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Corrosion issues of ethanol blends

and the effect of water

ABLCNext Conference – San FranciscoAfternoon Track B – Ethanol, Diesel and Jet FuelsNovember 11, 2014By: Hans Keuken, CEO

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Composition of ethanol containing fuels

Code

Composition

Countries Western

Europe

today

USA today

(Western

Europe in

near future)

2010 USA

EPA

approval

cars > 2000

Brazil USA /

Europe

Brazil

E5 E10 E15 E25 E85 E100

min 95%

gasoline

max 5%

anhydrous

ethanol

max 10%

anhydrous

ethanol

min 90%

gasoline

max 15%

anhydrous

ethanol

min 85%

gasoline

min 75%

gasoline

100%

hydrous

ethanol

(contains

on average

5.3 vol.%

water)

max 25%

anhydrous

ethanol

max 85%

anhydrous

ethanol

min 15%

gasoline

~5.3% water

Gasoline blends for

use in regular cars

Flex Fuel

Vehicles

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Hydrous & anhydrous ethanol

•Hydrous ethanol can be distilled up to 3.5 volume%

water (limit = azeotrope)

•Anhydrous ethanol is further dehydrated to contain

less water typically < 1%

•Dehydration units require additional capital &

operating cost (energy)

•Brazilian prices in US$/ltr. can be found at www.cepea.esalq.usp.br/english/ethanol/?id_page=243

Hydrous ethanol is approximately 15% cheaper

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Conventional wisdom in blending

•Gasoline and water do not mix (2-liquid-phase system).

•One expects simply water to create corrosion.

•Ethanol has to be free of water to be blended in gasoline.

•Blends of dry ethanol with gasoline will pick-up water, e.g. from air humidity, logistical systems.

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Shell confirmation hydrous ethanol for E10+ in EU

Shell Research - Amsterdam Sept. 2006

- Straight gasoline: haziness observed at -5ºC

- Straight gasoline + 5% hydrous Ethanol (hE5): haziness observed at -34ºC

- 10, 15 and 20% hydrous Ethanol: haziness could not be detected at -60ºC

Phase separation is not observed in any of the

above blends!

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Phase Stability Ethanol Blends in EU

7

E10E15

E85

ANP

ASTM D 4806

EN15376 ANP Hydrous

(E100)

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Effect of 1% TBA (C4 alcohol)

8

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Phase Stability Ethanol Blends European E1-E5 versus

US E10 and US E15 based on RFA 2012 data

9

E85

ANP

ASTM D 4806

EN15376 ANP Hydrous

(E100)

US

E10

US

E15

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A lower aromatic content results in a lower water tolerance

E15 blend can tolerate approximately

0.75v% water at 60°F

Copyright © 2012 Renewable Fuels Association.

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Wet Corrosion Tests by Sasol

• Sasol’s “wet corrosion” tests (ASTM D665) of E2 and E10 on aluminum parts.

• Wet corrosion is corrosion in the presence of water

• Sasol found:

• The E0 and E2 blends were corrosive during the wet corrosion test.

• These fuels required additisation in order to prevent wet corrosion.

• The E10 blends were not corrosive in the wet corrosion test.

Presented at the XVIII International Symposium on Alcohol Fuels

(Delhi – India ISAF 2010)

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Ternary Diagram & Phase Separation

12

Weight Percent Ethanol

20%

40%

60%

80%

ETHANOL

WATER

20%

40%

60%

80%

Weight P

erce

nt W

ater

GASOLINE 20%40%60%80%

Weight Percent Gasoline

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Conductivity E10’s adding salt water

Salt Water E10, dry E10, 0.2% water E10, 0.5% water

0,10% 0,003 0,010 0,015

0,20% 0,015 0,008 0,010

0,30% 0,006 0,010 0,011

0,40% 0,015 0,009 0,010 salt drops out

0,50% 0,203 0,009 0,012 free water

0,60% 0,276 0,009 0,012

0,70% 0,259 0,009 0,012

0,80% 0,201 0,020 0,013

0,90% 0,185 0,018 0,013

1,00% 0,182 0,018 0,012

Test by SGS to see if more

hydrous E10 picks up more

salts?

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Conductivity E10’s adding salt water

Conductivity E10's adding salt water

-0,050

0,000

0,050

0,100

0,150

0,200

0,250

0,300

0,00% 0,20% 0,40% 0,60% 0,80% 1,00% 1,20%

% salt water (3 gram/liter) added

Co

nd

uc

tiv

ity E 10 dry

E10, 0.2% water

E10, 0.5% water

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Sulfate deposits in E85

•Sulfate deposits block injectors in E85 Flex Fuel Vehicles in Sweden when they drive on E85 only.

• The solubility of the Ca, K, Mg and Na sulfates in E85 happens to be almost zero ppm.

•Brazil does not have sulfates blocking injectors, but they use full hydrous E100 instead of anhydrous E85.

•Besides the effect of solubility, these K, Na, Ca and Mg sulfates also form hydrates.

These hydrated crystals will probably not survive and disintegrate when exposed to the higher temperatures in the injectors.

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Clean injector after 35.000 km partly driving on hydrous E85

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Solubility of Na2SO4 in E85

Vol.% water in the fuel ethanol 0.01 0.11 0.25 1.01 2.51 5.01

Sulfate content E85 (adding 1000 mg/kg Na2SO4) 0.09 0.11 0.14 0.18 12.9 40.6

Precipitation

85% of current max. spec = 3,4 ppm

0

5

10

15

20

25

30

35

40

45

0 1 2 3 4 5 6

Su

lfa

te s

olu

bil

ity (

pp

m(m

))

Vol.% water

E85 - SO42- solubility

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Dry Corrosion Research Japan (JARI) SAE paper 2005-01-3708 Appendix 3.1 Copyright © 2005 SAE International

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Dry Corrosion Research Japan (JARI)SAE paper 2005-01-3708 Appendix 1.1 Copyright © 2005 SAE International

Material in

fuel systemType

Gasoline

100%

E50 with

150 ppm water

(overall) *

E50 with

500 ppm water

(overall) *

E50 with

2000 ppm water

(overall) *

E50 with

10.000 ppm water

(1%, overall) *

Aluminum A1050 OK complete dissolution complete dissolution complete dissolution OK

Aluminum A6061 OK complete dissolution complete dissolution OK OK

Aluminum ADC12 OK reduction in mass reduction in mass OK OK

Steel change in surface OK OK OK change in surface

Copper change in surface change in surface change in surface change in surface change in surface

Nickel OK OK OK OK OK

Zinc OK change in surface change in surface OK change in surface

Tin OK change in surface change in surface change in surface OK

Legend: OK No change observed

change in surface change in color for instance, but no reduction in mass

* 1 vol% overall water in E50 means a concentration of 2 vol% water in the added ethanol

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Alcoholate (dry) corrosion of aluminum

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Alcoholate (dry) corrosion of aluminum

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Dry corrosion E5, E10, E15 and E20

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Water as inhibitor in E100

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Effect of water on alcoholate corrosion

A little water works as fluoride in

toothpaste and avoids corrosion

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Hydrous ethanol standard (NTA 8115) for E10+ blending

at 2,52%

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“Water Injection”70 years proven technology!

2010

1940’s

1983

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Energy efficiency in a modern down sized turbo

charged Volvo S60 T4F (Flex Fuel Vehicle)

2,15

2,2

2,25

2,3

2,35

2,4

2,45

2,5

2,55

2,6

2,65

0,00% 1,00% 2,00% 3,00% 4,00% 5,00% 6,00% 7,00%

Water fraction (vol)

MJ

co

ns

um

ed

pe

r k

m

Normal Distance Long Distance

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Tests results by the European Commission

Emission tests of hydrous versus anhydrous to quantify the effect of

a higher water content in ethanol containing gasoline.

E10 - hE10

E15 - hE15

E70 - hE70

E85 - hE85

“The results suggest that there are no marked differences on the

regulated and unregulated emissions when hydrous ethanol blends are used instead of anhydrous ethanol blends.”

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Netherlands in 2008 hE15 opening by Minister Cramer

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Currently 181 gas stations selling hydrous E15

6.5 years experience

Approximately:

5000 tankings/day

and

100,000 cars

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General technical conclusions

• E10 in the US is less corrosive than E10 in Europe due to a higher water content in the ASTM D 4806.

• We need a minimum water content in fuel ethanol.

• We still need a maximum water content to avoid phase separation (wet corrosion) issues also in mixed tanking scenario’s.

• More hydrous ethanol blends do not pick up more contaminants.

• A higher water content in E85 avoids sulfate deposits blocking injectors.

• Water injection has a positive effect on the Well to Wheel energy efficiency and reduces overall emissions.

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• The water tolerance of the current US gasoline is not high enough to allow full hydrous E15 throughout the country.

• Full hydrous E85 is feasible next to an anhydrous E10 or E15.

This will not result in phase separation in mixed tanking scenarios!

• Hydrous E85 can be 10% cheaper than the current anhydrous E85 and could stimulate the sales of E85 and help to overcome the blending wall.

• Skipping expensive dehydration units would be of interest for new

2G advanced ethanol plants.

“Hydrous ethanol” potential in US

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