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biofuels biodiesel: additives Are significant improvements in the quality of biodiesel and its blends possible

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

Europe’s 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 directive’s 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

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.

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

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Figure 1

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 problems, such as higher levels of

70 february 2007

Dr. Robert Quigley is a Product Manager within The Lubrizol Corporation’s fuels, refinery and oilfield

Dr. Robert Quigley is a Product Manager within The Lubrizol Corporation’s 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.

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

additives have reduced many of the problems encountered with biodiesel Figure 2 biofuels international    

Figure 2

biofuels international

 
 

biofuels biodiesel: additives

biofuels biodiesel: additives blends, such as fuel system corrosion, water separation and increased fuel foaming.

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.

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.

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

oxidation of the FAME to low- molecular weight acids. As illustrated in Figure 6, use of a multifunctional diesel fuel additive formulated with an effective corrosion inhibitor can dramatically reduce the

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

corrosive 30 tendency of biodiesel fuels. 24 25 22 20 17.5 15 13 10 3.6%
corrosive
30
tendency of
biodiesel fuels.
24
25
22
20
17.5
15
13
10
3.6%
5
1
000
0
1.1%
3
5
7
10
Standing Time (min)
0.0%
Figure 5
B0
B10 Base
B10 + Dispersant
B5 Base
Additive
Test Fuel
90
is well known
that the
80
70
unsaturated
60
50
fatty acids
found in
40
30
20
10
0
0.0
1.0
2.0
3.0
Multifunctional Additive Relative Treat
typical
feedstocks,
such as rape
and soy, are
the cause of

fuel. Treating the B10 blend with

a

typically used in the market reduced power loss by 70% compared to the untreated fuel.

dispersant at a treat rate

4.0%

3.5%

3.0%

2.5%

2.0%

1.5%

1.0%

0.5%

0.0%

Figure 4

Impact on water separation and corrosion

It

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

is well known that blending

this susceptibility. These unsaturated fatty acids may react with atmospheric oxygen, forming peroxides and result in a variety of problematic degradation byproducts, including corrosive, low- molecular weight acids and bio- polymers. These byproducts are the principal cause of sludge and lacquer in diesel fuel injection systems, and they also contribute to fuel filter plugging. For this reason, vehicle and fuel

injection equipment manufacturers have expressed concern about the careful control of oxidation stability. In Europe, biodiesel oxidation

Figure 6

Foaming

Blending FAME into

conventional mineral diesel fuel can worsen the foaming tendency, which becomes evident when filling a vehicle’s fuel tank at a service station. Testing carried out with the industry BNPe laboratory bench test has shown significant increases in foam decay time as the proportion of RME is increased from 5% to 30% (Figure 7). However, the same testing shows that pure B100 does not foam. Treatment of B5 to B30 blends with multifunctional diesel fuel additives containing an antifoam component shows excellent control of this increased

foaming tendency.

120

100

80

60

40

20

0

of this increased foaming tendency. 120 100 80 60 40 20 0 B0 Figure 7 B30

B0

Figure 7

B30

Biodiesel Content

B5

B100

50 45 40 35 30 25 20 15 10 5 0 B0 B5 B30 B100
50
45
40
35
30
25
20
15
10
5
0
B0
B5
B30
B100
Mineral Fuel - RME blend
50 45 40 35 30 25 20 15 10 5 0 B0 B5 B30 B100 Mineral

Base

Disp

Figure 3

The impact an RME B10 blend has on nozzle fouling and

power loss was also assessed

in the Peugeot DW-10 engine.

control. Another concern is the possibility that biodiesel and its blends can

cause 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

Base + MFDA
Base
+ MFDA

biofuels international

february 2007 71

biofuels biodiesel: additives stability is controlled through the Rancimat test in the EN 14214 specification,

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.

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.

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

low-

temperature 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

performance of many biodiesel types and their

blends. As with traditional cold flow additives for diesel fuel, the additive must be matched to the

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 low- temperature 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 seen in diesel fuels, where base fuel properties determine the amount of

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 low- temperature 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.

20 18.7 18 16 14 12.9 12 10 8.0 7.6 8 6 4.5 4 2
20
18.7
18
16
14
12.9
12
10
8.0
7.6
8
6
4.5
4
2
0
None
BHT
TBHQ
DEV 1
DEV 2
Antioxidant

Figure 9

Cold-weather

performance

All biodiesels are not created

equal when it comes to cold- weather

operability. As with diesel

fuels,

biodiesels and

blends with

mineral fuel

can form

7 6 6 5 4.5 4 3 2.5 2 1 0 0 10 20 30
7
6
6
5
4.5
4
3
2.5
2
1
0
0
10
20
30
40
50

Time after production (days)

Figure 8

Selection of an appropriate antioxidant additive is critical because many have been found to be ineffective in FAMEs. Some antioxidants, such as tert- butyl hydroquinone (TBHQ), may be very effective but are not feasible commercially due to extremely high cost. Beta- hydroxytoluene (BHT) has a reasonably good impact on oxidation stability, so it is typically used in the biodiesel industry, even though treat rates tend to be high. Improved antioxidants that provide a better balance between cost and performance may be needed. Figure 9 compares Rancimat induction times for RME, both untreated and treated, with several antioxidants. BHT improves the induction time over the specification minimum, while TBHQ has a dramatic impact on

0 0.0% 0.3% 0.6% 1.8% -2 -4 -3 -6 -8 -7 -10 -9 -12 -14
0
0.0%
0.3%
0.6%
1.8%
-2
-4
-3
-6
-8
-7
-10
-9
-12
-14
-16
-15
Flow Improver %Weight

Figure 11

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 cold- weather operation. Such quality improvements cost-effectively reassure consumers of the performance of these fuels, thereby increasing their acceptance in the wider marketplace.

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

solids as ambient temperatures drop. Biodiesels with a higher saturated fatty ester content form more solids and begin to form precipitates at significantly higher temperatures than those containing higher amounts of unsaturated fatty esters. For example, biodiesel produced from rapeseed has the best low- temperature properties of all major classes of vegetable oil feedstock. Soybean-derived biodiesel has intermediate low- temperature performance, and

biodiesel made from palm and coconut oils, which are

PP (ºC) CFPP (ºC) 20 15 10 5 0 -5 Rape Soy Palm Tallow -10
PP (ºC)
CFPP (ºC)
20
15
10
5
0
-5
Rape
Soy
Palm
Tallow
-10
-15
-20
Biodiesel Feedstock
Figure 10

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