U.S. patent application number 15/452750 was filed with the patent office on 2017-06-22 for method of making hydrocarbon liquids.
The applicant listed for this patent is JOHNSON MATTHEY PUBLIC LIMITED COMPANY. Invention is credited to Vincent Brian CROUD, Duncan MCCALLIEN.
Application Number | 20170175017 15/452750 |
Document ID | / |
Family ID | 44243949 |
Filed Date | 2017-06-22 |
United States Patent
Application |
20170175017 |
Kind Code |
A1 |
MCCALLIEN; Duncan ; et
al. |
June 22, 2017 |
METHOD OF MAKING HYDROCARBON LIQUIDS
Abstract
A method of marking a hydrocarbon liquid includes the step of
adding to the liquid, as a tracer compound, a compound of Formula
I: ##STR00001## wherein at least one of R.sup.1-R.sup.4 is selected
from: i. a bromine or fluorine atom; ii. a partially or fully
halogenated alkyl group; iii. a branched or cyclic C.sub.4-C.sub.20
alkyl group; iv. an aliphatic substituent linking two positions
selected from R.sup.1-R.sup.4 in Formula I to one another; or v. a
phenyl group substituted with a halogen atom, an aliphatic group or
halogenated aliphatic group. The tracer compounds are resistant to
removal from the fuel by chemical laundering or by contact with
absorbents such as charcoal.
Inventors: |
MCCALLIEN; Duncan; (Durham,
GB) ; CROUD; Vincent Brian; (Sheffield South
Yorkshire, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JOHNSON MATTHEY PUBLIC LIMITED COMPANY |
London |
|
GB |
|
|
Family ID: |
44243949 |
Appl. No.: |
15/452750 |
Filed: |
March 8, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14116554 |
Dec 12, 2013 |
9625440 |
|
|
PCT/GB2012/051016 |
May 9, 2012 |
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15452750 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 2230/16 20130101;
G01N 33/2882 20130101; Y10T 436/13 20150115; C10L 1/226 20130101;
C10L 1/003 20130101 |
International
Class: |
C10L 1/00 20060101
C10L001/00; C10L 1/226 20060101 C10L001/226; G01N 33/28 20060101
G01N033/28 |
Foreign Application Data
Date |
Code |
Application Number |
May 11, 2011 |
GB |
1107871.4 |
Claims
1. A composition comprising a hydrocarbon fuel or octane and a
tracer compound, characterised in that said tracer compound
comprises a compound of Formula I: ##STR00004## wherein at least
one of R.sup.1-R.sup.4 is selected from a group consisting of: i. a
bromine or fluorine atom; ii. a partially or fully halogenated
alkyl group; iii. a branched or cyclic C.sub.4-C.sub.20 alkyl
group; iv. an aliphatic substituent linking two positions selected
from R.sup.1-R.sup.4 in Formula I to one another; and v. a phenyl
group substituted with a halogen atom, an aliphatic group or
halogenated aliphatic group; and further wherein none of
R.sup.1-R.sup.4 consists of a hydroxyl group or an amino group.
2. The composition according to claim 1, wherein said tracer
compound is present at a concentration of from 1 to 500 ppbv.
3. The composition according to claim 1, comprising more than one
tracer compound.
4. The composition according to claim 1, wherein said hydrocarbon
fuel or octane comprises a diesel fuel, a gasoline fuel or a
solvent.
5. The composition according to claim 1 wherein at least 50% of the
tracer compound is retained in the hydrocarbon fuel or octane after
a sample of the hydrocarbon fuel or octane containing from 10 to 15
ppbv of the tracer compound has passed through a column of fresh
activated charcoal.
6. The composition according to claim 1, wherein at least 50% of
the tracer compound is retained in the hydrocarbon fuel or octane
after a sample of the hydrocarbon fuel or octane containing from 10
to 15 ppbv of the tracer compound has passed through a column of
fresh powdered sepiolitic clay.
7. The composition according to claim 1, wherein at least 50% of
the tracer compound is retained in the hydrocarbon fuel or octane
after a sample of the hydrocarbon fuel or octane containing from 10
to 15 ppbv of the tracer compound has been vigorously agitated in
contact with 10% aqueous HCl.
8. The composition according to claim 1, wherein at least 50% of
the tracer compound is retained in the hydrocarbon fuel or octane
after a sample of the hydrocarbon fuel or octane containing from 10
to 15 ppbv of the tracer compound has been vigorously agitated in
contact with 10% aqueous NaOH.
9. The composition according to claim 1, wherein at least 50% of
the tracer compound is retained in the hydrocarbon fuel or octane
after a sample of the hydrocarbon fuel or octane containing from 10
to 15 ppbv of the tracer compound has been vigorously agitated in
contact with methanolic KOH.
Description
[0001] The present invention concerns marking hydrocarbon liquids
with tracer materials, in particular hydrocarbons which are taxable
or liable to be subject to tampering or substitution such as
gasoline and diesel fuels for example.
[0002] It is well known to add tracers to hydrocarbon liquids. A
typical application is the tagging of hydrocarbon fuels in order to
identify the liquid at a subsequent point in the supply chain. This
may be done for operational reasons, e.g. to assist in
distinguishing one grade of fuel from another, or for other
reasons, in particular to ensure fuel quality, deter and detect
adulteration and to provide a means to check that the correct tax
has been paid. Apart from fuels, other products, such as vegetable
oils may be marked to identify the product produced at a particular
source, or certified to a particular standard.
[0003] One problem which is known to exist with the marking of fuel
liquids in particular, is the potential for the tracer to be
removed, by evaporation from the fuel, by degradation of the tracer
through ageing or exposure to environmental conditions such as
heat, sunlight or air or alternatively by deliberate removal of the
tracer for unlawful purposes such as for avoidance of tax. Methods
for deliberate removal of tracers include adsorption of the tracer
onto common adsorbent materials such as charcoal or clays, exposure
to radiation, such as ultraviolet light, oxidation etc. A useful
fuel tracer therefore needs to be resistant to removal by these
common methods and also to more sophisticated treatments such as
treatment with acids and/or bases. It is an object of the invention
to provide a method of marking hydrocarbon liquids which is more
resistant to removal of the tracer than known methods.
[0004] EP 1580254 and EP 0509818 each describe hydrocarbon markers
based on substituted bis(phenyl)diazine compounds in which at least
one of the substituents on one of the aromatic rings is an OH
group. This type of compound has been found to be less resistant to
removal from hydrocarbons than the compounds used as tracers in the
present invention. WO99/67346 and WO2003/078551 describe the use of
substituted bis(phenyl)diazine compounds in which at least one of
the substituents on one of the aromatic rings is a tertiary amino
group. In each of WO99/67346 and WO2003/078551 the tracer compounds
are designed to be extractable from hydrocarbons using a solution
of an acid in order to detect the tracer compound. These compounds
are therefore clearly not resistant to removal from hydrocarbon
liquids using acid laundering methods in contrast to the tracers of
the present invention.
[0005] According to the invention we provide a method of marking a
hydrocarbon liquid comprising the step of adding to said liquid, as
a tracer compound, a compound of Formula I:
##STR00002##
[0006] wherein at least one of R.sup.1-R.sup.4 is selected from:
[0007] i. a bromine or fluorine atom; [0008] ii. a partially or
fully halogenated alkyl group; [0009] iii. a branched or cyclic
C.sub.4-C.sub.20 alkyl group; [0010] iv. an aliphatic substituent
linking two positions selected from R.sup.1-R.sup.4 in Formula I to
one another; or [0011] v. a phenyl group substituted with a halogen
atom, an aliphatic group or halogenated aliphatic group
[0012] and further wherein none of R.sup.1-R.sup.4 consists of a
hydroxyl group or an amino group.
[0013] We further provide, according to the invention, a
composition comprising a hydrocarbon liquid and a tracer compound,
characterised in that said tracer compound tracer compound
comprises a compound of Formula I, where Formula I is as described
above.
[0014] We further provide, according to the invention, a method of
identifying a hydrocarbon liquid comprising the steps of marking
said liquid by the method of marking according to the invention,
and subsequently analysing a sample of a hydrocarbon liquid for the
presence of said tracer compound to determine whether said sample
is a sample of said marked hydrocarbon liquid.
[0015] The hydrocarbon liquid may be a pure compound such as hexane
or octane or it may comprise a mixture of compounds such as a
distillation fraction having a particular range of boiling points.
The hydrocarbon liquid may be intended for use as a chemical, a
solvent or a fuel. In preferred embodiments the hydrocarbon liquid
comprises a diesel fuel, a gasoline fuel or a solvent. The
invention is of particular use for marking liquid hydrocarbon fuels
such as gasoline and diesel fuels. In one particular application a
low-tax fuel such as an agricultural diesel may be marked in order
to detect any subsequent sale and use for purposes such as
road-vehicle fuel which would normally be taxed more highly. In
such cases unlawful dilution or substitution of a more highly taxed
fuel with the low-taxed fuel may be detected by analysis of the
highly taxed fuel to determine whether the tracer is present.
Therefore in these cases, it is highly beneficial to use a tracer
compound in the low-taxed fuel which is not easily removed, or
laundered, from the fuel to a level at which it can no longer be
detected. We have found that compounds of Formula I are resistant
to removal from hydrocarbon fuels by several known methods of fuel
laundering.
[0016] Preferably, when any one of R.sup.1-R.sup.4 is a halogen or
halogenated alkyl group, the halogen atom is selected from bromine
or fluorine and the halogenated alkyl group is a bromoalkyl or
fluoroalkyl group. The halogenated alkyl group(s) may be partially
or fully halogenated, linear or branched, acyclic or cyclic
aliphatic groups. Preferred halogenated alkyl groups include
trifluoromethyl, 1,1-difluoroethyl, fluoroallyl, heptafluoropropyl,
tridecafluorohexyl, heptadecafluorooctyl. Most preferably at least
two of R.sup.1-R.sup.4 in Formula I consist of a halogen atom or a
halogenated alkyl group.
[0017] Alkyl group substituents may be straight chain or branched
acyclic or cyclic aliphatic groups, preferably consisting of 4-12
carbon atoms. Branched or cyclic aliphatic groups are preferred.
Preferred groups include tert-butyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl (neo-pentyl), 1,1-dimethylbutyl,
1-ethyl-1-methylpropyl, 2,2-dimethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1-ethyl-2,2-dimethylpropyl,
1-methylethyl-2,2-dimethylpropyl, 1,1,3,3-tetramethylbutyl,
cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl,
4-methylcyclohexyl, 2-ethylhexyl, 1-adamantyl, 2-adamantyl and
decahydronaphthyl groups. Particularly preferred alkyl group, or
haloalkyl group, substituents contain quaternary substituted carbon
atoms, such as tertiary butyl.
[0018] It is preferred that none of R.sup.1-R.sup.4 includes fused
aromatic rings such as naphthyl or anthracenyl, saturated
heterocycles where the heteroatom is anything other than oxygen,
unsaturated heterocycles, amino, imino, N-oxide, nitro, hydroxyl,
carboxyl, ester, amide, acetal, thiol, thiol ethers, disulfides,
sulfoxide, sulfone, sulfonate, phosphite ester, phosphate ester,
cationic, anionic or zwitterionic groups; or metal containing
substituents. It is possible, however, to use a molecule containing
one of the above unpreferred groups provided that sufficient
halogen, halogenated alkyl or bulky alkyl groups of the preferred
type are present in the molecule to provide resistance to
laundering.
[0019] Preferred tracer compounds in one embodiment have
R.sup.1-R.sup.4 each selected from the group consisting of a
bromine or fluorine atom; a partially or fully halogenated alkyl
group; a branched or cyclic C.sub.4-C.sub.20 alkyl group; an
aliphatic substituent linking two positions selected from
R.sup.1-R.sup.4 in Formula I to one another; or a phenyl group
substituted with a halogen atom, an aliphatic group or halogenated
aliphatic group. Suitable tracer compounds include bis(3,5-bis
trifluoromethyl-phenyl)-diazene, bis(3,5-bis
t-butyl-phenyl)-diazene, bis(3-t-butyl,
5-trifluoromethyl-phenyl)-diazene, and (3,
5-di-trifluoromethyl-phenyl)-(3,5-di-t-butylphenyl)-diazene.
[0020] Preferred tracer compounds have a boiling point greater than
100.degree. C., especially greater than 140.degree. C. at normal
atmospheric pressure. A higher boiling compound is more difficult
to remove by evaporation techniques including aeration by stirring
or sparging air through the marked fuel. Preferably the tracer
compound has a boiling point within the distillation range of the
hydrocarbon liquid or within 10.degree. C. of the boiling point of
the hydrocarbon liquid,
[0021] Preferably the tracer compound has a boiling point which is
within the distillation range of the hydrocarbon liquid to be
marked. More preferably, the tracer compound has a boiling point
which is within the central 90% of the distillation range of the
hydrocarbon liquid to be marked. Diesel has a boiling range from
180-390.degree. C. Gasoline has a boiling range from
25-215.degree.. When a hydrocarbon liquid which has a boiling
range, such as diesel or gasoline, is to be marked, then a tracer
compound having a suitable boiling point would be selected based
upon the boiling range of the liquid. When a hydrocarbon having a
defined boiling point, such as hexane, is to be marked then the
tracer compound is preferably selected to fall within 10 degrees of
the boiling point of that hydrocarbon liquid. The tracer compound
is a liquid at room temperature or it is a solid which is soluble
in the quantities at which it is to be used either in the liquid or
in a master-batch formulation.
[0022] The tracer compound is added to the hydrocarbon liquid in
such an amount as to provide a concentration of the tracer compound
which is detectable by readily available laboratory methods capable
of identifying the tracer compound in the liquid at the
concentrations used. Suitable methods include, but are not limited
to, gas chromatography coupled with a suitable detector such as an
electron capture detector or a mass spectrometer, or
spectrophotometric or colorimetric analysis, especially UV-visible
(UV/vis) spectrophotometry. The hydrocarbon liquid may be
identified as a hydrocarbon liquid containing the tracer by
comparing the spectrum or other form of analytical result obtained
from analysing the sample with a spectrum or result obtained from
analysing a standard sample of a known hydrocarbon liquid
containing a known concentration of the tracer. The sample result
or a characteristic feature of the result, such as a peak area, may
be compared with a value for a corresponding result or
characteristic of a standard sample which is held in a memory of a
data processing device. Alternatively the result from the sample
may be interpreted without referring to a known standard result or
sample.
[0023] Typically, the concentration of tracer in the liquid is
within the range from 1 ppbv (part per billion by volume) to 100
ppbv, the actual amount used depending on the detection method and
limit of detection of the particular tracer compound used. The
tracer compound may be present at a higher concentration than 100
ppbv, for example up to 500 ppbv or even up to 1 ppmv (part per
million by volume), although when the product to be marked is a
high-volume commodity such as a motor-fuel, economic considerations
usually favour lower levels of tracer compound. The tracer compound
may be supplied and added to the hydrocarbon liquid, in the form of
a concentrated dosing solution (or master-batch) of the tracer
compound in a solvent.
[0024] In this case the preferred solvent is a liquid which is
similar to the liquid to be marked, although a different solvent,
e.g. a hexane or mixed paraffins solvent may be used provided the
presence of such a solvent can be tolerated in the hydrocarbon
liquid to be marked. The concentrated dosing solution can be added
to the hydrocarbon liquid to be marked so as to produce the
required final concentration of the tracer compound by dilution.
More than one tracer compound may be added to the liquid.
[0025] The selected tracer compound(s) is resistant to laundering
by adsorption on activated charcoal or clay. In a preferred
embodiment, at least 50% (more preferably at least 60%, especially
at least 80%) of the tracer compound is retained in the hydrocarbon
liquid after a sample of the liquid containing the tracer compound
has passed through a column of fresh activated charcoal. The test
to be applied for resistance to laundering by adsorption on a solid
adsorbent is described below. Preferably at least 50% (more
preferably at least 60%, especially at least 80%) of the tracer
compound is retained in the hydrocarbon liquid after a sample of
the liquid containing the tracer compound has passed through a
column of fresh sepiolite clay.
[0026] Preferably the selected tracer compound(s) is resistant to
laundering by chemical treatment with an acid or a base. In
preferred embodiments, at least 50% (more preferably at least 75%)
of the tracer compound is retained in the hydrocarbon liquid after
a sample of the liquid containing 10-15 ppbv of the tracer compound
has been vigorously agitated in contact with 10% aqueous HCl.
Preferably at least 50% (more preferably at least 75%) of the
tracer compound is retained in the hydrocarbon liquid after a
sample of the liquid containing 10-15 ppbv of the tracer compound
has been vigorously agitated in contact with 10% aqueous
H.sub.2SO.sub.4. Preferably at least 50% (more preferably at least
75%) of the tracer compound is retained in the hydrocarbon liquid
after a sample of the liquid containing 10-15 ppbv of the tracer
compound has been vigorously agitated in contact with 10% aqueous
NaOH. Preferably at least 50% (more preferably at least 75%) of the
tracer compound is retained in the hydrocarbon liquid after a
sample of the liquid containing 10-15 ppbv of the tracer compound
has been vigorously agitated in contact with methanolic KOH (3M
aqueous KOH diluted 1:10 in methanol). The test procedure for
resistance to laundering by these chemical treatments is described
below.
[0027] The invention will be further described in the following
examples. In the Examples, the test methods which are used are
described below. The meaning of ppb v/v is parts per billion based
on the volume of liquid tracer compound in the total volume of
liquid. In the following tests, T1 is bis(3,5-bis
trifluoromethyl-phenyl)-diazene.
[0028] Test for Resistance to Removal by a Solid Adsorbant
(Charcoal, Clay or Silica Gel)
[0029] A 30 cm long chromatography column, having an inside
diameter of 1 cm, is filled with the solid adsorbent to a depth of
about 15 cm. The adsorbent is supported in the column on a glass
frit. 15 ml of a diesel fuel containing 10 ppb v/v of the test
tracer compound is added to the column and allowed to percolate
through the adsorbent bed under gravity. The liquid eluting from
the column is collected, sealed into an autosampler vial and
analysed immediately by gas chromatography-mass spectrometry
(GC-MS). The amount of tracer detected in the collected liquid is
reported below in Table 1, as a percentage of the original
concentration.
[0030] The adsorbents used were:
[0031] Charcoal:--a powdered activated Norit.TM. charcoal (type
RBAA-3) from Fluka (product number 29238),
[0032] Sepiolitic clay: a pure fine sepiolite clay from RS
Minerals
[0033] The above test procedure was carried out using 50 ml of
diesel fuel marked with 10 ppb v/v of the tracer compound and the
eluted liquid was collected in an open beaker before being passed
through a second column packed with fresh adsorbent. The liquid
from the second column was collected in an open beaker before being
passed through a third column packed with fresh adsorbent. A sample
of the liquid collected from each column was taken for analysis by
GC-MS and the concentration of the tracer in the eluted liquid is
shown in Table 1 as a percentage of the original concentration.
When the concentration is greater than 100%, it is believed that
the diesel fuel was retained on the adsorbent in preference to the
tracer so that the solution became more concentrated.
TABLE-US-00001 TABLE 1 Tracer Sepiolitic clay Charcoal compound
1.sup.st pass 2.sup.nd pass 3.sup.rd pass 1.sup.st pass 2.sup.nd
pass 3.sup.rd pass T1 98 93 87 102 111 112
[0034] Test for Loss of Tracer Compound on Standing
[0035] 1 ml of diesel fuel marked with 10 ppb v/v of the test
tracer compound was placed in an open topped 2m1autosampler vial,
and repeatedly analysed by GC-MS over the course of one day after
standing in normal laboratory conditions to determine the
concentration of the tracer compound in the diesel. The samples
were interspersed with sealed calibration standards to correct for
any instrument drift over the period of analysis. The concentration
of the tracer in the liquid is shown in Table 2 as a percentage of
the original concentration. When the concentration is greater than
100%, it is believed that the diesel fuel evaporated more quickly
than the tracer so that the solution became more concentrated.
TABLE-US-00002 TABLE 2 T1 Concentration of tracer after 24 104
hours (%)
[0036] Test for Resistance to Removal by Chemical Treatment
[0037] A quantity of the diesel fuel marked with 13 ppb v/v of the
test tracer compound was shaken vigorously with an equal volume of
a chemical agent selected from 10% HCl in deionised water, 10%
H.sub.250.sub.4 in deionised water, 10% NaOH in deionised water and
methanolic KOH (3M aqueous KOH diluted 1:10 in methanol). The
mixture was allowed to settle, then shaken for a further minute
before settling again. A sample of the diesel layer was analysed by
GC-MS and the concentration of the tracer in the treated diesel
liquid is shown in Table 3.
TABLE-US-00003 TABLE 3 Tracer 10% 10% 10% compound HCl
H.sub.2SO.sub.4 NaOH KOH/MeOH T1 94 94 89 84
COMPARATIVE EXAMPLE
[0038] The compound shown below, corresponding to "Dye 7" of EP
1580254, was made according to the following procedure.
##STR00003##
[0039] Aniline (1.517 ml) was added to a beaker containing
hydrochloric acid (2 ml) and de-ionised water (10 ml). The mix was
then placed into an ice bath and cooled to <5.degree. C. Once
the mix was cold enough, a solution of sodium nitrite (1.808 g) in
water (20 ml) was prepared and added to the aniline mix slowly over
10 minutes, keeping the temperature below 5.degree. C. The mixture
was then left to stir in an ice bath for 30 minutes. After 30
minutes, sulfamic acid (1.62 g) was added to the mixture. A
solution of nonylphenol (3.68 g) in toluene (20 ml) was added to
the reaction mix and stirred vigorously. A solution of sodium
acetate (20 g) in water (100 ml) was added to the reaction mix as a
buffer over 30 minutes ensuring that it was kept cold. The mixture
was then left to stir for another 5 hours and allowed to warm in
the process.
[0040] The reaction mix was then added to a separating funnel and
diluted with toluene (20 ml). The mixture was shaken and then left
to settle. The organic phase was then washed with de-ionised water
(100 ml) three times. It was then dried over anhydrous magnesium
sulphate and the solvent removed on a rotary evaporator yielding a
dark yellow oil.
[0041] A 10 mg/L solution of the prepared comparative dye was
prepared in a synthetic test fuel, made
[0042] by mixing together 76% iso-octane, 16% toluene, 5% t-butyl
methylether and 3% ethanol (all quantities vol/vol). 10 ml of
synthetic test fuel marked with the test tracer compound was
[0043] shaken vigorously for 1 minute with 0.5 g of activated
charcoal (decolourising) obtained from Sigma Aldrich (product
number 161551). The mixture was allowed to stand
[0044] for 1 minute and then shaken for a further minute before
being filtered to remove the
[0045] adsorbent. A sample of the fuel was analysed by UV/Vis
spectrophotometry and the percentage of the tracer remaining was
calculated.
[0046] This test procedure was repeated for a sample of the
synthetic fuel containing bis(3,5-bis
trifluoromethyl-phenyl)-diazene (T1), with the analysis of the
sample being made by GC-MS because T1 is not susceptible to
detection by UV/vis. Both results are shown in Table 4. The test
shows that T1 is more resistant to removal by shaking with
activated charcoal than the comparative example containing a
phenolic moiety described in EP1580254.
TABLE-US-00004 TABLE 4 % of original concentration remaining after
treatment Tracer compound with activated charcoal Dye 7 of 16%
EP1580254 T1 87%
* * * * *