better analysis counts

Three ways to effectively monitor total

3 Ways to Effectively Monitor Total
chlorine in liquid hydrocarbons
Chlorine in Liquid Hydrocarbons
Kyle
Authors: Kyle Kuwitzky
Kuwitzky, andProduct
Senior Leslie Johnson
Manager XOS
and Leslie Johnson, Applications Scientist

C
BACKGROUND orrosion at petroleum refineries is a critical
Corrosion at petroleum

nternational, sional
problem
all over the world. InStates
the United
a professional
all over
refineries

association
association
the world.
is a critical
States
alone, NACE alone,
dedicated
problem
NACE
In the United
International,
dedicated to
to reducing
a profes-
the eco-
Clora 2XP delivers
twice 2XP
Clora
twice
the precision
delivers
thechlorine
for total precision
educing the economic
nomic impactimpactofofcorrosion,
corrosion, has
has shown
shown that $3.7 for total chlorine
analysis in liquid
hat $3.7 billion in direct
billion costs are
in direct realized
costs annuallyannually from
are realised analysis in liquid
hydrocarbons
rom maintenance, vessel
maintenance, expenditures, and
vessel expenditures, foulingand fouling as hydrocarbons
such as aromatics,
as a result of acorrosion. 1
This huge figure
result of corrosion. This huge
1 does notfigure does not such as aromatics,
distillates, heavy
ake into account the estimated loss of as much as distillates, heavyoils,
take into account the estimated loss of as much fuels and crude
$12 billion in profits due to decreased capacity, unit fuels and
as $12 billion in profits due to decreased capacity, as well ascrude
aqueous
outages, and premature turnarounds that result from oils, as well as
corrosion.
unit outages, and premature turnarounds that solutions. Compliant
2
aqueous solutions.
result from corrosion. 2
with ASTM D7536
Compliant with
CHALLENGE and D4929
ASTM D7536
Challenge
Chlorine in crude oil, if not removed, can hydrolyze methodology,
and D4929 Clora
during processing to form
Chlorine in hydrochloric
crude oil, if acid. The crudecan hydro-
not removed, methodology,
2XP is ideal forClora 2XP
testing is ideal
related for testing
to catalyst poisoning
oil desalter islyse
the first line of defense in the prevention
during processing to form hydrochloric acid. related to catalyst
in reformers, poisoning
and sites in reformers,
with catalytic crackers and
of corrosion, but
Theincrude
order to oilprovide
desaltera proper
is the defense,
first line of defence and sites with catalytic
hydrocrackers. crackers
In addition, and sulphur
its automatic
an effective chloride monitoring solution
in the prevention of corrosion, must be but in order to hydrocrackers. In addition, its automatic
correction is perfect for high sulphur and low chlorine
mplemented.provide
Many refiners rely on
a proper semi-periodic
defence, an effective chloride sulfur correction
applications, suchisas
perfect
crude for highVGO.
oil and sulfur and by
Powered
esting of inorganic chlorides to get the job done. low chlorine applications, such as crude oil
monitoring solution must be implemented. Many MWDXRF, Clora 2XP does not require gasses or high
However, what if a desalter upset occurs in between and VGO. Powered by MWDXRF,
refiners rely on semi-periodic testing of inorganic temperature processes, equating to Clora 2XP
easy operation
esting periods? Worse yet, what if an organic chlorine does not require gasses or high temperature
slug is presentchlorides to get the
in the incoming job The
crude? done. However,
desalter will what if a and minimal maintenance requirements.
processes, equating to easy operation and
emove only thedesalter upset inorganic
extractable occurs inchlorides,
between nottesting periods? minimal maintenance requirements.
Worse
organic chlorides, andyet,anywhat if an
chlorides thatorganic chlorine slug is
pass through
he desalter have the potential
present of causingcrude?
in the incoming foulingThe
and desalter will In this paper, we will discuss the most popular
corrosion issues.
remove only the extractable inorganic chlorides, Clora procedures utilised by petroleum laborato-
Even refinersnotwhoorganic chlorides,
don’t rely and any testing
on semi-periodic chlorides that pass ries around the world to measure total chlorine
ypically only through the desalter
monitor inorganic have While
chlorine. the potential
this of causing for corrosion mitigation:
fouling
s very important and corrosion
for desalter issues.
efficiency, it does not • Organic Chlorides by ASTM D4929
Even refiners who don’t rely on semi-periodic
capture all threats. • Total Chlorine by Modified ASTM D7536 with
testing typically only monitor inorganic chlo- Accu-flow
NTRODUCTION
rine. While this is very important for desalter effi- • Organic and Inorganic Chlorides Using Water
Since its launch in 2007,
ciency, Clora
it does notBenchtop
®
Analyzer
capture all threats. Extraction
has been widely adopted by refineries and test labs In this paper, we will discuss the most popular Clora
or monitoring chlorine in petroleum. With over 200 procedures utilized by petroleum laboratories around the
Introduction worldOrganic chlorides
to measure by ASTM
total chlorine D4929 mitigation:
for corrosion
systems in the field, XOS customers know they can
Since its launch in 2007, Clora® Benchtop On October 15, 2017, ASTM approved the addi-
rust Clora for testing products from crude oil to • Organic Chlorides by ASTM D4929
and VGO. has been widely adopted by refineries tion of Procedure C to D4929 Standard Test
naphtha cuts Analyser
• Total
and test labs for monitoring chlorine in petro- Chlorine
Method forbyDetermination
Modified ASTM of D7536 with Accu-flow
Organic Chloride
leum. With over 200 systems in the field, XOS Content
• Organic andin Crude Chlorides
Inorganic Oil. Procedure C uses X-ray
Using Water
Fluorescence (XRF) to determine the chlorine
customers know they can trust Clora for testing Extraction
products from crude oil to naphtha cuts and VGO. content in the crude oil naphtha fraction. This
. Koch, Gerhardus H., et. Al. “Corrosion Costs and Preventive Strategies in the United States.” NACE International.
. “Petroleum Refinery Gap Analysis.” NACE Technical Coordination Committee, 18 Oct. 2008.
www.digitalrefining.com/article/1001474 February 2018 1
d
Figure 1: D4929 Reproducibility
a
Procedure C test method precision
d was determined by an interlabora-
c tory study (ILS) designed to replicate
the original D4929 Precision A and B
ILS. Eight ILS participants distilled
ic ten crude oil blends of varying nom-
inal organic chloride concentrations
in blind duplicate, and the resultant
naphtha cuts were washed and ana-
lysed by multiple XRF techniques. The
Procedure C precision varied by XRF
type, and as a result there are separate
o precision statements for MWDXRF,
MEDXRF, and EDXRF. Figures 1 and 2
compare the calculated precision state-
ments obtained from the Procedure C
d
Figure 1 D4929 Reproducibility study with the original Procedure A and
Figure 2: D4929 Repeatability B precision statements.
Figure 1 illustrates the calculated
d reproducibility for all D4929 proce-
Figure 2: D4929 Repeatability dures using the published precision
e statements in D4929. It demonstrates
that Clora (MWDXRF) has better repro-
ducibility than the other Procedure
e C XRF techniques and exhibits equiva-
lent or better reproducibility than Pro-
cedure B (microcoulometry). In a recent
review of the ASTM crude oil profi-
ciency testing program, Procedure B
is the most commonly used procedure
for organic chloride analysis, though
this may change with the addition of
Procedure C to D4929. Figure 2 illus-
trates the calculated repeatability for all
Figure 2 D4929 Repeatability of the D4929 procedures, and Proce-
F
dure C MEDXRF and MWDXRF (Clora)
is an important step forward, as users will be consistently exhibit better repeatability than
able to officially use XOS’ Clora, Clora 2XP, and Procedure B.
F Sindie +Cl analysers for organic chloride analysis The addition of Procedure C to D4929 provides
in crude oil without ASTM method modification. a precise, easy to use alternative to Procedures
Traditionally, users of D4929 distill a crude A and B. XOS’ Clora, Clora 2XP, and Sindie +Cl
oil sample
provides a precise, to 400°F,
easy to wash the resulting naph- analysers comply with D4929 Procedure C.
tha fraction by caustic to remove H2S and then
XOS’ Clora, Clora 2XP, and
water to remove inorganic chlorides, and then use Total chlorine by modified ASTM D7536
9 Procedure C.
Procedure A or Procedure B to determine chlo- with Accu-flow
provides a ride
precise, easyChloride
content. to content of the crude is X-ray Fluorescence (XRF) spectrometry, while
XOS’ Clora, Clora
then 2XP, andby back calculation. Procedure
determined widely used for total sulphur testing, has tradi-
9 Procedure C.
A determines chloride content by sodium biphe- tionally been an ineffective tool for the direct
nyl reduction followed by potentiometry, and 2
measurement of total chlorides in crude oil due
Procedure B uses combustion and microcoulom- to the settling effects of inorganic chloride salts
etry to determine chloride content in the naphtha during the measurement process. This settling
fraction. 2
leads to poor precision and an industry pref-

2 February 2018 www.digitalrefining.com/article/1001474

allows for the direct measurement of total chlorine 4 and 5 show the static measurement increasing over
ASTM D4929, and delivers results in just minutes. However, the Accu-flow measurement remains
water wash extraction or sample distillation, as in time, leading
Figure 4: toChlorine
an inaccurate total chlorineCrude
in Aasgard measurement.
Oil
throughout the measurement period Figure
and is rep
4929, and delivers results in just minutes. However, the Accu-flow measurement remains stable
Figure 3 Static vs. Accu-flow multiple measurements, as seen Static
in Table 1.
throughout the measurement period and is repeatable over
erence for other multiple measurements, as seen in Table 1.
3 measurement or
Table 1: Average Chlorine Concentration of Accu-flow Repeats
Aasgard Crude Chlorine Bonga Crude Chlori
sample extraction Flow Sample
Table 1: Average Chlorine Concentration of Accu-flow (ppm)
Repeats (ppm)
techniques.
1 55.9 82.9
To address the Flow Sample Aasgard Crude Chlorine Bonga Crude Chlorine
(ppm) 2 (ppm) 55.1 84.2
effects of particu-
3 54.9 83.8
late settling, XOS 1 55.9 82.9
introduced a con- Average 55.3 83.6
2 55.1 84.2
tinuous sample Std. Dev 0.53 0.67
3 54.9 %RSD 83.8 0.96% 0.80%
flow option to their
Average
M o n o c h r o m a t i c Figure 3 55.3 83.6
Wavelength Dis- Std. Dev 0.53 0.67
Figure 4: Chlorine in Aasgard Crude Oil Figure 5: Chlorine in Bonga Crude
persive XRF (MWDXRF) %RSD benchtop 0.96% 0.80% vs. Accu-flow
Static vs. Accu-flow Static
chlorine spectrometer: Clora with Accu-
flow. The Accu-flow process uses a step-
4: per inmotor
Chlorine Aasgard for continuous
Crude Oil injection Figure 5: Chlorine in Bonga Crude Oil
of crude oil during the sample meas- Figure 4 Chlorine in Aasgard crude oil static vs Accu-flow
vs. Accu-flow Static vs. Accu-flow
urement, eliminating the settling of
inorganic chloride salts. This process
allows for the direct measurement of
total chlorine without water wash extrac-
tion or sample distillation, as in ASTM
D4929, and delivers results in just
minutes.
The Accu-flow design works for crude
oils with a maximum viscosity of 2000
cSt at 70°F. A 60 ml crude oil sample is
injected at a 20 ml/min flow rate into
the yellow tubing shown in Figure 3. The
sample flows from the yellow tubing
through the Accu-flow insert assembly,
where the sample is exposed to X-rays.
The sample then flows through the black
drain tube and is collected outside the
analyser. Typical measurement time is Figure 5 Chlorine in Bonga crude oil static vs Accu-flow
three minutes.
Depending on the crude viscosity and Average chlorine concentration of Accu-flow repeats 3
rate of inorganic chloride settling, the
difference between static and Accu-flow
measurement results can be quite dra- Flow sample Aasgard crude chlorine, Bonga crude chlorine,
ppm ppm
matic. In the following examples, four 1 55.9 82.9
samples of two crude oils have been 2 55.1 84.2
run either statically or using Accu-flow 3 54.9 83.8
for a three minute measurement time. Average 55.3 83.6
Std. Dev 0.53 0.67
In order to illustrate the behaviour of %RSD 0.96% 0.80%
chlorine during the measurement, 30-
second data points have been taken Table 1
within the three minute measurement
interval and graphed accordingly. Figures However, the Accu-flow measurement remains
4 and 5 show the static measurement increasing stable throughout the measurement period and is
over time, leading to an inaccurate total chlorine repeatable over multiple measurements, as seen
measurement. in Table 1.

www.digitalrefining.com/article/1001474 February 2018 3

 Organic
INORGANIC CHLORIDES PROCEDURE
and inorganic chlorides using A: Crude Oil Sample
water Preparation
before and after filtration. Subtract any
water extraction Depending on crude type and composition, it may be
EXTRACTION interferences from the inorganic
hard to obtain a stable homogenous sample. Viscous or
chlorine result.
echniques areAlthough
capable ofall total techniques are capable of • Note 5: When pipetting the water sample, expel
onlyXRF
asphaltene and bitumen aircontaining
from the crudes
pipetteare particularly
with some sample preparation,
only total elemental Clora,
analysis, with some sample when initially putting it into
difficult to water extract. The addition of toluene or xylene
w, Clora 2XP,preparation,
and Sindie +Cl can also
Clora, Clora with Accu-flow, Clora the water sample to keep oil (often present as a
to these types of crudes will increase the solubility of
erize inorganic andand
2XP, organic chlorides
Sindie in also be used to charac- thin film on the surface of the water) out of the
+Cl can
heavier crude components leading to a more homogenous,
ot water extraction, crude oil may
terise inorganic andbeorganic chlorides in crude measured
less viscous sample that is more sample cup.
efficiently water
rganic chloride
oil.and inorganic
Using a hotchloride
water extraction, crude oil may • Note 6: When calculating inorganic chlorine,
extracted.
e organic chlorides staying in the crude
be separated into its organic chloride and inor- use the weight of the crude in the calculation. Do
organic chlorides precipitating into the Prepare approximately 25 ml of 50/50 wt% crude to
ganic chloride constituents with the organic not use the combined weight of the solvent and
an then be used to measure each solvent (toluene or xylene) mixture per Note 1. Shake
chlorides staying in the crude or
organic and inorganic chlorides. While
oilhomogenize
layer and the crude.
the crude oil sample prior to obtaining a
inorganic
have successfully chlorides
used this sampleprecipitating into the
specimen forwater
dilution. A 12.5 g crude to 12.5 g solvent
layer.this
que, unfortunately, Clora can then
technique has be used mixture
to measure each
will work Procedure
well for A: crude
most crudes. oil sample
See Note 2 preparation
mitations. Notlayer to determine
all crude organic andregarding
oils are easily inorganic chlo-contamination
chlorine Dependinginon crude When
solvents. type and composition, it
sample preparation technique
rides. While manyhaslaboratories analyzing chlorine content
have successfully may with Clora,
be hard toremember to
obtain a stable homogenous sam-
repeatability used
and poor
thisbetween-lab multiply the
sample preparation technique, measuredple.
unfortu- results by 2 to or
Viscous account for this and bitumen con-
asphaltene
dilution.
nately, this technique has crude-dependent limi- taining crudes are particularly difficult to water
will assist the tations. Not all crude
user in separating oils are easily extracted and extract. The addition of toluene or xylene to
chlorine PROCEDURE B: Water Extraction Using a
this sample
organic and inorganic preparation technique has variable these types of crudes will increase the solubility
counterparts Separatory Funnel
ion methods.within-lab repeatability and poor between-lab of heavier crude components leading to a more
Weigh 25 grams of crude into a separatory funnel. Make
reproducibility. homogenous,
sure to shake or homogenize the crudeless viscousbefore
oil sample sample that is more
Procedures A-C will assist the user in
obtaining sepa- efficiently
a specimen. Add 75 ml water extracted.
(see Note 3) of boiling
o prepare the crude/solvent mixture by
rating chlorine in crude oil into DI its organic
water. and diluted
For solvent Prepare
crudes,approximately
use 25 grams 25 of ml of 50/50 wt%
ot volume.
inorganic counterparts using crude/solvent water extractionmixture crude
(as prepared in the(toluene
to solvent Crude Oilor xylene) mixture per
and toluene or xylene should be
methods. Sample Preparation section)
Note 1.toShake
75 ml boiling DI water. the crude oil sam-
or homogenise
by Clora prior to use to check ple prior to obtaining a specimen for dilution. A
Cap the separatory funnel and shake vigorously for two
ne contamination. Any chlorine
Procedure Notes: 12.5 g crude to 12.5 by g solvent
minutes. Periodically degassing the sample venting mixture will work
nation in the DI water should be
• Note 1: Be sure to prepare the crude/solvent
the stopcock wellgas
will prevent forbuildup.
most crudes. See Note
Let the sample sit 2 regarding chlo-
ed from the inorganic chlorine result,
mixture by weight, not volume. undisturbed for ten to rine
fifteencontamination
minutes. Carefully in pipette a When analysing
solvents.
chlorine contamination from the solvent
Note
e subtracted •from 2:organic
the DI water and toluenesample
chlorine
of the
or xylene crude for
should Clora analysis,
chlorine contentmaking
with Clora,sure toremember
take to multi-
the sample from the middle of the sample layer
be analysed by Clora prior to use to check for ply the measured results by 2 to account for this without
chlorine contamination. Any picking up
dilution.
g the density of water = 1 g/ml, then contamination
chlorine contamination in
quals volume. Therefore, 75 ml water = from the water
the DI water should be sub- Procedure B: water
phase. Drain
tracted from the inorganic extraction
the water
using a
stomers using paper filters,
result,suchandasany chlo- separatory
chlorine
n 125 mm grade 1 filter paper circles, sample fromfunnel
rine contamination from the Weigh
the bottom 25 ofgrams of crude
orted that the filter paper can add to the
solvent should be
content. This can be verified by testing
subtracted into
the a
separatory separatory fun-
frombefore
evels in DI water the and organic
after chlorine nel.
funnelMake sure to shake or
Subtract anyresult.
interferences from the for Clora
homogenise the crude oil
• Note 3: Assuming the den-
c chlorine result. analysis.before
sample It obtaining a
sity of water = 1 g/ml, then is importantAdd 75 ml (see
specimen.
petting the water sample, expel air from to make sure
weight
te when initially equals
putting it intovolume.
the water There- Note 3) of boiling DI water.
fore,present
75 ml as water = 75 there are no diluted crudes,
o keep oil (often a thin filmg. For solvent
particulates
• Noteout4:
urface of the water) of theSome
measured custom- use 25 grams of crude/sol-
present in the
up. ers using paper filters, such vent mixture (as prepared in
water sample,
as Whatman 125 mm grade
lculating inorganic chlorine, use the
the Crude
so filter if Oil Sample Prepa-
the crude in1thefilter paper Do
calculation. circles,
not usehave ration
necessarysection) to 75 ml boil-
bined weight ofreported
the solventthatand thecrude.
filter paper ing
(seeDINote
water. 4).
can add to the chlorine con- Cap the separatory funnel
tent. This can be verified by and shake vigorously for two
testing chlorine levels in DI Separatory funnel Separatory Funnel minutes. Periodically degas-

4 February 2018
4
www.digitalrefining.com/article/1001474
 Analyze the crude phase to quantify the amount of organic equations on page 6 to calculate org
chlorine (and non-extractable inorganic chlorine) in the
crude sample. In order to ensure the extraction process

sing the sample by venting the stopcock will pre-

vent gas build-up. Let the sample sit undisturbed Repeat Measurements
for ten to fifteen minutes. Carefully pipette a Repeat
sample of the crude for Clora analysis, mak-
ing sure to take the sample from the middle of
Number of Measurements 10
MEASURE
the sample layer without picking up contamina-
tion from the water phase. Drain the water sam-
Measurement Time, Sec. 30
ple from the bottom of the separatory funnel for
Clora analysis. It is important to make sure there
Repeat Delay, Sec. 1 DELAY

are no particulates present in the water sample,

so filter if necessary (see Note 4). Done

Procedure C: organic, inorganic, and total

chlorine analysis with Clora with Clora and Clora 2XP analysers is 10 repeats.
Table 2
In general, pipette 5-8 ml of sample into a sample Run the sample accordingly and look for increas-
cup and test with Clora using XRF Settle Time
film (Etnom Sample
ing measurement values Crude A within the individual Crude B
hh:mm:ss Repeat Cl (ppm) cts/30s
for Clora and Sindie +Cl, Prolene for Clora 2XP). sample repeats. Continually increasing measure- Cl (ppm) cts/30s
Remember to punch a vent hole in the sample ment
0:00:30 1 values indicate
2.51 an incomplete 81 extraction.
36.15 A 960
cup. The standard analysis time for samples con- second (or third) extraction may be necessary.
0:01:00 2 3.28 101 35.31 938
taining >1 ppm chlorine is 300 s. If the sample For example, on the repeats screen below, if
0:01:30
contains <1 ppm chlorine, a 600 s measurement the 3recommended 2.59measurement 83 time is 37.91 300 s, 1006
0:02:00 4 2.51
time is suggested for optimal results with Clora run (10) 30-second repeats on one sample and 81 44.76 1185
and Sindie +Cl. For samples containing 0:02:30<0.5 examine 5 the individual
2.51 repeat81 measurements 52.00for 1374
ppm chlorine measured with Clora 2XP, 0:03:00meas- upward6 trending.3.39 If the total measurement
104 time
55.52 1466
ure two samples (new sample cup each time) for is 600 s, run (10) 60-second repeats. Keep the
0:03:30 7 2.47 80 59.88 1580
300 s each and use the average of the two results. repeat delay at 1 second. Don’t forget to use sul-
If the two results have a ≥0.2 ppm 0:04:00
difference, phur 8 correction 3.24
if necessary. 100 63.86 1684
measure a third sample to determine0:04:30 which of If9the measurement2.97 results93indicate trending
65.85 1736
the two samples is an outlier. Discard any outlier (crude
0:05:00 10 B in Table 2.902), return the 91 crude or crude/
76.87960 2024
measurement results. solvent sample to the separatory funnel or cen-
Average 2.84 52.81
In addition, if the sample contains >0.5 wt% trifuge tube and extract again using a new ali-
sulphur (>0.1 wt% sulphur when measuring quot of hot DI water. If the measurement results
with Clora 2XP), use of sulphur correction may indicate a successful extraction (crude A in Table
improve the accuracy of the results. Analyse a 2), use the average measurement result and
blank solvent sample (if diluting crude sam- the provided equations on page 6 to calculate
ple) and a blank DI water sample to account for organic chlorine.
any diluent interferences (see
Note 2).
Analyse the crude phase to
quantify the amount of organic Settle Time Sample Crude A Crude B
chlorine (and non-extractable hh:mm:ss Repeat Cl, ppm cts/30s Cl, ppm cts/30s
0:00:30 1 2.51 81 36.15 960
inorganic chlorine) in the crude 0:01:00 2 3.28 101 35.31 938
sample. In order to ensure the 0:01:30 3 2.59 83 37.91 1006
extraction process has been 0:02:00 4 2.51 81 44.76 1185
successful, check the crude or 0:02:30 5 2.51 81 52.00 1374
0:03:00 6 3.39 104 55.52 1466
crude/solvent mixture for set- 0:03:30 7 2.47 80 59.88 1580
tling while performing the 0:04:00 8 3.24 100 63.86 1684
measurement. To do this, divide 0:04:30 9 2.97 93 65.85 1736
the recommended measurement 0:05:00 10 2.90 91 76.87960 2024
Average 2.84 52.81
time (as described above) into
30 or 60 second repeats, noting
that the maximum repeat input Table 2

www.digitalrefining.com/article/1001474 February 2018 5

 Organic 2 x Chlorine
= Organic –
Chlorine Interferences
Chlorine (ppm)
(ppm) (ppm)

EQUATIONS TO CALCULATE ORGANIC CHLORINE

• The
Forwater phase ofcrude
undiluted the sample is measured to quantify the
samples: To account for the dilution of the inorganic crude chlorine
amount of inorganic chlorine in the crude sample. Pipette into the water phase of the sample, we will use the
a water sample for analysis (see Note 5). following equations to calculate inorganic chlorine. If
Total Measured running multiple extractions, combine the extraction water,
Particulate matter, ifChlorine
Organic present in the
= sample,
OrganicwillChlorine
often be in mix well, and measure sample per directions above.
the water layer. Filter the sample if necessary (see Note Remember to use the total weight of water used for
(ppm) (ppm)
4). Cloudy water is normal and does not require filtration. extraction. See Note 3 regarding the weight of water used
for this calculation. See Note 6 regarding the use of crude
It is best to use a water based calibration curve to test weight vs. crude/solvent weight in the following inorganic
low chlorine concentration water samples in order to chlorine calculations.
• compensate
For 50/50 for wt% diluted
oxygen crude effects.
absorption samples:High oxygen
content, if not accounted for, will result in reduced counts
and a falsely low chlorine value. If a dedicated water curve
Total Solvent
Measured
has not been developed, multiply the results obtained
Organic = 2 x Chlorine
Organic –
using a hydrocarbon calibration curve by 250% (i.e. 2.50).
Chlorine Interferences
Chlorine (ppm)
(ppm) (ppm)

EQUATIONS TO CALCULATE INORGANIC CHLORINE

• For 50/50 wt% diluted crude or undiluted crude oil samples on water based curve:
The water phase of the sample is measured to quantify the To account for the dilution of the inorganic crude chlorine
amount of inorganic chlorine in the sample. Pipette DI waterinto
crude inorganic
measured andthefilterwater phasex
ofweight
the sample,
of we will use the
–
a water sampleTotal for analysis (see Note 5). (ppm)
chlorine following
interferences (ppm)equations to calculate
water inorganic chlorine. If
used (g)
Inorganic running multiple extractions, combine the extraction water,
Particulate matter, =
if present in the sample, will often be in
Chlorine mix well, and measure sample per directions above.
Filter the sample if necessary (see Note
the water layer.(ppm) Weight of crude Remember
used (g) to use the total weight of water used for
4). Cloudy water is normal and does not require filtration. extraction. See Note 3 regarding the weight of water used
for this calculation. See Note 6 regarding the use of crude
It• is
For 50/50
best wt%adiluted
to use water crude
basedsamples or undiluted
calibration crude oil samples on hydrocarbon based curve:
curve to test weight vs. crude/solvent weight in the following inorganic
low chlorine concentration water samples in order to chlorine
measured
2.5 x effects. High oxygen inorganic DI watercalculations.
and filter x weight of
compensate for oxygen absorption –
interferences (ppm) water used (g)
Total chlorine (ppm)
content, if not accounted for, will result in reduced counts
Inorganic
and a falsely low chlorine= value. If a dedicated water curve
Chlorine
has not been developed, multiply the results obtainedWeight of crude used (g)
(ppm)
using a hydrocarbon calibration curve by 250% (i.e. 2.50).

To obtain total chlorine, simply add inorganic and organic results together.
EQUATIONS TO CALCULATE INORGANIC CHLORINE

• For
6
The50/50 wt%phase
water dilutedofcrude
the or undiluted
sample crude oil samples
is measured to on
Itwater based
is best curve:
to use a water based calibration curve
quantify the amount of inorganic chlorine in the to test low chlorine concentration water sam-
measured DI water and filter weight of
crude sample. Pipette a water sampleinorganic
for analysis
– ples x
in order to compensate
interferences (ppm)
for oxygen absorption
water used (g)
Total chlorine (ppm)
(see Note 5).Inorganic effects. High oxygen content, if not accounted for,
matter,= if present in the sample, will result in reduced counts and a falsely low chlo-
ParticulateChlorine
(ppm)
will often be in the water layer. Filter the sample Weight of crude
rine used If
value. (g)a dedicated water curve has not been
if necessary (see Note 4). Cloudy water is normal developed, multiply the results obtained using a
and
• Fordoes
50/50not
wt%require filtration.
diluted crude samples or undiluted crude oilhydrocarbon calibrationbased
samples on hydrocarbon curvecurve:
by 250% (i.e. 2.50).

2.5 x measured inorganic DI water and filter x weight of

–
chlorine (ppm) interferences (ppm) water used (g)
Total
Inorganic =
Chlorine
(ppm) Weight of crude used (g)

To obtain total chlorine, simply add inorganic and organic results together.

6 February 2018 CONCLUSION www.digitalrefining.com/article/1001474

Corrosion mitigation strategies are an important part of ensuring safe refinery operation and maximizing
profitability. Clora has become a critical part of identifying potential corrosion events and monitoring the
effectiveness of these mitigation strategies. With over a decade of experience supporting refiner’s needs to
monitor chlorine, XOS can provide many different solutions for monitoring organic, total, and inorganic chlorine
 To account for the dilution of the inorganic ONLINE
crude chlorine into the water phase of the sam­ Online chlorine
ple, use the provided equations to cal­culate inor- analysis in liquid
ganic chlorine. If running multiple extractions, hydrocarbon
combine the extraction water, mix well, ONLINEandCHLORINE process
ANALYSIS streams
IN LIQUID HYDROCARBON
measure sample per directions above. Remember
PROCESS STREAMS With ever-changing
With ever-changing crude quality and
to use the total weight of water used for extrac- crude quality and
blends, chlorine levels can shift quickly,
tion. See Note 3 regarding the weight ofmakingwater blends,
real-time analytical chlorine levels
results
invaluable. Clora Online delivers
®

used for this calculation. See Note 6 regarding thecontinuouscan

real-time, shift
analysis quickly,
of total
chlorine from 0.2 ppmw up to 3000
use of crude weight vs crude/solvent weight in making real-time
ppmw. By monitoring desalted crude,
the following inorganic chlorine calculations.
a plant can optimizeanalytical
performance and results
immediately see impacts of crude
invaluable.
changes (including organic chloride). Clora
Conclusion Powered by MWDXRF®, Clora Online
Online delivers
uses ASTM D7536 technology and is
Corrosion mitigation strategies are an important real-time, continuous
ATEX and NIC certified.

part of ensuring safe refinery operation and max- analysis of total

imising profitability. Clora has become a critical chlorine from
part of identifying potential corrosion events and 0.2 ppmw up to
monitoring the effectiveness of these mitigation REFERENCES 3000 ppmw. By monitoring desalted crude, a
NACE International, Effect of Nonextractable Chlorides on Refinery
strategies. With over a decade of experience sup-and Fouling,
Corrosion plant
NACE can optimise
International performance
Publication 34105, Item and
24226.immediately
porting refiner’s needs to monitor chlorine, XOS see impacts of crude changes (including organic
can provide many different solutions for moni- chloride). Powered by MWDXRF®, Clora Online
toring organic, total, and inorganic chlorine in
©XOS all rights reserved. Clora, Clora 2XP, Sindie +Cl,
uses ASTM D7536 technology
and MWDXRF are registered trademarks of XOS.
and is ATEX and
1.518.880.1500 • info@xos.com • xos.com
crude oil. NIC certified.

1.518.880.1500 • info@xos.com • xos.com

©XOS all rights reserved. Clora, Clora 2XP, Sindie +Cl, and
MWDXRF are registered trademarks of XOS.

References LINKS
1. Koch, Gerhardus H, et al, Corrosion Costs and Preventive
Strategies in the United States, NACE International. More articles from: XOS
2. Petroleum Refinery Gap Analysis, NACE Technical Coordination
Committee, 18 Oct 2008. More articles from the following categories:
NACE International, Effect of Nonextractable Chlorides on Refinery Instrumentation, Automation and Process Control
Corrosion and Fouling, NACE International Publication 34105, Laboratory, R&D and Quality Control
Item 24226. Sulphur Removal and Recovery

www.digitalrefining.com/article/1001474 February 2018 7