Experimental Studies On CO Corrosion of Rubber Materials For Packer Under Compressive Stress in HTHP Gas Wells

Experimental Studies on CO2 Corrosion of
Rubber Materials for Packer under

Compressive Stress in HTHP Gas Wells
Prof. Yuanhua Lin
Southwest Petroleum University

2016 .09
Licensed for the exclusive use of NATIONAL COMPOSITES CENTRE downloaded on 22/12/2016 at 15:38:01. Must not be reproduced,
forwarded or distributed except in accordance with NATIONAL COMPOSITES CENTRE's agreement with Applied Market Information Ltd.
明德笃志博学创新
This document is digitally watermarked.
Outline
一. About me and my current interests
二. Experimental Studies on CO2 Corrosion
of Rubber Materials for Packer under
三. Next work
1. About me
 CNPC Key Lab for Tubular Goods Engineering:

Vice director
 School of Material Science and Engineering:
Dean
 State Key Lab of Oil and Gas Reservoir
Geology and Exploration:
Researcher
 E-mail: yhlin28@163.com
 Mobile: +86-13908085550
 Major: Oil well construction engineering
2. My current interests
 Oil well construction engineering
 Corrosion failure mechanism of non-metal material
 CO2 and H2S corrosion and material selection
 Anti-corrosion inhibitors and sulphur remover
 Mechanics and design of OCTG
Scale Corrosion Failure

Anti-corrosion
ihibitors
2. My current interests
 Develop the specially designed equipment
for full-scale test, or test under the true field
corrosion situation
 Solubility measurement of H2S
 Packer rubber corrosion for CO2
2. My current interest
 Develop the specially designed equipment for
full-scale test, or test under the true field
corrosion situation
 Full-scale test equipment of the packer rubber
 Erosion test system
load
Corrosion
Corrosion
midia
medium
Outline
三. Next work
Outline
1. Packer problems
2. Recent advances
3. Experimental methods
4. Water components
5. Experimental results
6. Summaries
1. Packer problems
Seal bubbling
Sealing ability of packer decreases

Equipment corrosion and deformation
The packer seal bubbling
The smaller load bearing capacity
Cause sustained casing pressure, and increased
operating risks and costs
1. Packer problems
 Packers for the development of oil & gas
fields, functions:
 Separate zone production
 Separate zone water injection
 Acid fracturing, etc...
1. Packer problems
 Problems for packer rubber still exists
 High salinity of produced water and high content of CO2
 The changes of temperature, pressure, flow rate and
other environment factors
 Bearing load and stress under down-hole conditions
Failure of packer
Corrosion of packer rubber
Scale of tubing
2. Recent advances
 Experiments and measurements

 Initial studies usually addressed the change of volume,
quality, tensile strength and hardness of rubber
materials after corrosion in a free state –H. L. Wang and
D. Z. Zeng, etc.
 Recent laboratory investigations of corrosive medium
attack on packer’s sealing ability mainly used O-ring
samples of different rubber materials exposed to various
conditions –N. B. Moore, J. Yamabe, D. G. Young, Q.
Chen, J. Zhu, G. X. Liu and A. Koga, K.
2. Recent advances
 Summary of recent advances
Previous work mainly focused on understanding the
mechanical properties alteration of rubber in a free state
and used non-standard samples, which could not simulate
actual down-hole conditions best in a gas well.
 Object of this study

Evaluate corrosion performances of rubber materials upon
exposure to both gaseous phase and liquid phase of CO2
in a compressive stress state.
 Medium: produced water (not simulated water)
 Materials:
 HNBR (Hydrogenated Nitrile Butadiene Rubber)
 NBR (Nitrile Butadiene Rubber)
 FKM (Fluorine Rubber)
 Micro-analysis methods: SEM, EDS
 Experimental devices:
Self-developed compression Schematic diagram of high

device for corrosion
forwarded or distributed except inexperiment temperature
accordance with NATIONAL COMPOSITES CENTRE's high
agreement with Applied Market pressure
Information Ltd. autoclave
 Experimental situations without load
Stress Temperature Partial pressure

Sample Notes
(kN) (℃) of CO2 (MPa)
NBR 0 90 1 Control group
NBR 0 90 1 Gaseous phase
NBR 0 90 1 Liquid phase
HNBR 0 90 1 Control group
HNBR 0 90 1 Gaseous phase
HNBR 0 90 1 Liquid phase
FKM 0 90 1 Control group
FKM 0 90 1 Gaseous phase
FKM 0 90 1 Liquid phase
 Experimental situations with load
Stress Temperature Partial pressure
Sample Notes
(kN) (℃) of CO2 (MPa)
NBR 0, 3, 6, 9, 12 Room condition - Control group
NBR 0, 3, 6, 9, 12 110 1 Gaseous phase
NBR 0, 3, 6, 9, 12 110 1 Liquid phase
HNBR 0, 3, 6, 9, 12 Room condition - Control group
HNBR 0, 3, 6, 9, 12 110 1 Gaseous phase
HNBR 0, 3, 6, 9, 12 110 1 Liquid phase
Temperature Compression Release

Sample Compressibility Notes
(℃) time (h) time (h)
NBR Room temperature 25% 24 0.5 Control group
NBR Room temperature 25% 24 0.5 Gaseous phase
NBR Room temperature 25% 24 0.5 Liquid phase
HNBR Room temperature 25% 24 0.5 Control group
HNBR Room temperature 25% 24 0.5 Gaseous phase
HNBR Room temperature 25% 24 0.5 Liquid phase
EDS Analysis
of HNBR
Initial state
EDS Analysis
of NBR
 Two rubbers were mainly composed of element C, O, Si, Fe, Zn, etc…
 Its physical and chemical properties depended on different content of
those element.
4. Water components
Ion concentrations of simulated formation water with load (mg/L)
Total
K++Na+ HCO3 - Cl- SO4 2- Ca2+ Mg2+ pH
mineralization
21930 120 59410 250 12540 1255 4.74 95510
 Simulated formation water contains: K+ , Na+ , Cl- , Ca2+ , and Mg2+
 The pH is 4.47
Ion concentrations of simulated formation water without load (mg/L)

Total
K++Na+ HCO3 - Cl- SO4 2- Ca2+ Mg2+ pH
mineralization
5265 1278 6464 505 75 21 6.8 14608
 Simulated formation water contains: K+ , Na+ , Cl- , Ca2+ , and Mg2+

 The pHfor the
Licensed isexclusive
6.8 use of NATIONAL COMPOSITES CENTRE downloaded on 22/12/2016 at 15:38:01. Must not be reproduced,
Outline
 Experimental results
 Experimental results without load
 Experimental results with load
5. Experimental results without load-Tensile properties
30 500
Initial state Gaseous phase corrosion Liquid phase corrosion Initial state
450 Gaseous phase corrosion
25
400 Liquid phase corrosion
Elongation at break (%)

Tensile strength (MPa)
20 350
300
15 250
200
10 150
100
5 50
0
0
NBR HNBR FKM
NBR HNBR FKM
 Tensile strength and elongation change presented a

decrease after corrosion both in gaseous phase and
liquid phase as compared to that in the initial state.
 Decrease of tensile properties in liquid phase was much
more severe than that in gaseous phase environment.
明德笃志博学创新This document is digitally watermarked.
5. Experimental results without load-Hardness
100
90 Initial state Gaseous phase corrosion Liquid phase corrosion
80
70
Hardness (HA)
60
50
40
30
20
10
0
NBR HNBR FKM
Hardness change presented a decrease after corrosion

both in gaseous phase and liquid phase as compared to
that in the initial state.
Decrease of hardness in liquid phase was much more
severe than that in gaseous phase environment.
5. Experimental results without load
 Morphology analysis of dumbbell-shaped simples
 Corrosion resistance of FKM and HNBR was better than that of NBR.
 Rubber exposed to liquid CO2 exhibited greater reactivity than gaseous.
 Slight bubbling and deformation after corrosion appeared.
 NBR
HNBR
FKM
Initial Licensed
State
forwarded
for the exclusive use of NATIONAL COMPOSITES CENTRE downloaded on 22/12/2016 at 15:38:01. Must not be reproduced,
Gaseous
or distributed except phase
in accordance with NATIONAL corrosion
COMPOSITES CENTRE's agreementLiquid phase
with Applied Market Informationcorrosion
Ltd.
5. Experimental results without load
 Morphology Analysis of O-ring simples
 NBR corrosion presented severe deformation than HNBR and FKM.
 Corrosion in liquid phase is more serious than that in gaseous.
Gaseous
phase
Liquid
phase
Initial State NBR HNBR FKM

Outline
 Experimental results
 Experimental results without load
 Experimental results with load
5. Experimental results with load-Weight change
HNBR NBR
 Rate of weight change presented a increase after corrosion

both in gaseous phase and liquid phase under
compression state as compared to that in the initial state.
 Rate of weight change in liquid phase was much more
severe than that in gaseous phase environment.
5. Experimental results with load-Hardness
HNBR NBR
 Hardness presented a decrease after corrosion both in

gaseous phase and liquid phase of CO2 under a
compression state as compared to that in the initial state.
 Corrosion in gas phase was much more severe than that
in liquid phase environment.
5. Experimental results with load-Compression set
HNBR NBR
 Compression set of rubber samples after corrosion in

gaseous and liquid CO2 increased.
 Compression set was more severe in liquid CO2.
 The existence of Load would aggravate CO2 corrosion
to rubber materials.
5. Experimental results with load
 Morphology and Microstructure Analysis - HNBR for example
 Presented different degrees of damage and deformation.
 Deformation increased when the load value become larger.
 Dissolution and swelling after corrosion appeared.
Initial State
After Corrosion
5. Experimental results with load
Morphology and Microstructure Analysis - HNBR for example
5. Experimental results with load-SEM analysis
 Shallow and small size holes presented on the surfaces after corrosion.
 Corrosion became more serious with increasing compression load.
 Corrosion in liquid phase was much more serious than gaseous
phase.
5. Experimental results with load load-EDS analysis
 HNBR Samples
 After Corrosion
 Gaseous Phase
Line Apparent Wt % Atomic Standard

Element k Ratio Wt %
Type Concentration Sigma % Label
C K series 2.99 0.02995 63.91 1.15 85.69 C Vit
O K series 0.48 0.00162 4.72 0.44 4.75 SiO2
Mg K series 0.02 0.00013 0.24 0.26 0.16 MgO
Si K series 0.31 0.00246 3.71 0.32 2.13 SiO2
S K series 0.00 0.00000 0.00 0.00 0.00 FeS2
Ca K series 0.15 0.00131 1.67 0.29 0.67 Wollastonite
Fe K series 0.47 0.00466 6.07 0.56 1.75 Fe
Zn K series 1.35 0.01348 19.68 1.17 4.85 Zn
Total Licensed for the exclusive use of NATIONAL COMPOSITES CENTRE downloaded 100.00
on 22/12/2016 at 15:38:01. Must not100.00
be reproduced,
5. Experimental results with load-EDS analysis
 HNBR Samples
 After Corrosion
 Liquid Phase
Line Apparent Wt % Atomic

Element k Ratio Wt % Standard Label
Type Concentration Sigma %
C K series 2.48 0.02478 57.87 1.34 84.22 C Vit
O K series 0.49 0.00165 4.78 0.50 5.22 SiO2
Mg K series 0.02 0.00010 0.21 0.32 0.15 MgO
Si K series 0.01 0.00010 0.16 0.35 0.10 SiO2
S K series 0.00 0.00000 0.00 0.00 0.00 FeS2
Fe K series 0.49 0.00486 6.36 0.64 1.99 Fe
Zn K series 1.98 0.01984 29.84 1.37 7.98 Zn
Total: 100.00
Licensed for the exclusive use of NATIONAL COMPOSITES CENTRE downloaded on 22/12/2016 at 15:38:01. Must not100.00
be reproduced,
 NBR Samples
 After Corrosion
 Gaseous Phase
Apparent Wt % Atomic Standard

Element Line Type k Ratio Wt %
Concentration Sigma % Label
C K series 10.21 0.10210 70.94 0.64 85.87 C Vit
O K series 1.12 0.00375 4.70 0.41 4.28 SiO2
Na K series 5.04 0.02126 7.18 0.22 4.54 Albite
Al K series 0.15 0.00110 0.26 0.05 0.14 Al2O3
Si K series 0.26 0.00209 0.42 0.06 0.22 SiO2
Cl K series 5.53 0.04837 9.03 0.21 3.70 NaCl
Fe K series 0.62 0.00625 1.20 0.13 0.31 Fe
Zn K series 0.60 0.00601 1.21 0.21 0.27 Zn
Au M series 2.18 0.02179 4.00 0.32 0.30 Au
Total: 100.00 100.00
 NBR Samples
 After Corrosion
 Liquid Phase
Apparent Wt % Atomic Standard

Element Line Type k Ratio Wt %
Concentration Sigma % Label
C K series 3.40 0.03398 35.01 0.61 84.69 C Vit
O K series 0.26 0.00086 1.02 0.16 1.85 SiO2
Na K series 0.06 0.00024 0.19 0.12 0.24 Albite
Mg K series 0.00 0.00001 0.01 0.09 0.01 MgO
Si K series 0.13 0.00102 0.53 0.10 0.55 SiO2
S K series 0.18 0.00154 1.01 0.21 0.92 FeS2
Cl K series 0.02 0.00016 0.10 0.11 0.08 NaCl
Fe K series 0.09 0.00090 0.49 0.20 0.26 Fe
Zn K series 1.32 0.01323 7.22 0.47 3.21 Zn
Au M series 8.82 0.08821 54.14 0.69 7.99 Au
Total: Licensed for the exclusive use of NATIONAL COMPOSITES CENTRE downloaded
100.00
on 22/12/2016 at 15:38:01. Must 100.00
not be reproduced,
6. Summaries
 Tensile mechanical properties of rubber materials
were weakened after corrosion by supercritical CO2
 Corrosion resistance of FKM and HNBR was better
than that of NBR
 Rubber samples exposed to liquid CO2 exhibited
greater reactivity as compared to gaseous CO2.
 Temperature and CO2 partial pressure (MPa) have a
greater impact on corrosion failure of rubbers than
load (kN).
 The existence of load would aggravate CO2 corrosion
to rubber.
6. Summaries
 Rubber samples corroded in liquid phase of CO2
showed the greatest decrease of hardness and
increase of weight change rate and compression set
than that in gaseous phase of CO2.
 Both kinds of rubbers showed decrease of hardness
and increase of weight change rate and compression
set under a compressive stress state.
 Rubber corrosion is affected not only by its chemical
composition, but also by the conditions.
 Dissolution and aging were the typical failure modes
of rubber.
Outline
三. Next work
1. Research division
 State Key Laboratory of Oil and Gas
Reservoir Geology and Exploitation
 CNPC (China National Petroleum Corp.)

Tubular Goods Engineering
 CNPC pilot test base for high H2S Reservoir
Pay much more attention to the specially

designed equipment for full-scale test or test for
the true field co-exist of H2S and CO2 situation !!
2. Equipment
 Static autoclave for multi-phase
 Self-developed equipment (C276, 8L, 70MPa, 180℃)
 Corrosion evaluation for non-metal material (HTHP)
 Evaluation for multi-phase liquid and erosion

 CO2+H2S test
Thanks！

Experimental Studies On CO Corrosion of Rubber Materials For Packer Under Compressive Stress in HTHP Gas Wells

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Experimental Studies On CO Corrosion of Rubber Materials For Packer Under Compressive Stress in HTHP Gas Wells

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Experimental Studies on CO2 Corrosion of

Rubber Materials for Packer under

Prof. Yuanhua Lin

Southwest Petroleum University

一. About me and my current interests

二. Experimental Studies on CO2 Corrosion

of Rubber Materials for Packer under

Compressive Stress in HTHP Gas Wells

 CNPC Key Lab for Tubular Goods Engineering:

Scale Corrosion Failure

一. About me and my current interests

二. Experimental Studies on CO2 Corrosion

of Rubber Materials for Packer under

Compressive Stress in HTHP Gas Wells

Sealing ability of packer decreases

 Experiments and measurements

 Object of this study

Self-developed compression Schematic diagram of high

 Experimental situations without load

Stress Temperature Partial pressure

Temperature Compression Release

Ion concentrations of simulated formation water without load (mg/L)

 Simulated formation water contains: K+ , Na+ , Cl- , Ca2+ , and Mg2+

 Experimental results without load

 Experimental results with load

Elongation at break (%)

 Tensile strength and elongation change presented a

Hardness change presented a decrease after corrosion

 Corrosion in liquid phase is more serious than that in gaseous.

Initial State NBR HNBR FKM

 Experimental results without load

 Experimental results with load

 Rate of weight change presented a increase after corrosion

 Hardness presented a decrease after corrosion both in

 Compression set of rubber samples after corrosion in

Morphology and Microstructure Analysis - HNBR for example

Line Apparent Wt % Atomic Standard

Line Apparent Wt % Atomic

Apparent Wt % Atomic Standard

Apparent Wt % Atomic Standard

一. About me and my current interests

二. Experimental Studies on CO2 Corrosion

of Rubber Materials for Packer under

Compressive Stress in HTHP Gas Wells

 CNPC (China National Petroleum Corp.)

 CNPC pilot test base for high H2S Reservoir

Pay much more attention to the specially

 Corrosion evaluation for non-metal material (HTHP)

 Evaluation for multi-phase liquid and erosion

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