Title of Invention

"ODORANT MIXTURE FOR ODORLESS GAS FUEL"

Abstract i -15- ABSTRACT COMPOSITION AS ODORANT FOR A GASEOUS FUEL The invention concerns a composition for use in particular as odorant of a gas fuel, more particularly of natural gas, comprising: 0.1 to 49.9 particles by weight of at least one alkyl sulphur (I) of formvila: R^-S-R^, wherein R^ and R^, identical or different, represent: an alkyl radical comprising 1 to 4 carbon atoms; or R^ and R^ together with the sulphur atom to which they are boimd represent a saturated or unsaturated ring including 3 to 5 carbon atoms, optionally substituted by a C1-C4 alkyl or C1-C4 alkenyl; 50 to 99.8 parts by weight of at least two alkyl acrylates (11) the alkyl radicals of which comprise 1 to 12 carbon atoms, preferably 1 to 8; 0.001 parts by weight of at least one compound (III) inhibiting polj^nerization of the alkyl acrylates (11).
Full Text ODORANT MIXTURE FOR AN ODOURLESS GASEOUS FUEL
5 [0001] The present invention relates to the field of odorants for gaseous fuels,
in particular odourless gaseous fuels, and has nnore especially as subject
matter a composition comprising at least one alkyl sulphide and at least two
alkyl acrylates which makes possible the detection of gas leaks and the
prevention of the risks of explosion which result therefrom.
10 [0002] Town gases and coke oven gases, which were obtained by thermal
processes, were used for a long time in the past as gaseous fuels, both for
public lighting and for domestic requirements. These gases comprised highly
odoriferous components. Consequently, they had a strong specific odour, so
that a gas leak could be easily detected.
15 [0003] In contrast, the gaseous fuels currently used, whether natural gas,
propane, butane, liquefied petroleum gas (or LPG) or even oxygen (for example
for welding operations), are essentially odourless, either because of their origin
or because of the purification treatment which they have received.
[0004] Thus, if leaks are not noticed in time, the rapid formation occurs of
20 mixtures of gaseous fuels and of air which can explode, with consequently a
high risk potential.
[0005] For these safety reasons, the natural gas moving in gas pipelines is
odorized by injection (in specialized stations) of appropriate additives known as
odorants.
25 [0006] Natural gas is generally conveyed odourless, after an appropriate
purification treatment, from the production sites to the consuming countries,
either via gas pipelines or (in liquid state) in specialized ships (methane
carriers). In France, for example, natural gas is thus received in a limited
number of injection stations where the odorant is injected, so that the natural
30 gas, both that which moves through the French gas pipeline network and that
which is stored in underground tanks, is odorized, which makes possible easy
detection in the event of a leak, wherever in the network it occurs.
- 3 -
[0007] In other countries, natural gas may be distributed over the area of the
^ country by a network of pipelines in which it moves without odorant, the natural
gas then being odorized as it enters the towns in which it is consumed, which
requires an even higher number of injection stations.
5 [0008] Storage tanks are generally maintained under an atmosphere of
nitrogen or of natural gas in order to limit, at this stage, the risks of explosion.
[0009] Alkyl sulphides, used as odorants, alone or as a mixture, are known.
Mention may be made, for example, of diethyl sulphide, dimethyl sulphide,
methyl ethyl sulphide or tetrahydrothiophene, which are widely used for their
10 excellent properties, in particular which are capable of triggering a feeling of
alarm in people in the event of an accidental leak of natural gas thus odorized
and of initiating the necessary protective operations.
[0010] However, during the combustion of natural gas, these products
generate an amount of sulphur dioxide which, however low it might be,
15 becomes not insignificant when an overall balance is carried out on the scale of
a country or of a region, in particular with a high level of industrialization or
urbanization. Thus, by way of example, the combustion of a natural gas
odorized with tetrahydrothiophene at a concentration of 10 mg/Sm^ (or number
of m^ of the gas, measured under standard temperature and pressure
20 conditions) generates 7.3 mg/Sm^ of sulphur dioxide.
[0011] In the general context of better consideration of environmental
constraints, it is therefore desirable to reduce the amounts of SO2 discharged to
the ecosphere via odorants based on alkyl sulphides present in natural gas
during the combustion of the latter.
25 [0012] Furthermore, the use of alkyl acrylates as components of gas odorant
mixtures is disclosed in the literature.
[0013] As an example, Patent Application DE 19837066 mentions a process
for the odorization of natural gas by addition of a mixture comprising an alkyl
acrylate, a nitrogenous compound of pyrazine type and an antioxidant.
30 However, this mixture exhibits the disadvantage of not having an odour
characteristic of gas and is thus capable of being misinterpreted in the event of
a gas leak. The risk is, of course, the non-detection of this leak and an
explosion, if the concentration of gas in the air reaches its lower explosive limit.
[0014] Patent JP 55-137190 also discloses an odorant mixture combining ethyl
acrylate with a specific sulphur compound, in this instance tert-butyl mercaptan
5 (or TBM). However, the major disadvantage of this mixture is that, because of
the chemical reactivity of TBM with ethyl acrylate, the 2 components of the
odorant mixture have to be stored in the various injection stations in separate
tanks and also require separate injection pumps and heads for introduction into the gas pipeline. This results, in view of the complex logistics for the odorization ^ ^
10 of natural gas set out above, in a considerable increase in the costs of the
injection stations resulting from the necessary multiplication in the storage tanks
and injection pumps and heads.
[0015] Furthermore, Patent Application WO 2004/024852 discloses an odorant
consisting of four components, including an aikyi acrylate, an alkyl sulphide and
15 an antioxidizing stabilizing agent, such as fert-butylhydroxytoluene,
hydroquinone, and the like.
[0016] It is an aim of the present invention to provide a novel odorant mixture
which overcomes in particular the disadvantages of the odorant mixtures of the
prior art set out above.
20 [0017] A subject-matter of the present invention is thus a composition which
can be used in particular as odorant for a gaseous fuel, more particularly
natural gas, comprising:
from 0.1 to 49.9 parts by weight of at least one alkyl sulphide (I) of
formula:
25 R^-S-R2
in which R^ and R^, which are identical or different, represent:
an alkyl radical comprising from 1 to 4 carbon atoms; or
R^ and R^, taken with the sulphur atom to which they are
attached, represent a saturated or unsaturated ring comprising from 3 to 5
30 carbon atoms which is optionally substituted by a C1-C4 alkyl or C1-C4 alkenyl
radical;
— 6 —
" " • ~ ^^^ "^' " " ""
from 50 to 99.8 parts by weight of at least two alkyl acrylates (II), the
" alkyl radicals of which comprise from 1 to 12 carbon atoms, preferably from 1 to
8;
from 0.001 to 0.1 part by weight of at least one compound {III) which
5 inhibits the polymerization of the alkyl acrylates (II) and which is active in the
presence or in the absence of oxygen, preferably comprising a stable nitroxide
radical of formula (IV):
R4
\ .
N O
R3
in which:
10 - R^ and R^, which are identical or different, each represent a
tertiary or secondary hydrocarbon radical comprising from 2 to 30 carbon
atoms, preferably from 4 to 15, and optionally one or more heteroatoms chosen
from sulphur, phosphorus, nitrogen or oxygen; or
R^ and R^, taken with the nitrogen atom to which they are
15 attached, represent a cyclic hydrocarbon radical comprising from 4 to 10 carbon
atoms, preferably from 4 to 6, the said radical optionally being substituted.
[0018] The composition according to the invention confers on gaseous fuels, in
particular on natural gas, after its injection into the latter, a high odorant power
comparable to that obtained with the odorants based on alkyl sulphide of the
20 prior art, allowing any person present in the vicinity of a leak to recognize the
latter and to take the appropriate safety measures. This high odorant power is
obtained at the same time as a significant reduction in the amounts of SO2
discharged to the ecosphere after combustion lof the gas thus odorized.^ Finally, this composition, because'of the absence of reactivity between the compounds
25 (I) and (II), can be employed in injection stations using a single storage tank, a
single injection pump and a single injection head, which results in considerably )
simplified logistics. \.
[0019] According to a preferred alternative fomri of the composition according
^ to the invention, the composition comprises from 5 to 14.95 parts by weight of
compound(s) (I), from 85 to 94.95 parts by weight of compounds (II) and from
0.005 to 0.05 part by weight of compound(s) (III).
5 [0020] Preference is given to the use, as alkyl sulphide(s) (I), of
tetrahydrothiophene (THT), methyUethyl sulphide (MES), dimethyl sulphide
(DMS) and/or diethyl sulphide (DES).
[0021] The acrylic acid esters (II) are chosen in particular from methyl, ethyl, npropyl,
isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl and
10 dodecyl acrylaies.
[0022] According to a preferred embodiment of the composition according to
the invention, use is made of a combination of alkyl acrylates comprising in
particular ethyl acrylate and advantageously of a combination of alkyl acrylates
comprising in particular methyl acrylate and ethyl acrylate. The preferred
15 combinations of alkyl acrylates comprising ifi particular methyl acrylate and
ethyl acrylate generally comprise 20 to 40 parts by weight of methyl acrylate per
100 parts by weight of the methyl acrylate + ethyl acrylate total.
[0023] According to a very particularly preferred alternative form of the
invention, use is made of a composition comprising tetrahydrothiophene, methyl
20 acrylate and ethyl acrylate.
[0024] The presence in the composition according to the invention of
compound(s) (III) has the effect of inhibiting the polymerization of the acrylates,
which are very reactive monomers which can spontaneously polymerize. Such
an uncontrolled polymerization is capable of placing in danger people found
25 close to injection stations, such as residents or workers in charge of
maintenance, due to the risk of explosion. If this polymerization occurs during
storage, including, for example, in storage tanks or vessels of injection stations,
it can also result in rapid fouling, indeed even blocking, of the pipes between
the storage tank and the injection point. Such a phenomenon can result in an
30 uncontrolled fall in the concentration of the odorant in the natural gas, which
increases the risk related to an undetected gas leak.
-1-
"~— - ^ ^ - ^ - -
[0025] The compounds of formula (IV) are known per se and their preparation
W is, for example, described in the work "Synthetic Chemistry of Stable Nitroxides"
by L. B. Volodarsky et aL, CRC Press. (1993), ISBN: 0-8493-4590-1.
[0026] Inhibitors of formula (IV) exhibit the advantage, in contrast to other
5 inhibitors, such as radical inhibitors belonging to the family of the
hydroquinones, of not requiring storage of the odorant mixture under air. This is
because storage under air is rendered necessary for radical inhibitors of
hydroquinone type owing to the fact that the active form of the inhibitor is a
molecule comprising a radical which is formed following reaction with oxygen.
10 [0027] In point of fact, it is highly advantageous, in designing injection stations,
to be able to store the odorant mixture in the appropriate vessel under natural
gas pressure. Such an embodiment makes it possible advantageously to
increase the efficiency of the injection pumps.
[0028] The inhibitors of formula (IV) also offer the advantage, for the same
15 reason, of being able to be used in tanks for storage under nitrogen,
encountered in some stations for the injection of natural gas.
[0029] According to a particularly preferred alternative form, use is made, as
inhibitor of formula (IV), of a compound derived from tetramethylpiperidine oxide
(also denoted by the term TEMPO) of formula (IVa):
CH3
/ ^ ^ " ' .
R5 ( N—O
CH3
20
in which R^ represents a hydroxyl, amino, R^COO- or R^CON- group
where R^ is a C1-C4 alkyl radical.
[0030] It is preferable advantageously to choose the compound of formula (III)
from at least one of the following compounds:
25 - compound (A), known as N-(tert-butyl)-N-(1-[ethoxy(ethyl)-
phosphino]propyl)nitroxide, of formula:
- 5 -
H3C L-C"3
N O*
Et
compound (B), known as N-(terf-butyl)-N-(1-diethylphosphono-
2,2-dimethylpropyl)nitroxide, of formula:
H3C
O^ N O
Et ^O P (
CH3
5 - compound (C), known as N-(tert-butyl)-N-(2-methyl-1-phenylpropyl)
nitroxide, of fonnula:
H3C
\ = = : / \ CH3
H3C
[0031] Another subject-matter of the invention is a process for the odorization
of an odourless gaseous fuel comprising the addition of an effective amount of v
10 the composition comprising at least one alkyl sulphide, at least two alkyl acrylates and at least one compound (III) which inhibits the polymerization of 1
alkyl acrylates and which is stable in the presence and in the absence of oxygen, preferably of formula (IV). The amount of the said composition can be
determined by a person skilled in the art by means of systematic tests, taking
15 into account the specific characteristics of the gaseous fuel and of the
distribution networks. Purely by way of indication, this effective amount can be
" between 1 and 500 mg/Sm^, preferably between 2 mg/Sm^ and 50 mg/Sm^.
[0032] Tlie composition according to tlie invention described above can be
used as is or else can be diluted in a solvent or a mixture of solvents which is
5 inert with regard to acrylates. Mention may be made, as examples of solvents,
of cyclohexane or n-hexane.
[0033] The dilution of the composition can reach 85%, i.e. 15 parts by weight
of the composition according to the invention are diluted in 85 parts by weight of
solvent.
10 [0034] The gaseous fuels to which the process according to the invention
applies comprise: natural gas, propane, butane, liquefied petroleum gas (or
LPG) or even oxygen or also hydrogen, such as that generated by fuel ceils.
[0035] Natural gas is a preferred gaseous fuel according to the present
invention due to its very widespread use and to the scale of the distribution
15 networks, making it particularly desirable to reduce any danger resulting from
the risk of leakage.
[0036] As regards natural gas, the composition which can be used as odorant
is added by injection in specialized stations according to conventional
techniques employedis this field.
20 [0037] Finally, a subject-matter of the invention is a gaseous fuel, preferably a
natural gas, comprising an amount of between 1 mg/Sm^ and 500 mg/Sm^,
preferably between 2 mg/Sm^ and 50 mg/Sm^, of the composition comprising at
least one alkyl sulphide, at least two alkyl acrylates and at least one compound
(III), preferably of fomnula (IV).
25 [0038] The following examples are given purely by way of illustration of the
invention and should not under any circumstances be interpreted as limiting the
scope thereof.
Example 1 (reference): Odorization of natural gas with tetrahydrothiophene
30
[0039] 10mg per Sm^ of tetrahydrothiophene are injected into natural gas
using an appropriate laboratory device.
[0040] The content of sulphur dioxide formed, after combustion of the gas thus
" odorized which has a high odorant power, is equal to 7.3 mg/Sm^.
Example 2:
5
[0041] The following composition is obtained by simple mixing of the weights
of the components indicated in the liquid state, with the exception of hydroxy-
TEMPO, which is a solid:
Ethyl acrylate 58.6 g 58.66 parts by weight
Methyl acrylate 29.3 g 29.33 parts by weight
Tetrahydrothiophene 120 g 12.00 parts by weight
Hydroxy-TEMPO 0.1 g 0.01 part by weight
[0042] Example 1 is subsequently repeated, the tetrahydrothiophene being
10 replaced by the composition according to the invention thus prepared.
[0043] The gas thus odorized is subjected to an olfactory test, from which it
emerges that the gas thus odorized has a good alerting power (high odorant
power similar to that of the composition of Example 1).
[0044] The content of sulphur dioxide formed, after combustion of the gas thus
15 odorized, is equal to 0.87 mg/Sm^.
Example 3:
[0045] The following composition is obtained by simple mixing of the weights
20 of the components indicated in the liquid state:
Ethyl acrylate 58.6 g 58.66 parts by weight
Methyl acrylate 29.3 g 29.33 parts by weight
Tetrahydrothiophene 120 g 12.00 parts by weight
N-(teAf-Butyl)-N-(1-diethylphosphono- 0.1 g 0.01 part by weight
2,2-dimethylpropyl) nitroxide
[0046] Example 1 is subsequently repeated, the tetrahydrothiophene being
replaced by the composition according to the invention thus prepared.
- — ^^A^r^ —
[0047] The gas thus odorized is subjected to an olfactory test, from which it
V emerges that the gas thus odorized has a good alerting power (high odorant
power similar to that of the composition of Example 1).
[0048] The content of sulphur dioxide formed, after combustion of the gas thus
5 odorized, is equal to 0.87 mg/Sm^.
I:







4
«
-12-
^ We claim:
1. A Composition for use as odorant for a gaseous fuel, more particularly nahiral gas,
comprising:
(a) from 5 to 14 % of parts by weight of at least one alkyl sulphide (I) of formula:
R1-S-R2
in which R i and R 2, which are identical or different, and are selected from
an alkyl radical comprising from 1 to 4 carbon atoms; or
a saturated or unsaturated ring comprising from 3 to 5 carbon atoms when taken with
the sulphur atom to which they are attached which ring is optionally substituted by a Ci-
C4 alkyl or C1-C4 alkenyl radical;
(b) from 85 to 94.95% parts by weight of at least two alkyl acrylates (II), the alkyl radicals
of which comprise from 1 to 12 carbon atoms,
(c) from 0.005 to 0.05% parts by weight of at least one compovind (IE) which inhibits the
pol)mierization of the alkyl acrylates (11) in the absence of oxygen, preferably comprising
a stable nitroxide radical of formula (IV):
\ .
N—O
in which R ^ and R *, which are identical or different, and are selected from
a tertiary or secondary hydrocarbon radical comprising from 2 to 30 carbon atoms and
optionally one or more heteroatoms chosen from sulphur, phosphorus, nitrogen or
oxygen, or
4
-13-
a cyclic hydrocarbon radical comprising from 4 to 10 carbon atoms taken with the
nitrogen atom to which they are attached, said radical optionally being substituted.
2. The composition as claimed in claim 1, wherein the alkyl sulphide (I) is chosen from
tetrahydrothiophene (THT), methyl ethyl sulphide (MES), dimethyl sulphide (DMS),
diethyl sulfide (DES), or mixtures thereof.
3. The composition as claimed in claim 1 or 2, wherein the alkyl acrylates (II) are chosen
from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl,
heptyl, octyl, dodecyl acrylates or mixtures thereof.
4. The composition as claimed in claim 3, wherein the alkyl acrylates (II) comprise
methyl acrylate and ethyl acrylate.
5. The composition as claimed in any preceding claim, preferably comprising
tetrahydrothiophene (I), methyl acrylate (II) and ethyl acrylate (II).
6. The composition as claimed in claim 1, wherein the inhibitors of formula (IV) is a
compound derived from tetramethylpiperidine oxide of formula (IVa):
r>H3
^ ^ C H 3
in which R^ is selected from hydroxyl, amino, R^COO" or RCON- group where R^ is a Ci-
C4 radical.
4
-14-
7. The composition as claimed in claim 1, wherein the compound of formula (III) is
chosen from N-(tert-butyl)-N-(l-[ethoxy (ethyl) phosphino] propyl) nitroxide, N-(tertbutyl)-
N-(l-diethylphosphono-2,2-dimethylpropyl) nitroxide and / or N-(tert-butyl)-N-
([2-methyl-l-phenyl] propyl) nitroxide or mixtures thereof.
8. A composition as claimed in claim 1 wherein in that the alkyl radicals of said at least
two alkyl acrylates (II), comprise from 1 to 8 carbon atoms.
9. A composition of claim 1 wherein said tertiary or secondary hydrocarbon radical
comprising from 4 to 15 carbon atoms.
10. A composition as claimed in claim 1 wherein said cyclic hydrocarbon radical
comprising from 4 to 6 carbon atoms taken with the nitrogen atom to which they are
attached.
11. A composition as claimed in claim 2 wherein said alkyl sulphide is
tetrahydrothiophene (THT).
12. A process for odorization of an odourless gaseous fuel which comprises adding to
said gaseous fuel an effective amount of pure or diluted composition as claimed in
claims 1 to 11 wherein the gaseous fuel comprises an amount of between 1 mg/Sm^ and
500 mg/Sm3, preferably between 2 mg/Sm^ and 50 mg/Sm^ of the composition.
Dated this the 28* day of April 2008. | 1 f\ fS
Rashmi Gupta
of Subramaniam & Associates
Agent for the Applicant

Documents:

3475-delnp-2008-Abstract-(07-08-2013).pdf

3475-delnp-2008-abstract.pdf

3475-delnp-2008-Claims-(07-08-2013).pdf

3475-delnp-2008-claims.pdf

3475-delnp-2008-Correspondence Others-(16-05-2013).pdf

3475-delnp-2008-Correspondence Others-(24-10-2013).pdf

3475-delnp-2008-Correspondence-Others-(07-08-2013).pdf

3475-delnp-2008-Correspondence-Others-(27-06-2013).pdf

3475-delnp-2008-correspondence-others.pdf

3475-delnp-2008-Description (Complete)-(07-08-2013).pdf

3475-delnp-2008-description (complete).pdf

3475-delnp-2008-form-1.pdf

3475-delnp-2008-Form-2-(07-08-2013).pdf

3475-delnp-2008-form-2.pdf

3475-delnp-2008-Form-3-(16-05-2013).pdf

3475-delnp-2008-Form-3-(27-06-2013).pdf

3475-delnp-2008-form-3.pdf

3475-delnp-2008-form-5.pdf

3475-delnp-2008-GPA-(07-08-2013).pdf

3475-delnp-2008-pct-210.pdf

3475-delnp-2008-Petition-137-(27-06-2013).pdf


Patent Number 258306
Indian Patent Application Number 3475/DELNP/2008
PG Journal Number 01/2014
Publication Date 03-Jan-2014
Grant Date 30-Dec-2013
Date of Filing 28-Apr-2008
Name of Patentee ARKEMA FRANCE
Applicant Address 4-8, COURS MICHELET, F-92800 PUTEAUX, FRANCE
Inventors:
# Inventor's Name Inventor's Address
1 CHARLES, PATRICK 77, CHEMIN DES ECOLES, F-64230 SAUVAGEON, FRANCE
2 CHARLES, PATRICK 77, CHEMIN DES ECOLES, F-64230 SAUVAGEON, FRANCE
PCT International Classification Number C10L 3/00
PCT International Application Number PCT/FR2006/051015
PCT International Filing date 2006-10-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/740,483 2005-11-29 France
2 0510362 2005-10-11 France