8.

55

Sulfur-in-Oil Analyzers

TO RECEIVER

SAMPLE

D. H. F. LIU

(1995)

B. G. LIPTK

AT

(2003)

S
Flow Sheet Symbol

Type of Sample:

Crude and fuel oils, diesel, gasoline, middle distillates, kerosene, gas oil, jet fuel, and
lubricating oils

Method of Analysis:

A. X-ray absorption
B. X-ray fluorescence
C. Pulsed UV
D. Purged spectrometer

Range:

A. 00.5 to 05% sulfur; 0.6 to 1 g/ml density

B. Lower detection limit is 50 ppm
C. Down to 1 ppm w/w sulfur in diesel, gasoline, kerosene, and jet fuel
D. 40 ppm to 5%

Inaccuracy:

A. 0.5% of full scale or 0.005 wt% S

B. 15 ppm at a concentration of 300 ppm
C. Repeatability at 1 ppm is 0.02 ppm
D. 3% of concentration

Sensitivity:

A. 0.5% of full scale or 0.0005 g/cm

Cost:

A, B. $40,000 to $80,000
C. $55,000 to $65,000
D. About $75,000

Partial List of Suppliers:

Berthold Technologies (www.berthold.com.au)

Horiba (www.horibalab.com)
ISL (www.isl-france.com)
Rigaku MSC (www.msc.com)
Shimadzu Corp. (www.shimadzu.com)
Spectronex (www.spectronex.com)
Spectro Inc. (D) (www.spectroinc.com)
Thermo Onix (C) (www.thermo.com)
Yokogawa Corp. (A, B) (www.yokogawa.com/)

INTRODUCTION

X-RAY ABSORPTION ANALYZER

On-line analysis of sulfur in oil products is imperative,

because environmental authorities are tightening the limits
on sulfur levels in petroleum products. Limitations of 300
ppm in blended gasoline and 500 ppm in diesel are not
uncommon. Even with an excellent hydrotreating capability,
these limits are often difficult to meet, so processing must be
carefully monitored. The timely information provided by
continuous on-line monitoring is necessary to consistently
meet sulfur content limits, especially when blending the various product or feed streams.

The x-ray absorption technique has been used for many years,
in the laboratory and on line, to measure total sulfur content
in liquid petroleum products. The intensity of x-rays, after
they pass through a liquid hydrocarbon sample, depends on
the density and elemental composition of that sample.
For x-ray radiation in the region of 10 to 20 KeV, sulfur
has a much greater mass absorption coefficient than does
carbon and hydrogen. At 20 KeV, the mass absorption coefficients of carbon and hydrogen are about equal, so that
changes in x-ray absorption due to C:H ratio are negligible.
1641

2003 by Bla Liptk

1642

Analytical Instrumentation

Therefore, the changes in x-ray absorption depend mostly on

sample density and sulfur content. The ionization current (Is)
can be expressed as
Is = Io exp [ t{( 5 CH ) C5 + CH}]

8.55(1)

where
3
= density of liquid to be measured (in g/cm )
t = effective length of the liquid cell (in cm)
2
5 = mass absorption coefficient of sulfur (in cm /g)
CH = mass absorption coefficient of carbon and hydrogen
2
(in cm /g)
CS = sulfur concentration ratio by weight
Method of Operation
Figure 8.51a illustrates the operation of an x-ray absorption
type sulfur-in-oil analyzer. The x-rays emitted from an
americium-241 source bombard a target, producing secondary x-rays at 20 KeV. These penetrate a beryllium 5 mm thick

back-plate and a thin Teflon plate, pass through the sample

cell, and enter the ionization chamber.
The current from the ionization chamber detector is the
input to the sulfur converter. This input is compared with the
zero set signal from a standard current source. The difference
between these signal currents is the input to the picodiode
electrometer, where the differential current is amplified to
provide an output signal to the S-set sulfur converter unit.
At the S-set unit, the signal is linearized, compensated
for density at the zero point by the signal from the density
converter, and converted to a voltage signal that is proportional to the sulfur concentration and density. After span
adjustment, the signal is transmitted to the divider unit. This
unit divides the sulfur concentration signal from the S-set
unit by the density signal (calibrated at the sample temperature of the sulfur detector). The divider unit produces a 4 to
20 mA DC output signal proportional to total sulfur content.
The most sensitive range of the system is 0 to 0.5 wt%
sulfur, with a repeatability of 0.01 wt%. The density mea3
surement has a sensitivity of 0.0005 g/cm .
Figure 8.55b shows a block diagram of the measurement
electronics and describes the components of the three separate partsthe density measurement system, the hydrogen
content measurement system, and the sulfur measurement
system.
X-RAY FLUORESCENCE
X-ray fluorescence (XRF) measurement of sulfur in oil is
recognized as an ASTM laboratory procedure. An on-line
XRF analyzer system has three main component blocks: sampling, analysis, and control. In these units, a continuous
stream of process sample passes through a flow cell with Becoated window. The coating maximizes both the life and the
x-ray transmission of the window. The sample is excited by
a low-level radiation source that causes the sulfur atoms to

2003 by Bla Liptk

emit their characteristic fluorescent x-rays. The x-ray intensity is measured by a high-resolution proportional counterdetector over a period of time, and the resultant data are
processed by a microprocessor to yield the average total
sulfur content in the stream.
The assays are updated every 2 to 10 min, depending on
the analysis precision desired. Precision is typically 15 ppm
at 300 ppm concentration, and the lower detection limit of
this sensor is 50 ppm.
PULSED UV FLUORESCENCE
The pulsed ultraviolet fluorescence (PUVF) type of total
sulfur analyzer takes a liquid sample and vaporizes it before
measuring the sulfur contents. The package, shown in Figure
8.55c, includes the main components of a sample injection
valve, carrier gas flow control system, mixing chamber,
combustion chamber, and detector subassembly.
The sample injection valve periodically transfers a small
amount of sample liquid (approximately 1.0 l) into an air
carrier gas. The air/sample mixture passes through the mixing
chamber to ensure complete mixing and then flows to the
combustion chamber, where all sample components are combusted into SO2, CO2, and H2O at about 1100C. The PUVF
detector accurately measures the amount of SO2 produced
during combustion of the sample.
The operation of the pulsed UV fluorescence analyzer
takes advantage of the fact that SO2 molecules absorb ultraviolet (UV) light and become excited at one wavelength, then
decay to a lower energy state, while emitting UV light at a
different wavelength. Specifically,
SO2 + hv1 SO*2 SO2 + hv2

8.55(2)

The sample flows into the fluorescence chamber, where

pulsating UV light excites the SO2 molecules. The condensing lens focuses the pulsating UV light into a mirror assembly, which contains four selective mirrors that reflect only
the wavelengths that excite SO2 molecules.
As the excited SO2 molecules decay to their lower energy
states, they emit UV light that is proportional to the SO2
concentration. The bandpass filter allows only the wavelengths emitted by the excited SO2 molecules to reach the
photomultiplier tube (PMT), which detects the UV light
emission from the decaying SO2 molecules. The photodetector, located at the back of the fluorescence chamber, continuously monitors the pulsating UV light source and is connected to a circuit that compensates for fluctuations in the
intensity of the UV light.
This analyzer, on a weight basis, measures down to 1 ppm
sulfur in diesel, gasoline, kerosene, and jet fuel. It has a
repeatability of 0.02 ppm (2 sigma RSD = 0.25%) making
its sensitivity highly suitable for critical process control
applications. Such applications might include the measurement of the sulfur content of hydrocarbon products and controlling the fuel blending process.

8.55 Sulfur-in-Oil Analyzers

Is
ELECTRO
METER
Ts

MULTIPLEXER

TEMPERATURE/
VOLTAGE
CONVERTER

TD

AD
CONVERTER
(1)

CPU

DISPLAY
CODE SWITCH

BUS

FREQUENCY
COUNTER

POWER SUPPLY
CIRCUIT

SULFUR SIGNAL
4 TO 20 mA

DA CONVERTER
(ISOLATOR)

AD CONVERTER (2)
Fx

1643

DENSITY SIGNAL
4 TO 20 mA

ADJUSTMENT DIALS

POWER SUPPLY
100 V/115V AC

S-SET
SULFUR
CONVERTER

CALIBRATION UNIT
TANK
AIR

PRESSURE
GAUGE

SAMPLE
INLET

THERMO
METER

FLOW
METER

SULFUR SIGNAL
DENSITY SIGNAL

SULFUR DETECTOR

NEEDLE VALVE
DENSITY

DETECTOR
DRAIN

SAMPLE
OUTLET

CALIBRATION
SAMPLE OUTLET

BRACKET FOR MOUNTING

LIQUID CELL
TARGET
RADIATION
SOURCE
ASSEMBLY

VIBRATOR

ELECTRODE
PICK-UP

RADIATION SOURCE
BACK-PLATE
TERMINAL BOX

FREQUENCY
OUT

IONIZATION CHAMBER
TEFLON PLATE
TRANSISTOR TEMP. DETECTOR
TRANSISTOR
TEMP. DETECTOR
PIEZOELECTRIC
ELEMENT

FIG. 8.55a
X-ray absorption type sulfur-in-oil analyzer. (Courtesy of Yokogawa.)

2003 by Bla Liptk

OSCILLATION
AMPLIFIER

TEMPERATURE
OUT

1644

Analytical Instrumentation

SULPHUR

OIL-OUTPUT
AMPLIFIERDISCRIMINATOR
SOURCE
Cm244
10 mci

ADAPTION-UNIT

DIGITAL-DISPLAY

RATEMETER

SCINTIL
COUNT

SIGNAL-PROCESSOR

%S

U
s = f (U.p.H)
U

HV-UNIT

AUTOMDECAYCOMPENS.
FOR
Cm 244 178.

HV-CHECK

AUTOMH.V. CONTR

H2

ANALOG-DISPLAY DENSITY

ADAPTION-UNIT

RATEMETER
RELAY OUTPUT (MIN/MAX)

SCINTIL
COUNT

TEMPERATURE

AUTOMDECAYCOMPENS.
FOR
Ca 137-30.

HV-CHECK

H.V.-UNIT
AUTOMH.V.-CONTR.

P1 100

RELAY OUTPUT (MIN/MAX)

EXT
SWITCH

DENSITY

AMPLIFIERDISCRIMINATOR

OUTPUT 0/4 TO 20 mA (IS)

J

DENSITYSIGNAL
TRANSFORM

SOURCE
Cs - 137
75 mCi

RANGESELECTOR

H2

OUTPUT 0/4 TO 20 mA

U
I

TEMPERATURE

SOURCE
Am-Bc
100 mCi

AMPLIFIERDISCRIMINATOR

ADAPTION-UNIT
ANALOG-DISPLAY HYDROGEN
f

SCINTIL
COUNT

RATEMETER
H.V.-UNIT

H.V.-CHECK

OIL-INLET

ANALOG OUTPUT 0/4 TO 20 mA

AUTOMH.V.-CONTR.

HYDROGEN

FIG. 8.55b
Block diagram of the measurement electronics for three separate measurements: density, hydrogen content, and sulfur content.

60000

Concentration in PPM

50000

CONCENTRATION (PPM)

SULFUR RESPONSE

0
250
500
1000
5000
10000
25000
50000

19.1
249
490
977
4986
9996
24357
51667

40000

30000

20000

10000

0
1

Intensity Ratio

FIG. 8.55c
On-line total sulfur analyzer for gasoline, diesel, kerosene, jet fuel,
or gas oil applications. (Courtesy of ThermoOnix.)

2003 by Bla Liptk

FIG. 8.55d
Calibration curve for a fuel analysis spectrometer, which is provided
with optics for sulfur measurement. (Courtesy of Spectro Inc.)

8.55 Sulfur-in-Oil Analyzers

FUEL ANALYSIS SPECTROMETER

To use fuel analysis spectrometers for on-site sulfur analysis,
it is necessary to prevent the atmospheric oxygen from
absorbing the sulfur. This is achieved by the use of nitrogen
or argon purged optics. Such units can be useful in measuring the sulfur content of gas turbine fuels or of lubricating
oils.
Because of the small size of the optics, the purge gas
consumption is small, <3 l/min. The minimum detectable
sulfur concentration is 40 ppm, and the maximum of the
calibrated range is 5% (50,000 ppm). Figure 8.55d illustrates
a sulfur calibration curve. The intensity ratio shown on that
curve is the ratio between the outputs of the measuring and

2003 by Bla Liptk

1645

reference photomultiplier tubes. The reference used is the

carbon sensitive wavelength (193.05 nm), while sulfur is
measured at 180.73 nm. The measurement error is usually
<3% over the calibrated range.

Bibliography
Clevett, K. S., Process Analyzer Technology, John Wiley & Sons, New York,
1986, 314321.
Greyson, J. C., Carbon, Nitrogen and Sulfur Pollutants, Marcel Decker, New
York, 1990.
Hidy, G. M., Atmospheric Sulfur, Academic Press, New York, 1994.
Ramanujan, R. S. and Fitzgibbon, P., X-ray fluorescence for on-line elemental analysis, Control, March 1990.