Note: Descriptions are shown in the official language in which they were submitted.
CA 02375614 2001-11-29
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FUEL COMPOSITION
This invention relates to fuel compositions, in particular a gasoline
composition for
use in motor vehicles, for or for use in aircraft.
For many years manufacturers of spark ignition combustion engines have been
striving for higher efficiency to make optimum use of hydrocarbon based fuels.
But such
engines reduire gasolines of good octane number has been achieved in
particular by
addition of organo lead additives, and latterly with the advent of unleaded
gasolines, by
addition of MTBE. But combustion of any gasoline gives rise to emissions in
the
exhaust gases, e.g. of carbon dioxide, carbon monoxide, nitrogen oxides (NOx)
and toxic
hydrocarbons and such emissions are undesirable.
Unleaded Motor gasolines have been discovered producing low emissions on
combustion.
In a first aspect the present invention provides use of component (a), which
is at
least one of (i) a substantially aliphatic hydrocarbon refinery stream of MON
value of at
least 85, at least 70% in total of said stream being branched chain alkanes,
said stream
being obtainable or obtained by distillation from a refinery material as a cut
having Initial
Boiling Point of at least 15°C and a Final Boiling Point of at most
160°C, said Boiling
Points being measured according to ASTMD2892, and (ii) at least one branched
chain
alkane of MON value of at least 90 and boiling point in the range 15-
160°C, especially
apart from 2,2,3-trimethylbutane and 2,2,3-trimethylpentane, in an unleaded
gasoline of
MON at least 80 to reduce the emission levels on combustion of said gasoline.
'
In a second aspect the present invention provides a method of reducing
emissions
of exhaust gases in the combustion of an unleaded gasoline fuel of MON at
least 80
SUBST6TUTE SHEET (MULE 26)
CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
which comprises having present in said gasoline at least 10% of component (a)
as
defined above.
In a third aspect the present invention provides use in a spark ignition
combustion
engine of an unleaded gasoline fuel of MON at least 80 which comprises at
least 10% of
component (a) as defined above to reduce emissions of exhaust gases.
In a fourth aspect the present invention provides an unleaded composition
having a
Motor Octane Number (MON) of at least 80 comprising at least 2 or at least 5%,
in
particular at least 10%, such as 5-70% (by volume of the total composition) of
component (a), which is a substantially aliphatic hydrocarbon refinery stream,
of MON
value of at least 85, at least 70% in total of said stream being branched
chain alkanes,
said stream being obtainable or obtained by distillation from a refinery
material as a cut
having Initial Boiling Point of at least I 5°C and Final Boiling Point
of at most 160°C,
said Boiling Points being measured according to ASTMD2892, and as component
(g) at
least S% of at least one paraffin, aromatic hydrocarbon compound or olefinic
hydrocarbon of bp60-160°C, with not more than S% of the total
composition, e.g. less
than 1 %, of hydrocarbon of by more than 160°C, especially compounds
with at least 2
hydrocarbyl rings such as naphthenes, and preferably less than S% e.g. less
than 4% of
triptane or 2,2,3 trimethyl pentane. All boiling points quoted herein are at
atmospheric
pressure.
In a fifth aspect the present invention also provides an unleaded composition
having a Motor Octane Number (MON) of at least 80 comprising at least 5% in
particular at least 10%, such as 5-70% (by volume of the total composition) of
component (a), which is at least one branched chain alkane of MON value of at
least 90
and of boiling point in the range 15-160°C e.g. 15-100°C, said
alkane being preferably
present in amount of at least 10, 20 or 30% (especially 10-SO%) of the total
saturated
content of said composition, and as component (g) at least S% of at least one
paraffin,
aromatic hydrocarbon compound or olefinic hydrocarbon of bp60-160°C,
with not more
than 5% of the total composition, e.g. less than 3%, of hydrocarbon of by more
than
160°C, especially naphthenes and preferably less than 5% e.g. less than
4% of triptane or
223 trimethyl pentane.
In a sixth aspect the present invention provides an unleaded blend composition
having a Motor Octane Number (MON) of at least 81 or 85 and Research Octane
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WO 00/77130 PCT/GB00/02282
Number (RON) of at least 91 or 94 which comprises component (a) a total of at
least
1 S% by volume of the blend composition of at least one branched chain
hydrocarbon,
which is an alkane of 8-12 carbon atoms with 3 methyl or ethyl branches
(hereinafter
called a compound (A)) there being a minimum of at least 10% by volume (of the
blend
composition), of at least one individual compound (A) and component (g) at
least one
liquid hydrocarbon (e.g. paraffin, aromatic hydrocarbon or olefin) or mixture
thereof of
bp60-160°C having a MON value of at least 70 and RON value of at least
90, the total
amount of component (g) being at least 20%, with the preferred proviso that
the blend
composition contains less than 5% of 223 trimethyl pentane, and especially
less than 1 or
0.5%, and especially less than 0.5%, in total of 223 trimethyl butane and 223
trimethyl
pentane.
In a seventh aspect of the present invention provides an unleaded blend
composition of MON value of at least 81 or 85 and RON value of at least 91 or
94
which comprises component (a) as defined in the previous paragraph and as
component
1 S (g) at least 20% in total of one or more refinery streams (e.g. such as
those described
below in relation to any of (b) to (e) below)), such that the blend
composition contains in
total at least 70% of saturated hydrocarbons.
In the first aspect the substantially aliphatic refinery stream contains at
least 90%
aliphatic hydrocarbons (e.g. at least 95%) and at most 10% in total (e.g. at
most 5%) of
nonaliphatic hydrocarbons, such as cycloaliphatics e.g. cyclopentane,
cyclohexane,
alkenes such as linear or branched, ones e.g. butenes, pentenes, hexenes,
heptenes and
octenes, and possibly, but preferably not, aromatic hydrocarbons such as
benzene and
toluene. The MON value of said stream is at least 85, e.g. at least 87, or 90
or 92, in
particular less than 100, e.g. 85-96 or 87-95, such as 87-90 or 90-95. The RON
value of
said stream may be 0.5-3.5 especially I .0-3.5 or 0.5-2.5 units above its MON
value, such
as RON values of 88-98, or 89.5-96. In said stream at least 70% in total are
branched
chain alkanes, there being 1 or at least 2 e.g. 2-10 of such alkanes;
especially present are
2-4 such alkanes, each in amount of at least 10% or especially 20% e.g. 20-60%
in said
stream. Thus the stream may contain at least 70% isopentane, or at least 10%
(e.g. 10-
40%) of each of 2,3dimethyl butane (e.g. 20-40%), isopentane, 2,3 dimethyl
pentane
(e.g. 20-40%) and 2,4 dimethyl pentane (e.g. 20-40%), or at least 10% (e.g. 10-
40%) of
each of 2,3 dimethyl butane, 23 and 24 dimethyl pentanes (e.g. 20-40%), and
isooctane
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(e.g. 20-40%). Streams containing less than 30% isopentane e.g. 5-25%
isopentane may
be preferred, especially if the composition contains at least 5% of triptane
or 2,2,3
trimethyl pentane. The total of branched chain alkanes in said stream is at
least 70%
such as 70-85%, the remainder if any being linear alkanes such as n-butane, n-
pentane
and/or non aliphatics as described above.
The aliphatic refinery stream is usually derived from a refinery material
which is an
alkane conversion product, made by reacting one or more alkanes or alkenes,
e.g. of 3-5
carbon atoms, especially branched compounds, such as reaction of an alkane and
an
alkene e.g. isobutane and isobutene. Examples of such a conversion product are
alkylates, which may be made by such a reaction. Alkylates are known refinery
products,
see e.g. Our Industry Petroleum, by British Petroleum Co., London, 4th Ed.
Publ. 1970
page I 87. Acid catalysts are usually used in such reactions. These may be
soluble
catalysts such as protic acids e.g. hydrogen fluoride or sulphuric or
phosphoric acids, or
insoluble catalysts such as zeolites or heteropoly acids from Mo or W. The
alkylates
usually have a boiling range with IBP of at least 15°C and FBP in the
range 170-210°C,
e.g. 175-190 or 185-205°C. The refinery stream for use in the
compositions of the
invention is preferably made as a distillation cut from said material e.g.
alkylate, the cut
being at 15-60 (e.g. 30-60), 60-80, 80-90, 90-95, 95-100, 100-103, 103-106,
106-110,
110-115, 115-125, 125-140 or 140-160°C; a blend of different cuts may
be used e.g. 15-
60, with at least one of 60-80, 80-90, 90-95 and 95-100 or 60-80 with at least
one of 80-
90, 90-95, 95-100, 100-103 or 103-106°C or a combination e.g. 80-106 or
90-106°C.
Preferably the cut is of product distilled from alkylate over a temperature
range of 15-
160° or 15-140°C, especially 15-100 or 30-100°C or 60-
160°C, 60-140 e.g. 60-100 or
90-125°C. Cuts with temperatures in the range 15-160°C
especially 90-125°C or
15-100°C such as 60-100°C have been found to give unleaded
gasolines which on
combustion gave reduced total hydrocarbon emissions and reduced carbon oxide,
e.g.
COZ emissions, compared to those from whole alkylate or in particular cuts
above 160°C.
The cut from alkylate above 160°C can be used in jet fuel, diesel or
kerosene, while the
cut from alkylate from 160°C or 100°C downwards can be used in
gasolines. Cuts of 60-
160°C can be used in summer gasolines because of their reduced Reid
Vapour Pressure.
Cuts below 100°C can also be used to boost the volatility of unleaded
gasolines e.g. to
help provide gasolines with % evaporated at 100°C values of at least
46.
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WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Advantageously the cut has a boiling range of at least part of 90-
106°C, e.g. 90-95,
95-100, 100-103 or 103-106°C, as these give optimum octane rating
coupled with good
emissions. These cuts may be used as such in the compositions and gasolines of
the
invention but may be mixed with at least one cut of higher by e.g. 106-110,
110-115,
S 115-125 or 125-140°C such as 106-125°C (preferably in
proportion of 5:1 to 1:30 or at
least one cut of lower by e.g. 60-80 or 80-90, such as 60-90°C
(preferably in proportions
of 9:1 to 1:9 such as 5:1-1: I).
Preferably however the cut in at least part of by 90-106°C is used as
sole or main
component (a) in the compositions, gasolines and uses of this invention with
component
(g); these can provide clean high octane unleaded gasolines, in particular
ones free of
oxygenate, with RON value of at least 97 and MON value at least 86 with low
emissions.
Example of such compositions and gasolines are those with RON, 97-99.5 or 97.5-
99,
MON 86.5-89, RVP SS-65 kPa e.g. 55-60 kPa, % evaporated at 70°C,
12-35%,
evaporated at 100°C 46-62%, % evaporated at 150°C 95-100%, %
evaporated at 180°C
97.5-100%, density 0.715 to 0.74 e.g. 0.72-0.738 kg/l, benzene 0.5-1.5% e.g.
0.5-1%,
aromatics 16-28% e.g. 16-23%, olefins 3-14% such as 4-12%. They may be made
from
mixtures of butane 0 or 0.5-6.6%, full boiling range alkylate I-25% e.g. 5-
20%, light
hydrocrackate 0 or I S-2S%, full range steam cracked spirit 10-45% naphtha 0
or 0.5-
5%, full range catalytically cracked spirit 0 or I-S% 2,2,4 trimethylpentane 0
or 0.5-25%
such as 0.5-S%, and alkylate cuts) usually in total amount 25-45%. The amounts
of the
latter may be cut by (90-95, 9S-100, 100-103, 103-106°C) used alone 25-
4S%, or blends
of one or more of those cuts I-40% (in total in overall composition) and 5-40%
of cuts
by 15-60, 60-80 (especially 3-15%) by 106-I 10, 110-115, 1 I S-125°C
(especially 7-40%,
e.g. 7-20%).
In addition the remaining cuts i.e. those above and below the 90-
106°C cut
especially those boiling in part of the 15-80°C range and those boiling
in part of the 106-
12S°C range, can be combined e.g. in proportion S: I-1:5, and the
combination used as
component (a) in composition, gasolines and uses of this invention with
component (g);
these can provide clean lower octane unleaded gasolines, in particular ones
free of
oxygenates, with RON values of at least 92 and MON values of at least 80 also
with low
emissions. Example of such compositions and gasolines made from a blend of
high and
low by cuts are those with RON 92-98 e.g. 92-95 or 95-98, MON 80-88 e.g. 80-84
or
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WO 00/77130 PCT/GB00/02282
84-88, RVP SO-65 kPa e.g. 50-55 or 55-60 kPa, % evaporated at 70°C, 12-
35%,
evaporated at 100°C 46-62%, % evaporated at 150°C 94-100%, %
evaporated at 180°C
97.5-100%, density 0.715 to 0.74 e.g. 0.72-0.738 kg/I, benzene 0.5-1.5% e.g.
0.5-1%,
aromatics 13-28% e.g. 13-20%, olefins 3-14% such as 3-10%. They may be made
from
mixtures of butane 0 or 0.5-3%, full boiling range alkylate 10-40% e.g. 15-
30%, full
range steam cracked spirit 15-50% e.g. 15-35%, naphtha 0 to 10-20%, and
alkylate
cuts) usually in total amount 25-45%. The amounts of the latter may be 5-25%
(in total
of the overall composition) of one or more of cuts of 15-60, 60-80 and 80-
90°C and 10-
30% in total (of the overall composition) of cuts of 106-I 10, 110-115, 11 S-
125°C
especially 110-125°C.
By this means, substantially all the alkylate can be converted into 2 clean
fuel products of
higher and lower octane level.
Thus in a further aspect the present invention also provides a process for
preparing
at least 2 clean compositions suitable for production of gasolines, which
comprises
fractionating a reaction product comprising a majority of isoalkanes e.g.
isomerization or
alkylation product e.g. of by 15-160°C to produce a first cut boiling
in at least part of the
range 90-106°C, and a second cut boiling at a temperature lower than
said first cut and
third cut boiling at a temperature above said first cut, blending said first
cut as
component (a) with component (g) as defined above to produce a first high
octane
unleaded gasoline composition of RON at least 97 and MON value at least 86
with low
emissions on combustion, and incorporating said second and third cuts as
component (a)
with component (g) as defined above to produce at least one second high octane
unleaded gasoline composition of RON at least 92 and MON value at least 80
with low
emissions on combustion. In both cases these gasolines can be obtained without
the
need of oxygenate octane booster.
The present invention also provides a method of producing fuels which
comprises
distilling said reaction product e.g. alkylate to produce a first cut above
160°C and a
second cut below 160°C, and mixing said first cut with other liquid
hydrocarbon blend
ingredients to form a jet fuel, diesel or kerosene, and mixing said second cut
with other
liquid gasoline blend ingredients to form motor gasoline.
Component (g) present in the compositions of the invention is usually at least
one
paraffin, aromatic and/or olefinic hydrocarbon of by less than 160°C.
Examples of said
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WO 00/77130 CA 02375614 2001-11-29 pCT/GB00/02282
components are components (b)-(f) below, each of which or 2 or more of which
may be
present.
In the second aspect of the invention, examples of the branched chain alkane
(usually of 4-12 e.g. 4-8 carbons) which is component (a) are iso alkanes of 4-
8 carbons,
in particular isobutane, isopentane and isooctane, and dimethyl alkanes, such
as 2,3-
dimethyl butane. The branched chain alkane usually has at least one,
preferably two
methyl groups on carbon atom 2 in the alkane chain. The branched alkane
usually
provides at least 30% e.g. 30-80%, such as 50-80% of the total saturated
content of the
composition or of the total saturated content of the alkylation cut, the
remainder being
substantially other branched chain alkanes not meeting the specified
definition e.g. of by
of 100-160°C, or lower MON value and/or linear hydrocarbons e.g. of 4-8
carbons as
described above. Small amounts of cycloalkanes as described above may also be
present
in the saturate content.
The compositions of the invention usually contain less than 5% triptane or 223
trimethyl pentane, especially less than 4.9% or 1%, and in particular are
substantially free
of triptane and 223 trimethyl pentane (e.g. with less than 0.5% or 0.1 % in
total of both if
present). However, if desired and especially with cuts boiling above
60°C e.g. 60-160 or
60-100°C, triptane and/or 223 trimethyl pentane may be present in
amount of at least 5
or 8% such as 5-20% in the composition.
In the composition of the invention, component (g) may be component (b) which
is
at least one saturated liquid aliphatic hydrocarbon having 4 to 12, 4-10 such
as 5-10 e.g.
5 - 8 carbon atoms. In another embodiment component (b) is contained in at
least one of
isomerate, full range alkylate with FBP more than 170°C, straight run
gasoline, light
reformate, light hydrocrackate and aviation alkylate. Preferably the
composition
comprises at least one of an olefin (e.g. in amount of I-30% e.g. 8-18%)
and/or at least
one aromatic hydrocarbon (e.g. in amount of 1-50%, especially 3-35%) and/or
less than
5% of benzene. The composition may preferably comprise S-40% component (a),
less
than 1% benzene and have a Reid Vapour Pressure at 37.8°C measured
according to
ASTMD323 of 30-120kPa. The composition is usually an unleaded motor gasoline
base
blend composition.
The branched chain alkanes e.g.compounds A may be alkanes of 8-12 carbon
atoms (especially 8-10 or 8 or 10 carbons) with 3 methyl and/or ethyl
branches. Methyl
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W~ 00/77130 CA 02375614 2001-11-29 PCT/GB00/022g2
branches are preferred. The compounds usually have their longest chain of
carbon
atoms, hereinafter called their backbone chain, with 4-6 chain carbon atoms
(especially 4
or 5) to which the methyl, and/or ethyl branches are attached. Advantageously,
especially in relation to the first to tenth groupings as described further
below, there are
no branched groups constituting the branches other than methyl or ethyl, and,
in the
backbone chain of carbon atoms, there are especially no linear alkyl groups of
more than
2 carbons nor 1,2 ethylene or 1,3 propylene groups in the chain, and
especially no
methylene groups in the chain except as part of an ethyl group; thus there are
especially
no n-propyl or n-butyl groups forming part of the backbone chain. Preferably,
when in
the composition there is at least one compound (A) alkane of 9-12 e.g. 9 or 10
carbons,
there is usually as well less than 50% or 10% of an 8 carbon alkane compound
(A).
The compounds can have 1 or 2 methyl or ethyl groups attached to the same
carbon atom of the backbone chain, especially 1 or 2 methyl groups and 0 or 1
ethyl
groups. The carbon atom in the backbone at which the branching occurs is non-
terminal
i.e. is an internal carbon in the backbone chain, especially the 2, 3 and/or 4
numbered
carbon in the backbone. Thus advantageously the compound has geminal methyl
substituents on position 2, 3 or 4 carbon atom, especially position 2, but in
particular
position 3.
In a first grouping of compounds A, there is one pair of geminal methyl branch
substituents, and they are on position 2.
In a second grouping of the compounds A there is 1 pair of geminal methyl
branch
substituents on a 4-6 carbon chain backbone. The compounds of the second
grouping
advantageously have a MON value of at least 100.
In a third grouping of the compounds, there is one geminal methyl branch
grouping
i.e. -CMe2- on the backbone, while on one of the adjacent carbon atoms of the
backbone,
there is a methyl or ethyl branch, especially a methyl branch.
In a fourth grouping of the compounds there is one pair of geminal methyl
branches on the 2 position backbone carbon and there is a methyl branch on the
3
position backbone carbon. Such compounds usually have a RON value of at least
111.
Advantageously the compounds are of 8 or 10 carbon atoms.
In a fifth grouping the compound A has 3 methyl or ethyl substituents on
different
back bone carbon atoms, especially on vicinal carbon atoms.
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In a sixth grouping the compounds have a linear backbone chain of 4 or 6
carbons
and have 3 methyl branches, one pair of which is one geminal group (CMez)
especially in
the absence of a 1,2 ethyl group in the backbone.
In a seventh grouping, the compounds have a linear backbone chain of 5 or 6
S carbons and have 3 branches one pair of which is in one geminal group, are
usually liquid
at 25°C and generally have a RON value of greater than 105. Especially
there are only
methyl branches; such compounds usually have a MON value of at least 101.
Advantageously in an eighth grouping the compounds A contain 1 chain carbon
atoms with geminal methyl branches, with one branch on the vicinal carbon atom
to the
geminal one, and any ethyl -C- chain group in the backbone chain has 5 carbon
atoms i.e.
is (Ethyl)2CH or Ethyl CMez-.
A particularly preferred sub-class (ninth grouping) for the compound A is
alkanes
with 3 methyl or ethyl substituents which are (i) on vicinal internal carbon
atoms, with a
total of 4, 5 or 6 carbon atoms in said substituents.
Or (ii) with a total of 3 carbon atoms in said substituents and a one terminal
CHMe2 group.
Or (iii) with a total of 3 carbon atoms in said substituents and contain only
secondary internal carbon atoms in the longest carbon atom chain.
Among this sub-class are preferred (i) and (ii) and especially with geminal
methyl
groups on an internal chain carbon atom.
In another aspect of the invention there is provided an unleaded blend
composition
having a MON value of at least 81 or 85 and RON value of at least 91 or 94,
which
comprises component (a) a total of at least 1 S% of one or more branched
alkane
compounds A' of 8-12 carbons (especially with 4-6 backbone carbon atoms), with
3
methyl or ethyl branches and at least 2 backbone carbon atom which are
secondary
and/or tertiary carbon atoms, (subject of course to there being not more than
one tertiary
backbone carbon atom) with the proviso that if there are only 2 such carbon
atoms, then
one is tertiary, there being a minimum of at least 10% (by volume of the
composition) of
at least one individual compound A', and component (b) of nature and in amount
as
described herein, with the preferred proviso as described above. In the above
component
Al, which may be the same or different from A, there may thus in a tenth
grouping be in
the backbone internal (i.e. non-terminal) carbon atoms which are (i) 1
tertiary and 1 sec,
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in particular (ii) with the tert and a sec. carbon vicinal or (iii) 1 tertiary
1 sec. and 1
primary especially with vicinal tert and sec. carbons or vicinal or non-
vicinal sec. carbons
or (iv) 3 sec. carbons, with at least 2 e.g. 3 vicinal. The compounds A'
usually are free
from 2 primary internal backbone carbon atoms on vicinal carbons i.e. as in
1,2-ethylene
group. Preferably any primary internal backbone carbon atoms are not between,
e.g.
adjacent on both sides to, a tert. and/or sec. carbon on the one hand and a
sec. carbon on
the other hand. Especially at least the said 2 backbone carbon atoms above in
compounds A' are vicinal.
In another category, the eleventh grouping is of compounds A' which contain
(with proviso that they only have 3 branched groups )(i) as one end of the
backbone a
group of formula CHR'R2 where each of R' and RZ, which are the same or
different is a
methyl or ethyl group or (ii) as one end of the backbone a group of formula
CR'RZR3
where R' and RZ are as defined above and R3 is methyl or ethyl. Preferred are
such
compounds A' which have both (i) and (ii), especially when the CHR'RZ group is
CHMe2 when the compound has 8 carbons or a backbone of 5 carbons and when all
internal carbon atoms in the backbone chain are secondary or tertiary (subject
to a total
of 3 branched groups).
The compounds A or A' may have a boiling point at 1 bar pressure of 129-
150°C
110-129°C, or 90-109°C. In particular the boiling point is
preferably at least 105°C e.g.
105-175°C, with the proviso that compound A or A' is Not 223 trimethyl
pentane or is
at least 112°C such as 112-175°C.
In another category the compounds A or A' may have 3 methyl and/or ethyl
branches on a 4-6 carbon backbone, and especially a ratio of carbon atom in
branches to
carbon atoms in the backbone chain of at least 0.55: I e.g. 0.55-0.9:1 such as
0.63-0.9:1.
The compounds usually have 9 carbons, unless the above ratio is at least 0.63
or 0.75.
Preferred compounds are 223 trimethyl pentane (A3), 224 trimethyl pentane
(isooctane) (A4) 22 MeZ 3 ethyl pentane (AS), 233 trimethyl pentane (A6) 24
dimethyl 3
ethyl pentane (A8), and 234 trimethyl pentane (A9). The branched hydrocarbon
may
also not be 224 trimethyl pentane and/or 223 trimethyl pentane.
The compounds A and A' are either known compounds and may be made
according to the published literature, or are novel and may be made by
conventional
methods known per se in the literature (e.g. as described in Kirk Othmer
Encyclopaedia
CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
of Chemical Technology 3rd Ed. Publ. Wiley). Examples of suitable methods of
preparation are known carbon-carbon coupling techniques for making alkanes.
The
technique may involve reactions of one or more usually 1 or 2 alkyl chlorides,
bromides
or iodides with an elemental metal of Group IA, IIA, IB or IIB of the Periodic
Table in
Advanced Inorganic Chemistry by F.A.Cotton + G.wilkinson, Pub. Interscience
New
York 2nd Ed. 1966, especially sodium, magnesium, or zinc. The alkyl halide is
usually a
branched chain one of 3-6 carbons, in particular with methyl or ethyl
branches, and
especially with the halogen atom attached to a CMe2 group in one of the alkyl
halides.
Preferably a halide is of formula MeCMe2X or EtCMe2X, where X is Cl, B or I
and the
other halide is a secondary halide e.g. of formula RR'CH-X where each of R and
R' is
methyl or ethyl, such as isopropyl or sec butyl or sec amyl halide or a
primary branched
alkyl halide e.g. of formula R"CH2X, where R" is a branched alkyl group 3-5
carbons
with methyl or ethyl branches, such as isopropyl, isobutyl or isoamyl.
Alternatively both
halides can be secondary e.g. of formula RR'CHX, as defined above and
R"'R"'CHX
1 S where R"' is methyl or ethyl and R'v is as defined for R", such as
isopropyl or one can
be secondary (as above) and one can be primary e.g. methyl or ethyl halide.
The
methods of coupling optimum for any particular compound A or A' depend on
availability of the precursor alkyl halides) so that in addition to the above
kinds,
coupling via methyl or ethyl halides with branched alkyl halides of 6-9
carbons may also
be used. The alkyl halides) can react together in the presence of the metal
(as in a
Wurtz reaction with sodium), or one can react first with the metal to form an
organometallic compound e.g. a Grignard reagent or organo zinc, followed by
reaction
of the organometallic with the other alkyl halide. If desired the Grignard
reagent
reaction can be in the presence of a metal of Group IB or IIB, such as silver,
zinc or
copper (especially high activity copper). If desired the Grignard reagent from
one or
both alkyl halides can be reacted with the latter metal to form other alkyl
metallic species
e.g. alkyl silver or alkyl copper compounds, which can disproportionate to the
coupled
alkane. The Grignard reagents) can also react with a cuprous halide to form
alkyl
copper species for disproportionation. Finally an organometallic compound,
wherein the
metal is of Group IA or IIA e.g. Li or Mg can be coupled by reaction with a
cuprous
complex to give a coupled alkane.
The above organometallic reactions are usually conducted under inert
conditions,
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CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
i.e. anhydrous and in the absence of oxygen e.g. under dry nitrogen. They are
usually
performed in an inert solvent e.g. a dry hydrocarbon or ether. At the end of
the reaction
any residual organometallic material is decomposed by addition of a compound
with
active hydrogen e.g. water or an alcohol, and the alkanes are distilled off,
either directly
or after distribution between an organic and aqueous phase.
Examples of preparations of highly branched alkanes are described in F L
Howard
etal, J Res. Nat. Bur. Standards Research Paper RP1779, Vol 38 March 1947 pp
365-
395. The disclosures of is document is incorporated herein by reference.
The crude alkanes made by the above processes may be used as such in the
blends
of the invention or may be purified further e.g. by distillation first.
If desired the compounds, especially of 8 carbon atoms may be obtained by
fractional distillation of refinery streams e.g. straight run gasolines, or
alkylation products
e.g. of isoalkanes of 3-S carbons with alkanes of 3-5 carbons (as described
above)
Other known methods of making the alkanes A or A', are reaction of alkyl
metallic
compounds e.g. Grignard reagents with carbonyl compounds such as aldehydes,
ketones,
esters, or anhydrides to form branched chain carbinols, which are dehydrated
to the
corresponding olefin, which is hydrogenated to the alkane. Thus 2,3,4-
trimethyl pentane
may be made from isopropyl magnesium bromide and methyl isopropyl ketone
(followed
by dehydration and hydrogenation), and 2,2-dimethyl 3 ethyl pentane,
from ethyl magnesium chloride and di isopropyl ketone.
The present invention also provides an unleaded formulated motor gasoline
which
comprises said composition of the first to seventh aspects of the invention
and at least
one gasoline additive e.g. motor or aviation gasoline additive.
The component (a) may be present in amount of 5-95% or 8-90% such as 10-
90%, or 15-65% e.g. 20-55% or 10-40% such as 20-35% by volume or 40-90% such
as
40-SS% or 55-80% or 8-35% such as 8-20% by volume. Unless otherwise stated all
percentages in this specification are by volume, and disclosures of a number
of ranges of
amounts in the composition or gasoline for 2 or more ingredients includes
disclosures of
all sub-combinations of all the ranges with all the ingredients.
The invention in its first to fourth aspects will be further described with
alkylate
cuts exemplifying the refinery stream component (a) but others may be used
instead or as
well.
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WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
The composition of the invention may also contains as component (b) at least
one
liquid saturated hydrocarbon of 5-10 carbons especially predominantly branched
chain C7
or Cg compounds e.g. iso C~ or iso C8. This hydrocarbon may be substantially
pure e.g.
n-heptane, isooctane or isopentane or a mixture e.g. a distillation product or
a reaction
product from a refinery reaction e.g. alkylate. The hydrocarbon may have a
Motor
Octane Number (MON) of 0-60 but preferably has a MON value of 60-96 such as
isomerate (bp 25-80°C). Research Octane Number RON may be 80-105 e.g.
95-105,
while the ROAD value (average of MON and RON) may be 60-100.
Component (b) which is different from component (a) may comprise a
hydrocarbon component having boiling point (preferably a final boiling point)
of at least
82°C, such as 85-150°C but less than 225°C e.g. less than
170°C or 160°C and usually is
of Motor Octane Number of at least 92 e.g. 92-100; such components are usually
alkanes of 7-10 carbons especially 7 or 8 carbons, and in particular have at
least one
branch in their alkyl chain, in particular 1-3 branches, and preferably on an
internal
carbon atom and especially contain at least one -C(CH~)2- group.
The volume amount of the component (b) in total (or the volume amount of
mixtures comprising component (b), such as the total of each of the following
(if present)
(i)-(iv)) (i) catalytic reformate, (ii) heavy catalytic cracked spirit, (iii)
light catalytic
cracked spirit and (iv) straight run gasoline in the composition is usually 10-
80% e.g.
25-70%, 40-65% or 20-40%, the higher percentages being usually used with lower
percentages of component (a).
Component (b) may be a mixture of the liquid saturated hydrocarbons e.g. a
distillation product e.g. naphtha or straight run gasoline or a reaction
product from a
refinery reaction e.g. alkylate including full range alkylate (bp 30-
190°C) isomerate (bp
25-80°C), light reformate (bp 20-79°C) or light hydrocrackate.
The mixture may contain
at least 60% or at least 70% w/w e.g. 60-95 or 70-90% w/w liquid saturated
aliphatic
hydrocarbon.
The compositions of the invention may contain mixtures of component (a) e.g.
alkylate cut of 15-100°C with full range boiling alkylate (i.e. of FBP
greater than 170°C
e.g. 190°C) in a ratio of 9:1 to 1:9 in particular 5-9:5-1 or 1-3:9-7.
If desired such
mixtures may be made by dividing the full range alkylate into first and second
portions, a
first portion being distilled to provide the desired cut and then the cut
mixed with the
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WO 00/77130 PCT/GB00/02282
second portion. The residue from the cut can be used elsewhere as described
above.
Volume amounts in the composition of the invention of the component (b)
mixtures (primarily saturated liquid aliphatic hydrocarbon fractions e.g. the
total of
isomerate, full range alkylate, naphtha and straight run gasoline (in each
case (if any)
present in the composition) may be 4-60%, such as 4-25% or preferably 10-55%
such as
25-45%. Full range alkylate or straight run gasoline are preferably present
for
component (b), optionally together but preferably in the absence of the other,
in
particular in amount of 2-50% such as 10-45 e.g. 10-25%, 25-45% or 25-40%. The
compositions of the invention may also comprise naphtha e.g. in volume amount
of 0-
25% such as 2-25%,10-25% or 2-10%.
The compositions may comprise as component (c) a hydrocarbon component
which is a saturated aliphatic hydrocarbon of 4-6 carbons and which has a
boiling point
of less than 80°C under atmospheric pressure, such as 20-50°C,
and especially is itself of
Motor Octane Number greater than 88 in particular at least 90 e.g. 88-93 or 90-
92.
Examples of the hydrocarbon component include alkanes of 4 or 5 carbons in
particular
iso-pentane, which may be substantially pure or crude hydrocarbon fraction
from
reformate or isomerate containing at least 30% e.g. 30-80% such as 50-70%, the
main
contaminant being up to 40% mono methyl pentanes and up to SO% dimethyl
butanes.
The hydrocarbon component may be an alkane of boiling point (at atmospheric
pressure)
-20°C to +20°C e.g. n and/or iso butane optionally in blends
with the CS alkane of
99.5:0.5 to 0.5:99.5, e.g. 88:12 to 75:25. n Butane alone or mixed with
isopentane is
preferred, especially in the above proportions, and in particular with a
volume amount of
butane in the composition of up to 20% such as 1-I S% e.g. 1-8, 3-8 or 8-15%.
Cycloaliphatic hydrocarbons e.g. of 5-7 carbons such as cyclopentane or
cyclohexane may be present but usually in amounts of less than 15% of the
total e.g. I-
10%.
Volume amounts in the composition of the total of isomerate, full range
alkylate,
naphtha, straight run gasoline, 4-6 carbon liquid aliphatic hydrocarbon (as
defined above)
and cycloaliphatic hydrocarbon (in each case if present) may be 5-60%, such as
8-25%,
I S-55% such as 30-50%.
The compositions of the invention also preferably contain as component (d) at
least
one olefin, (in particular with one double bond per molecule) which is a
liquid alkene of
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WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
5-10 e.g. 6-8 carbons, such as a linear or branched alkene e.g. pentene,
isopentene
hexene, isohexene or heptene or 2 methyl 2 pentene, or a mixture comprising
alkenes
which may be made by cracking e.g. catalytically or thermally cracking a
residue from
crude oil, e.g. atmospheric or vacuum residue; the mixture may be heavy or
light
catalytically cracked spirit (or a mixture thereof). The cracking may be steam
assisted.
Other examples of olefin containing mixtures are "C6 bisomer", catalytic
polymerate, and
dimate. The olefinic mixtures usually contain at least 10% w/w olefins, such
as at least
40% such as 40-80% w/w. Preferred mixtures are (xi) steam cracked spirit (xii)
catalytically cracked spirit (xiii) C6 bisomer and (xiv) catalytic polymerate,
though the
optionally cracked catalytically spirits are most advantageous. Amounts in the
total
composition of the olefinic mixtures especially the sum of (xi) - (xiv) (if
any present)
maybe 0-55, e.g. 10-55 or 18-37 such as 23-35 or 20-55 such as 40-55% or 23-
40%
Amounts of (xi) and (xii) (if present) in total in the composition are
preferably 18-55,
such as 18-35, 18-30 or 35-55% (by volume).
The olefin or mixture of olefins usually has an MON value of 70-90, usually a
RON value of 85-95 and a ROAD value of 80-92.
The volume amount of olefins) in total in the gasoline composition of the
invention may be 0% or 0-30%, e.g. 0.1-30% such as 1-30% in particular 2-25, 5-
30,
(especially 3-10), 5-18.5, 5-18 or 10-20%. Preferably the composition contains
at least
1 % olefin and a maximum of 18% or especially a maximum of 14%, but may be
substantially free of olefin.
The compositions may also contain as component (e) at least one aromatic
compound, preferably an alkyl aromatic compound such as toluene or o, m, or p
xylene
or a mixture thereof or a trimethyl benzene. The aromatics may have been added
as
single compounds e.g. toluene, or may be added as an aromatics mixture
containing at
least 30% w/w aromatic compounds such as 30-100% especially 50-90%. Such
mixtures may be made from catalytically reformed or cracked gasoline obtained
from
heavy naphtha. Example of such mixtures are (xxi) catalytic reformate and
(xxii) heavy
reformate. Amounts of the single compounds e.g. toluene in the composition may
be 0-
35%, such as 2-33% e.g. 10-33%, while amounts of the aromatics mixtures
especially
the total of the reformates (xxi) & (xxii) (if any) in the composition may be
0-50%, such
as 1-33% e.g. 2-1 S% or 2-10% or 15-32% v/v, and total amount of reformates
(xxi),
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
(xxii) and added single compounds (e.g. toluene) may be 0-SO% e.g. 0.5-20% or
5-40,
such as I S-35 or 5-25% v/v.
The aromatics usually have a MON value of 90-110 e.g. 100-I 10 and a RON value
of 100-120 such as 110-120 and a ROAD value of 95-1 10. The volume amount of
aromatic compounds in the composition is usually 0% or 0-50% such as less than
40%
or less than 28% or less than 20% such as 1-50%, 2-40%, 3-28%, 4-25%, 5-20%
(especially 10-20%), 4-10% or 20-35% especially of toluene. The gasoline
composition
may also be substantially free of aromatic compound. Amounts of aromatic
compounds
of less than 42%, e.g. less than 35% or especially less than 30% are
preferred.
Preferably the amount of benzene is less than 5% preferably less than I .5% or
1% e.g.
0.1-I% of the total volume or less than 0.1% of the total weight of the
composition.
The compositions may also contain as component (f) at least one oxygenate
octane
booster, usually of Motor Octane Number of at least 96-105 e.g. 98-103. Tlae
oxygenate
may be any organic liquid molecule containing and preferably consisting of, CH
and at
1 S least one oxygen atom e.g. I-S of by less than 225°C. The octane
booster is usually an
ether e.g. a dialkyl ether, in particular an asymmetric one, preferably
wherein each alkyl
has 1-6 carbons, in particular one alkyl being a branched chain alkyl of 3-6
carbons in
particular a tertiary alkyl especially of 4-6 carbons such as tert-butyl or
tert-amyl, and
with the other alkyl being of I-6 e.g. I-3 carbons, especially linear, such as
methyl or
ethyl. Examples of such oxygenates include methyl tertiary butyl ether (MTBE),
ethyl
tertiary butyl ether and methyl tertiary amyl ether. The oxygenate may also be
an alcohol
of I-6 carbons e.g. ethanol. The oxygenate may also be an organic carbonate
e.g. a
dialkyl carbonate with I-3 carbon atoms in each alkyl e.g. dimethyl carbonate.
The volume amount of the oxygenate may be 0 or 0-25% such as 1-25%, 2-20%,
2-10% or S-20% especially 5-15%, but advantageously less than 3% such as 1-3%
(especially of MTBE and/or ethanol). The oxygenate may also be substantially
absent
from the composition or gasoline of the invention.
Thus the present invention produces an unleaded blend composition of MON value
at least 81 or 85 and RON value at least 91 or 94 which comprises (a) a total
of at least
1 S% of one or more branched hydrocarbon compound A or A' there being a
minimum of
at least 5% of at least one individual compound A or A' and (b) at least 20%
of at least
one different liquid hydrocarbon of bp60-160°C having a MON value of at
least 70 and
16
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
RON value at least 90 especially when (b) is not within the definition of A or
A', in
particular when (a) is a trimethyl pentane. Examples of the liquid
hydrocarbons are
paraffins, such as linear or branched chain alkanes of 4-8 carbons, such as
isobutane,
butane, isopentane, dimethyl alkanes such as 23 dimethyl butane, cycloalkanes,
such as
cyclopentane and cyclohexane, aromatics and olefins.
Another unleaded blend composition of the invention of MON value of at least
81
or 85 and RON value of at least 91 or 94 comprises component (a) as above and
component (b) at least 20% of at least one of a straight run naphtha, alkylate
isomerate
(bp25-80°C) heavy reformate, light reformate (bp20-79°C),
hydrocrackate, aviation
alkylate (bp30-190°C), straight run gasoline, cracked spirit, such as
heavy or light
catalytic cracked spirit or steam cracked spirit. The straight run products
are produced
directly from crude oil by atmospheric distillation. The naphtha may be light
naphtha of
bp30-90°C or medium naphtha of bp90-150°or heavy naphtha of by
I50-220°C.
In the blends of the invention, the amount of at least one individual
compounds A
or A' is usually at least 5%, or at least 10 or 15%, such as 5-60%, e.g. 15-
60%, or 8-
25%, 20-35% or 30-SS% or 2-10%. The amount of compound A4 if present is
usually
at least 10% of the composition. Total amounts of trimethyl pentanes in the
blend are
preferable less than 69% of the blend, but advantageously at least 26%
(especially when
the amount of aromatics is less than 17%. If a 9 or 10 carbon alkane is (a),
then the
amount of 2,2,4-trimethyl pentane is especially less than 70 or 50%. More than
one such
compound A or A' may be present e.g. of higher and lower RON in weight ratios
of 9: I
to 0.5:99.5, such as 0.5:1 to 5:1 or 5:95 to 20:80, particularly for mixtures
of
compounds with higher or lower boiling points (atmospheric pressure) e.g.
those in
which the compounds A and/or A' have boiling points differing by at least
10°C e.g. at
least 40°C such as 10-70°C or 20-50°C the relative
amounts being as described above.
Total amounts of all compounds A and A' (if any) in the blend may be I S-70
e.g. I S-60,
15-40 or 30-55% or 40-60%.
The blend may also comprise predominantly aliphatic refinery streams such as
naphtha, straight run gasoline (also known as light naphtha by 25-
120°C), alkylate and
isomerate. Amounts in total of these may be 10-70%, such as 10-30, 30-70 or 35-
65%.
Amounts of naphtha may be 0-70% or 1-70% such as 10-30, 30-70 or 35-65%, while
amounts of light naphtha may be 0 or I-70 such as I-20 or especially 30-65%,
and
17
WU X0/77130 CA 02375614 2001-11-29 pCT/GB00/02282
amounts of medium naphtha may be 0 or 1-55, such as 3-20 or 15-SS%. The volume
ratio of light to medium naphtha may be 50:1 to 1:50, such as 0.5-20:1 or
1:0.5-S0.
Amounts of alkylate or isomerate (if present) may be 0.5-20% such as 1-10%,
while
amounts of hydrocrackate may be 0.5-30% e.g. 10-30%.
The blends of the invention usually contain in total at least 70% of
saturates, such
as 70-98% or 70-90% or 90-98%.
If desired and especially for aviation gasoline, the blends may contain a
hydrocarbon component which is a saturated aliphatic hydrocarbon of 4-6
carbons and
which has a boiling point of less than 80°C under atmospheric pressure,
such as 20-50°C,
and especially is itself of Motor Octane Number greater than 88 in particular
at least 90
e.g. 88-93 or 90-92. Examples of the hydrocarbon component include alkanes of
4 or 5
carbons in particular iso-pentane, which may be substantially pure or crude
hydrocarbon
fraction from reformate or isomerate containing at least 30% e.g. 30-80% such
as 50-
70%, the main contaminant being up to 40% mono methyl pentanes and up to 50%
1 S dimethyl butanes. The hydrocarbon component may be an alkane of boiling
point (at
atmospheric pressure) -20°C to +20°C e.g. n and/or iso butane
optionally in blends with
the CS alkane of 99.5:0.5 to 0.5:99.5, e.g. 88:12 to 75:25. n Butane alone or
mixed with
isopentane is preferred, especially in the above proportions, and in
particular with a
volume amount of butane in the composition of up to 20% such as 1-15% e.g. 1-
8, 3-8
or 8-15%, especially 1-3.5%.
The hydrocarbon component boiling less than 80°C, in particular
isopentane, may
also be present in compositions of the invention which contain at least one
compound A
or A' of at least 10 carbon atoms. Relative amounts of these compounds A or A1
to the
low boiling component e.g. isopentane, may be 1-9:9-1 such as 5-9:5-1,
especially with
less than 20% of A or A' in the composition.
Cycloaliphatic hydrocarbons e.g. of 5-7 carbons such as cyclopentane or
cyclohexane may be present but usually in amounts of less than 1 S% of the
total e.g. 1-
10%.
The blend of the invention contains at least one component (a) and component
(g) and, (optionally (c) to (f), as well, and the formulated unleaded gasoline
also contains
at least one gasoline additive e.g. a motor gasoline or aviation gasoline
additive, for
example as listed in ASTM D-4814 the contents of which is herein incorporated
by
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WO 00/77130 PCT/GB00/02282
reference or specified by a regulatory body, e.g. US California Air Resources
Board
(CARB) or Environmental Protection Agency (EPA). These additives are distinct
from
the liquid fuel ingredients, such as MTBE. Such additives may be the lead free
ones
described in Gasoline and Diesel Fuel Additives, K Owen, Publ. By J.Wiley,
Chichester,
UK, 1989, Chapters 1 and 2, USP 3955938, EP 0233250 or EP 288296, the contents
of
which are herein incorporated by reference. The additives maybe pre-combustion
or
combustion additives. Examples of additives are anti-oxidants, such as one of
the amino
or phenolic type, corrosion inhibitors, anti-icing additives e.g. glycol
ethers or alcohols,
engine detergent additives such as ones of the succinic acid imide,
polyalkylene amine or
polyether amine type and anti-static additives such as ampholytic surface
active agents,
metal deactivators, such as one of thioamide type, surface ignition inhibitors
such as
organic phosphorus compounds, combustion improvers such as alkali metal salts
and
alkaline earth metal salts of organic acids or sulphuric acid monoesters of
higher
alcohols, anti valve seat recession additives such as alkali metal compounds,
e.g. sodium
or potassium salts such as borates or carboxylates e.g. sulpho succinates, and
colouring
agents, such as azodyes. One or more additives (e.g. 2-4) of the same or
different types
may be used, especially combinations of at least one antioxidant and at least
one
detergent additive. Antioxidants such as one or more hindered phenols e.g.
ones with a
tertiary butyl group in one or both ortho positions to the phenolic hydroxyl
group are
preferred in particular as described in Ex. l hereafter. In particular the
additives may be
present in the composition in amounts of 0.1-100ppm e.g. 1-20ppm of each,
usually of
an antioxidant especially one or more hindered phenols. Total amounts of
additive are
usually not more than 1000ppm e.g. 1-1000ppm
The compositions and gasolines are free of organolead compounds, and usually
of manganese additives such as manganese carbonyls.
The compositions and gasolines may contain up to 0.1% sulphur, e.g. 0.000-
0.02% such as 0.002-0.01 %w/w.
The motor gasoline compositions of the invention in particular those based on
the
distillation cuts e.g. alkylate cuts usually have a MON value of 80 to less
than 98, such as
80-95, 83-93, 85-90 or 93-98. The RON value is usually 90-115 e.g. 102-115 or
preferably 90-102 preferably 90-100 e.g. 90-99, such as 90-93 e.g. 91, or 93-
98 e.g.
94.5-97.5, or 97-101 while the ROAD value is usually 85-107 e.g. 98-106 or
preferably
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WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
85-98 such as 85-95 e.g. 85-90, or 90-95 or 95-98. Preferred gasoline
compositions
have MON 80-83, RON 90-93, and ROAD 85-90, or MON 83-93, RON 93-98 and
ROAD 85-95 or MON 85-90, RON 97-101 and ROAD 91-96. The Net calorific value
of the gasoline (also called the Specific Energy) is usually at least 18000
Btu/lb e.g. at
least 18500, 18700 or 18,900 such as 18500-19500, such as 18700-19300 or 18900-
19200; the calorific value may be at least 42MJ/kg e.g. at least 43.5 MJ/kg
such as 42-45
or 43-45 such as 43.5-44.5MJ/kg. The gasoline usually has a boiling range
(ASTM
D86) of 20-225°C, in particular with at most 5% e.g. 0-5% or 1-3%
boiling in the range
161-200°C. The gasoline is usually such that at 70°C at least
10% is evaporated while
50% is evaporated on reaching a temperature in the range 77-120°C
preferably 77-116°C
and by 185°C, a minimum of 90% is evaporated. The gasoline is also
usually that 8-50%
e.g. 10-50% may be evaporated at 70°C, 40-74% at 100°C,70-99.5%
e.g. 70-97% at
150°C and 90-99% may be evaporated at 180°C; preferably at least
46% e.g. 46-65%
has been evaporated by 100°C. The Reid Vapour Pressure of the gasoline
at 37.8°C
measured according to ASTM D323 is usually 30-120, e.g. 40-100 such as 61-80
or
preferably 50-80, 40-65, e.g. 40-60 or 40-50Kpa.
The unleaded motor gasolines of the invention preferably comprise the
component
(a) and have a RON value of at least 98, MON value of at least 87.8, an RVP of
less
than 60 K Pa e.g. 40-60 kPa less than 35% aromatics, less than 15% olefins, 10-
45%
evaporated at 70°C, 46-60% evaporated at 100°C, and more than
88% evaporated at
150°C. Their density is preferably at least 0.71 e.g. 0.71 to 0.78 such
as at least 0.7122
or at least 0.72 such as 0.7122 to 0.7264 kg/l.
The gasoline compositions of the invention in particular those based the
branched
chain alkanes for component (a) in particular in its fifth to seventh aspects
usually have a
MON value of 80 to 94 such as 85-90, or 90-94-. The RON value is usually 90-
105 e.g.
98-102 , or 93-98 e.g. 94.5-97.5, or 97-101 while the ROAD value is usually 85-
102 e.g.
98-102 or 85-95. Preferred gasoline compositions have MON 83-93, RON 93-98 and
ROAD 85-95 or MON 85-90, RON 94-101 and ROAD 89-96. The Net calorific value
of the gasoline (also called the Specific Energy is usually as described above
as are the
boiling ranges measured according to ASTM D86 and the RVP.
The gasoline compositions, when free of any oxygenates usually have a H:C atom
ratio of at least 1.8:1 e.g. at least 2.0:1 or at least 2.1 or 2.2:1, such as
1.8-2.3:1 or 2.0-
CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
2.2:1. Advantageously the gasoline composition meets the following criteria.
Atom H:C x [1 + oxy] x [ Net Heat of Combustion + ROAD] ? y,
200
wherein Atom H:C is the fraction of hydrogen to carbon in the hydrocarbons in
the
composition, oxy means the molar fraction of oxygenate, if any in the
composition, Net
Heat of Combustion is the energy derived from burning l 1b (454g) weight of
fuel (in
gaseous form) in oxygen to give gaseous water and carbon dioxide expressed in
Btu/lb
units [MJ/kg times 430.35], and y is at least 350, 380, 410 or 430, in
particular 350-440
e.g. 380-420 especially 400-420.
Preferably the motor gasoline of this invention comprises 10-90% of component
(a), 10-80% of component (b), 0-25% naphtha, 0-15% of butane, 5-20% of olefin,
3-
28% aromatics and 0-25% oxygenate, in particular with 5-20% aromatics and 5-
15%
olefins.
In a preferred embodiment of this invention the motor gasoline of this
invention
contains 8-65% of component (a) (especially 15-35%), 0.1-30% such as 2-25%
olefins,
especially 3-14% and 0-35% aromatics such as 0-30% e.g. 5-35, 5-20 (especially
S-15%)
or 20-30%, and 5-50% component (b) mixtures e.g. 10-45% such as 20-40%. Such
gasolines may also contain oxygenates, such as MTBE especially in amount of
less than
3% e.g. 0.1-3% and especially contain less than 1.0% benzene e.g. 0.1-1% and
especially
olefins less than 18% e.g. 0.1-15%. Such gasolines preferably have RON of 96-
99,
MON 86-90 and ROAD values of 91-94.5.
Examples of motor gasolines of the invention are ones with 5-25% component
(a),
S-15% olefins, 15-35% aromatics and 40-65% component (b), in particular 15-25%
component (a), 7-15%, olefins 15-25% aromatics and 45-52% component (b)
mixture of
RON value 96.5-97.5, or 5-15% component (a), 7-15% olefins, 15-25% aromatics
and
55-65% compound (b) of RON value 94.5-95.5.
Examples of motor gasolines of the invention are ones having 1-1 S% e.g. 3-12%
butane, 0-20% e.g. 5-15% ether e.g. MTBE, 20-80 e.g. 25-70% of refinery mixed
liquid
(usually C~-C9)streams (apart from naphtha) (such as mixtures of (i)-(iv)
above), 0-25%
e.g. 2-25% naphtha, S-70% e.g. 15-65% component (a), with RON 93-100 e.g. 94-
98,
MON 80-98 e.g. 83-93 or 93-98, and RVP 40-80 such as 40-65Kpa. Such gasolines
usually contain 1-30% e.g. 2-25% olefins and 2-30% e.g. 4-25% aromatics.
Amounts of
21
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
olefins of 15-25% are preferred for RON values of 94-98 e.g. 94-96 and 2-15%
e.g. 2-
7% for RON values of 96-100 such as 96-98.
Other examples of fuel compositions of the invention contain 8-18% component
(a), 10-50% e.g. 25-40% of total component (b) mixture, 5-40% e.g. 20-35% of
total
aromatics mixture 15-60, e.g. 15-30% or 40-60% of total olefinic mixture and 0-
15%
total oxygenate e.g. 3-8% or 8-15%. Especially preferred compositions have 8-
18%
component (a), 25-40% total mixed component (b) mixture, 20-35% total
aromatics, and
15-30% total olefinics, or 8-18% component (a), 15-40% total mixed component
(b)
mixture, 3-25% total aromatics mixture, and 40-60% total olefinic mixture.
Further examples of fuel compositions contain 20-40% component (a), 8-55% of
the total component (b) mixture, e.g. 5-25% or 35-55%, and 0 or 5-25% e.g. 18-
25%
total aromatics mixture, 0-55 especially 10-55 or 40-55% total olefin mixture,
especially
preferred compositions having 20-40% component (a), 5-25% total component (b)
mixtures, 3-25% total aromatics mixture and 40-60% total olefinic mixture, or
20-40%
component (a), 35-55% total component (b) mixture 15-30% total aromatics
mixture
and 0-15% e.g. 5-15% total olefin mixture, or in particular 20-40% component
(a), 25-
45% or 30-50% total component (b) mixture, 2-15% total aromatics mixture 18-
35%
total olefins mixture, and especially 3-10% or 5-18% olefins, and 10-35% such
as 10-
20% aromatics (e.g. 10-18%).
Other examples of fuel compositions contain 30-55% e.g. 40-55% component (a),
5-30% total component (b) mixture, 0-10% total aromatic mixture, 10-45%
olefinic
mixture and 0-15% oxygenates especially with the total of oxygenates and
olefinic
mixture of 20-45%. Other examples of fuel compositions contain 55-70%
component
(a), 10-45% total component b, e.g. 10-25% or 35-45%, and 0-10% e.g. 0 or 0.5-
5%
total aromatics Mixture, and 0-30% total olefinics mixtures, e.g. 0 or 15-30%,
especially
55-70% component (a), 10-25% total component (b) 0 or 0.5-5% total aromatics
mixture and 15-30% total olefinic mixture.
Particularly preferred examples of fuel composition comprise 15-35% e.g. 20-
35%
component (a), 0-18.5% e.g. 2-18.5% olefin, 5-40% e.g. 5-35% aromatics 25-65%
saturates and less than 1% benzene, and 18-65% e.g. 40-65% component (a), 0-18-
5%
e.g. 5-18.5% olefins, 5-42% e.g. 5-28% aromatics, 35-55% saturates and less
than 1%
benzene.
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CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
Another fuel composition may comprise 25-40% e.g. 30-40% such as 35% of
alkylate (especially full by range alkylate with IBP 30°C or more and
FBP greater than
165°C), 10-25% e.g. 15-25% such as 20% of isomerate, 10-25% e.g. 15-25%
such as
20% of light hydrocrackate and 20-35% e.g. 20-30% such as 25% of component (a)
and
optionally 0-5% butane. Such a composition is preferably substantially
paraWnic and is
substantially free of olefins and aromatics.
A further gasoline composition which provides a specific aspect of the present
invention comprises 2-20% e.g. 5-15% component (a) especially an alkylate cut
at 15-
100°C, 20-40% e.g. 25-35% full boiling range alkylate e.g. of FBP 175-
200°C (especially
with a sum of component (a) and alkylate of 35-45%) 25-40% olefinic mixtures
such as
steam cracked spirit, 5-20% e.g. 7-15% reformate, 10-25% e.g. 12-20% toluene
and
0.1-3% e.g. 0.5-2.0% butane. A preferred gasoline of the invention e.g. the
last one
usually RON 98-101, MON 86-89 E100°C (% evaporated at 100°C) 45-
55 e.g. 48-52,
aromatics 30-40% such as 30-35%, olefins 3-15% e.g. 5-10%, and total saturates
of 50-
65% e.g. 55-60%. Such a composition is free of added oxygenates. The toluene
may be
replaced by an equal volume of heavy reformate.
A further gasoline composition of particular value comprises 0.5-5% e.g. 2-4%
butane, 10-30% e.g. 15-25% full range alkylate (e.g. of FBP 175-200°C),
10-40% such
as 20-35%) component (a), especially of alkylate cut 110-115, 115-125, 15-160,
or 15-
100°C (in particular with the total of alkylate and component (a) of 35-
60% e.g. 40-
55%, catalytic reformate 30-50%, and bisomer 5-15%, MON 87-90, RON 98-101 and
ROAD 93-95. Such a composition is also free of oxygenate.
Other motor fuel compositions of the invention may have different ranges of
the
Antiknock Index (also known as The ROAD Index), which is the average of MON
and
RON.
For ROAD Indexes of 85.5-88.5, the compositions may comprise 8-30%
component (a) e.g. 15-30%, and 10-50% e.g. 20-40% total component (b) mixture,
5-
30%, e.g. 5-20% total olefins and 10-40 e.g. 15-35% total aromatics, or 8-30%
component (a), 10-50% total component (b) mixture, 5-40% total aromatic
mixtures e.g.
20-30% and 10-60% e.g. 30-55% total olefinic mixtures.
For ROAD Indexes of 88.5-91.0 the compositions may comprise 5-25% (or 5-
15%) component (a), 20-45% total component (b) mixture, 0-25% e.g. 1-10 or 10-
25%
23
WU 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
total olefins, and 10-35% e.g. 10-20% or 20-35% total aromatics or 5-25% (5-
15%)
component (a), 20-45% total component (b) mixture, 0-35% total aromatic
mixtures e.g.
1-15 or 15-35%, and S-65% e.g. 5-30 or 30-65% total olefinic mixtures.
For ROAD Indexes of 91.0-94.0 the fuel compositions of the invention may
S comprise 5-65% e.g. 5-20, 20-30, 30-65 or 40-65% component (a) and 5-40% (5-
35%)
e.g. 5-12 or 12-40% (12-30%) total component (b) mixture 1-30% e.g. 1-10 or 10-
25%
total olefins and S-SS% e.g. S-15 or 15-35 or 35-55% total aromatics, or the
above
amounts of component (a) with 0-SS e.g. 0.5-25% e.g. 10-25% or 25-55% of
aromatic
fractions and 0 or 10-60% e.g. 10-30% or 35-60% total olefin fractions.
For ROAD values of 94-97.9, the fuel compositions may comprise 20-65%
component (a) e.g. 40-65% component (a), 0-15% e.g. S-15% total olefins, 0-20%
e.g.
5-20% total aromatics and 5-50 e.g. 30-50% total component (b) mixture, or the
above
amounts of component (a) and total component (b) mixture with 0-30% e.g. 10-
30%
aromatic fractions and 0-30 e.g. 5-30% olefinic fraction, or the above amounts
of
1 S component (a) e.g. 20-40% component (a), total component b mixture, total
olefins and
total aromatics, with 2-15% aromatic fractions and 18-35% olefinic fractions.
Among preferred blends of the invention especially for the fifth to seventh
aspects
are unleaded blends comprising as component (a) at least 10% of at least one
individual
compound A or A' and component (b) as defined above, with the provisos that
(i) when
the compound A or A' is a trimethylpentane, then the blend contains 10-65% of
total
trimethyl pentanes, and at least 10% of an alkane of 6 or 7 carbons and MON
value of at
least 70 and RON value of at least 90, and preferably contains less than 5% of
2,2,3-
trimethylpentane and 2,2,3-trimethyl butane, and (ii) when the compound A or
A' is an
alkane of 9 or 10 carbon atoms, then blend contains at least 10% of an alkane
of 6 or 7
carbons of MON at least 70 and RON at least 90, and preferably contains less
than S% in
total of 2,2,3-trimethyl pentane and 2,2,3-trimethyl butane. In the case of
proviso(i) this
blend preferably comprises at least 26% (or 30%) in total of alkanes of 7 or 8
carbons of
MON at least 70 and RON at least 90, and/or contains less thanl7% in total of
aromatics.
Preferred formulated unleaded gasolines of the invention comprise at least one
gasoline additive and the preferred unleaded blend in the previous paragraph
with the
proviso (iii) when the compound A or A' is a trimethyl pentane, then the blend
contains
24
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
10-65% of total trimethyl pentanes and less than 5% of 2,2,3-trimethyl pentane
and
2,2,3-trimethyl butane, and (iv) when the compound A or A' is an alkane of 9
or 10
carbon atoms, the blend preferably contains less than 5% in total of 2,2,3-
trimethyl
pentane and 2,2,3-trimethyl butane.
S Preferred blends and gasolines of the invention especially in the fifth to
seventh
aspects can have MON values of 80-94 e.g. 80-85 or 90-94, RON values of 90-105
e.g.
90-95 or 97-105, ROAD values of 85-102, compound A or A' contents of 30-60%
e.g.
40-60% (comprising 1 or 2 compounds A or A'), total naphtha contents of 35-65%
(e.g.
35-55%) and 1-5% butane, the blends containing 1-8% e.g. 2-6% aromatics, 0-1%
olefins and 91-99% (e.g. 94-98%) saturates. These are substantially aliphatic
blends and
gasolines of high octane numbers, without the use of oxygenates such as MTBE,
and
also substantially saturated.
Other high octane blends and gasolines of the invention especially in the
fifth to
seventh aspects can have MON values of 80-95 e.g. 85-95, RON values of 90-100
e.g.
95-100, ROAD values of 85-97, compound A or A' contents of 30-60% e.g. 30-50%
(comprising 1 or 2 compounds A or A', medium naphtha contents of 5-30% and
contents of total olefinic fraction such as steam cracked spirit of 30-50% and
1-S%
butane, the blends containing 10-25% aromatics e.g. 12-18% aromatics, 4-14%
olefins
e.g. 6-12%, and 60-90% such as 70-80% saturates. These high octane materials
are
obtained without the use of oxygenates.
Further blends and gasolines of the invention can have MON values of 84-90,
RON values of 93-98, ROAD values of 86-94, and contain compound A or A' in
amount
of 15-35%, total naphtha of 40-65% and olefinic fractions such as steam
cracked spirit of
15-45% and 0 or 1-5% butane, with aromatic contents of 5-25% such as 10-18%
olefin
contents of 2-14% and saturate contents of 70-90%.
Other blends and gasolines of the invention can contain 10-35% compound A or
A', and naphtha 30-50%, hydrocrackate 10-30% alkylate and/or isomerate 2-10%,
and
reformate 3-12%.
The present invention also provides a blend comprising component (a) and
usually
at least one motor gasoline additive, e.g. as described above, in particular
with the blend
comprising not more than 5% in total e.g. less than 1 % of hydrocarbon of by
more than
160°C, and preferably less than 5%, e.g. less than 4% of triptane or
223 trimethyl
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
pentane. Examples of component (a) are described above, but it is preferably
an alkylate
cut, in particular a cut of 15-100°C.
The invention can provide gasolines e.g. motor or aviation gasoline, in
particular of
91, 95, 97, 98 RON values, with desired high Octane Levels but low emission
values on
combustion in particular of at least one of total hydrocarbons, NOx, carbon
monoxide,
and carbon dioxide, especially of both total hydrocarbons and carbon dioxide.
Thus the
invention also provides the use of a component (a) particularly a compound A
or A' e.g.
A3, 4, 6 or 9 or an alkylate cut of 15-160°C e.g. bpl5-100°C
especially 15-60°C or 90-
106 in unleaded gasoline e.g. motor or aviation gasoline of MON at least 80
e.g. 80 to
less than 98, e.g. as an additive to or component therein, to reduce the
emission levels on
combustion, especially of at least one of total hydrocarbons, NOx, carbon
monoxide and
carbon dioxide especially both of total hydrocarbons and carbon dioxide. The
invention
also provides a method of reducing emissions of exhaust gases in the
combustion of
unleaded gasoline e.g. motor or aviation gasoline fuels of MON of at least 80
which
1 S comprises having at least 10% component (a), in particular a compound A or
A' e.g.
A3, 4, 6 or 9 or an alkylate cut of by I S-160°C or I S-100°C
especially 15-60°C or 90-
106°C present in the fuel which is a gasoline of the invention. The
invention also
provides use of an unleaded gasoline of the invention in a spark ignition
combustion
engine to reduce emissions of exhaust gases. The compositions of the invention
may be
used in supercharged or turbocharged engines, or in normally aspirated ones.
The
component (a), preferably a compound A or an alkylate cut of by 15-
160°C or by 15-
100°C especially 1 S-60°C or 90 to 106°C can reduce one
or more of the above emission
levels better than amounts of alkylate or a mixture of aromatics and oxygenate
at similar
Octane Number and usually decrease the fuel consumption as well.
Automobile exhaust emissions vary very much depending on the vehicle
technology and whether the engine is hot or cold, even with engines whose
exhaust gases
pass through a catalytic converter before reaching the outside environment. In
a cold
engine, the effects of friction, lubricants and the nature of fuel
vapourisation among
others, differ from those with a hot engine in an unpredictable way, and it is
with cold
engines that most tailpipe emissions are produced, because of enriched
fuelling and, for
those vehicles with catalytic converters, because the catalytic converter
becomes
increasingly effective at reducing emissions when it becomes hot. For the
latter vehicles
26
CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
as well, a Lambda sensor upstream of the converter controls the fueUair ratio
entering
the engine, but this is not effective with a cold engine (resulting in an
unregulated fuel/air
ratio). It is only after the cold start period that the sensor quickly becomes
eB'ective,
(resulting in a regulated fueUair ratio), even when the catalyst is not yet
hot enough to be
effective. Thus cold start operations are different from hot running
operations and yet
contribute to a large amount of tailpipe emissions. The period of cold start
relates to a
period of time or distance, which may vary, depending on how the car is driven
and/or
ambient conditions e.g. up to 2 km or 4 or 2 min, or a temperature at which
the engine
coolant (e.g. radiator water temperature) is below SO°C. The car engine
may also be
deemed cold if it has not been operated for the previous 4hr before start,
usually at least
6hr before start.
Gasolines of the invention with component [a], especially one which is a
stream
obtained by or obtainable by distillation as a cut of B.Pt. 15-100C, give
reduced
emissions on cold start compared to base fuel.
1 S Thus the present invention also provides of method of reducing emissions
of
exhaust gases in the combustion of unleaded gasoline fuels of MON of at least
80 e.g. 80
to less than 98 from cold start of a spark ignition combustion engine, which
comprises
having a component[a] present in the fuel which is a gasoline of the
invention. In the
compositions, gasolines, methods and uses of the invention the component (a)
is
preferably used in an emission-reducing effective amount, in particular at
cold start.
The gasolines of the invention may be used in internal combustion spark
ignition
engines. They may be used to power moving vehicles on land and/or sea and/or
in the
air; the invention also provides a method of moving such vehicles by
combustion of a
gasoline of the invention. The vehicle usually has a driver and especially
means to carry
at least one passenger and/or freight.
The engine sizes for motor gasoline use are usually at least 45cc e.g. 45-
10000cc
e.g. at least 200cc, such as 500-10000cc, in particular 950-2550, such as 950-
1550, or
1250-1850cc, or 2500-10000cc such as 2500-5000 or 5000-9000cc. The engines
have
at least 1 cylinder, but preferably at least 2 or 3 cylinders, e.g. 3-16,
especially 4-6 or 8
cylinders; each cylinder is usually of 45-1250cc e.g. 200-1200cc, in
particular 240-520cc
or 500-1000cc. The engines may be 2 stroke engines, but are preferably 4
stroke.
Rotary engines e.g. of the Wankel type may be used. The motor engines may be
used to
27
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
power vehicles with at least 2 wheels e.g. 2-4 powered wheels, such as motor
bicycles,
tricycles, and 3 wheeled cars, vans and motor cars, in particular those
vehicles legislated
for use on a public highway but also off road e.g. 4 wheeled drive vehicles,
sports cars
for highway use, and racing cars, including drag racing cars and track racing
cars. Power
from the engine will preferably be connected to the driving wheels via a
gearbox and
clutch system, or other form of drive train system, to achieve the transition
from a
stationary to a mobile state. The engine and drive train will best allow a
range of actual
vehicle road speed of between 1-350km/h, preferably between 5-130km/h and
allow for
continuous variation of speed thereof. The road speed of the vehicle is
usually reduced
by a braking mechanism fitted to the vehicle, the braking being generally
applied by
friction. The engine may either by air or water cooled, the air motion induced
by a
moving vehicle being used to directly, or indirectly cool the engine. The
vehicle
comprises a means to facilitate a change of vehicle direction, e.g. a steering
wheel or
stick. Usually at least 10% of the vehicle distance travelled is carried out
at greater than
1 S Skm/h.
The engines using aviation gasoline are usually in piston driven aircraft,
i.e. with at
least one engine driving a means for mechanically moving air such as at least
one
propeller. Each engine usually drives at least one propeller driving shaft
with 1 or 2
propellors. The aircraft may have 1-10 propellers e.g. 2-4. The aircraft
engines usually
have at least 2 cylinders, e.g. 2 to 28 cylinders, each of which is preferably
greater than
700cc in volume, such as 700-2000cc e.g. 13 l Occ. The total engine size is
usually 3700-
SOOOOcc e.g. 3700 to 12000cc for single or twin engined passenger light
aircraft, 12000
to 45000cc for 2 or 4 engined freight or airline use (e.g. 15-200 passengers,
such as SO
to 1 SO passengers). The engines may have an engine power to weight ratio of
at least
0.3Hp/lb wt of engine, e.g. 0.3-2Hp/lb, and may have a power to cylinder
volume of at
least 0.5 (Hp/cu.in) e.g. 0.5-2. Cylinders may be arranged in rows, V
formation, H
formation, flat ('horizontally opposed') or radially around a common propeller
drive
shaft. One or more rows/circles of cylinders may be used, e.g. flat 2, flat 4,
flat 6, V12, 2
or 3 circles of 7 cylinders etc. Every cylinder has one and more preferably at
least two
spark plugs. A gear system may optionally be used to drive the propeller and
or a
supercharger. Alternatively, an exhaust turbo charger may also be present.
Exhaust
outlets may be individual or run into a common manifold and preferably point
in the
28
W~ 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
opposite direction to forward flight. Fins may be present on the exterior of
the engine
for air cooling. Greater than 90% of the distance travelled by the engine,
when in use, is
usually spent at 500 feet or more above ground level. Typically, during
greater than
90% of the time when the engine is running, the engine operates at above I
OOOrpm e.g.
between 1000 to 3500 rpm.
The aircraft usually has at least one tank having a capacity of at least 1001,
especially with a total capacity of at least 10001.
The gasolines of the invention may be made in a refinery by blending the
ingredients to produce at least 200,0001/day of gasoline such as 1-l Omillion
1/day. The
gasoline may be distributed to a plurality of retail outlets for motor
gasoline, optionally
via wholesale or bulk outlets e.g. holding tanks, such as ones of at least 2
million 1
capacity e.g. S-15 million 1. The distribution may be by pipeline or in tanks
transported
by road, rail or water, the tanks being of at least 50001 capacity. At the
retail sites e.g.
filling station, the motor gasoline is dispensed to a plurality of users, i.e.
the drivers of
1 S the vehicles, e.g. at a rate of at least 100 or 1000 different users per
day. For aviation
use, the gasoline is usually made in a refinery to produce at least 1000
barrels per day (or
100,0001/day) such as 0.1-2 million 1/day. The avgas is usually distributed by
tanker by
road, rail or water, or pipelines directly to the airport distribution or
holding tanks, e.g.
of at least 300,0001 capacity, from whence it is distributed by pipeline or
tanker (e.g. a
mobile refuelling bowser to fuel a plurality of aircraft, e.g. at least 5/day
per tank; the
aircraft may have one or more on-board tank each of at least 1001 capacity.
The aviation gasolines of the invention comprising component (a) preferably
have
RVP of 38-49 kPa, 10-40% evaporated at 75°C, at least 50% evaporated at
105°C at
least 90% evaporated at 135°C and the sum of temperature of 10%
evaporated with that
of SO% evaporation greater than 135°C.
The present invention is illustrated in the following Examples.
Example 1
An alkylate of IBP 31.9°C and FBP 191.3°C was a refinery grade
product obtained
commercially by HF catalysed reaction of refinery grade isobutene and
isobutane. This
alkylate was then distilled according to ASTMD2892 to give a series of cuts at
the
temperatures below in Table 1 with the analyses give in % w/w for their main
components (present in at least 1 % w/w).
29
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Table 1
A B C D E F G
Temp 15-60 60-80 80-90 90-95 95-100 100-103 103-106
H J K L M N
Temp 106-110110-115115-125 125-140140-160160-FBP
Analyses
A. Butane 9.1, isopentane 74.8, n-pentane 5.9, 2,3-Dimethyl butane 5.6, 2-
Methyl
pentane 1.8.
B. Isopentane 12.9, n-Pentane 3.8, 2,3-dimethyl pentane 20.7, 2-methyl pentane
7.4,
3-methyl pentane 3.8, 2,4-dimethyl pentane 26.8, Benzene l, 2,3-dimethyl
pentane 12.2,
isooctane 8Ø
C. Isopentane 2.3, 2,3-dimethyl butane 10.4, 2-Methyl pentane 3.8, 3-Methyl
pentane
2.1, 2,4-dimethyl pentane 23.4, 2,3-dimethyl pentane 20.4, isooctane 31.5.
D. 2,3-dimethyl butane 3.5, 2-Methyl pentane 1.3, 2,4-dimethyl pentane 16.5,
2,3-
dimethyl pentane 19.9, isooctane 51.5.
E. 2,4-dimethyl pentane 7.2, 2,3-dimethyl pentane 14.3, isooctane 67.1, 2,5-
dimethyl
hexane 1.8, 2,4-dimethyl hexane 2.0, 2,3,4-trimethyl pentane 2.1, toluene 1.2,
2,3,3-
trimethyl pentane 1Ø
F. 2,4-dimethyl pentane 1.8, 2,3-dimethyl pentane 7.5, isooctane 68.2, 2,5-
dimethyl
hexane 4.1, 2,4-dimethyl hexane 4.7, 2,3,4-trimethyl pentane 6.0, toluene 1.4,
2,3,3-
trimethyl pentane 3.1, high boilers 1.3
G. 2,3-dimethyl pentane 4.5, isooctane 57.8, 2,5-dimethyl hexane 6.0, 2,2,3-
trimethyl
pentane 1.3, 2,4-dimethyl hexane 7.0, 2,3,4-trimethyl pentane 11.4, toluene
1.3, 2,3,3-
trimethyl pentane 6.3, higher boilers 3Ø
H. 2,3-dimethyl pentane 1.3, isooctane 39.5, 2,5-dimethyl hexane 7.9, 2,2,3-
trimethyl
pentane 1.7, 2,4-dimethyl hexane 9.2, 2,3,4-trimethyl pentane 20.1, toluene
1.1, 2,3,3-
trimethyl pentane 12.1, high boilers 6.9.
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WO 00/77130 PCT/GB00/02282
Isoparaffin n-ParaffinsAromatics Others
J 92% Cs - 0.6% C7
7% C9
K 58.8% Cs - 1.7% Cg
38.8% C9
7.8% C8 - 11.8% Cg Total 1.9
L 72.8% C9
5.6% Coo -
28.0% C9 Total 1.2 6.8% Cg
M 46.5% C1o 4.9% C9
12.4% C11
N 8.0% Coo Total 1.2 1.2% Cg Total 49.9%higher
37.5% C~, 1.6% C9 boilers > C1~
Examples 2 and 3
A base Fuel was blended from 3.0 parts butane, 22.0 parts full range alkylate
(as
used as feed in Ex. I ) 40 parts catalytic reformates 10 parts bisomer,75
parts of this base
fuel were blended with 25 parts of alkylate cut J to give blend Ex.2, and also
separately
with 25 parts of alkylate cut K to give blend Ex.3, and 25 parts of heavy
reformate to
give Comp. Blend.
3 Formulated gasolines were made, each containing one of the above blends and
a
I Smg/I of a phenolic antioxidant 55% minimum 2,4 dimethyl-6-tertiary butyl
phenol 15%
minimum 4 methyl-2, 6-ditertiary-butyl phenol with the remainder as a mixture
of
monomethyl and dimethyl-tertiary butyl phenols. The gasolines of Ex.2 and 3
meet the
European 2005 specification without use of oxygenates.
In each case the gasolines were tested for MON and RON, and their Reid Vapour
Pressure at 37.8°C. The results are shown in table 2, which also shows
these properties
for alkylate cuts A-M. The distillation properties of the blend Ex.2,3 and
comp. Blend
were tested according to ASTM D86 and shown in Table 3.
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WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Table 2
Boiling PointRVP ' MON Cal Val.Benz
C kPa RON Btu/lb % w/w
Comp. 35-185 59.7 102.289.4 18339 1.86
Blend
Blend 34-172 57.2 99.6 89 18734 1.95
Ex.2
Blend 32-172 57.4 99.7 88.5 18733 1.94
Ex.3
Cut A 1 S to 60 - 90.8 87.8 19433 0.14
Cut B 60 to 80 - 88.8 86.3 19088 1.07
Cut C 80 to 90 - 91.2 89.7 19044 0.67
Cut D 90 to 95 - 93.5 92.6 19010 0.33
Cut E 95 to 100 - 95.5 94.8 18968 0.08
Cut F 100 to 103 - 95.7 94.8 18935 0.01
Cut G 103 to 106 - 94.9 93.6 18958 0.00
Cut H 106 to 110 - 94.2 92.0 19010 0
Cut J 110 to 115 - 91.8 87.8 19156 0.01
Cut K 115 to 125 - 92.2 85.8 19157 0.01
Cut L 125 to 140 - - - 18949 0
Cut M 140 to 160 - - - 18898 0
Cut N 160 to FBP - - - 19005 0
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CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
Table 3
Comp. BlendEx.2 Ex.3
Initial Boiling Point 34.7 34.2 31.6 deg
C C
OS % Recovered 56.4 57.9 57.1 deg
C
% Recovered 68.6 68.7 68.6 deg
C
% Recovered 87.4 84.4 85.1 deg
C
% Recovered 101.8 94.7 96.0 deg
C
% Recovered 113.8 101.5 103.5 deg
C
% Recovered 124.9 107.1 109.3 deg
C
% Recovered 135.5 1 11.6 I 14.1 deg
C
% Recovered 145.1 116.1 118.8 deg
C
% Recovered 154.5 122.1 124.8 deg
C
% Recovered 165.0 137.8 137.5 deg
C
% Recovered 173.9 155.4 154.2 deg
C
Final Boiling Point 185.2 171.9 171.6 deg
C C
Loss % Vol 2.3 1.4 1.3 % vol
Recovery % Vol 96.6 97.3 97.5 % vol
Residue % Vol 1. I 1.3 1.2 % vol
Evaporated Volume @ 12.7 11.9 11.9 -
70C
Evaporated Volume @ 30.5 38.5 36.1 -
100C
Evaporated Volume @ 77.1 94.9 95.2 -
150C
RVP k Pa - 57.2 57.4 -
Density kg/1 - 0.7415 0.7423
Example 4
The emission characteristics on combustion of the formulated gasolines of
comp.
5 Blend, Ex.2 and 3, and the cuts A-N were compared.
The fuels were tested in a single cylinder research engine at a speed/load of
SO/14.3
rps/Nm with a LAMBDA setting of 1.01, and the ignition setting was optimized
for the
comparative blend. The emissions of CO, CO2, total hydrocarbons, Nox, were
measured
from the exhaust gases. The results were averaged. The results were as follows
as
33
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
shown in Table 4 expressed as the change in emissions compared to comp. Blend
and in
addition the percentage gravimetric change in the Fuel Consumption.
Table 4
Ex. CO COz THC Nox Consumption
Comp 0.0% 0.0% 0.0% 0.0% 0.0%
2 -3.1% -4.1% -4.0% -3.7% -2.3%
3 -3.0% -3.1% -3.1% -2.5% -2.1%
A -38.6% -10.8% -33.1% -11.3% -7.2%
B -31.4% -9.1% -17.7% -14.5% -6.1%
C -21.9% -9.7% -10.5% -18.2% -5.7%
D -18.4% -8.9% -8.1% -19.3% -5.3%
E -9.4% -9.2% -4.0% -22.1 -4.9%
%
F -4.1% -9.3% -1.7% -22.2% -4.8%
G -5.1% -9.7% 0.6% -20.7% -S.5%
H 2.0% -9.3% 0.9% -18.7% -5.0%
J -3.0% -9.0% -5.0% -18.0% -5.4%
K -3.2% -9.2% 1.4% -16.7% -5.5%
L 0.2% -6.1 3 .0% -15.0% -3 .6%
%
M -3.5% -7.2% 3.1% -18.5% -4.2%
N -1.3% -4.8% 43.7% -18.2% -1.9%
S
As the research engines were not fitted with catalysts in their exhausts, the
reductions in emissions provide an indication of the benefits of reduced
emissions
downstream of the exhaust catalyst before any exhaust catalyst has heated up
and
became operable; this corresponds to cold start condition.
Examples 5 and 6
Blends are made in the manner of Ex.2 and 3 from the base Fuel (75 parts) and
cut
A (25 parts) to give Ex.S and separately with combined cuts B-E (25 parts) to
give Ex.6.
Formulated gasolines are made as in Ex.2 and 3. They give reduced emissions
compared
to the Comp. Blend.
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WO 00/77130 CA 02375614 2001-11-29 pCT/GB00/02282
Example 7
A blend is made up with the following ingredients, steam cracked spirit 32.0%,
full
range alkylate (as the feed to Ex.l) 30%, cut A-E 10%, Reformate 11.0%,
toluene
16.0%, butane 1.0%. A formulated gasoline also contains 15mg/1 of the
antioxidant of
Ex.2/3. The properties of the fuel are as follows in Table 5
Table 5
RON 99. 8
MON 87.9
Cal Val. Btu/Ib18616
S ppm 7.3
RVP kPa 56.8
Benz % w/w 0.75
E70C I 8.9
E 100C 50.0
E 150C 93.5
E 180C 98.0 I
Aromatics 34.2
Olefins 8.2
Saturates 57.6
Oxygenates 0.0
This gasoline also gives reduced emissions.
Examples 8-11 and Comparative Ex. A
Various unleaded blends were made up with each of compounds A4, A6, A9, 225
trimethyl hexane in each case blended with various refinery streams as shown
in Table S,
as well as Comp Ex. A with heavy reformate.
6 formulated gasolines were made, each containing one of the above blends and
l5mg/1 of the phenolic antioxidant used in Ex.2-3.
In each case the gasolines were tested for MON and RON, and their Reid Vapour
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Pressure at 37.8°C. The results are shown in table 5, which also shows
their analyses
and distillation profile (according to ASTM D86).
The emission characteristics on combustion of the formulated gasolines of Ex.
8-11
and Comp. A were determined.
The fuels were tested as in Ex. 4 in a single cylinder research engine at a
speed/load of 20/7/2rps/Nm with LAMBDA setting of 1.01, and the ignition
setting was
optimised for the comparative blend A. The emissions of CO, COZ total carbon
oxides,
total hydrocarbons, NoX were measured from the exhaust gases as was the Fuel
Consumption (expressed in g/hlWhr). The results were averaged and compared to
the
comparative Ex.A. The degrees of change were as given in Table 6.
20
30
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CA 02375614 2001-11-29
WO 00/77130 PCT/GB00/02282
Table 5
Comp 8 9 10 11
A
Base
Fuel
Formulation % v/v
Butane 3 3 3 3 3
Full range catalytically20 20 20 20 20
cracked spirit
Alkylate 40 40 40 40 40
Light hydrocracked 7 7 7 7 7
spirit
Full range steam 10 10 10 10 10
cracked spirit
Heavy reformate 20
2,2,5-Trimethylhexane 20
(A 17)
2,2,4-Trimethylpentane 20
(A4)
2,3,3-Trimethylpentane 20
(A6)
2,3,4-Trimethylpentane 20
(A9)
Density kg/1 0.74870.7159 0.71220.7192 0.7176
C:H 1 : 1 : 1:2.0901 : 1:2.091
1.889 2.085 2.091
C% w/w 86.4 85.2 85.17 85.16 85.16
H% w/w 13.6 14.8 14.83 14.84 14.84
RON 97.0 96.6 97.8 97.1
MON 86.3 87.0 86.9 86.2
RVP kPa 54.7 57.1 56.1 56.1
T10% C 52.9 56.3 57.2 57.2
T50% C 107.0 93.6 97.7 97.4
T90% C 166.1 146.3 146.3 146.3
Benzene % v/v 0.6 0.6 0.6 0.6 0.6
Aromatics % v/v 29.4 9.4 9.4 9.4 9.4
(Olefins % v/v 9.0 9.0 9.0 9.0 9.0
37
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
0
O ~T~ M
i
0 0 0
O
z
U o o v o
0
E-~ o
. .
_
y o so 0
O O '~t~D N O
U p N N N '~t
N
w
a
N
O p o0O o0
O
U p N M fV
~t
i i ~ i O
cd
N
4.
\ \
O o 00O ~ O
U o ,~~ ,-. ..c
~
.-.,--.N ,-. V
0
N
O
d
c -b
~ o ,-.~ ~,
0
W U con
w
38
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Examples 12-23
Blends were made up from the following ingredients, butane, full boiling range
alkylate (as used in the feed in Ex. 1) catalytic reformate, light
hydrocrackate full boiling
range steam cracked spirit, naphtha, straight run gasoline full range
catalytically cracked
S spirit and 2,2,4 trimethyl pentane. In addition most of the blends contained
one or more
alkylate cuts as described in Ex. 2 and 3. The analyses of the blends and
their properties
were as shown in Table 7.
15
25
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W~ 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Table 7
EXAMPLE 12 13 14 15 16 17
Butane 0.99 1.87 4.09 2.68 5.37 5.66
Full ran a alk late 20 20 9.35 10 10 10
Catal is reformate 16.72 4.5 12.83 17.44 21.16 15.38
Li ht h drocrackate
Full range stream 47.69 53.63 35.1 42.52 16.05 20
cracked
s irit
Na htha 3.39 0.76
Strai ht run asoline 0.97
Full range catalytically 2.93
cracked s irit
224 Trimeth 1 entane 14.6 20 1.26
A1 late cut 1 S to
60 C
A1 late cut 60 to
80C
A1 late cut 80 to
90C
Al late cut 90 to 38.63
95C
A1 late cut 95 to 27.36
100C
Alk late cut 100 to 42.77
103C
Alk late cut 103 to 44.3
106C
Alk late cut 106 to
110C
Alk late cut 110 to
115C
Alk late cut 11 S
to 125C
Pro erties
RON 99.2 99.1 98 98.8 98 98
MON 87 87 87 87 88.4 87.9
RVP kPa 60 60 60 60 60 60
Eva 70C %v/v 30.2 32.4 28.7 28.2 16.5 16.3
Eva 100C %v/v 52.5 56.5 60 54.4 49 49
Eva t 150C %v/v 93.7 94.8 98.5 96.3 100 99.8
Eva 180C %v/v 97.9 98 98.6 98.2 100 99.8
Densit k 1 0.74040.73010.7254 0.73760.726 0.7236
Benzene % w 1 0.51 0.76 1 1 0.78
Aromatics % w 27.8 22.2 20.8 26.4 19.9 17.9
Olefins % w 12.4 13.9 9.1 11.1 4.7 6.4
The blends give reduced emissions on combustion.
W~ X0/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Table 7 (continued)
EXAN1I'LE 18 19 20 21 22 23
Butane 4.56 3.03 4.06 1.13
Full ran a al late 17.54 22.3 19.93 1.76 5.29
S
Catal is reformate 8.51 17.18 12.17 18.06 21.03 1.81
Li ht h drocrackate 19.75
Full range stream 32.85 30.29 29.8 38.12 17 26.15
cracked
s irit
Na htha 0.79
Strai ht run asoline
Full range catalytically 2.98
cracked s irit
224 Trimeth 1 entane
A1 late cut 15 to S 12.34
60 C
A1 late cut 60 to 5 S
80C
Al late cut 80 to
90C
A1 late cut 90 to 5 5 32
95C
Al late cut 95 to 5 5 32.69 39.1
100C
Alk late cut 100 to 5 9.04
103C
A1 late cut 103 to 3.44 2.15 5
106C
A1 late cut 106 to 33.1
110C
Al late cut 110 to 10 15
115C
Al late cut 115 to 10
125C
Pro erties
RON 98 98 98 98.7 98 98
MON 87 87 87 87 87.9 87
RVP kPa 60 60 60 60 60 60
Eva 70C %v/v 20.5 22.6 21.4 30.4 27.8 22.1
Eva 100C %v/v 49 49 49 59.3 59.4 54.4
Eva 150C %v/v 98.4 96.4 97.3 98 100 99.7
Eva 180C %v/v 100 99.2 99.7 98.5 100 99.8
Densit k 0.725 0.731 0.7253 0.73340.7219 0.7295
Benzene % w 0.56 0.92 0.7 1 1 1
Aromatics % w 17.2 21.8 18.5 25.2 20.3 22
Olefins % w 8.5 7.9 7.7 9.9 5.6 6.8
The blends give reduced emissions on combustion.
41
WO 00/77130 CA 02375614 2001-11-29 PCT/GB00/02282
Examples 24-28
Blends were made up from the following ingredients, butane, full boiling range
alkylate (as used in the feed in Ex. 1 ) catalytic reformate, full boiling
range steam
cracked spirit, naphtha. In addition the blends contained two or more alkylate
cuts as
described in Ex. 2 and 3. The analyses of the blends and the properties were
as shown in
Table 8.
Table 8
Example 24 25 2G 27 28
Butane 0.14 I .76
Full ran a alk late 37.7 28.47 17.19 23.81
Catal is reformate 11.12 12.64 19.4 8.97 2.03
Full range stream 23.57 28.75 28.59 24.17 44.56
cracked
s irit
Na htha 13.05 13.41
Alk late cut 15 to 5 5 S
60 C
Alk late cut 60 to 5 5 S 5 5
80 C
Al late cut 80 to 10 10 10
90 C
Alk late cut 90 to
95 C
Alk late cut 95 to
100 C
Alk late cut 100
to 103 C
Alk late cut 103
to 106 C
Alk late cut 106
to 110 C
Alk late cut 110 17.61 I S 3 .06 S
to 115 C
Alk late cut 115 S I 5 1 S 15
to 125 C
Pro erties
RON 96.7 96.9 97.3 93 93
MON 86.3 85.8 85.7 83 81.2
RVP kPa 60 60 60 52.8 56.8
Eva 70 C %v/v 24.1 24.9 22.9 20.9 30.2
Eva 100 C %v/v 49 49 49 49 56.5
Eva 150 C %v/v 95.5 95.2 95.3 95.1 95.3
Eva 180 C %v/v 99.5 100 100 100 100
Densit k I 0.72 0.72570.73360.7254 0.7293
Benzene % w 0.62 0.71 1 0.53 0.35
(Aromatics % w 15.6 18.4 22.6 15.6 18.6
'Olefins % w 6.1 7.5 7.5 6.3 11.5
The blends give reduced emissions on combustion.
42
