Ip 470
Ip 470
Ip 470
This standard does not purport to address all of the safety problems associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability
of regulatory limitations prior to use.
Aluminium and silicon are normally found in IP 367, Petroleum products — Determination and
association with each other in residual fuels, and application of precision data in relation to methods
may be specified, separately or in combination, as of test. (/ ISO 4259)
an estimate of catalyst fines content.
3 Principle
2 Normative references
A weighed test portion, together with an ashing
The following normative documents contain agent, is ignited and burnt, and the residual carbon
provisions which, through reference in this text, removed by heating in a muffle furnace. The residue
constitute provisions of this standard. For dated is fused with a dilithium tetraborate/lithium fluoride
references, subsequent amendments to, or revisions flux and the fused mixture digested in a solution of
of, any of these publications do not apply. However, tartaric acid and hydrochloric acid. For vanadium a
parties to agreements based on this standard are
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
4 Reagents and materials 4.10.1 Nitric acid solution (1 + 1). Mix equal
volumes of nitric acid (4.10) and water.
4.1 General
4.11 Lanthanum Chloride solution
All reagents shall be of analytical reagent grade or
of higher purity and water shall be of at least grade 4.11.1 Lanthanum/hydrochloric acid solution
3 purity as specified in ISO 3696.
Dissolve 60 ± 1 g La2O3in approx. 600 ml water
4.2 Potassium hydrogensulfate (KHSO4) and 200 ml hydrochloric acid solution (1 + 4)
(4.7.3) in a 1 000 ml volumetric flask. Make up to
Fused solid. the mark with water.
4.7.2 Hydrochloric acid solution (1 + 2). Mix one 4.12.1.1 Dissolve 1 000 g ± 0,001 g of aluminium
volume of hydrochloric acid (4.7) with two volumes metal wire, of minimum purity 99,9 % Al, in 50 ml
of water. hydrochloric acid (4.7) with gentle heating in a
400 ml beaker (5.13). Cool, transfer to a 1 000 ml
4.7.3 Hydrochloric acid solution (1+4). Mix one volumetric flask (5.9), and dilute to the mark with
volume of hydrochloric acid (4.7) with four volumes water.
of water.
4.12.2 Silicon standard solution. Use either a
commercially available silicon standard solution of
4.8 Flux
1 000 mg/l silicon content, or prepare in the manner
described in 4.12.2.1.
Mixture of 90 % (m/m) dilithium tetraborate
(Li2B4O7) and 10 % (m/m) lithium fluoride (LiF).
470.2
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
4.12.2.1 Fuse 2,140 g ± 0,001 g of silicon 4.12.7 Calcium standard solution. Use a
dioxide, of minimum purity 99,99 % SiO2, with commercially available calcium standard solution of
8 g of sodium hydroxide in a zirconium crucible 1 000 mg/l calcium content.
fitted with a close-fitting lid (5.4) at dull red heat
until a clear melt is obtained. Cool and dissolve the 4.12.7.1 Dissolve 2,498 g ± 0,001 g of calcium
solidified melt in 100 ml of hydrochloric acid carbonate (CaCO3) in water in a 400 ml beaker
solution (4.7.2) in a 400 ml beaker (5.13). Cool, (5.13) with 100 ml water and add dropwise 10 ml
transfer to a 1 000 ml volumetric flask (5.9), make of hydrochloric acid solution (4.7.1). Transfer to a
up to the mark with water, followed by immediate 1 000 ml volumetric flask (5.9), make up to the
transfer to a plastic bottle (5.15) for longer-term mark with water, and mix.
storage.
4.12.8 Zinc standard solution. Use a commercially
4.12.3 Vanadium standard solution. Use either a available zinc standard solution of 1 000 mg/l zinc
commercially available vanadium standard solution content.
of 1 000 mg/l vanadium content, or prepare in the
manner described in 4.12.3.1. 4.12.8.1 Dissolve 1 000 g ± 0,001 g of zinc metal
in minimum volume of hydrochloric acid solution
4.12.3.1 Dissolve 1 000 g ± 0,001 g of vanadium (1 + 1)(4.7.1) in a 400 ml beaker (5.13). Transfer
metal, of minimum purity 99,9 % V, in 40 ml of to a 1 000 ml volumetric flask (5.9), make up to the
nitric acid (4.10) with gentle heating in a 400 ml mark with water, and mix.
beaker (5.13). Cool, transfer to a 1 000 ml
volumetric flask (5.9) and make up to the mark with 5 Apparatus
water.
5.1 General
4.12.4 Nickel standard solution. Use either a
commercially available nickel standard solution of The apparatus requirements are detailed in 5.2 to
1 000 mg/l nickel content, or prepare in the manner 5.16. All glassware and the zirconium crucible shall
described in 4.12.4.1. be sodium-free and carefully cleaned with hot
hydrochloric acid solution (4.7.1) and rinsed
4.12.4.1 Dissolve 1,000 g ± 0,001 g of nickel thoroughly with water to eliminate contamination.
metal of minimum purity 99,9 % Ni, in 40 ml of
nitric acid solution (4.10.1) with gentle heating in a 5.2 Atomic absorption spectrometer
400 ml beaker (5.13). Cool, transfer to a 1 000 ml
volumetric flask (5.9) and make up to the mark with Use an instrument with a modulated hollow cathode
water. lamp or other source of modulated resonance
radiation of sodium/aluminium/silicon/ vanadium/
4.12.5 Iron standard solution. Use either a nickel/iron/calcium/zinc. It shall be fitted with an
commercially available iron standard solution of air/acetylene burner, a dinitrogen oxide (nitrous
1 000 mg/l iron content, or prepare in the manner oxide)/acetylene burner, and a light detector with a
described in 4.12.5.1. suitable measuring and readout system. The scale
shall be linear in absorbance, or of light intensity.
4.12.5.1 Dissolve 1,000 g ± 0,001 g of iron metal
of minimum purity 99,9 % Fe, in 40 ml of 5.3 Platinum basin
hydrochloric acid solution (4.7.1) with gentle
warming in a 400 ml beaker (5.13). Cool, transfer to Of 100 ml capacity with a minimum diameter of
a 1 000 ml volumetric flask (5.9) and make up to 70 mm. Clean the basin with fused potassium
the mark with water. hydrogensulfate (4.2).
4.12.6.1 Dissolve 2,542 g ± 0,001 g of sodium An alternative cleaning technique is to use hot
chloride (NaCl) in water in a 400 ml beaker (5.13). hydrochloric acid (4.7.1.) however the precision of this
Transfer to a 1 000 ml volumetric flask (5.9), make method is based on the potassium hydrogen sulphate
technique only.
up to the mark with water, and mix.
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5.7 Muffle furnace 100 ml and 1 000 ml capacity, suitable for long-
term storage of dilute acid solutions.
Electric, capable of being maintained at
temperatures of 525 °C ± 25 °C and 925 °C ± 5.16 Analytical balance
25 °C, and preferable having apertures at front and
rear to allow passage of a slow, natural draught of Capable of weighing to the nearest 0,2 mg.
air. Ensure that the refractory walls are in good
condition, with no loose particles. 6 Samples and sampling
5.8 Hot plate 6.1 Unless otherwise specified, laboratory
samples shall be obtained by the procedures
Electric, with or without a magnetic stirring described in IP 475 or IP 476.
capability.
6.2 Thoroughly mix samples in their containers
5.9 Volumetric flasks immediately prior to withdrawal of the test portions.
Place the sample container in the oven (5.6) and
100 ml, 25 ml and 1 000 ml capacity, complying maintain the sample at 50 °C to 60 °C until all the
with the requirements of ISO 1042, class A. sample is fluid and of uniform viscosity. Insert the
shaft of the mixer (5.5) into the sample container so
5.10 Pipettes that the head of the shaft is immersed to
approximately 5 mm from the bottom of the
1 ml, 2 ml, 5 ml, 10 ml, 20 ml and 25 ml capacity, container. Mix the sample for approximately 5 min.
complying with the requirements of ISO 658, class
A. 6.3 Efficient mixing of the sample is essential to
the accuracy and precision of this test method.
NOTE 4 - Auto-dispensing pipettes may be used as an Hand shaking alone will invalidate results.
alternative provided that they meet the requirements
detailed above. 7 Procedure
5.11 Pipettes 7.1 Test portion mass
1 ml and 2 ml capacity, graduated in 0,1 ml Select a mass of test portion, between 20 g and
subdivisions, complying with the requirements of 50 g, to yield approximately 1,3 mg of aluminium.
ISO 835-2.
NOTE 6 - The mass of test portion selected based on the
NOTE 5 - Auto-dispensing pipettes may be used as an aluminium content, will suffice for the silicon
alternative provided that they meet the requirements determination as both elements are usually found in
detailed above. residual fuels associated with each other. Where the
levels of other elements are low, it may be necessary to
5.12 Measuring cylinders take the maximum mass (50 g) of test portion, and dilute
the test solutions as required for the aluminium and
10 ml, 25 ml, 50 ml and 100 ml capacity, with silicon determinations.
subdivided graduations, complying with the
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
7.2 Test solution preparation 7.2.6 Remove the basin and cool the fusion melt
to room temperature. Add 50 ml tartaric
7.2.1 Immediately after homogenization, transfer acid/hydrochloric acid solution (4.9.1) to the basin
the test portion from the container to the weighed and place on the hot plate (5.8). Maintain at a
platinum basin (5.3). Re-weigh the basin and moderate temperature without boiling.
contents to the nearest 0,1 g to obtain the test
portion mass. NOTE 10 - Excessive evaporation of the solution could
lead to precipitation of an insoluble form of silica.
7.2.2 If the sulphur content of the sample is below
NOTE 11 - Prolonged heating may be required to dissolve
0,3 % m/m add 0,3 g of ashing agent (4.3) to the
the solidified melt completely and obtain a solution.
basin, distributing it as evenly as possible over the Agitation, or the use of magnetic stirring may be
surface of the basin contents. employed to speed dissolution of the solidified melt.
Prepare a blank test portion containing only the 7.2.7 Allow the solution to cool and then transfer
ashing agent, and use it for the complete procedure it to a 100 ml volumetric flask (5.9) with water,
in this clause. washing the basin several times to ensure that the
transfer is quantitative. Make up to the mark with
7.2.3 Warm the basin and contents gently with a water, and transfer immediately to a 100 ml plastic
Bunsen flame until the test portion ignites. Maintain bottle (5.15).
the contents of the basin at a temperature such that
most of the combustible material is removed and 7.2.8 For vanadium determination only, transfer
only carbon and ash remain. 5,0 ml of the lanthanum solution (4.11.1 or 4.11.2)
into a 25 ml volumetric flask and fill to the mark
NOTE 7 - If the sample contains considerable amounts of with the test solution (7.2.7)
moisture, foaming and frothing may cause loss of test
portion.
NOTE 12 - Transfer to a plastic bottle is thought to be
desirable as the dilute acid solution will contain
If foaming and frothing occur, discard the test tetrafluoroboric acid (HBF4) from solution of flux.
portion and add 1 ml to 2 ml of propan-2-ol (4.4) However, storage tests have shown that there is no
before heating. If foaming and frothing are not attack of glassware in the short term (up to one week),
sufficiently reduced, add 10 ml of toluene/propan-2- and that the solution does not contain free fluoride 'ion'
ol mixture (4.6) to a further test portion and mix above the 5 mg/l level.
thoroughly. Place several strips of filter paper (5.14)
in the mixture before warming gently. 7.3 Preparation of blank solution
NOTE 8 - When the paper begins to burn, the greater part 7.3.1 Prepare a blank solution containing only
of the water will have been removed. 0,4 g flux (4.8) and 50 ml of the tartaric
acid/hydrochloric acid solution (4.9.1), diluted to
7.2.4 Place the basin and its contents in the 100 ml, and transfer immediately to a 100 ml
muffle furnace (5.7), preheated to a temperature of plastic bottle (5.15).
525 °C ± 25 °C. Ensure that the basin contents
are not contaminated with refractory from the 7.3.2 Vanadium blank solution. Prepare a zero-
furnace walls, as this will contribute to erroneous concentration solution containing 0,3 g flux, 50 ml
silicon results. Maintain the muffle furnace at this of the tartaric acid/hydrochloric acid solution (4.9.1)
temperature until all the carbon has been removed and 20 ml of the lanthanum solution (4.11.1 or
and only ash remains. 4.11.2) diluted to 100 ml and transfer immediately
to 100 ml plastic bottle.
NOTE 9 - This may take overnight.
7.4 Preparation of calibration solutions
7.2.5 Cool the basin to room temperature, add
0,4 g of flux (4.8), and mix it with the ash. Place 7.4.1 Aluminium and silicon. Prepare a 250 mg/l
the basin and contents in the muffle furnace aluminium or silicon working solution by diluting
preheated to a temperature of 925 °C ± 25 °C for 25 ml of the 1 000 mg/l standard solution (4.11.1
5 min. Remove the basin and ensure contact of the or 4.11.2) to 100 ml with water. To each of four
flux with the ash. Replace the basin in the muffle clean 100 ml volumetric flasks (5.9), add 0,4 g flux
furnace and maintain the temperature at 925 °C ± (4.8) and 50 ml of the tartaric acid/hydrochloric acid
25 °C for a further 10 min. solution (4.9.1). To successive flasks add
470.5
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
2 ml, 4 ml, 10 ml and 20 ml of the 250 mg/l 20 ml of the 100 mg/l vanadium working solution
aluminium or silicon working solution and dilute to and dilute to 100 ml with water.
100 ml with water.
NOTE 15 - The calibration solutions contain 5 mg/l,
NOTE 13 - The calibration solutions contain 5 mg/l, 10 mg/l, 15 mg/l and 20 mg/l of vanadium.
10 mg/l, 25 mg/l and 50 mg/l of aluminium or silicon
respectively. 7.4.4 Storage. Transfer all standards immediately
after preparation to 100 ml plastic bottles (5.15).
7.4.2 Nickel, iron, sodium, calcium and zinc.
Prepare a 100 mg/l nickel, iron, sodium, calcium or 7.5 Setting up the spectrometer
zinc working solution by diluting 10 ml of the
1 000 mg/l standard solution (4.12.4, 4.12.5, 7.5.1 General. Consult and follow the
4.12.6, 4.12.7 or 4.12.8) to 100 ml with water. To manufacturer’s instructions for the operation of the
each of four clean 100 ml volumetric flasks (5.9), atomic absorption spectrometer (5.2).
add 0,4 g flux (4.8) and 50 ml of the tartaric
acid/hydrochloric acid solution (4.9.1). To NOTE 16 - Design differences between spectrometers
successive flasks add 5 ml, 10 ml, 15 ml and 20 ml make it impracticable to specify the required
of the 100 mg/l calcium, zinc, nickel, iron or sodium manipulations.
working solution and dilute to 100 ml with water.
WARNING - Correct operating procedures are
NOTE 14 - The calibration solutions contain 5 mg/l, required for safety as well as for reliability of
10 mg/l, 15 mg/l and 20 mg/l of calcium, zinc, nickel, iron results. An explosion can result from flame blow-
or sodium respectively. back unless the correct burner head and operating
sequence are used.
7.4.3 Vanadium. Prepare a 100 mg/l vanadium
working solution by diluting 10 ml of the 1 000 mg/l 7.5.2 Settings. Fit the hollow cathode lamp for the
standard solution (4.10.3) to 100 ml with water. To element of interest and set the lamp current to that
each of four clean 100 ml volumetric flasks (5.9), recommended by the manufacturer. Set the
add 0,3 g flux (4.8), 50 ml of the tartaric monochrometer to the specified wavelength (see
acid/hydrochloric acid solution (4.9.1) and 20 ml of Table 1) and adjust the wavelength control to get
the lanthanum solution (4/11/1 or 4.11.2). To maximum output.
successive flasks add 5 ml, 10 ml, 15 ml and
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
7.5.3 Calibration curve. Prepare a calibration curve 7.5.4.2 Spectrometers with digital readout and
prior to analysis of each group of samples and after built-in (non-microprocessor-controlled) curvature
any change in instrumental conditions, as variations correction and scale expansion facilities. Follow the
occur in the instrument behaviour. The mode of manufacturer’s operating instructions aspirating the
calibration depends on the type of readout facility appropriate calibration solution, to set the digital
on the instrument. readout to read directly in the required units,
carrying out a curvature correction programme if
NOTE 17 - Readings may vary over short times from such necessary.
causes as buildup of deposits on the burner slot or in the
nebulizer. The visual appearance of the flame is a useful Aspirate the test solution and read the element
check to detect changes of condition. content of each test solution and solution blank
directly from the readout given by the digital display
7.5.4 Analysis of the test solution. Analyze one of from the spectrometer.
the calibration standards after every fifth test
sample. If the result indicates that the calibration 7.5.4.3 Spectrometers with digital readout
has changed by greater than 5% drift (see note 14), microprocessor-controlled calibration facilities.
recalibrate the instrument. Follow the manufacturer’s operating instructions,
aspirating the appropriate calibration solution and
If it is found that a test solution gives a metal using the recommended calibration programme to
content above the highest content of any calibration obtain a direct readout in element content; the
solution, dilute it in the same matrix, i.e. blank element content of each test and blank solution can
solution (7.3), to bring it within the range of thus be directly obtained after aspiration of the test
calibration solutions. solution.
To ensure that analysis is carried out within linear
calibration, the metal content in the final analysis
8 Calculation
solution shall not exceed 10 mg/l for vanadium and
Calculate E, the content of the element of interest
sodium.
as Al, Si, V, Ni, Fe, Ca, Zn or Na respectively in
milligrams per kilogram from the following equation:
7.5.4.1 Spectrometers with meter readout. Aspirate
the calibration solution, blank solution and test
100cd
E = ÕÕÕ
solution sequentially into the flame and record the
meter reading. Aspirate the blank solution between
m
each test solution.
where
If the spectrometer output is linear in absorbance,
c is the element content of interest in
plot a calibration graph of net absorbance
mg/l as read from the calibration
(calibration solution absorbance minus blank solution
graph or direct readout;
absorbance) against element content in mg/l. From
d is the dilution factor, calculated
this calibration graph, estimate the element content
from the volumes and aliquots taken
of each sample solution after similarly computing its
to produce the test solution;
net absorbance.
m is the mass of the test portion, in
grams.
If the spectrometer output is proportional to
transmission (i.e. light intensity), calculate the net
NOTE 18 - Dilution factor, d, for vanadium is 1,25 (25 ml/20
absorbance, A, using the following equation:
ml) unless no further dilution procedures are carried out.
470.7
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Al, Si, V, Ni, Fe, Ca, Zn, Na IN FUEL OIL - AAS, IP 470
Zn Ca Na Fe Ni V
mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
mg/kg r R r R r R r R r R r R
1 0,26 0,58 0,60 1,30 0,79 2,33 0,75 3,26
10 1,49 3,26 2,23 4,75 2,38 5,19 3,43 7,51 2,80 8,28 2,37 10,31
50 4,97 10,91 5,95 9,75 6,25 13,62 9,00 19,73 6,77 20,06 5,29 23,04
100 10,60 16,00 9,47 20,64 9,92 29,37 7,48 32,59
200 10,58 46,09
300 12,96 56,44
400 14,96 65,18
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11 Test report
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