Moray S. Stark,* John R. Lindsay Smith, Julian J. Wilkinson Department of Chemistry, University of...
51
Moray S. Stark,* John R. Lindsay Smith, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK STLE 2006: Calgary 7 th - 11 th May 2006 The Degradation of Hydrocarbons Base Fluids at Elevated Temperatures Department of Chemistry
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Transcript of Moray S. Stark,* John R. Lindsay Smith, Julian J. Wilkinson Department of Chemistry, University of...
Moray S. Stark,* John R. Lindsay Smith, Julian J. Wilkinson
Department of Chemistry, University of York, York YO10 5DD, UK
STLE 2006: Calgary 7th- 11th May 2006
The Degradation of Hydrocarbons Base Fluids
at Elevated Temperatures
Department of Chemistry
[email protected] www.york.ac.uk/res/gkg
Moray S. Stark,* John R. Lindsay Smith, Julian J. Wilkinson
Department of Chemistry, University of York, York YO10 5DD, UK
STLE 2006: Calgary 7th- 11th May 2006
The Degradation of Hydrocarbons Base Fluids
at Elevated Temperatures
Chemical Mechanisms of Base Fluid Oxidation
Viscosity Modelling of Oxidised Base Fluid
Department of Chemistry
The Degradation of Hydrocarbons Base Fluids
at Elevated Temperatures
No. of Carbons
XHVI™ 8.2 (average) 39(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
+ ROO. .
+ ROOH
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
O
+ RH
OH
+ R.
Department of Chemistry
Traditional Alkane Oxidation Mechanism
+ ROO. .
+ ROOH
.+ O2
OO
OO
+ RH
OO
H
+ R.
OO
H
O
O + H
O
+ RH
OH
+ R.
O
+ H2O
OO
H
Department of Chemistry
Traditional Alkane Oxidation Mechanism
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
Pristane 19
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
No. of Carbons
XHVI™ 8.2 (average) 39
Hexadecane 16
Pristane 19
Squalane 30
(random example)
Models of Hydrocarbon Base-Fluids
Department of Chemistry
Tertiary Carbons in Base-Fluids
0
5
10
15
20
25
PA
O
Gro
up
III
iso
de
wa
xed
Gro
up
III
hyd
rocr
ack
ed
Gro
up
II
Gro
up
I
tert
iary
C (
%)
range
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAO’s and Mineral OilsPresentation, STLE Annual Meeting, Houston, 2002
Tertiary Carbons in Base-Fluids
S. McKenna, M. Casserino, K. Ratliff, Comparing the Tertiary Carbon Content of PAOs and Mineral OilsPresentation, STLE Annual Meeting, Houston, 2002
0
5
10
15
20
25
PA
O
Gro
up
III
iso
de
wa
xed
Gro
up
III
hyd
rocr
ack
ed
Gro
up
II
Gro
up
I
Sq
ua
lan
e
Pris
tan
e
tert
iary
C (
%)
range
Bench-Top Reactors
Department of Chemistry
time (min)
Department of Chemistry
Oxidation of Branched Alkanes : GC Analysis
Pristane Oxidation: 1000 mbar O2, 170 ºC, 20 minutes
GC conditions: ZB-5 column, 50-340 ºC, 6 ºC min-1
Product Identification: EI-MS and CI-MS
Department of Chemistry
Oxidation of Branched Alkanes : Alcohols
{e.g.
OH
Department of Chemistry
Oxidation of Pristane : Tertiary Alcohols
OH
OH
Department of Chemistry
Oxidation of Pristane : Secondary Alcohols
e.g.
{
OH
Department of Chemistry
Oxidation Products : Alcohols, Pristan-2-ol
OH
0
20
40
60
80
100
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
0
20
40
60
80
100
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
Department of Chemistry
Oxidation Products : Alcohols, Pristan-6-ol
OH
OH
0
20
40
60
80
100
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
Department of Chemistry
Oxidation Products : Secondary Alcohols
OH
OH
OH
e.g.
0
20
40
60
80
100
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
Department of Chemistry
Oxidation Products : Ratio of Alcohols
OH
OH
OH
e.g.
4.3secondary
tertiary
0
20
40
60
80
100
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
Department of Chemistry
Oxidation Products : Ratio of Alcohols
OH
OH
OH
e.g.
15
Hsecondary per
Htertiaryper
Department of Chemistry
Formation of Alcohols
OO H
O.
Department of Chemistry
Formation of Alcohols
OO H
O.
O OH.
+ RH + R.
Department of Chemistry
Formation of Volatile Products
OO H
O.
O OH.
+ RH + R.
O.O .+
O
O
Department of Chemistry
Formation of Volatile Products
+
+ RH
O
O
Department of Chemistry
Formation of Volatile Products
+
+ RH
O
O
+ .
Department of Chemistry
Formation of Volatile Products
+ RH
O
Department of Chemistry
Oxidation of Branched Alkanes : Pristanones
e.g.{
Department of Chemistry
Formation of Volatile Ketones and Alkanes
O
0
10
20
30
40
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
Department of Chemistry
Formation of Volatile Ketones and Alkanes
0
10
20
30
40
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
O
Department of Chemistry
Formation of Volatile Ketones and Alkanes
0
10
20
30
40
0 20 40 60 80
Time (min)
Co
nce
ntr
atio
n (
10-3
mo
l d
m-3
)
O
O
+
Department of Chemistry
Reactions of Alkyl Radicals
.+ RH .+ R
Department of Chemistry
Reactions of Alkyl Radicals
.+ RH .+ R
OO
+ O2 .
Department of Chemistry
Reactions of Alkyl Radicals
.+ RH .+ R
OO
+ O2 . OO
H+ RH
Department of Chemistry
Reactions of Alkyl Radicals
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
Department of Chemistry
Reactions of Alkyl Radicals
.+ RH .+ R
OO
+ O2 . OO
H+ RH
O
H + H2O
O
OH
Department of Chemistry
Formation of Volatiles : Lactones
{
O
O
O
O
Department of Chemistry
Formation of Volatiles : Lactones
{
O
O
O
O
O
OHOH
- H2O
Paris Taxis
Lubricant Viscosity Increase During Use
Department of Chemistry
0
5
10
15
0 10 20 30 40 50 60
Distance (1000 km)
Vk1
00 (
cSt)
Oil Change Oil Change
Viscosity Increase due to Lubricant Degradation
Due to Formation of:
Polar Products Alcohols, Carboxylic Acids, etc.
Polymeric Products Dimers, Trimers, etc. of Base Fluid
Insoluble Products Aggregating Particles
e.g. Soot, Micelles of Highly Polar Products
Department of Chemistry
Viscosity Increase due to Lubricant Degradation
Department of Chemistry
Conditions : Pristane (tetramethylpentadecane) Oxidation in Flow ReactorContinuous O2 flow, Sampling at 6 minutes, 150 - 210 ºC
0
20
40
60
80
100
120
140 160 180 200 220
Temp ºC
Vis
cosi
ty in
crea
se (
%)
1.44
1.84
2.24
2.64
3.04
Visco
sity (cSt)
Viscosity Modelling : Effect of Polar Products
dodecane - docecanol model mixtures
Department of Chemistry
0
100
200
300
400
500
600
700
0 20 40 60 80 100
Alcohol/Alkane (%)
Vis
cosi
ty (
%)
0
2
4
6
8 Visco
sity (cSt)
OH
+
Viscosity Modelling : Effect of Polar Products
dodecane - docecanol model mixtures
Department of Chemistry
0
100
200
300
400
500
600
700
0 20 40 60 80 100
Alcohol/Alkane (%)
Vis
cosi
ty (
%)
0
2
4
6
8 Visco
sity (cSt)
OH
+
Viscosity Modelling : Effect of Polar Products
dodecane - docecanol model mixtures
Department of Chemistry
95
100
105
110
0 2 4 6 8 10
Alcohol/Alkane (%)
Vis
cosi
ty (
%)
1.3
1.4
1.5
Visco
sity (cSt)
OH
+
Conclusions
Chemical Mechanisms for Formation of Polar Products
Volatile Products
Viscosity Increase during Lubricant Oxidation
NOT due to Polar Oxidation Products
Department of Chemistry
Future Work
Quantify Polymeric Products
Examine Consequent Viscosity Change
Acknowledgements
University of Leeds Martin Priest, Peter Lee
University of York Trevor Dransfield
Shell Ian Taylor
Infineum Chris Booth, Simon Chung
Financial Support
Shell Global Solutions, Infineum, EPSRC
Moray Stark [email protected] www.york.ac.uk/res/gkg
