Methods for testing

biodegradation of lubricants

Umweltvertrgliche Schmierstoffe 24.11.2010-26.11.2010

TAE Esslingen
November 2010 Dr. Ben Mller-Zermini Folie 1
The Coordinating
g European
p Council
for the Development of performance tests for fuels, lubricants and other fuels

CEC is an Industry-
Industry-based organisation which develops
Test Methods for the performance testing of Automotive
Engine Oil, Fuels & Transmission Fluids.

engine tests rig tests laboratory tests

November 2010 Dr. Ben Mller-Zermini Folie 2

 The Coordinating
g European
p Council
for the Development of performance tests for fuels, lubricants and other fuels

Quality Surveillance of CEC

The quality standards of CEC are very high:
Steady monitoring of results coming from mandatory tests with
Reference Oils
Active Surveillance group for each test method
- Discussion and removal of arising problems
- Arrange and conduct regular Round Robin Tests
E
Every participating
ti i ti llaboratory
b t mustt b
be certified
tifi d according
di tto ISO
17025
Online
O li T Testt Monitoring
M it i System
S t since
i 2009
Several Support Groups to assist Development Groups in difficult
questions
ti
November 2010 Dr. Ben Mller-Zermini Folie 3
Biodegradation Test Procedure
CEC--L-33-
CEC 33-A-93 (unsupported)

Preparation of flasks:
0-day flasks 21--day flasks
21 poisoned flasks
3 flasks 3 flasks 2 flasks
bi ti and
biotic d abiotic
bi ti
no loss 100% abiotic loss
loss
E t ti off flasks:
Extraction fl k
with Freon or Tetrachloroethylene Determination
Analysis of extract: of oil loss
Infrared spectroscopy
November 2010 Dr. Ben Mller-Zermini Folie 4
 CEC--L-33-
CEC 33-A-93
Analysis
Extraction solvent must not have C-
C-H-bonds
- only a few solvents can be used such as 1,1,2-
T i hl
Trichlorotrifluoroethane
ifl h (F
(Freon)) or T
Tetrachloroethene
hl h
92,3
example IR spectra:
80
2930 cm-11 Freon, without oil
70
0% oil
60
21 day flask
50 0 day flask
%T
40

66% oil
30

20
solvent
l t which
hi h contains
t i
10
C-H bonds not
100% oil
0,0
3400 0
3400,0 3200 3000
cm-1
2800 260 applicable

November 2010 Dr. Ben Mller-Zermini Folie 5

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CEC--L-33-
CEC 33-A-93
Problems

Freon destroys ozone in atmosphere (it is a CFC!!)

laboratory work with Freon is difficult
volatile liquid with high density Cl F
Freon is very expensive (750 / 2,5
2 5 L)
Cl F

Tetrachloroethene is toxic F Cl

Cl Cl

N Xn
Cl Cl

November 2010 Dr. Ben Mller-Zermini Folie 6

 Alternative analysis
CEC--TDG-
CEC TDG-L-103

Using gas chromatography instead of infrared spectroscopy

like
lik in
i DIN EN ISO 9377
9377--2 (H 53):
53)
Determination of hydrocarbon oil index (hydrocarbons in water)
infrared spectroscopy - IR gas chromatography - GC
determination of C-
C-H bonds determination of C-
C-H bonds
because of absorbance of infrared because of combustion after
light only a few solvents separation in components
applicable many solvents applicable

November 2010 Dr. Ben Mller-Zermini Folie 7

 Alternative analysis
CEC--TDG-
CEC TDG-L-103

In a mini round robin test CEC-

CEC-TDG-
TDG-L103 showed
goodd correlation
l ti bbetween
t GC andd IR analysis
l i
In this test the results obtained from GC analysis
were even more precise than the results obtained
from IR analysis
IR GC
R (RL110) 6,2 3,5
R (TMP
(TMP--Ester) 8,4 5,1

November 2010 Dr. Ben Mller-Zermini Folie 8

Second Problem: Sample introduction
CEC--TDG-
CEC TDG-L-103
For a fast biodegradation the sample must be fine dispersed in the
water phase. Bacteria cannot enter in oil phase, only oil/water
i t f
interface can bbe used
d as food.
f d

In CEC-L-33-A-93 mother
solution solvent was Freon. Due
to its
it s high density it kept the test
oil on the bottom flask and led to
a fine dispersion
p of oil in water.

November 2010 Dr. Ben Mller-Zermini Folie 9

Second Problem: Sample introduction
CEC--TDG-
CEC TDG-L-103

How can oil be dispersed in water without Freon?

possible solutions possible problems
using a solid carrier
carrier, ee.g.
g glass fibres extraction of oil residues from carrier
or sand not in all cases possible
using polar solvents for mother oil sample solubility ?
solution, e.g. esters
using detergents or emulsifiers extraction step difficult
phase separation!
ultrasonic sound only short-term efficiency

November 2010 Dr. Ben Mller-Zermini Folie 10

 Results of method development
CEC--TDG-
CEC TDG-L-103
Results of method development CEC
CEC--TDG-
TDG-L-103:
Sample preparation in polar solvent homogenous dispersion
Reduction of sample size less chemicals necessary
Extraction with a hydrocarbon not dangerous for the environment
GC--analysis high precision
GC

unpolar hydrocarbon polar ether

November 2010 Dr. Ben Mller-Zermini Folie 11

 CEC-TDG-
CEC-TDG-L-103
time schedule

Conclusion of phase 1 End of 2010

Approval of phase 1 Q1 2011
Round Robin Test (phase 2) Q2 2011
Conclusion of phase 2 Q3 2011
Approval off phase 2 Q 2011
Q4

November 2010 Dr. Ben Mller-Zermini Folie 12