Fuel and related compositions – Liquid fuels – Aluminum or heavy metal – other than lead – containing
Reexamination Certificate
1997-10-27
2002-12-03
Medley, Margaret (Department: 1714)
Fuel and related compositions
Liquid fuels
Aluminum or heavy metal, other than lead, containing
C044S363000, C044S364000, C044S366000, C044S369000, C044S433000, C044S434000
Reexamination Certificate
active
06488724
ABSTRACT:
The invention relates to an additive for improving the properties of heavy oils and to heavy oils containing this additive.
Heavy oils are obtained in the processing of petroleum types (crude oils) and are residues of processing operations such as distillation and atmospheric pressure or reduced pressure, thermal or catalytic cracking and the like. From the chemical viewpoint, these residual furnace fuels or residual engine fuels (bunker C oils) essentially comprise paraffinic, naphthenic and aromatic hydrocarbons, some of high molecular weight. The high molecular weight components, also termed asphaltenes, are not present in dissolved form, but in a more or less dispersed form, which gives rise to numerous problems. Thus, asphaltenes and likewise other poorly soluble or insoluble compounds (for example oxygen compounds, nitrogen compounds and sulfur compounds) and products of ageing, in the absence of effective dispersants, separate out from the oil phase, forming an extremely undesirable two-phase system. In the presence of water, or even only moisture, in addition, sludge formation can occur. All these higher-molecular weight compounds and contents in the heavy oil, in addition, adversely affect the oil combustion process, for example owing to intensified soot formation.
Heavy oils, in particular in the form of heavy fuel oils (Marine Fuel Oils) and of mixtures of heavy fuel oils and heavy distillates (Inter Fuel Oils) are used in large amounts, primarily as furnace fuel in industrial plants and power stations and as engine fuel for relatively slow-burning internal combustion engines, in particular marine engines. In the prior art, therefore, numerous proposals have already been made for additives which are intended to exclude the disadvantageous properties described of the heavy furnace fuel oils and engine fuel oils, that is, in particular, the formation of two phases by asphaltenes and other higher-molecular weight fractions, sludge formation and the impairment of combustion.
Thus, FR-A-2 172 797 describes basic iron salts of organic acids and FR-A-2 632 966 describes a mixture of iron hydroxide and a basic calcium soap as auxiliaries to enhance the combustion of heavy oils. U.S. Pat. No. 4,129,589 recommends highly basic and oil-soluble magnesium salts of sulfonic acids as oil additives. The more recent publication EP-A-476 196 describes, as oil additive, a mixture essentially comprising (1) at least one oil-soluble carbonyl manganese compound, (2) at least one oil-soluble neutral or basic alkali metal salt or alkaline earth metal salt of an organic acid component and (3) at least one oil-soluble dispersant selected from the group consisting of the succinimides. In addition, mention may also be made of U.S. Pat. No. 5,421,993, which describes alkoxylated fatty amines and fatty amine derivatives as corrosion inhibitors, demulsifiers and pour point depressants for crude oils.
It has now been found that the combination of alkoxylated fatty amine compounds and organic metal salts is a particularly effective additive for heavy oils, in particular with regard to emulsifying and/or dispersing asphaltenes, sludge and the like and also with regard to improving oil combustion.
The additive according to the invention essentially comprises
a) 1 to 99% by weight, preferably 20 to 80% by weight, and in particular 40 to 60% by weight, of at least one amine compound of the formula (I) below
in which
n is 1, 2, 3 or 4,
A is a radical of the formulae (II) to (V)
where R is a C
6
to C
22
alkyl, preferably a C
6
to C
18
alkyl, and m is 2, 3 or 4, preferably 2 or 3,
x is a number from 5 to 120, preferably 10 to 80,
R
1
is H, CH
3
or H and CH
3
, where the oxyalkylene radicals are arranged randomly or in blocks, and
b) 1 to 99% by weight, preferably 20 to 80% by weight, and in particular 40 to 60% by weight, of at least one oil-soluble or oil-dispersible neutral or basic metal salt compound containing a metal of the first main group of the Periodic Table of the Elements, of the second main group, of the first subgroup, of the second subgroup, of the fourth subgroup, of the sixth subgroup, of the eighth subgroup or of the lanthanide group (rare earth metals) of the Periodic Table of the Elements and a carboxylic acid, sulfonic acid, acid ester of phosphoric acid or acid ester of sulfuric acid containing a hydrocarbon radical of in each case 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms, as acid component, percentages by weight based on the additive.
Component a) of the additives according to the invention is an amine compound in accordance with formula (I). These alkoxylated fatty amines and fatty amine derivatives are prepared by conventional alkoxylation methods, by reacting an amine in accordance with radical A in formula (I) with x mol of ethylene oxide alone (R
1
is H and the polyoxyalkylene radical comprises ethylene oxide units) or with x mol of propylene oxide alone (R
1
is CH
3
and the polyoxyalkylene radical comprises propylene oxide units) or with x mol of ethylene oxide and propylene oxide simultaneously or in succession (R
1
is H and CH
3
and the polyoxyalkylene radical comprises ethylene oxide and propylene oxide units which are present in a random distribution or in blocks). The reaction is generally carried out at a temperature of 100 to 180° C. in the presence or absence of an alkali or acid alkoxylation catalyst in the absence of air. Preferred amine compounds as component a) correspond to the formula (VI) below
in which
n
is 1, 2, 3 or 4,
A
is a radical of the above specified
formulae (II) to (V),
a
is a number from 5 to 30, preferably 8 to 20,
b
is a number from 5 to 50, preferably 10 to 30, and
c
is a number from 0 to 40, preferably 0 to 20.
The amine compounds of the formula (VI) and their preparation are described extensively in U.S. Pat. No. 5,421,993 mentioned at the outset, which is herein incorporated by reference. They are obtained by alkoxylation of amines of the specified formula (II) to (V), initially with ethylene oxide, and then with propylene oxide, with addition of bases such as alkali metal hydroxides. The reaction is performed in stages at a temperature of preferably 100 to 160° C. The amount of catalyst/base used is generally 0.5 to 3.0% by weight, based on the starting amine used. The molar amount of ethylene oxide and propylene oxide per mol of starting amine corresponds to the specified values of a and b and the values of c. In detail, reference is made to said U.S. Pat. No. 5,421,993. The following summary gives examples of suitable amine compounds (a
1
to a
6
) according to Formula (I) as component a):
TABLE 1
Formula (I)
Compound
A
R
a
b
c
a
1
II
C
14
to C
18
alkyl unsaturated
22
33
0
a
2
III
C
14
to C
18
alkyl unsaturated
6
9
0
a
3
V
C
14
to C
18
alkyl unsaturated
22
33
0
a
4
IV
C
14
to C
18
alkyl unsaturated
22
33
0
a
5
III
C
14
to C
18
alkyl unsaturated
12
28
25
a
6
III
C
14
to C
18
alkyl unsaturated
12
28
15
Preferred metals in the metal salt compound of the component b) are the alkali metals or alkaline earth metals (first and second main group of the Periodic Table of the Elements), copper or silver (first subgroup), zinc or cadmium (second subgroup), titanium or zirconium (fourth subgroup), molybdenum, chromium or tungsten (sixth subgroup), iron, cobalt or nickel (eighth subgroup) and lanthan, cerium or ytterbium (lanthanide group). Particularly preferred metals are the alkaline earth metals, such as barium, beryllium, calcium or magnesium, copper, zinc, zirconium, molybdenum, iron, nickel, cerium or ytterbium.
Preferred acids in the metal salt compound of the component b) are aliphatic carboxylic acids having 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms. The aliphatic radical can be unbranched or branched, saturated or unsaturated. The aliphatic carboxylic acids are preferably fatty acids having 8 to 40 carbon atoms, preferably 12 to 30 carbon atoms. The aliphatic carboxylic acids and fatty acids can be of synthetic or natural type, and they can be present as such or as a mixture of
Byström Hakan
Feustel Michael
Hertel Günther
Richards Geoffrey
Clariant GmbH
Hanf Scott E.
Jackson Susan S.
Medley Margaret
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