5 17 11 11 7.3 Scrap pre-1980 vehicles 3.2 2.2 33 42 15 19 Scrap pre-1988 vehicles 14.6 17 44 67 2.6 3.9 Repair worst 20% of vehicles 4 0.88 50 61 57 69 Repair worst 40% of vehicles 8 1.76 68 83 39 47 ------------------------------ ...part III