biofuels biodiesel: additives

Are significant improvements in the quality of biodiesel and its blends possible with the use of quality multifunctional diesel fuel additives, antioxidants and cold flow additives, in areas of concern such as fuel system corrosion?

Biodiesel: The good, the bad and additives

by Robert Quigley

Europes biodiesel market

The use of biodiesel as a road transportation fuel is increasing throughout Europe as member states seek to comply with the European Directive 2003/30/EC. Figure 1 illustrates the estimated volume of biodiesel that will be required to meet the directives target of 5.75% biofuel consumption by the end of the decade. Pure biodiesel (B100) continues to be used, particularly by fleets. However, blending of up to 5% biodiesel into mineral fuel is now widespread, with Germany being the leading consumer. As long as the biodiesel component complies with the EN 14214 standard, the resulting blend is permitted
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within the EN 590 specification for diesel fuel. Current CEN (European Committee for Standardisation) discussions are focused on permitting the proportion of biodiesel in blends to rise to 10%. As a result of this widespread presence of biodiesel, some multifunctional diesel fuel additives have been specifically designed to perform in biodiesel and its blends.

Dr. Robert Quigley is a Product Manager within The Lubrizol Corporations fuels, refinery and oilfield additives group. His responsibilities cover diesel and gasoline additives in the European market area. Dr. Quigley has worked in the field of fuel additive chemistry since obtaining his D. Phil. degree in transition metal chemistry from the University of Sussex, UK, in 1992. He has been granted five patents and has authored a number of papers on subjects including additive performance in biodiesel and diesel fuel lubricity improver technology.

Performance concerns
Substituting biodiesel for conventional fossil fuels is widely considered to have societal benefits, such as reducing greenhouse gas emissions and supporting rural agricultural economies. However, there are potential problems when using it in vehicles. Biodiesel blends can show an increase in water separation and fuel foaming, compared to pure fossil fuels. In addition, blending with low-stability biodiesel can lead to fuel system 2010 problems, such as higher levels of

injector deposits and corrosion arising from the generation of low- molecular weight acids. OEMs and fuel injection equipment manufacturers have reported this type of damage in the field. In addition, advanced direct injection engines may lose significant power when poor quality biodiesel blends are used. An effective performance diesel fuel additive can help guard against such problems.

Other well understood issues include reduced oxidation stability and cold filtration properties, when compared to standard mineral diesel fuels (Figure 2).

Additives
Quality multifunctional diesel fuel additives have reduced many of the problems encountered with biodiesel

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Figure 1

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biofuels biodiesel: additives

blends, such as fuel system corrosion, water separation and increased fuel foaming. Injector fouling tests show that multifunctional additives can reduce the injector deposit levels generated when biofuel blends are used. Specialised flow improvers are also available to address the challenging low-temperature operability profile of many biodiesel fuels, while specific antioxidants can help to stabilise the fuel against the degradation that may lead to fuel system deposits and corrosion. The RME used in the blend did not contain antioxidant additives. The results of keep clean testing for dispersant treated and base blends are shown in Figure 4. These indicate greater power loss with the unstabilised B10 fuel compared to the pure mineral fuel. Treating the B10 blend with a dispersant at a treat rate typically used in the market reduced power loss by 70% compared to the untreated fuel.
4.0% 3.5% 3.0% 2.5% 2.0% 1.5% 1.0% 0.5% 0.0% B0 B10 Base Test Fuel B10 + Dispersant 0.0% 1.1% 3.6%

oxidation of the FAME to lowmolecular weight acids. As illustrated in Figure 6, use of a multifunctional diesel fuel additive formulated with an effective corrosion inhibitor can dramatically reduce the corrosive 30 tendency of 24 biodiesel fuels. 25
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Oxidation stability
One of the most significant current concerns with the use of biodiesel fuels is their reduced oxidation stability compared to standard mineral diesel fuels. It

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Fuel Injector Cleanliness

A key and frequently raised concern about using biodiesels is their impact on injector cleanliness and the potential for serious injector coking and nozzle fouling. The standard CEC (Co-ordinating European Council for development of performance tests) 10-hour XUD-9 test procedure was used to compare the performance of untreated and dispersant additive treated rapeseed methyl ester (RME) mineral diesel blends. For comparative purposes, the same petroleum diesel fuel was evaluated in the test. These results are shown in Figure 3. The results show that using a dispersant at a treat rate typically used in the market is effective in fuels containing fatty acid methyl ester (FAME), and there are significant improvements in injector cleanliness compared to base fuel.
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B5 Base Additive

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Impact on water separation and corrosion

It is well known that blending biodiesel into mineral fuel results in reduced water separation capability, which can cause problems such as fuel filter blocking, increased fuel system corrosion and microbial contamination. For example, Figure 5 shows results from ASTM D1094 water separation testing of a base B5 blend sampled from the German market. The extremely poor water separation properties of the fuel are evident. In comparison, the presence of multifunctional diesel fuel additive provides excellent emulsion control. Another Base concern is the Disp possibility that biodiesel and its blends can cause B100 increased corrosion of the vehicle fuel injection system. In addition to the risks from higher levels of water entrainment in the fuel, corrosion also can result from

Figure 3

The impact an RME B10 blend has on nozzle fouling and power loss was also assessed in the Peugeot DW-10 engine.

is well known that the 70 unsaturated 60 fatty acids 50 found in 40 30 typical 20 feedstocks, 10 such as rape 0 0.0 1.0 2.0 3.0 and soy, are Multifunctional Additive Relative Treat the cause of this Figure 6 susceptibility. These unsaturated fatty acids may Foaming react with atmospheric oxygen, Blending FAME into forming peroxides and result in conventional mineral diesel fuel a variety of problematic can worsen the foaming degradation byproducts, tendency, which becomes including corrosive, lowevident when filling a vehicles molecular weight acids and biofuel tank at a service station. polymers. These byproducts are Testing carried out with the the principal cause of sludge industry BNPe laboratory bench and lacquer in diesel fuel test has shown significant injection systems, and they also increases in foam decay time as contribute to fuel filter plugging. the proportion of RME is For this reason, vehicle and fuel increased from 5% to 30% injection equipment (Figure 7). However, the same manufacturers have expressed testing shows that pure B100 concern about the careful does not foam. Treatment of B5 control of oxidation stability. to B30 blends with In Europe, biodiesel oxidation multifunctional 120 diesel fuel 100 additives 80 containing an Base 60 antifoam + MFDA 40 component 20 shows excellent 0 control of this B0 B5 B30 B100 increased Biodiesel Content foaming tendency. Figure 7
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biofuels biodiesel: additives

stability is controlled through the Rancimat test in the EN 14214 specification, with a minimum induction time requirement of six hours. Use of the Rancimat method is also being explored in the United States, where a lower three-hour induction time is being considered for the predominantly soy-based methyl esters produced there. Biodiesels that do not meet the minimum induction time standard need to be stabilized with an antioxidant additive. Although an untreated biodiesel fuel made from a feedstock such as rape may meet the European specification when it is produced, its oxidative stability can rapidly degrade during distribution and storage (Figure 8), making use of an antioxidant advisable.
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stability. However, because the cost of TBHQ is approximately ten times more than BHT, it is not feasible on a net treat cost basis. Several developmental antioxidants show effective performance at lower net treat costs than BHT.
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Cold-weather performance

All biodiesels are not created equal when it comes to cold6 6 weather 5 4.5 operability. As 4 with diesel 3 2.5 fuels, 2 biodiesels and 1 blends with 0 0 10 20 30 40 50 mineral fuel Time after production (days) can form solids as Figure 8 ambient temperatures drop. Biodiesels with a higher Selection of an appropriate saturated fatty ester content antioxidant additive is critical form more solids and begin to because many have been found form precipitates at significantly to be ineffective in FAMEs. higher temperatures than those Some antioxidants, such as tertcontaining higher amounts of butyl hydroquinone (TBHQ), unsaturated fatty esters. For may be very effective but are example, biodiesel produced not feasible commercially due to from rapeseed has the best lowextremely high cost. Betatemperature properties of all hydroxytoluene (BHT) has a major classes of vegetable oil reasonably good impact on feedstock. Soybean-derived oxidation stability, so it is biodiesel has intermediate lowtypically used in the biodiesel temperature performance, and industry, even though treat rates biodiesel made from palm and tend to be high. coconut oils, which are Improved antioxidants that PP (C) CFPP (C) provide a better balance 20 between cost and performance 15 may be needed. Figure 9 10 5 compares Rancimat induction 0 times for RME, both untreated Rape Soy Palm -5 and treated, with several -10 antioxidants. BHT improves the -15 -20 induction time over the Biodiesel Feedstock specification minimum, while Figure 10 TBHQ has a dramatic impact on

extremely high in saturated fatty acids, behaves extremely poorly at low temperatures. These trends are illustrated in Figure 10, where pour and cold filter plugging points are charted for some significant biodiesel feedstock types. The higher the percentage of biodiesel in a blend with mineral fuel, the poorer the lowtemperature properties are likely to be. However, biodiesel blends of B5 or less typically exhibit cold-weather performance similar to the base diesel fuel. Flow improver additives are available that will improve the cold-weather 0 0.0% performance of -2 many biodiesel -4 -3 types and their -6 blends. As with -8 traditional cold -10 flow additives -12 for diesel fuel, -14 the additive -16 must be matched to the Figure 11 composition of the biodiesel. A particular additive might work well in RME but have no effect on soy methyl ester (SME), or vice versa. In Europe, where B100 is routinely used in engines, the most severe measure of lowtemperature operability is meeting a Cold Filter Plugging Point (CFPP) for B100 of less than -20 C. Cold flow additives for RME, with treat rates in the range of 1500 to 3000 ppm, exist to meet this specification. Different sources of RME may require varying amounts of additive to reach the specification. This situation is analogous to that Tallow seen in diesel fuels, where base fuel properties determine the amount of
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additive required. It is also possible to improve the cold-weather operability of soy-derived biodiesel with specialised flow improver additives (Figure 11). Compared to rapeseed-derived methyl esters, these fuels are typically harder to treat for improved lowtemperature performance and, accordingly, additive treat rates of the specialized additives required are significantly higher than those needed for RMEs. It is important to use caution when choosing a flow improver additive for biodiesel-mineral fuel blends. Some additive chemistries can have negative effects when blended into biodiesel blends in which the diesel portion was previously treated with a traditional diesel cold flow additive. Testing can be performed to avoid this scenario.
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Conclusions
Significant improvements in the quality of biodiesel and its blends are possible with the use of quality multifunctional diesel fuel additives, antioxidants and cold flow additives in areas of concern such as detergency, water separation, fuel system corrosion, foaming and oxidation, and during coldweather operation. Such quality improvements cost-effectively reassure consumers of the performance of these fuels, thereby increasing their acceptance in the wider marketplace. Q
For further information on this topic, please contact: biofuels@lubrizol.com. This article was written by Robert Quigley, Diesel and Gasoline Additives Product Manager, Lubrizol Limited

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