H2SMeasurementinCrude

S Measurement in Crude
COQAMeeting
COQA
Meeting
March1,2012
H t
Houston,TX
TX
1

H2SMeasurementinCrude
S Measurement in Crude
ProjectObjectives
Project Objectives
Testingframeworkforanalysisandsampling
6 ProvidemostaccurateH2Svalues
Provide most accurate H2S values
6 Reduceanalyticalerror,technicianvariability

Educatetransportationoperators
Educate transportation operators
6 H2Spotentialofcrudesinsystem
6 Healthandsafetyissues

Alloperatorsusingthesametestmethod
andcomparingthesamedata
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H2SMeasurementinCrude
S Measurement in Crude
AvailableTestingMethodologies
g
g
ASTMD5705
6 Easytoperform,lowequipmentcosts
f
6 OnlymeasuresvaporphaseH2S

H2SMeasurementinCrude
S Measurement in Crude
AvailableTestingMethodologies,cont.
g
g ,
ASTMD5623
6 Providesspeciationbetween(sulfurcompounds)
6 Highequipmentcosts($80K)
Hi h
i
($80K)
6 Requiresexperiencedtechniciantooperate.
6 Notpracticalformostterminaloperators

H2SMeasurementinCrude
S Measurement in Crude
AvailableTestingMethodology,cont.
Available Testing Methodology cont
UOP163
6 Easytoperform,lowequipmentcosts
y p
,
q p
6 Datainterpretationrequiresskilledtechnician
6 OnlymeasuresliquidphaseH2S

17ppm

34ppm

H2SMeasurementinCrude
S Measurement in Crude
AvailableTestingMethodology,cont.
Available Testing Methodology cont
IP570
6 ModifiedforusewithCrudeOils
Modified for use with Crude Oils
6 Operatorindependent,littletechnicaltraining
required.NOinterpretationrequired.
6 MeasuresbothliquidandvaporphaseH2S

Method Scope Comparison

MethodScopeComparison
D5623 Applicabletodistillate,gasolinemotorfuelsandother
petroleumliquidswithaFBP<230C.Range0.1100mg/kg

D5705 Applicabletoresidualfueloil.Applicabletoliquids5.5@
pp
pp
q
@
40Cto50and100C.Range54000ppmv.

UOP163
UOP 163 Applicabletogasoline,naphtha,lightcycleoils,and
Applicable to gasoline naphtha light cycle oils and
similardistillatesthatareliquidatambienttemperatureand
pressure.Lowerquantitationlimitis1.0mg/kg.

IP570 Applicabletomarinefuels.Range050mg/kg(Note:
Methodandinstrumenthasbeenmodifiedtoaccommodatefor
the volatile nature of crude/condensate products to limit the
thevolatilenatureofcrude/condensateproductstolimitthe
interferencefromlightendcomponents.)
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H2SMeasurementinCrude
S Measurement in Crude
AnalysisProtocol
Analysis Protocol
6 Aseachsamplewasopenedthefullsetoftestswas
completedimmediately,priortoopeningthenext
sample.
6 Sampleswererefrigerateduntilopened.

AnalysisData
Analysis Data
SampleDescription

WTS

ASTMD445

ASTMD5002

ASTMD5191

y@
Density@15C
y@
VaporPressure
p
Viscosity@20C
cSt
kg/m3
DVPE(kPa)
19.65
877.6
35.1

UOP163

ASTMD5705 ASTMD5623

H2S

Mercaptan
p
H2S Vapor
p
mg/kg
ppmv
36
0
1

IP570

H2S
mg/kg
24.2

H2S
mg/kg
0.54

TK1106

13.82

856.9

16.7

16

15.0

0.00

PeaceSour
Peace
Sour
PeaceSour
PeaceSour

4 91
4.91

816 2
816.2

54 9
54.9

110
126
127

0
0
0

>2000
>2000
>2000

74 9
74.9
67.6
70.8

124.6
124
6
108.2
126.9

OSA

6.311

865.2

20.6

0.0

0.00

Koch
Koch
Koch

9 392
9.392

839 4
839.4

57 3
57.3

104
105
104

0
0
0

>2000
>2000
>2000

76 7
76.7
61.0
52.3

167.2
167
2
247.0
204.5

CRL403
CRL403
CRL 403
CRL403

1.345

749.7

85.5

26
27
28

237
248
234

241
295
268

17.2
19.1
17 7
17.7

8.6
16.4
64
6.4

CPM781
CPM781
CPM781

1.279

762.2

72.3

16
17
11

40
38
56

0.5
1
2

14.2
14.2
12.2

0.02
0.03
0.01

CPR025
CPR025
CPR025

1.028

750.3

80.7

34
34
34

222
220
225

11
12
11

17.2
11.9
13

0.09
0.09
0.10

H2S Measurement in Crude

H2SMeasurementinCrude
PotentialInterferences
Potential Interferences
Chlorides(halides?)
UOP163inflectionpointinterpretation
6 Davetoprovidecopiesofinflectioncurvestoall
6 Curveswereactuallyverycleanandrelativelyeasytointerpret

Corrosion
Corrosioninhibitors(nitrogenbased)
inhibitors (nitrogen based)
Mercaptans? D5623segregatesthemercaptans
andIP570VPPdevelopmentwasbasedonremoving
mercaptan andlighthydrocarboninterferences
Scavengers waterbasedcations?(HS scavengers
retaining partial H2S in ionic
retainingpartialH2Sin
ionic state)
state)
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H2SMeasurementinCrude
Follow Up Discussions
z

Agreed that future testing would include SAPA (saturates,

aromatics, polars, asphaltenes), C30+ compositional analysis,
Karl Fischer titration, and nitrogen testing by D4629
Agreed that future testing would be done on one only sample
from the triplicate sample sets
Agreed that samples to be tested would be CPR (Peace
condensate [Enbridge EP], CPM (Pembina Drayton Valley
condensate [Enbridge EP]), CRL (Plains Midstream
Rangeland
a ge a d condensate
co de sate [Enbridge
[ b dge EP]),
]), PEM ((Pembina
e b a sweet
crude [Kinder Morgan]), and TK1106 [Coffeyville Resources,
KS],
Agreed to proceed with testing matrix ASAP based on Dave
Murrays estimate of ~$5,000 analytical costs and end of
February completion estimate

H2S Measurement in Crude

H2SMeasurementinCrude
DoesanyoneinCOQAaudiencehaveany
Does anyone in COQA audience have any
experience/insightthatcouldstreamline
or focus our efforts??
orfocusourefforts??
Example:H2Sscavengers
6 Aretherenaturallyoccurringvarieties??
Are there naturally occurring varieties??
6 Wouldaminebasedcorrosioninhibitors,bug
killers,orsomethingelsebeinterfering??

PleasecontactBillLywood
6 7809919900orlywood@crudequality.com
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