Transcript NACE HF Alky Test TEG 119x Meeting

Handheld X-ray Fluorescence for PMI &
Residual Elements in HF Alkylation Units
Don Mears
Oil & Gas Industry Consultant
NACE San Antonio, Texas
March 16, 2010 TEG 119X Meeting
Presenter – Don Mears
• President of Analytical Training Consultants (ATC)
• 30+ years of Oil and Gas industry experience
• Heavy involvement in API work groups
• Author of the API RP 578 PMI Certification Course
• Certified API Training Provider
• Oil & Gas Industry Consultant for Thermo Fisher Scientific
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Agenda
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Thermo Fisher Scientific – The World Leader in Serving Science
Speaker Profile
Thermo Scientific Niton XRF Analyzer Evolution & History
How X-Ray Fluorescence (XRF) works
XRF Analysis Capabilities in Oil & Gas Industry
XRF X-Ray Tube and Detector Improvements
Why PMI According to API RP 578
HF Alkylation Field Test report on Residual Elements ( Cr, Ni, Cu )
Low Si ( < 0.10% ) Field Test in Carbon Steel Components in Refinery
Units
• PMI Solutions
• Questions
Special Thanks to the
Borger, Texas Refinery
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Thermo Fisher Scientific – An Important Mission
Enabling our customers to make the world…
Healthier
Cleaner
Safer
The world leader in serving science
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Unmatched Global Capabilities
Leading provider of analytical instruments,
equipment, reagents and consumables,
software and services for research, analysis,
discovery and diagnostics.
• 2009 revenues: More than $10 billion
• 35,000 employees in 40 countries
• Serving 350,000 customers
in 150 countries
Serving science in new and compelling ways
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M-PULSe
GC-ICP-MS, TS,
XRF, ICP
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GC
Flo-Cal 6000
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GC
Flo-Cal 6000
Sentinel PRO
GC
TVA1000B
Flo-Cal 6000
XRF
LevelPro
DensityPro
XRF, ICP
Flo-Cal 6000
SOLA II
FCC Fractionator
SOLA II TRACE
SOLA II
Blending
M-PULSe
Flo-Cal 6000
Flo-Cal 6000
Kril PRO
XRF
Flo-Cal 6000
Tracker XP
Flo-Cal 6000
XRF
SOLA II TRACE
SOLA II TRACE
Flo-Cal 6000
LIMS
SOLA II Lab
XRF, ICP
XRF
Tracker XP
GC-ICP-MS, TS, XRF,
ICP
M-PULSe
SOLA II
Blending
GC-ICP-MS, TS, XRF,
ICP
SOLA II
Blending
Sentinel PRO
Prima PRO
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Product Quality, Process Efficiency, Safety and Environmental Monitoring.
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Our Refining Products and Service Offerings
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Sulfur online process analyzer
Toxic vapor analyzer
Low-maintenance ultrasonic flow meter
Non-contacting coker interface sensor
Crude and tower level sensors
Lab Information Management Systems
(LIMS)
Sulfur speciation and total sulfur in fuels
Ultra-fast GC for simulated oil distillation
X-ray fluorescence (XRF) analyzer for
sulfur in fuels
Inductively coupled plasma (ICP)
analyzer for elemental analysis in
biofuels
Handheld XRF analyzer for positive
material identification (PMI)
World-class service offerings
Many more….
Brief History of Portable XRF
• Earliest XRF alloy analyzers
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Large and bulky, >20 Lbs
Two-piece devices
Battery lasted only few hours
Single element-sequential
First generation alloy
analyzer, the TN 9200,
Several minutes testing per sample
1960s
Primarily high alloy
Temperature and environmental conditions affect performance and
reliability
Evolution
• Since late 1960s, XRF has evolved through 7 generations; each
generation has added new capabilities
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Smaller
Faster
Better performance
Easier to use
• Today, nearly all alloys can be tested with these powerful tools
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How XRF Works
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Latest Developments in Handheld XRF: GOLDD Technology
• One-piece, 3 to 4 lbs
• Handheld, miniaturized
• 25 element simultaneous
• 30 elements total
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Variable excitation conditions
Hundreds of alloys
Ultra high speed
Lab-quality performance
• Field hardened
Handheld Thermo Scientific
Niton XRF analyzer being used
to inspect piping system
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Thermo Scientific Niton XRF Analyzers - Product Lineup
Niton® XL2
Value Leader
Niton XL3 GOLDD™
Performance Leader
Niton XL3
Feature Leader
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New GOLDD Technology
• Geometrically Optimized
• Improved system geometry to reduce the path
length from sample to detector
• Allows ~2X more x-rays to reach the detector
with ½ the power
• Large-area Drift Detector
• Light element detection in air (Mg, Al, Si, P, S)
• Increased sensitivity for tramp and trace
elements in alloys
• Doubling of the speed of alloy and metals testing
• Enhanced performance for difficult (nearly twin)
alloy separations
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X-Ray Tube and New Light Element Analysis in Air
• New miniaturized 50kV x-ray tube, Silver or Gold anode, excitation
source that provides higher sensitivity for heavy elements
• New ability to test for Mg, Al, Si, P & S without He purge or vacuum
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Complete System Optimization
• Synergy of complete system approach including
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SDD detector
50kV tube
Optimized geometry, and…
On-the-fly parameter optimization …
• Produces overall 10X performance gain with ½ the tube power
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GOLDD: Quantum Advancements with XL3 Analyzers
• 2 W, 50 kV X-ray tube, SDD GOLDD
• Improved sensitivity, speed, accuracy, precision, stability and confidence
• New ability to analyze residual elements
• New ability to determine light elements
Significantly lower LOD’s for critical elements
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3-Sigma LODs: Ti, Fe, and Cu Alloys; All Units %wt
TIME
Element
Sb
Sn
Pd
Mo
Nb
Zr
Bi
Pb
Se
W
Zn
Cu
Ni
Co
Fe
Mn
Cr
V
Ti
P
S
Si
Al
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60s per filter
Ti Base Wt. %
0.005
0.005
0.005
0.002
0.002
0.002
0.002
0.002
0.002
0.015
0.005
0.008
0.012
0.008
0.015
0.017
0.015
0.060
N/A
0.025
N/A
0.070
0.375
60s per filter
Fe Base Wt. %
0.006
0.008
0.006
0.002
0.002
0.002
0.002
0.009
0.002
0.015
0.005
0.009
0.020
0.080
NA
0.020
0.003
0.003
0.003
0.030
0.050
0.075
0.500
60s per filter
Cu Base Wt. %
0.008
0.015
0.010
0.002
0.003
0.003
0.003
0.003
0.002
0.015
0.030
N/A
0.011
0.005
0.007
0.007
0.005
0.003
0.003
0.040
0.060
0.080
0.700
Thermo Scientific Niton XRF Analyzers in Downstream
Process
Handheld
XRF
Analyzers
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Handheld XRF PMI Applications
• Existing piping systems
• Pipe fittings, valves & flanges
• Welds & welding consumables
• Longitudinal pipe and weld
fittings
• Weld overlays or cladding
• Low Si in H & S Service
• Components from distributors
• Forgings
• Instruments
• Bolting
• Expansion joints and bellows
• HF Alky- Residual Elements
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Refining Piping Systems Failure: The Challenge
• “41% of the 170 largest losses in the hydro-carbon process industry
resulted from failures of piping systems…”
Source: Marsh and McLennen (property protection and risk consultants)
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Guidelines and Application Procedures for API-RP 578 Using
XRF and OES Technologies
In response to increasing industry safety demands, Analytical Training
Consultants has produced the API Certification PMI Training Course
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Introduction
In today's risk-based QC environment, the need for positive material
identification (PMI) has grown dramatically in refinery and petrochemical
plant operations, requiring 100% alloy material verification for
designated critical components.
• Purpose of the Course
• To certify and re-certify (every 3 years) API 570 inspectors and
designated key personnel in understanding and applying API RP 578 in
the proper Use and Application of procedures for utilizing XRF and OES
technologies for PMI.
• 2 one-day sessions
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Classroom instruction on API RP 578 guidelines
Hands-on PMI field testing procedures.
Understanding of API RP 578 Guidelines
Application of proper XRF and OES PMI testing procedures
Inspection Program for HF ALKY Field Tests-API RP-571
• Priority for API 578 2nd Edition:
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Inspection Program for HF ALKY All Refineries-API RP-571
• Priority for API 578 2nd Edition:
• Residual Elements in Carbon Steels in Hydrofluoric Acid
Alkylation Units: Note: Carbon Steels in HF Acid service have been
reported to suffer increased corrosion rates based on the Residual
Elements (RE) in steels.
• In general, it has been reported that steels with a high RE content are
likely to suffer enhanced corrosion attack. Operators should review the
potential impact of this in HF service.
• A guideline is that for base metal of C> 0.18% wt% and Cu + Ni + Cr,
0.15% wt % is optimum. These values are critical as the type and
concentrations to be measured will directly affect the analytical methods
operations need to adopt.
• API RP 571—Pages 12,38
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Inspection Program for HF Alky Units – All Refineries
Priority for API RP 578 2nd Edition
• Residual Elements in Carbon Steels in Hydrofluoric Acid Alkylation Units
• Steels with a high RE content are likely to suffer enhanced corrosion attack.
• Optimal RE content guidelines:
C> 0.18 wt%
And
Cu + Ni + Cr < 0.20 wt %
• Sample preparation is very important:
• Al Oxide disc used with a right angle grinder (<10 sec)
• approx. 0.004” removed
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Cu
Ni
Cr
RE Sum
0.050
0.078
0.084
0.212
PMI Testing of CS Pipe Interactive-”Live Demonstration”
• ..\..\..\..\Desktop\NDTr 6.5.lnk
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Conoco Phillips Crude Unit Test Shot Results Low Si as
Discussed in API RP-939C
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Inspection Program for Low Si – All Refineries
Priority for API RP 578 2nd Edition
• Process Units Susceptible to Sulfidation:
• Carbon Steels with low silicon (0.10%) content can corrode at an accelerated rate
• Assets at risk from this type of degradation should apply PMI control to determine
Silicon levels.
• See API 571 and API RP 939-C
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High Temperature Sulfidic Corrosion - API RP 939-C
Low Si-33%,PMI-18%,Specification Break-17%
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High Temperature Sulfidic Corrosion-API RP-939-C
Field Test
• Distillate HDS Unit
• From Distillate Furnace to Distillate Reactor
• The 9 chrome piping circuit consists of approximately 400’ of 6”, 8” and 10” piping that
runs from the Furnace to the Reactor.
• In 2003 during a PMI and UT inspection of all chrome circuits in the unit a small section of
10” 5CR pipe approximately 9” in length was found in the 9CR circuit. Thickness
measurements of the 5CR showed severe thinning; approximate wall thickness remaining
was .04”.
• The 5CR section was cut out and a visual inspection confirmed that the 5CR section had
heavy thinning while the 9CR side of the weld was still relatively full thickness. The line
operates at about 710 degrees with Sulfur and Hydrogen in the stream.
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High Temperature Sulfidic Corrosion-API RP-939-C
& HF RE Levels High in Warehouse Test
ConocoPhillips Borger, Texas Jim-SN-36965 Shots on 8-26-09
Index
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Time
Duration
Line
Component
Pipe
Alloy1
Cr
Cu
Ni
Sum
Si
37
8/26/2009 16:48
9.64
A17F
Elbow
8"
Fe/CS : 0.00
0.03
0.05
< LOD
0.08
38
8/26/2009 16:49
40.2
A17F
Elbow
8"
Iron/CS : 0.22
0.03
0.06
< LOD
0.09
0.24
39
8/26/2009 16:52
22.51
A17F
Elbow
8"
No Match : *4.06
0.05
0.16
< LOD
0.21
0.59
40
8/26/2009 16:59
40.9
A17F
Flange
8"
Iron/CS : 0.24
0.06
0.04
< LOD
0.1
0.22
41
8/26/2009 17:04
21.15
A17E
Elbow
2"
No Match : *4.12
0.06
< LOD
< LOD
0.06
2.37
42
8/26/2009 17:05
23.63
A17E
Elbow
2"
Iron/CS : 0.24
0.04
< LOD
< LOD
0.04
0.39
43
8/26/2009 17:10
14.4
A17G
O-let
3/4"
No Match : *4.27
0.17
0.11
< LOD
0.28
1.38
44
8/26/2009 17:11
26.92
A17G
O-let
3/4"
TS-O6 : *3.99
0.17
0.13
< LOD
0.3
1.31
45
8/26/2009 17:13
29.06
A17G
O-let
3/4"
No Match : *4.07
0.17
0.13
< LOD
0.3
0.25
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8/26/2009 17:20
29.18
A17G
O-let
3/4"
No Match : *5.22
0.05
0.1
0.09
0.24
0.82
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8/26/2009 17:21
15.97
A17G
O-let
3/4"
Iron/CS : 0.30
0.04
0.09
< LOD
0.13
0.37
48
8/26/2009 17:27
60
A02F
Flange
4"
Iron/CS : *2.66
0.17
0.06
< LOD
Flange with
Low
Si-0.09
%0.23
0.09
49
8/26/2009 17:30
40.08
A02F
Flange
8"
Iron/CS : 1.42
0.11
0.24
< LOD
0.35
0.18
50
8/26/2009 17:33
36.8
A02F
Elbow
6
Iron/CS : 0.21
0.05
< LOD
< LOD
0.05
0.23
51
8/26/2009 17:38
28.44
A02F
Elbow
6
Iron/CS : *2.30
0.19
0.06
< LOD
0.25
0.16
Summary of Don’s Test Shots- HF-RE’s
Both in Warehouse and
Field Shots: 10 out of
33 Test Shots:
33%
RE’s Higher
than 0.20%
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XL3-S #36909
Residuals OK
Residuals High
Summery of Jim’s Test Shots in Both HF-RE’s & Crude Unit Low Si
• RE’s 33% Higher than
0.2%-(16 out of 44 shots)
XL3-S #36965
• Low Si – Only ~3% Lower
than 0.10%- (1 out of 37
shots)
XL3-S #36965
Si OK
Si Low
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Field Test with Six Samples Compared to Material
Certifications from Independent Laboratory
6 Samples ConocoPhillips Borger, TX- RE's in HF Alky RE's 1-27-10 XRF vs. M. Certification
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Index
Date/Time
SAMPLE
Test
Company/M
ethod
Alloy Names
Part
Description
Cr
Ni
Cu
SUM
Fe
5
11/19/2009 2:31
10198
ME Lab/OES
Fe/CS : 0.00
Weld Pad
0.02
0.01
0.03
0.06
98.20
6
1/27/2010 14:39
10198
Niton-HHXRF
Fe/CS : 0.00
Weld Pad
0.02
< LOD
0.03
0.05
98.62
7
1/27/2010 14:40
10198
Stork Services
Lab-OES
Fe/CS : 0.00
Weld Pad
0.03
0.01
0.04
0.08
NA
8
9
1/27/2010 14:40
11/19/2009 2:24
Average
10197
ME Lab/OES
Zn : 0.00
Fe/CS : 0.00
Avg of 5-7
Weld Pad
0.02
0.04
0.01
0.04
0.03
0.13
0.06
0.21
98.55
98.10
10
1/27/2010 14:43
10197
Niton-HHXRF
Fe/CS : 0.00
Weld Pad
0.04
< LOD
0.15
0.19
98.42
11
12
13
1/27/2010 14:44
1/27/2010 14:44
11/18/2009 11:09
10197
Average
s-10178
ME Lab/OES
Fe/CS : 0.00
Zn : 0.00
Fe/CS : 0.01
Weld Pad
Avg of 9-11
Weld Pad
0.05
0.03
0.03
0.04
0.04
0.02
0.15
0.15
0.08
0.24
0.22
0.13
NA
98.42
97.80
14
1/27/2010 14:47
s-10178
Niton-HHXRF
Fe/CS : 0.00
Weld Pad
0.03
< LOD
0.10
0.13
98.21
15
16
17
1/27/2010 14:48
1/27/2010 14:48
11/18/2009 11:25
s-10178
Average
s-10179
ME Lab/OES
Fe/CS : 0.00
Zn : 0.00
Fe/CS : 0.00
Weld Pad
Avg of 13-15
Weld Pad
0.04
0.03
0.04
0.02
0.02
0.02
0.10
0.09
0.04
0.16
0.14
0.10
NA
98.24
98.20
18
1/27/2010 14:51
s-10179
Niton-HHXRF
Fe/CS : 0.00
Weld Pad
0.04
< LOD
0.05
0.09
98.48
19
20
1/27/2010 14:51
1/27/2010 14:51
s-10179
Average
Fe/CS : 0.00
Zn : 0.00
Weld Pad
Avg of 17-19
0.04
0.03
0.02
0.02
0.05
0.04
0.11
0.09
NA
98.51
21
1/4/2007 0:00
s-3476-d
Taper-Lok
Lab/OES
Fe/CS : 0.00
flange
0.08
0.02
0.11
0.21
NA
22
1/27/2010 14:57
s-3476-d
Niton-HHXRF
Fe/CS : 0.00
flange
0.09
< LOD
0.11
0.20
99.11
23
24
1/27/2010 14:57
1/27/2010 14:57
s-3476-d
Average
Fe/CS : 0.00
Zn : 0.00
flange
Avg of 21-23
0.08
0.09
0.04
0.03
0.11
0.10
0.23
0.22
NA
99.11
25
3/12/2007 0:00
t-2714-a
Stork Services
Lab-OES
s-3476-d
Taper-Lok
Lab/OES
Fe/CS : 0.00
seal-ring
0.08
0.02
0.11
0.21
NA
26
1/27/2010 15:14
t-2714-a
Niton-HHXRF
Fe/CS : 0.00
seal-ring
0.08
< LOD
0.12
0.20
99.04
27
28
1/27/2010 15:15
1/27/2010 15:15
t-2714-a
Average
Stork Services
Lab-OES
t-2714-a
Fe/CS : 0.00
Zn : 0.00
seal-ring
Avg of 25-27
0.08
0.08
0.04
0.03
0.11
0.12
0.23
0.23
NA
99.07
Stork Services
Lab-OES
Stork Services
Lab-OES
Stork Services
Lab-OES
Thermo Scientific Niton XRF Analyzer PMI Solutions
Button Reader
Hotfoot
Extension
Pole
Buttons
Button
mounted
on plate
PMI-15
Certest
Wireless
Bar Code
Reader
CMB
Manual
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Wireless
Printer
GPS
Field Use for Hot Pipes and Difficult Access
Extension Pole /Tri-Pod
• Variable pole length
• Dual electronic triggers
• Clip on tri-pod adapter for
hands-free analysis of
samples on ground or table
37
Niton XL3 without heat shield: 599
F/315o C
Niton XL3 with heat shield : 842
F/450o C
PMI of Welds and Small Spot: WeldSpot™ and CamShot ™
• Electronic focusing of excitation beam
collimation to isolate small parts and
narrow weld beads
SAMPLE
DE
T
Standard collimation
8 mm dia
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SA`MPLE
DE
T
WeldSpot signal
reduced to 3mm dia
• On board CCD camera for verifying
and photographing sample area
tested
Niton Data Transfer (NDT©) Software
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Remote viewing and real time download
Secure tamper-proof NDT file download
Only “Secure” Data Files in Industry
Auto-exec to Excel
Lab quality data management
New software uploads
New calibration uploads
Empirical calibration capability
Multiple user passwords and permissions
Multiple custom data fields
Powerful FP Quantitative Software
Summary and Conclusions
• The new Thermo Scientific Niton GOLDD XRF analyzers provide:
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Near-lab quality performance in a 3-4 lb field-hardened package
Faster testing
Light element detection
More sensitive trace and tramp element determination
Ability to quantify fractional percent alloying elements
• Ultimate benefit is the most rapid and accurate alloy verification
• The new generation of handheld XRF alloy analyzers has brought the
power and reach of lab XRF spectroscopy to harsh field environments
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Oil & Gas PMI Market Overview
• What are the True PMI needs in
your company ???
• Where PMI can and should be used
for critical components?
Asset Recovery
Asset Management
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Questions
• Don Mears, Oil & Gas Consultant
• Thermo Scientific Niton Analyzers &
Analytical Training Consultants, (ATC)
1719 Burning Tree
Kingwood, Texas 77339
Cell Phone: 281-684-8881
ATC Office: 281-358-1177
Fax: 281-358-2177
www.API578.com
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