U.S. patent application number 12/171560 was filed with the patent office on 2010-01-14 for fuel composition with enhanced low temperature properties.
This patent application is currently assigned to Innospec Fuel Specialties, LLC. Invention is credited to Jack Burgazli, Jerry Burton, Dave Daniels.
Application Number | 20100005706 12/171560 |
Document ID | / |
Family ID | 41503843 |
Filed Date | 2010-01-14 |
United States Patent
Application |
20100005706 |
Kind Code |
A1 |
Burgazli; Jack ; et
al. |
January 14, 2010 |
FUEL COMPOSITION WITH ENHANCED LOW TEMPERATURE PROPERTIES
Abstract
Disclosed herein is a fuel oil composition comprising a
renewable fuel or a blend of petroleum based fuels with renewable
fuels, also containing an additives composition to enhance the base
and combined fuel's resistance to forming insoluble particulates
upon storage at diminished operating temperatures. Further
described is the additive package used to inhibit particulate
formation.
Inventors: |
Burgazli; Jack; (Middletown,
DE) ; Burton; Jerry; (Helsby Cheshire, GB) ;
Daniels; Dave; (Highlands Ranch, CO) |
Correspondence
Address: |
BURNS & LEVINSON, LLP
125 SUMMER STREET
BOSTON
MA
02110
US
|
Assignee: |
Innospec Fuel Specialties,
LLC
Newark
DE
|
Family ID: |
41503843 |
Appl. No.: |
12/171560 |
Filed: |
July 11, 2008 |
Current U.S.
Class: |
44/308 ;
44/300 |
Current CPC
Class: |
C10L 1/191 20130101;
C10L 1/1824 20130101; Y02E 50/13 20130101; C10L 1/1852 20130101;
C10L 1/2387 20130101; C10L 1/026 20130101; C10L 1/1985 20130101;
C10L 1/224 20130101; C10L 1/2225 20130101; Y02E 50/10 20130101;
C10L 1/238 20130101; C10L 10/14 20130101; C10L 1/2383 20130101;
C10L 1/2222 20130101; C10L 1/143 20130101; C10L 1/1826 20130101;
C10L 1/231 20130101; C10L 1/1963 20130101 |
Class at
Publication: |
44/308 ;
44/300 |
International
Class: |
C10L 1/18 20060101
C10L001/18; C10L 1/00 20060101 C10L001/00 |
Claims
1) A fuel oil composition comprising; a) a petroleum based
component; b) a renewable based component; and c) a particulate
inhibiting additive composition.
2) The composition of claim 1, wherein said petroleum based
component is selected from the group consisting of a middle
distillate fuel, a jet fuel, and a Fischer-Tropsch fuel.
3) The composition of claim 1, wherein said petroleum based
component comprises less than about 500 ppm by mass of sulfur.
4) The composition of claim 3, wherein said petroleum based
component comprises less than about 15 ppm by mass of sulfur.
5) The composition of claim 1, wherein said petroleum based
component is present in the fuel oil composition between about 0.1%
to about 99.9% v/v of fuel oil composition.
6) The composition of claim 1, wherein said petroleum based
component is present in the fuel oil composition between about 1%
to about 98% v/v of fuel oil composition.
7) The composition of claim 1, wherein said petroleum based
component is present in the fuel oil composition between about 2%
to about 95% v/v of fuel oil composition.
8) The composition of claim 1, wherein said petroleum based
component is present in the fuel oil composition between about 2%
to about 80% v/v of fuel oil composition.
9) The composition of claim 1, wherein said petroleum based
component is present in the fuel oil composition between about 2%
to about 50% v/v of fuel oil composition.
10) The composition of claim 1, wherein said renewable based
component is selected from the group consisting of a product
produced from the trans esterification of naturally occurring whole
oils derived from plants or animals, with an alcohol; or from the
esters formed by reacting a fatty acid derived from a naturally
occurring oils with an alcohol.
11) The composition of claim 10, wherein said naturally occurring
oils are selected from the group consisting of Soy, Palm, Palm
Kernel, Jetropha, Rapeseed, Linseed, Coconut, Corn, Cotton,
Cooking, Sunflower, Safflower, Tallow, Lard, Yellow Grease, Fish
Oils and combinations thereof.
12) The composition of claim 10, wherein said naturally occurring
oil is Rapeseed or blends thereof with other naturally occurring
oils.
13) The composition of claim 10, wherein said naturally occurring
oil is or blends thereof with other naturally occurring oils.
14) The composition of claim 10, wherein said alcohol is selected
from the group consisting of linear, branched, alkyl, aromatic,
primary, secondary, tertiary, and polyols.
15) The composition of claim 1, wherein said renewable based
component is present in the fuel oil composition between about 0.1%
to about 99.9% v/v of fuel oil composition.
16) The composition of claim 1, wherein said renewable based
component is present in the fuel oil composition between about 1%
to about 50% v/v of fuel oil composition.
17) The composition of claim 1, wherein said renewable based
component is present in the fuel oil composition between about 2%
to about 25% v/v of fuel oil composition.
18) The composition of claim 1, wherein particulate inhibiting
additive composition comprises one or more of: a) Agglomeration
Retarder b) Particulate Dispersants c) Particulate Settling
Inhibitor or d) Compatibility Enhancer
19) The composition of claim 18, wherein said Agglomeration
Retarder is prepared from monomers selected from the group
consisting of monomers represented by general formulas I and II:
##STR00009## wherein: R=a hydrogen atom, or an optionally
substituted hydrocarbon group having from 1 to 30 carbon atoms;
R.sup.1=H, or an optionally substituted hydrocarbon group having
from 1 to 30 carbon atoms; R.sup.2=a hydrogen atom, or an
optionally substituted C.sub.1-8 alkyl group; and R.sup.3=a
hydrogen atom, or an optionally substituted C.sub.1-8 alkyl group;
or R.sup.2 and R.sup.3 together with the connected carbon atom
represent an optionally substituted cycloalkyl or cycloalkylene
ring having 5-20 carbon ring atoms; ##STR00010## wherein: R=a
hydrogen atom, or an optionally substituted hydrocarbon group
having from 1 to 30 carbon atoms R', R''=a hydrogen atom or an
optionally substituted, C.sub.1-8 alkyl group R.sup.1=H, or an
optionally substituted hydrocarbon group having from 1 to 30 carbon
atoms x=between 0-5 n=between 1 and 100.
20) The composition of claim 1 9, wherein the proportions of the
monomers selected from the general formula I is 100% of the
polymer.
21) The composition of claim 19, wherein the proportions of
monomers selected from the general formula II is 100% of the
polymer.
22) The composition of claim 19, wherein the proportions of
monomers selected from the general formula I and II can be varied
to meet required properties, with the total adding up to 100%.
23) The composition of claim 18, wherein said Agglomeration
Retarder is present in the particulate inhibiting additive
composition between about 0.0% to about 80.0 % v/v of the additive
composition,
24) The composition of claim 18, wherein said Agglomeration
Retarder is present in the particulate inhibiting additive
composition between about 0.1% to about 70.0% v/v of the additive
composition.
25) The composition of claim 18, wherein said Agglomeration
Retarder is present in the particulate inhibiting additive
composition between about 10.0% to about 65.0% v/v of the additive
composition.
26) The composition of claim 18, wherein said Agglomeration
Retarder is present in the particulate inhibiting additive
composition between about 20.0% to about 60.0% v/v of the additive
composition.
27) The composition of claim 18, wherein said Particulate
Dispersant is selected from the group consisting of: (i)
substituted amines (ii) acylating nitrogen compound, and (iii)
nitrogen-containing condensates of a phenol and an aldehyde.
28) The composition of claim 18, wherein said Particulate
Dispersant is a hydrocarbyl Amine.
29) The composition of claim 18, wherein said Particulate
Dispersant is an aromatic amine or an aromatic polyamines.
30) The composition of claim 18, wherein said Particulate
Dispersant is a poly amine or polyamine alkoxylate.
31) The composition of claim 18, wherein said Particulate
Dispersant is derived from combination of a carboxylic acid
acylating agent and an amino compound to form an imido, amido,
amidine or acyloxy ammonium compound.
32) The composition of claim 31, wherein said acylating agent and
said an amino compound contain from about 10 to 200 carbon
atoms.
33) The composition of claim 31, wherein said acylating agent and
said an amino compound contain from about 20 to 100 carbon
atoms.
34) The composition of claim 18, wherein said Particulate
Dispersant is a combination of any two or more of a substituted
amine, an acylated nitrogen compound, and nitrogen-containing
condensates of a phenol and an aldehyde.
35) The composition of claim 18, wherein said Particulate
Dispersants is present in the particulate inhibiting additive
composition between about 0.0% to about 70.0% v/v of the additive
composition.
36) The composition of claim 18, wherein said Particulate
Dispersants is present in the particulate inhibiting additive
composition between about 0.1% to about 60.0% v/v of the additive
composition.
37) The composition of claim 18, wherein said Particulate
Dispersants is present in the particulate inhibiting additive
composition between about 10.0% to about 55.0% v/v of the additive
composition.
38) The composition of claim 18, wherein said Particulate
Dispersants is present in the particulate inhibiting additive
composition between about 20.0% to about 50.0% v/v of the additive
composition.
39) The composition of claim 18, wherein said Particulate Settling
Inhibitor is selected from the group consisting of: i) hydrocarbon
polymers, ii) oxyalkylene polymers, and iii) Nitrogen containing
polymers,
40) The composition of claim 39, wherein said hydrocarbon polymers
is selected from the group consisting of polymers represented by
the general formula: ##STR00011## wherein R=H, hydrocarbyl, or
hydrocarbylene with from 1 to 30 carbon atoms, or aryl or Q; Q=R,
COOR, OCOR, COOH, or OR; S=H or Q; T=H, R, COOR, or an aryl or
heterocyclic group; U=H, COOR, OCOR, OR, or COOH; V=H, R, COOR,
OCOR, COOH, or COOH; and x and y represent mole fractions (x/y)of
monomers, preferably within the range of from about 2.5 to about
0.4.
41) The composition of claim 39, wherein said oxyalkylene polymers
is selected from the group consisting of esters, ethers and
ester/ether polymers represented by general formulas: ##STR00012##
wherein R and R' may be the same or different, and wherein R,
R'=n-alkyl-, n-alkyl-CO--, n-alkyl-O-CO(CH2)x-, or
n-alkyl-O-CO(CH2)x-CO--; D=polyalkylene; and x is an integer from 1
to 60.
42) The composition of claim 39, wherein said Nitrogen containing
polymers is selected from the group consisting of amide, imide,
imidazoline, carbamate, urea, imine, and enamine derivatives of
primary or secondary amines.
43) The composition of claim 39, wherein said Nitrogen containing
polymers is selected from the group consisting of amide, imide,
imidazoline, carbamate, urea, imine, and enamine derivatives of
polyamines.
44) The composition of claim 43, wherein said polyamines are
represented by general formulas: ##STR00013## wherein: R, R' can be
a linear alkyl, a branched alkyl containing 1 to 30 carbon atoms,
aromatic, cyclic, polycyclic, poly alkoxy, or carbonyl; R,R'
alternatively contain hetero atoms such as O, N, S, and P; R' and
R' alternatively are incorporated in a ring system containing 3-12
members; x can be 1-6; and y can be 1-6.
45) The composition of claim 18, wherein said Particulate Settling
Inhibitor is present in the particulate inhibiting additive
composition between about 0.0% to about 70.0% v/v of the additive
composition.
46) The composition of claim 18, wherein said Particulate Settling
Inhibitor is present in the particulate inhibiting additive
composition between about 0.0% to about 60.0% v/v of the additive
composition.
47) The composition of claim 18, wherein said Particulate Settling
Inhibitor is present in the particulate inhibiting additive
composition between about 10.0% to about 55.0% v/v of the additive
composition.
48) The composition of claim 18, wherein said Particulate Settling
Inhibitor is present in the particulate inhibiting additive
composition between about 20.0% to about 50.0% wt/wt of the
additive composition.
49) 49 The composition of claim 18, wherein said Compatibility
Enhancer is selected from the group consisting of: monofunctional
alcohols, glycols, polyols, esters, ethers, glycol ether acetates,
ketones, glycol ethers, amides, amines, nitro compounds and
combinations of two or more thereof.
50) The composition of claim 18, wherein said Compatibility
Enhancer is present in the particulate inhibiting additive
composition between about 0.0% to about 80.0% v/v of the additive
composition.
51) The composition of claim 18, wherein said Compatibility
Enhancer is present in the particulate inhibiting additive
composition between about 10.0% to about 80.0% v/v of the additive
composition.
52) The composition of claim 18, wherein said Compatibility
Enhancer is present in the particulate inhibiting additive
composition between about 10.0% to about 70.0% v/v of the additive
composition.
53) The composition of claim 18, wherein said Compatibility
Enhancer is present in the particulate inhibiting additive
composition between about 10.0% to about 60.0% v/v of the additive
composition.
54) The composition of claim 1 8, wherein said Compatibility
Enhancer is present in the particulate inhibiting additive
composition between about 20.0% to about 60.0% v/v of the additive
composition.
55) The composition of claim 1, wherein said particulate inhibiting
additive composition is present in the renewable component (B100)
in the range of about 200 mg/l to about 8000 mg/l; or in the fuel
oil blend (renewable fuel petroleum fuel blend) in the range of
about 200 mg/l to about 8000 mg/l based on content of the renewable
fuel component in the fuel oil blend.
56) The composition of claim 1, wherein said particulate inhibiting
additive composition is present in the renewable component (B 100)
in the range of about 500 mg/l to about 6000 mg/l; or in the fuel
oil blend (renewable fuel petroleum fuel blend) in the range of
about 500 mg/l to about 6000 mg/l based on content of the renewable
fuel component in the fuel oil blend.
57) The composition of claim 1, wherein said particulate inhibiting
additive composition is present in the renewable component (B100)
in the range of about 1000 mg/l to about 4000 mg/l; or in the fuel
oil blend (renewable fuel petroleum fuel blend) in the range of
about 1000 mg/l to about 4000 mg/l based on content of the
renewable fuel component in the fuel oil blend.
58) The composition of claim 1, further comprising one or more
additives selected from the group consisting of: (a) low
temperature operability/cold flow additives, (b) corrosion
inhibitors, (c) cetane improvers, (d) detergents, (e) lubricity
improvers, (f) dyes or markers, (g) anti-icing additives, (h)
demulsifiers/anti haze additives, (i) antioxidants, (j) metal
deactivators, (k) biocides, (l) thermal stabilizers (m) antifoaming
agents, (n) static dissipater additives, and combinations
thereof.
59) A method of retarding particulate formation in renewable fuels
and blends of renewable fuels and petroleum fuels comprising:
treating the fuel or blend with a particulate inhibiting additive
composition.
60) A method for operating an internal combustion engine using a
fuel comprising a petroleum based component, a renewable based
component, and a particulate inhibiting additive composition.
Description
FIELD OF THE INVENTION
[0001] This invention relates generally to fuel oil compositions.
The invention more specifically relates to renewable fuels, and
blends of petroleum fuels with renewable fuels, in combination with
a novel additive composition designed to diminish particulate
formation upon storage of the renewable fuel and renewable fuel
petroleum fuel blends.
BACKGROUND OF THE INVENTION
[0002] The environmental impact of burning fossil fuels is a widely
recognized global issue. There are governmental and civil
initiatives to diminishing this detrimental effect. Two of the
major initiatives which are affecting the liquid fuel industry are
the EPA regulation to limit S content of on-road fuels, and the
ever increasing awareness for the need to use renewable fuels.
[0003] In order to meet emissions and fuel efficiency goals,
automotive Original Equipment Manufacturers (OEM's) are
investigating the use of NOx traps, particulate traps and direct
injection technologies. Such traps and catalyst systems tend to be
intolerant to sulfur, this coupled with the demonstrated adverse
environmental consequences of burning sulfur rich fuels has
resulted in a global effort to reduce the sulfur content of fuels
(Reference World-Wide Fuel Charter, April 2000, Issued by ACEA,
Alliance of Automobile Manufacturers, the entire teaching of which
is incorporated herein by reference). These low sulfur and
ultra-low sulfur fuels are becoming increasingly necessary to
ensure compliance with emissions requirements over the full useful
life of the latest technological generation of vehicles.
Governments are also introducing further legislation for the
reduction in particulate matter and fuel emissions.
[0004] In the United States, the Environmental Protection Agency
(EPA) regulations require that the sulfur content of on road fuel
meet the Ultra Low Sulfur specification, specifically less than 15
ppm by mass of sulfur in the finished fuel. Similar regulations are
also in place globally.
[0005] The method most commonly utilized to reduce the sulfur
content of fuels is referred to as "hydro-treating". Hydro-treating
is a process by which hydrogen, under pressure, in the presence of
a catalyst, reacts with sulfur compounds in the fuel to form
hydrogen sulfide gas and a hydrocarbon.
[0006] Globally there is a significant desire to utilize "green" or
"renewable fuels" as a source of energy. These fuels are gaining
popularity due to various social and political factors. The effect
of petroleum fuels on carbon dioxide emissions/global warming and
the dependence on foreign sources of fuel are a few of the
prominent factors driving popular support.
[0007] Renewable fuels are gaining greater market acceptance as a
cutter stock to extend petroleum diesel market capacity. The blends
of renewable fuels with petroleum diesel are being used as a fuel
for diesel engines, utilized for heating, power generation, and for
locomotion with ships, boats, as well as motor vehicles.
[0008] The renewable cutter stock portion of a blended fuel is
commonly known as bio-diesel. Bio-diesel is defined as fatty acid
alkyl esters of vegetable or animal oils. Common oils used in
bio-diesel production are rapeseed, soya, palm, palm kernel,
tallow, sunflower, and used cooking oil or animal fats, although
more exotic oil sources such as algae derived oils or Jetropha oil
are also gaining market interest.
[0009] Bio-diesel is prepared by reacting (trans-esterification)
whole oils with alcohols (mainly methanol) in the presence of a
catalyst (acid or base), such as sodium hydroxide or sodium
methoxide. This method of preparing bio-diesel, known as the CD
process, is described in numerous patent applications (see, DE-A 4
209 779, U.S. Pat. No. 5,354,878, EP-A-56 25 04, the entire
teachings of which are incorporated herein by reference).
[0010] Bio-diesel is a legally registered fuel and fuel additive
with the U.S. Environmental Protection Agency (EPA). In order for a
material to qualify as a bio-diesel, the fuel must meet ASTM D6751
(the entire teaching of which is incorporated herein by reference)
for the United States, and EN14214 (the entire teaching of which is
incorporated herein by reference) in Europe independent of the oil
or fat used or the specific process employed to produce the
additive. The ASTM D6751 specification is intended to insure the
quality of bio-diesel to be used as a blend stock for 20% and lower
blend levels, where as EN14214 is used to ensure quality in 100%
bio diesel to be used independently as a fuel as well as Bio diesel
to be used to prepare blends with petroleum fuels.
[0011] Renewable fuels are also being produced by newer and
different processes than the traditional trans-esterification
process used to produce conventional biodiesel. Examples of these
modern processes include BTL (biomass to liquid) based on
Fischer-Tropsch GTL (gas to liquid) technology, and "next
generation" bio diesel which utilizes hydro treating of bio derived
fats and oils to produce hydrocarbon fuels. Although these
renewable fuels have many positive political and environmental
attributes, they also have certain negative characteristics which
must be taken into consideration when utilizing the material as an
alternative fuel or as a blend stock for petroleum diesel. One of
the properties which are of particular concern in the industry is
the susceptibility of renewable fuels and renewable fuel/petroleum
fuel blends to form insoluble particulates during storage.
[0012] The present invention addresses fuel industry operability
concerns related to particulate formation in renewable fuels as
well as renewable fuels/petroleum diesel blends.
BRIEF SUMMARY OF THE INVENTION
[0013] The present invention relates generally to fuel
compositions. The invention more specifically relates to novel
additive composition to inhibit particulate formation in renewable
fuels (B100) and renewable fuels/petroleum fuel (Bxx) blends, and
to methods of using such compositions.
[0014] The renewable fuel composition comprises (i) a renewable
component, and (ii) a novel additive composition.
[0015] The blended fuel composition comprises (i) a petroleum based
component, (ii) a renewable component, and (iii) a novel additive
composition.
[0016] Another aspect of the invention as described herein is the
use of additives such as (a) thermal stabilizers, (b) corrosion
inhibitors, (c) cetane improvers, (d) detergents, (e) lubricity
improvers, (f) dyes and markers, (g) anti-icing additives, (h)
demulsifiers/anti-haze additives, (i) antioxidants, (j) metal
deactivators, (k) biocides, (l) static dissipater additives, (m)
low temperature operability/cold flow additives, and (n) antifoams;
in combination with the disclosed novel additive composition; in
combination with the renewable fuel and novel additive composition;
or in combination with the renewable fuel, petroleum fuel blend and
the novel additive composition, to not only directly enhance fuel
particulate inhibition, but also other fuel properties.
[0017] Another embodiment of the present invention is directed
toward a method for operating an internal combustion engine such as
a compression-ignition engine using as fuel for the engine, a
suitable petroleum based component, a suitable renewable based
component, and the described novel additive composition.
BRIEF DESCRIPTION OF THE DRAWING
[0018] FIG. 1 is a diagram of the receiving flask, 0.7 micron glass
fiber filter and funnel as a unit.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention relates generally to fuel oil
compositions. The invention more specifically relates to one or
more renewable fuels in combination with a particulate inhibitor
additive composition, or to the blends of petroleum fuels with
renewable fuels and the particulate inhibitor additive
composition.
[0020] Petroleum Fuel
[0021] In the present embodiment, the Petroleum Fuel is a
hydrocarbon derived from refining petroleum or as a product of
Fischer-Tropsch processes (well known to those skilled in the art).
The hydrocarbon may also be a solvent. The fuel products are
commonly referred to as petroleum distillate fuels.
[0022] Petroleum distillate fuels encompass a range of distillate
fuel types. These distillate fuels are used in a variety of
applications, including automotive diesel engines and in non
automotive applications under both varying and relatively constant
speed and load conditions such as power generation, marine, rail,
farming, and construction equipment applications.
[0023] Petroleum distillate fuel oils can comprise atmospheric or
vacuum distillates. The distillate fuel can comprise cracked gas
oil or a blend of any proportion of straight run or thermally or
catalytically cracked distillates. The distillate fuel in many
cases can be subjected to further processing such as
hydrogen-treatment or other processes to improve fuel properties.
The material can be described as a gasoline or middle distillate
fuel oil.
[0024] Gasoline is a low boiling mixture of aliphatic, olefinic,
and aromatic hydrocarbons, and optionally, alcohols or other
oxygenated components. Typically, the mixture boils in the range
from about room temperature up to about 225.degree. C.
[0025] Middle distillates can be utilized as a fuel for locomotion
in motor vehicles, air planes, ships and boats as burner fuel in
home heating and power generation and as fuel in multi purpose
stationary diesel engines.
[0026] Engine fuel oils and burner fuel oils generally have flash
points greater than 38.degree. C. Middle distillate fuels are
higher boiling mixtures of aliphatic, olefinic, and aromatic
hydrocarbons and other polar and non-polar compounds having a
boiling point up to about 350.degree. C. Middle distillate fuels
generally include, but are not limited to, kerosene, jet fuels, and
various diesel fuels. Diesel fuels encompass Grades No. 1-Diesel,
2-Diesel, 4-Diesel Grades (light and heavy), Grade 5 (light and
heavy), and Grade 6 residual fuels. Middle distillates
specifications are described in ASTM D-975, for automotive
applications (the entire teaching of which is incorporated herein
by reference), and ASTM D-396, for burner applications (the entire
teaching of which is incorporated herein by reference).
[0027] Middle distillates fuels for aviation are designated by such
terms as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1. The Jet fuels are
defined by U.S. military specification MIL-T-5624-N, the entire
teaching of which is incorporated herein by reference, and JP-8 is
defined by U.S. Military Specification MIL-T83 133-D, the entire
teaching of which is incorporated herein by reference. Jet A, Jet
A-1 and Jet B are defined by ASTM specification D-1655 and Def.
Stan. 91, the entire teachings of which are incorporated herein by
reference.
[0028] The different fuels described (engine fuels, burner fuels
and aviation fuels) each have further to their specification
requirements (ASTM D-975, ASTM D-396 and D-1655, respectively)
allowable sulfur content limitations. These limitations are
generally of the order of up to 15 ppm of sulfur for On-Road fuels,
up to 500 ppm of sulfur for Off-Road applications and up to 3000
ppm of sulfur for Aviation fuels.
[0029] Renewable Fuel (B100 Fuels)
[0030] In the present embodiment, a Renewable Fuel is an organic
material that is derived from a natural, replenishable feed stock
which can be utilized as a source of energy. Suitable examples of
renewable fuels include, but are not limited to, bio-diesel,
ethanol and bio-mass. Other renewable materials are well known to
those skilled in the art.
[0031] In the present embodiment, "bio-diesel" refers to all
mono-alkyl esters of long chain fatty acids derived from vegetable
oils or animal fats.
[0032] Bio-diesel is commonly produced by the reaction of whole
oils with alcohols in the presence of a suitable catalyst. Whole
oils are natural triglycerides derived from plant or animal
sources. The reaction of whole oil with an alcohol to produce a
fatty acid ester and glycerin is commonly referred to as trans
esterification. Alternatively, bio-diesel can be produced by the
reaction of a fatty acid with an alcohol to form the fatty acid
ester.
[0033] The fatty acid segments of triglycerides are typically
composed of C.sub.10-C.sub.24 fatty acids, where the fatty acid
composition can be uniform or a mixture of various chain lengths.
The bio-diesel according to the invention may comprise single feed
sourced components, or blends of multiple feed stocks derived from
vegetable(s), or animal(s) origin. The commonly used single or
combination feed stocks include, but are not limited to, coconut,
corn, castor, jetropha, linseed, olive, palm, palm kernel, peanut,
rapeseed, safflower, sunflower, soybean, tall oil, tallow, lard,
yellow grease, sardine, menhaden, herring and used cooking oils and
fats.
[0034] Suitable alcohols used in either of the esterification
processes can be aliphatic or aromatic, saturated or unsaturated,
branched or linear, primary, secondary or tertiary, and may possess
any hydrocarbon chain having lengths from about C-1 to about C-22.
The industry and typical choice being identified as methanol.
[0035] Bio-diesel composition is established by specification
parameters set forth in international specifications such as
EN12214 and ASTM D6751 (the entire teaching of which are
incorporated herein by reference). The fatty acid ester must meet
and maintain the established specification parameters set forth in
EN14214 or ASTM D6751, regardless of the whole oil feed source or
the process utilized for its production.
[0036] ASTM D6751 specification outlines the requirements for
bio-diesel (B100) to be considered as a suitable blending stock for
hydrocarbon fuels. EN14214 specifies requirements of bio diesel to
be used as both a fuel and as a blend stock for blending with
distillate fuels.
[0037] Renewable fuel can also encompass in addition to bio diesel
products produced from hydro treatment of oils and fats, and also
products of BTL processes. These processes are well known to those
skilled in the art.
[0038] Renewable Fuel, Petroleum Fuel Blend (Bxx Fuels)
[0039] The renewable fuel and petroleum fuel can be blended in any
proportion necessary wherein the final oil blend is appropriate to
be utilized as a fuel.
[0040] In the scope of the invention, the fuel can contain about
100% renewable fuels, however, the renewable content of the blend
is typically up to about 50% by volume of the finished fuel blend,
more typically up to about 35% by volume of the finished fuel
blend, and alternatively up to about 20% by volume of the finished
fuel blend.
[0041] The invention can be practiced at high renewable fuel
concentrations, wherein the renewable fuel content is greater than
about 15% by volume of the finished fuel blend. The invention is
also applicable at renewable fuel concentrations as low as about
15, 12.5, 12, 11, and 10% by volume of the finished fuel blend, and
even at very low renewable fuel concentrations as low as about 7.5,
5, 3, 2, 1, and 0.5% by volume of the finished fuel blend.
[0042] Particulate Inhibition Analyzed
[0043] During the research and development efforts to evaluate low
temperature operability properties of renewable fuels and renewable
fuel petroleum fuel blend fuels, it was discovered that use of
certain additive compositions can have a marked effect on retarding
insoluble material formation upon storage of renewable fuels and
renewable fuel petroleum fuel blend fuels at diminished
temperatures.
[0044] The possible causes of particulate formation are not fully
understood. However, industry technical leaders in Europe and
United States postulate the particulates may be due to very low
concentration of products of incomplete trans-esterification such
as mono-, di- and triglycerides, glycerine derivatives
(glycerides), natural sterols, or even saturated fatty acid methyl
esters present in the fuel.
[0045] These materials are believed to fall out of solution during
extended storage or cooling and eventually build large enough
particles to block fuel delivery systems.
[0046] Renewable fuel producers are attempting to make
manufacturing changes to address these problems. The primary
modification in manufacturing has been to institute a cold
filtration step to remove any insoluble materials that readily
precipitate out of the renewable fuel. However these precautions
have not been fully effective in addressing all particulate forming
material in the fuel.
[0047] Based on fuel industry experience, it is assumed that the
particulate formation problems in renewable fuels (B100-100% FAME)
and renewable fuel/petroleum fuel blends (Bxx blends) maybe
attributed to the poor low temperature operability properties of
the renewable fuels and renewable fuel/petroleum fuel blends.
[0048] Historically Low Temperature Operability (LTO) of fuel is a
measure of the inherent handling and use characteristics of the
fuel at diminished temperatures. A petroleum base fuel's LTO is
estimated by its cloud point (CP), pour point (PP) and it's Cold
Filter Plugging Point (CFPP). In Canada another method, Low
Temperature Flow Test (LTFT) is also employed.
[0049] The Cold Filter Plugging Point of a fuel is the temperature
at and below which wax in the fuel will cause severe restrictions
to flow through a filter screen. CFPP is believed to correlate well
with vehicle operability at lower temperatures.
[0050] CFPP of petroleum fuels in evaluated using ASTM D6371 (the
entire teaching of which is incorporated herein by reference),
IP-309 (the entire teaching of which is incorporated herein by
reference), and EN-116 (the entire teaching of which is
incorporated herein by reference).
[0051] Low Temperature Flow Test (LTFT) is very similar in
principle and function to CFPP and is evaluated using ASTM D4539
(the entire teaching of which is incorporated herein by
reference).
[0052] The petroleum diesel filtration methods (CFPP, and LTFT) are
referred to as surrogate test methods. These methods try to predict
the behavior of the fuel with respect to actual engine operating
conditions. There is substantial industry data relating CFPP with
actual field operability. The Cloud Point or wax appearance
temperature (WAT) of a fuel is the point at which first visible
crystals are detected in the fuel. Cloud point can be evaluated
using ASTM D2500, D5771, D5772, and D5773 (visible method), the
entire teachings of which are incorporated herein by reference, and
by IP-389 (crystal formation method), the entire teaching of which
is incorporated herein by reference.
[0053] The Pour Point is a standardized term for the temperature at
which an oil, for example, mineral oil, diesel fuel or hydraulic
oil, stops flowing upon cooling. Pour point of petroleum fuels can
be evaluated using ASTM D97 (the entire teaching of which is
incorporated herein by reference), and ISO-3016 (the entire
teaching of which is incorporated herein by reference).
[0054] The petroleum diesel physical evaluation methods (PP and CP)
are methods used to evaluate the fuel low temperature
characteristics. While these methods are not directly considered as
a surrogate test for engine performance, there is a common
belief/practice in the petroleum industry, wherein the use of a
fuel's cloud point is a very conservative predictor of fuel field
operability. Specifically, if the fuel is stored and used above the
fuel's cloud point, there are rarely if any field issues
attributable to fuel low temperature properties.
[0055] The current conventional diesel fuel low temperature
operability methods while being used extensively in the fuel
industry to predict fuel handling and use properties of petroleum
fuels, have not been found to be fully applicable to detect or
predict field problems associated with filter plugging in renewable
fuels and renewable fuel petroleum fuel blends.
[0056] This failure is directly evident in the CP method. Field
issues have arisen wherein B100, or Bxx fuels stored for as little
as 24 hours at temperatures above their cloud point have resulted
in filter plugging issues attributable to insoluble particulate
formation. Commonly the use of CP of a petroleum fuel is considered
as the most conservative predictor of fuel low temperature
operability. Generally LTO problems with petroleum diesel are
rarely, if ever encountered when operating above the cloud point of
the petroleum fuels.
[0057] The inapplicability of standard petroleum test can be due to
the new particulate formation phenomenon encountered with renewable
fuels and renewable fuel/petroleum fuel blends. The new phenomenon
can be caused by different chemical species in petroleum fuels, as
compared to renewable fuels and renewable fuel/petroleum fuel
blends and also possibly the difference in particulate formation
mechanisms between petroleum fuels and renewable fuels or renewable
fuel/petroleum fuel blends.
[0058] The formation of insoluble particulates upon storage of
renewable fuels as well as renewable fuel/petroleum fuel blends
have greatly increased the complexity of field operability
properties of fuels.
[0059] It is therefore anticipated that in certain climate regions,
difficulties associated with engines, such as clogging of fuel
passages or fuel filters, may occur in normal temperature ranges of
engine operation.
[0060] While there have been low temperature operability problems
associated with desulphurization of petroleum fuels, the diminished
low temperature operability characteristic such as deteriorated
fluidity at low temperature (i.e. increased pour point and/or cold
filter plugging point) have been as a whole anticipated by the fuel
industry. Additive packages to address ULSD CFPP, CP, and PP issues
are currently available, and for the most part have been successful
in treating ULSD low temperature issues.
[0061] The new particulate formation problems encountered with
renewable fuels (B100-100% FAME) and renewable fuel/petroleum fuel
blends (Bxx blends) have not previously been recognized in the
industry, or the issues resolved by the use of currently known or
used fuel additives.
[0062] The invention disclosed herein enhances the resistance of
the renewable fuel or the renewable fuel petroleum fuel blend to
forming insoluble particulates during extended storage or low
temperature operation.
[0063] Particulate Inhibitor Additive Composition
[0064] In the context of this invention, Agglomerates are defined
as union of similar or dissimilar materials to form a large mass.
Conglomerates are defined as a union of agglomerates to form a
larger mass. Particulates are defined as a union of conglomerates
and agglomerates to form an even larger mass.
[0065] An embodiment of the invention is the use of an additive
composition to inhibit agglomeration, conglomeration and
particulate formation in renewable fuels, and in mixtures of
renewable fuels and petroleum fuels
[0066] The novel additive composition selected to inhibit
agglomeration, conglomeration and particulate formation in fuels is
composed of a combination of any one of the material consisting of
i) Agglomeration Retarders, ii) Particulate Dispersants, iii)
Particulate Settling Inhibitor, and iv) Compatibility
Enhancers.
[0067] Agglomeration Retarders
[0068] Agglomeration Retarders are materials which inhibit the
initial association of hydrocarbon oxygenates like Fatty acid
Methyl Esters (FAME) as contained in bio diesel with other FAME's
for B100 fuels, and in the case of blended fuel, the association of
FAME components with other FAME's or with hydrocarbon or paraffin
components in petroleum fuels. The inhibition results in a
retardation of the rate of association of molecules required to
form agglomerates.
[0069] The Agglomeration Retarders utilized in the formulation are
selected from a group consisting of polymers derived from
derivatized acrylic acid monomers,
[0070] An embodiment of the invention is an Agglomeration Retarder
consisting essentially of homopolymers or co polymers of acrylic
acid, or acrylic acid derivatives.
[0071] The monomers which can be utilized to prepare the acrylate
polymers are selected from the group described by general formulas
I and II.
##STR00001##
wherein [0072] R=a hydrogen atom, or an optionally substituted
hydrocarbon group having from 1 to 30 carbon atoms; [0073] R=H, or
an optionally substituted hydrocarbon group having from 1 to 30
carbon atoms; [0074] R.sup.2=a hydrogen atom, or an optionally
substituted C.sub.1-8 alkyl group; and [0075] R.sup.3=a hydrogen
atom, or an optionally substituted C.sub.1-8 alkyl group; or [0076]
R.sup.2 and R.sup.3 together with the connected carbon atom
represent an optionally substituted cycloalkyl or cycloalkylene
ring having 5-20 carbon ring atoms;
##STR00002##
[0076] wherein: [0077] R=a hydrogen atom, or an optionally
substituted hydrocarbon group having from 1 to 30 carbon atoms
[0078] R', R''=a hydrogen atom or an optionally substituted,
C.sub.1-8 alkyl group [0079] R.sup.1=II, or an optionally
substituted hydrocarbon group having from 1 to 30 carbon atoms
[0080] x=between 0-5 [0081] n between 1 and 100.
[0082] The term "hydrocarbon" as used herein means any one of a
saturated or unsaturated alkyl group, wherein groups may be linear,
branched or cyclic, or a substituted or un-substituted aryl
group.
[0083] Suitable examples of optional substituents include; nitro
groups, alkyl groups, alkoxy, alkylthio, cyano, alkoxycarbonyl,
alkylamino, dialkylamino, (alkylcarbonyl)alkylamino,
(alkoxycarbonyl)-alkylamino, alkylcarbonylamino,
alkoxycarbonylamino and carboxylic, alkylcarboxylic (ester) and
hydroxyl groups.
[0084] An alkyl moiety as described as R', R'' selected as an
optional subsistent suitably has up to 8 carbon atoms, preferably
up to 4, and especially 1 or 2 carbon atoms. If having more than
two carbon atoms they may be branched, but are preferably
linear.
[0085] Preferably R represents a hydrogen atom or an optionally
substituted C.sub.1-4 alkyl group. Most preferably R represents a
hydrogen atom or a methyl group
[0086] Preferably R.sup.1 represents an optionally substituted (but
preferably unsubstituted) alkyl group or alkylene group or fatty
acid group or aryl group (for example a benzyl group). Most
preferably it represents an unsaturated alkyl group. Preferably
R.sup.1 has 8 or more carbon atoms, preferably 10 or more, and more
preferably 12, or more.
[0087] Preferably R.sup.2 and R.sup.3 represent a hydrogen atom or
an optionally substituted C.sub.1-4 alkyl group. Most preferably
R.sup.2 and R.sup.3 represent a hydrogen atom or a methyl
group.
[0088] The proportions of monomers of type I or type II, or
multiple monomers of a single type can be varied to meet required
properties, with the total adding up to 100 wt %.
[0089] Preferably the number average molecular weight (Mn) of the
acrylate polymer is in the range 750 to 100,000, more preferably
1,000 to 50,000, and most preferably 2,000 to 40,000 amu's.
[0090] The process of preparing these materials is described in
U.S. Pat. No. 6,409,778 (the entire teachings of which are
incorporated herein by reference).
[0091] The Agglomeration Retarders are present in the formulation
in the range of about 0% to about 80%, more preferably between
about 0.1% to about 70.0% v/v, even more preferably between about
10.0% to about 65.0% v/v, and most preferably between about 20.0%
to about 60.0% v/v of the additive composition.
[0092] Particulate Dispersants
[0093] Particulate Dispersants are materials which inhibit the
association of agglomerated Fatty acid Methyl Esters, or
agglomerated FAME's and hydrocarbon or paraffin components forming
larger conglomerates, and fiuther result in an inhibition of the
association of conglomerates required to form particulates.
[0094] Particulate dispersants as described in the present
invention are any suitable nitrogen-containing detergent or
dispersant known in the art for use in lubricants or fuel oils.
[0095] Preferably the dispersant is selected from:
[0096] (i) Substituted Amines,
[0097] (ii) Acylated Nitrogen Compounds, and
[0098] (iii) Nitrogen-Containing Condensates of a phenol and an
aldehyde.
[0099] i) Substituted Amines; wherein the amine Nitrogen is
directly attached to a hydrocarbon. The term "hydrocarbon" as used
herein means any one of a saturated or unsaturated alkyl group,
wherein groups may be linear, branched or cyclic, or a substituted
or un-substituted aryl group.
[0100] Substituted Amines can be described as hydrocarbyl amines,
wherein hydrocarbyl as used herein denotes a group having a carbon
atom directly attached to the remainder of the molecule. The
hydrocarbyl substituent in such amines contain at least 8 and up to
about 50 carbon atoms. Hydrocarbyl substituents can comprise up to
about 200 carbon atoms. Examples of hydrocarbyl groups include but
are not limited to methyl, ethyl, propyl, isopropyl, butyl and
isomers and polymers thereof.
[0101] Substituted Amines can be described as Aromatic amines or
Aromatic polyamines of the general formula:
##STR00003##
wherein, [0102] Ar is an aromatic nucleus of 6 to 20 carbon atoms,
[0103] R is H, C.sub.1-30, and [0104] z is from 2 to 8.
[0105] Specific examples of the aromatic polyamines are the various
isomeric phenylene diamines, the various isomeric naphthalene
diamines, etc.
[0106] Substituted Amines can be described as polyamines wherein
the polyamines can be described by the general formula:
##STR00004##
wherein [0107] R=hydrogen, a hydrocarbyl, [0108] R=1-30 carbon
atoms, with proviso that at least one R is a hydrogen atom, [0109]
n=whole number from 1 to 10 and [0110] X=C.sub.1-8.
[0111] Preferably each R is independently selected from hydrogen,
or a hydrocarbyl group. Examples of a hydrocarbyl groups include
but are not limited to methyl, ethyl, propyl, isopropyl, butyl and
isomers and polymers thereof. X is preferably a C.sub.1-8 alkylene
group, most preferably ethylene, and n can be an integer from 0 to
10.
[0112] Substituted Amines can be a mixture of polyamines for
example a mixture of ethylene polyamines. Specific examples of
polyalkylene polyamines (1) include ethylenediamine,
triethylenetetramine, tetraethylenepentamine, tri-(trimethylene)
tetramine, pentaethylenehexamine, hexaethyleneheptamine,
1,2-propylenediamine, and other commercially available materials
which comprise complex mixtures of polyamines.
[0113] Alternatively the amine or polyamine may be a
hydroxyalkyl-substituted amine or polyamine wherein the parent
amine or poly amine can also be converted to their corresponding
alkoxylates. The alkoxylates are products derived from the reaction
of 1-100 molar equivalents of an alkoxylating agent with the
nitrogen moiety. The required alkoxylating agents are chosen from
the group comprising: ethylene oxide, propylene oxide, butylene
oxide and epichlorohydrin, or their mixtures. The alkoxylates can
be produced from a single alkoxylating agent or alternatively from
a mixture of agents. The alkoxylate derived from mixtures of
alkoxylating agents can be prepared by stepwise addition of the
agents to the amine to form block polymers, or can be added as
mixed agents to form random block/alternating alkoxylates.
[0114] Substituted amines can include heterocyclic substituents
selected from nitrogen-containing aliphatic and aromatic
heterocycles, for example piperazines, imidazolines, pyrimidines,
morpholines, etc.
[0115] Specific examples of the heterocyclic- substituted
polyamines (2) are N-2-aminoethyl piperazine, N-2 and N-3 amino
propyl morpholine, N-3(dimethyl amino) propyl piperazine,
2-heptyl-3-(2 aminopropyl) imidazoline, 1,4-bis
(2-aminoethyl)piperazine, 1-(2-hydroxy ethyl) piperazine, and
2-heptadecyl-1-(2-hydroxyethyl)-imidazoline, etc.
[0116] (ii) Acylated nitrogen compounds: A typical class of
acylated nitrogen compounds suitable for use in the present
invention is those formed by the reaction of a carboxylic
acid-derived acylating agent and an amine. In such compositions the
acylating agent is linked to the amino compound through an imido,
amido, amidine or acyloxy ammonium linkage.
[0117] The acylating agent can vary from formic acid and its
acylating derivatives to acylating agents having high molecular
weight of the aliphatic substituents of up to 5,000, 10,000 or
20,000 amu. The acylating agent may be a mono- or polyearboxylic
acid (or reactive equivalent thereof), for example a substituted
succinic, or phthalic acid.
[0118] The acylating agent commonly possesses a hydrocarbyl
substituent. The term "hydrocarbyl" as used herein denotes a group
having a carbon atom directly attached to the remainder of the
molecule.
[0119] The hydrocarbyl substituent in such acylating agents
preferably comprises at least 10, more preferably at least 12, for
example 30 or 50 carbon atoms. Hydrocarbyl substituents can
comprise up to about 200 carbon atoms.
[0120] Preferably the hydrocarbyl substituent of the acylating
agent has a number average molecular weight (Mn) of between 170 to
2800, for example from 250 to 1500, preferably from 500 to 1500 and
more preferably 500 to 1100. An Mn of 700 to 1300 is especially
preferred.
[0121] Illustrative hydrocarbyl substituent groups include n-octyl,
n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl,
chloroctadecyl, triicontanyl, etc.
[0122] The hydrocarbyl based substituents may be made from homo- or
interpolymers (e.g. copolymers, terpolymers) of mono- and
di-olefins having 2 to 10 carbon atoms, for example ethylene,
propylene, butane-1, isobutene, butadiene, isoprene, 1-hexene,
1-octene, etc. Preferably these olefins are 1-monoolefins. The
hydrocarbyl substituent may also be derived from the halogenated
(e.g. chlorinated or brominated) analogs of such homo- or
interpolymers.
[0123] Alternatively the substituent may be made from other
sources, for example monomeric high molecular weight alkenes (e.g.
1-tetracontene) and chlorinated analogs and hydrochlorinated
analogs thereof, aliphatic petroleum fractions, for example
paraffin waxes and cracked and chlorinated analogs and
hydrochlorinated analogs thereof, white oils, synthetic alkenes for
example produced by the Ziegler and other methods known to those
skilled in the art. Any unsaturation in the substituent may if
desired be reduced or eliminated by hydrogenation according to
procedures known in the art.
[0124] Suitable hydrocarbyl based groups may contain
non-hydrocarbon moieties. For example they may contain up to one
non-hydrocarbyl group for every ten carbon atoms provided this
non-hydrocarbyl group does not significantly alter the
predominantly hydrocarbon character of the group.
[0125] Those skilled in the art will be aware of such groups, which
include for example hydroxyl, halo (especially chloro and fluoro),
alkoxyl, alkyl mercapto, alkyl sulfoxy, etc. Preferred hydrocarbyl
based substituents are purely aliphatic hydrocarbon in character
and do not contain such groups.
[0126] The hydrocarbyl-based substituents are preferably
predominantly saturated, that is, they contain no more than one
carbon-to-carbon unsaturated bond for every ten carbon-to-carbon
single bonds present.
[0127] Most preferably they contain no more than one
carbon-to-carbon non-aromatic unsaturated bond for every 50
carbon-to-carbon bonds present, and containing more than 8 carbon
atoms. Preferred polymeric hydrocarbyl-based substituents are
poly-isobutenes known in the art.
[0128] The nitrogen compounds can vary from ammonia itself to
hydrocarbyl amines. Hydrocarbyl as used herein denotes a group
having a carbon atom directly attached to the remainder of the
molecule. The hydrocarbyl substituent in such amines contain at
least 8 and up to about 50 carbon atoms. Hydrocarbyl substituent
can comprise up to about 200 carbon atoms. Examples of a
hydrocarbyl groups include but are not limited to methyl, ethyl,
propyl, isopropyl, butyl and isomers and polymers thereof.
[0129] Hydrocarbyl-Substituted Amines suitable for use in the fuel
compositions of the present invention are well known to those
skilled in the art and are described in a number of patents. Among
these is U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804;
3,755,433 and 3,822,209 (the entire teachings of which is
incorporated herein by reference). These patents describe suitable
hydrocarbyl amines for use in the present invention including their
method of preparation.
[0130] The amino compound can be a polyamine or a mixture of
polyamines, for example a mixture of ethylene polyamines. Poly
amino compounds useful for reacting with acylating agents include
polyalkylene polyamines of the general formula:
##STR00005##
wherein [0131] R=hydrogen, a hydrocarbyl, [0132] R=1-30 carbon
atoms, with proviso that at least one R is a hydrogen atom, [0133]
n whole number from 1 to 10 and [0134] x=C.sub.1-8.
[0135] Preferably each R is independently selected from hydrogen,
or a hydrocarbyl group. Examples of a hydrocarbyl group include but
are not limited to methyl, ethyl, propyl, isopropyl, butyl and
isomers and polymers thereof. X is preferably a C.sub.1-8 alkylene
group, most preferably ethylene, and n can be an integer from 0 to
10.
[0136] Specific examples of polyalkylene polyamines (1) include
ethylene diamine, diethylenetriamine, tetraethylenepentamine,
tri-(trimethylene) tetramine, pentaethylenehexamine,
hexaethyleneheptamine, 1,2-propylenediamine, and other commercially
available materials which comprise complex mixtures of
polyamines.
[0137] Alternatively the amine or polyamine may be a
hydroxyalkyl-substituted amine or polyamine wherein the parent
amine or poly amine can also be converted to their corresponding
alkoxylates. The alkoxylates are products derived from the reaction
of 1-100 molar equivalents of an alkoxylating agent with the
nitrogen moiety. The required alkoxylating agents are chosen from
the group comprising: ethylene oxide, propylene oxide, butylene
oxide and epichlorohydrin, or their mixtures. The alkoxylates can
be produced from a single alkoxylating agent or alternatively from
a mixture of agents. The alkoxylate derived from mixtures of
alkoxylating agents can be prepared by stepwise addition of the
agents to the amine to form block polymers, or can be added as
mixed agents to form random block/alternating alkoxylates. These
oxyalkylates can also be further derivatized with organic acids to
form esters.
[0138] Typical acylated nitrogen compounds are formed by the
reaction of a molar ratio of acylating agent: nitrogen compound of
from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from
2:1 to 1:2 and most preferably from 2:1 to 1:1. This type of
acylated nitrogen compounds compound and the preparation thereof is
well known to those skilled in the art
[0139] A further type of acylated nitrogen compound suitable for
use in the present invention is the product of the reaction of a
fatty monocarboxylic acid of about 10-30 carbon atoms and the
afore-described alkylene amines, typically, ethylene, propylene or
trimethylene polyamines containing 2 to 10 amino groups and
mixtures thereof.
[0140] A type of acylated nitrogen compound belonging to this class
is that made by reacting an hydrocarbyl amine or poly amine with
substituted succinic acids or anhydrides, or with aliphatic
mono-carboxylic acids having from 2 to about 22 carbon atoms.
[0141] Typical of the monocarboxylic acids are formic acid, acetic
acid, dodecanoic acid, butanoic acid, oleic acid, stearic acid, the
commercial mixture of stearic acid isomers known as isostearic
acid, tolyl acid, etc. Such materials are more fully described in
U.S. Pat. Nos. 3,216,936 and 3,250,715 (the entire teachings of
which is incorporated herein by reference). The fatty
mono-carboxylic acids are generally mixtures of straight and
branched chain fatty carboxylic acids containing 10-30 carbon
atoms. These include but are not limited to Rapeseed Oil Fatty
Acid, and Tall Oil Fatty Acids (TOFA). Fatty dicarboxylic acids can
also be used.
[0142] The mixture of fatty acids contain from 5 to about 30 mole
percent straight chain acid and about 70 to about 95 percent mole
branched chain fatty acids. Among the commercially available
mixtures are those known widely in the trade as isostearic acid.
These mixtures are produced as a by-product from the dimerization
of unsaturated fatty acids as described in U.S. Pat. Nos. 2,812,342
and 3,260,671 (the entire teachings of which is incorporated herein
by reference).
[0143] The branched chain fatty acids can also include those in
which the branch may not be alkyl in nature, for example phenyl and
cyclohexyl stearic acid and the chloro-stearic acids. Branched
chain fatty carboxylic acid/alkylene polyamine products have been
described extensively in the art. See for example, U.S. Pat. Nos.
3,110,673; 3,251,853; 15 3,326,801; 3,337,459; 3,405,064;
3,429,674; 3,468,639; 3,857,791 (the entire teachings of which is
incorporated herein by reference).
[0144] Acylated nitrogen compounds of this class can alternatively
be prepared by reacting a poly(isobutene)- substituted succinic
acid-derived acylating agent (e.g. anhydride, acid, ester, etc.)
wherein the poly(isobutene) substituent has between about 12 to
about 200 carbon atoms with a mixture of ethylene polyamines having
3 to about 9 amino nitrogen atoms per ethylene polyamine and about
1 to about 8 ethylene groups.
[0145] Many patents have described useful acylated nitrogen
compounds including U.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746;
3,310,492; 3,341,542; 3,444,170; 3,455,831; 3,455,832; 3,576,743;
3,630,904; 3,632,511; 3,804,763, 4,234,435 and U.S. Pat. No.
6,821,307 (the entire teachings of which is incorporated herein by
reference).
[0146] (iii) Nitrogen-Containing Condensates of Phenols, Aldehydes,
and Amino Compounds: Phenol/aldehyde/amine condensates are useful
as dispersants in the fuel. The compositions of the present
invention include those generically referred to as Mannich
condensates.
[0147] Mannich compounds can be made by reacting simultaneously or
sequentially at least one active hydrogen compound for example a
hydrocarbon-substituted phenol (e.g. an alkyl phenol wherein the
alkyl group has at least an average of about 8 to 200; preferably
at least 12 up to about 200 carbon atoms) having at least one
hydrogen atom bonded to an aromatic carbon, with at least one
aldehyde or aldehyde-producing material (typically formaldehyde or
a precursor thereof) and at least one amino or polyamino compound
having at least one NH group.
[0148] The amino compounds include primary or secondary monoamines
having hydrocarbon substituents of 1 to 30 carbon atoms or hydroxyl
substituted hydrocarbon substituents of 1 to about 30 carbon
atoms.
[0149] Another type of typical amino compound is the polyamines
described above in relation to acylated nitrogen-containing
compounds.
[0150] The Particulate Dispersants are present in the formulation
in the range of about 0% to about 70%, more preferably between
about 0.1% to about 60.0% v/v, even more preferably from about
10.0% to about 55.0% v/v, and most preferably between about 20.0%
to about 50.0% v/v of the additive composition.
[0151] Particulate Settling Inhibitor
[0152] Particulate Settling Inhibitors are materials which inhibit
conglomerated Fatty Acid Methyl Esters, or conglomerated FAME's and
hydrocarbon or paraffin components forming larger conglomerates,
and inhibition these conglomerates from settling out of
solution.
[0153] Three polymer families are considered suitable polymers as
part of the invention to function as Particulate Settling
Inhibitors. These are hydrocarbon polymers, oxyalkylene polymers
and nitrogen containing polymers.
[0154] Hydrocarbon polymers which can be used in accordance with
the invention are homo polymers and copolymers of two or more of
ethylenically unsaturated monomers, selected from the group
consisting of; alpha-olefins (e.g. styrene, 1-octene), unsaturated
esters (eg. vinyl acetate), and unsaturated acids and their esters
(eg. fumaric, itaconic acids, maleic anhydride and phthallic
anhydride).
[0155] The preferred polymers can be described by the general
formula:
##STR00006##
wherein: [0156] R=H, hydrocarbyl, or hydrocarbylene; with from 1 to
30 carbon atoms, or aryl or Q, [0157] Q=R, COOR, OCOR, COOH, or OR,
[0158] S=H or Q [0159] T=H, R, COOR, or an aryl or heterocyclic
group, [0160] U=H, COOR, OCOR, OR, or COOH, [0161] V=H, R, COOR,
OCOR, COOH, or COOH [0162] x and y represent mole fractions (x/y)of
monomers, preferably within the range of from about 2.5 to about
0.4.
[0163] It is generally desirable to utilize homo polymers or a
copolymer having at least 25 and preferably at least 40, more
preferably at least 50, molar per cent of the units which have side
chains containing at least 6, and preferably at least 10 atoms.
[0164] The suitable molar ratios of monomers in the co polymer are
preferably in the range of about 3 to 1 and 1 to 3.
[0165] Olefins that can be copolymerized with e.g. maleic anhydride
include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and
1-octadecene. The acid or anhydride group of the polymer can be
esterified by any suitable technique and although preferred it is
not essential.
[0166] Alcohols which can be used include normal alcohols such as
n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol,
and n-octadecan-1-ol and branched alcohols such as
1-methylpentadecan-1-ol or 2-methyltridecan-1-ol or a mixture
thereof.
[0167] The particularly preferred polymers are those having a
number average molecular weight, as measured by vapor phase
osmometry, of 1,000 to 100,000, more especially 1,000 to
30,000.
[0168] The polyoxyalkylene polymers which can be used in accordance
with the invention are polyoxyalkylene esters, ethers, ester/ethers
and mixtures thereof, particularly those containing at least one,
preferably at least two, C.sub.10 to C.sub.30 alkyl groups and a
polyoxyalkylene glycol group of molecular weight up to 5,000,
preferably about 200 to about 5,000, and the alkyl spacer group in
said polyoxyalkylene glycol containing from 1 to 6 carbon
atoms.
[0169] The preferred esters, ethers or ester/ethers can be
described by the general formula:
##STR00007##
wherein R and R' may be the same or different, and represented by
[0170] R, R'=n-alkyl-, n-alkyl-CO--, n-alkyl-O--CO(CH2)x-, or
n-alkyl-O--CO(CH2)x-CO-- [0171] D=polyalkylene; [0172] x is an
integer from 1 to 60.
[0173] The polyalkylene spacer segment (D) of the glycol can
encompass an alkylene group, in which the alkylene group has 1 to 6
carbon atoms. The spacer can be linear or branched. Common glycol
spacer segments are methylene, ethylene, trimethylene,
tetramethylene hexamethylene moieties which are substantially
linear, and propylene which has some degree of branching.
[0174] Nitrogen containing polymer where the polymer is composed of
derivatives of a primary or secondary amine, wherein an amine has
been converted to an amide, imide, imidazoline, carbamate, urea,
imine, or an enamine.
[0175] The nitrogen atom can be attached to a linear, branched,
saturated, unsaturated or a cyclic, hydrocarbon; or to aromatic or
poly aromatic groups, to hydrogens, or to a combination of these
groups. A non-exclusive list of chain lengths attached to the
nitrogen atom are in the range of about C.sub.1-C.sub.30 such as
butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, nonadecyl, eicosyl, uneicosyl, docosyl, tricosyl, and
tetracosyl, and in the case of secondary amines, the combinations
in the range of about C.sub.1-C.sub.30, are also suitable,
[0176] The amine functional class may also include poly amines. The
poly amines are described by the formula:
##STR00008##
wherein: [0177] R, R' can be a linear alkyl, a branched alkyl
containing 1 to 30 carbon atoms, aromatic, cyclic, polycyclic, poly
alkoxy, or carbonyl, [0178] R,R' alternatively contain hetero atoms
such as O, N, S, and P, [0179] R' and R' alternatively are
incorporated in a ring system containing 3-12 members; [0180] x can
be 1-6; and [0181] y can be 1-6.
[0182] Suitable polyamines of the present invention are the
polyethylene poly amines such as EDA (ethylenediamine), DETA
(diethylenetriamine), TETA (triethylenetetraamine) and their higher
homologs; their alkyl analogs (as exemplified, but not limited to,
N-coco-ethylenediamine, N-oleyl-ethylenediamine, and
N-butyl-ethylenediamine), and their analogs based on other
industrially available spacers such as propyl and hexyl (as
exemplified, but not limited to, dipropylenetriamine, and
bis-hexamethylenetriamine); and their subsequent derivatives such
as; ester amines, amido amines, imido amines, imidazolines,
carbamates, ureas, imines, and enamines.
[0183] The parent amine or poly amine can also be converted to
their corresponding alkoxylates. The alkoxylates are products
derived from the reaction of 1-100 molar equivalents of an
alkoxylating agent with the nitrogen moiety. The required
alkoxylating agents are chosen from the group comprising: ethylene
oxide, propylene oxide, butylene oxide and epichlorohydrin, or
their mixtures. The alkoxylates can be produced from a single
alkoxylating agent or alternatively from a mixture of agents. The
alkoxylate derived from mixtures of alkoxylating agents can be
prepared by stepwise addition of the agents to the amine to form
block polymers, or can be added as mixed agents to form random
block/alternating alkoxylates. These oxyalkylates can also be
further derivatized with organic acids to form esters.
[0184] The Particulate Settling Inhibitors are present in the
formulation in the range of about 0% to about 70%, more preferably
between about 0.1% to about 60.0% v/v, even more preferably between
about 10.0% to about 55.0% v/v, and most preferably between about
20.0% to about 50.0% v/v of the additive composition.
[0185] Compatibility Enhancers
[0186] Compatibility Enhancers are materials which are believed to
solubilize and break up agglomerated or conglomerated Fatty Acid
Methyl Esters, or agglomerated or conglomerated FAME's and
hydrocarbon or paraffin components, and retard their dissolution
from the bulk fuel.
[0187] The Compatibility Enhancer in the formulation may be a
single compound or a combination of compounds so as to form an
intertwined synergistic matrix. In some embodiments, the
Compatibility Enhancers are selected from monofunctional alcohols,
glycols, polyols, esters, ethers, glycol ether acetates, ketones,
glycol ethers, amides, amines, nitro compounds and combinations of
two or more of the foregoing.
[0188] In some embodiments, at least one of the Compatibility
Enhancers is a monofunctional alcohol. Examples of mono-functional
alcohols include C.sub.1-C.sub.30 alcohols, wherein the hydrocarbon
portion of the alcohol can be linear, branched, saturated,
unsaturated, or cyclic, or an aromatic or poly aromatic.
[0189] Some examples of mono-functional alcohols include n-propyl
alcohol, isopropyl alcohol, n-butyl alcohol, amyl alcohol,
2-ethylhexanol, decyl alcohol, and 1-octadecanol.
[0190] In some embodiments, at least one of the Compatibility
Enhancers is a polyol. Some examples of polyols include glycols
such as ethylene glycol, polyethylene glycol, propylene glycol,
diethylene glycol, dipropylene glycol, triethylene glycol,
tripropylene glycol. In some embodiments, the polyol used is
propylene glycol.
[0191] In some embodiments, at least one of the Compatibility
Enhancers is a glycol ether. As used throughout this application, a
"glycol ether" shall define a molecule having the structure of a
glycol, except that the molecule possesses an ether linkage to an
alkyl group from one of the oxygen atoms in the glycol. Thus a
mono-alkyl ether of ethylene glycol, for example, has the structure
of ethylene glycol with an ether linkage connected to an alkyl
group instead of one of the two hydroxyl groups normally found on
ethylene glycol. By way of further example, "ethylene glycol mono
butyl ether" refers to a molecule having the structure of ethylene
glycol with an ether linkage connected to a butyl group. Further, a
reference to a number of carbons on the ether refers to the number
of carbons in an alkyl group attached to the ether linkage. Thus, a
"C.sub.3-C.sub.10 glycol ether" refers to a glycol ether in which
the alkyl group attached to the ether has three to ten carbons.
[0192] In some embodiments, the glycol ether Compatibility Enhancer
includes more than one ether linkage defined as a polyglycol ether.
The polyglycol ethers are generally products of an alcohol reacted
with ethylene or propylene oxide. The repeating glycol unit is
preferably less than 16 more preferably less than 8, and most
preferably 3 or less.
[0193] Some examples include; ethylene glycol monopropyl ether,
ethylene glycol monobutyl ether, ethylene glycol monohexyl ether,
ethylene glycol mono-2-ethylhexyl ether, diethylene glycol
monomethyl ether, diethylene glycol monoethyl ether, diethylene
glycol monopropyl ether, diethylene glycol monobutyl ether,
propylene glycol monomethyl ether, propylene glycol monoethyl
ether, propylene glycol monopropyl ether, propylene glycol
monobutyl ether, dipropylene glycol monomethyl ether, dipropylene
glycol monoethyl ether, dipropylene glycol mono-n-propyl ether,
dipropylene glycol mono-n-butyl ether.
[0194] In some embodiments, the glycol ether is selected from a
combination of two or more glycol ethers.
[0195] In some embodiments, at least one of the Compatibility
Enhancers is an ester. Ester Compatibility Enhancers include
C.sub.2-C.sub.30 esters. The carbon atoms on either side of the
ester linkage can be linear, branched, saturated, unsaturated, or
cyclic, or aromatic or poly aromatic.
[0196] Some examples of ester Compatibility Enhancers include
methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate,
n-butyl acetate, isobutyl acetate, tert-butyl acetate, amyl
acetate, methyl amyl acetate, n-propyl propionate, n-butyl
propionate, isobutyl isobutyrate, 2-ethylhexyl acetate, ethylene
glycol diacetate, dimethyl adipate, dimethyl succinate, dimethyl
glutarate, C.sub.8-C.sub.30 fatty acid methyl esters, propylene
glycol diacetate (diacetoxypropane), and combinations of two or
more thereof. In some embodiments, the longest hydrocarbon chain in
the ester Compatibility Enhancer contains C.sub.1-C.sub.8
atoms.
[0197] In some embodiments, at least one of the Compatibility
Enhancers is a glycol ether ester. Glycol ether esters have
structures similar to glycol ethers except that they possess an
ester linkage in the place of the hydroxy group on the
corresponding glycol ether.
[0198] The glycol ether and polyglycol ether are as described
previously. The ester portion on the molecule is formed by reacting
the terminal hydroxyl group of the glycol with an acyl bearing
moiety. The acyl bearing moiety can contain between about 3-30
carbon atoms, wherein the hydrocarbon portion can be linear,
branched, saturated, unsaturated, or cyclic or aromatic or poly
aromatic.
[0199] The esters may also be prepared by esterifying
polyethoxylated fatty acids, or esterifying polyglycols to form
diesters of polyethers, or esterifying polyethoxylated alcohols to
form ether esters
[0200] Examples of suitable glycols are polyethylene glycols (PEG)
and polypropylene glycols (PPG) having a molecular weight of from
100 to 5,000, preferably from 200 to 2,000.
[0201] Diesters, or ether/esters and mixtures thereof are suitable
as additives. It is preferred that a major amount of the dialkyl
compound be present. In particular, C.sub.6 to C.sub.30 ether
esters and diesters of polyethylene glycol, polypropylene glycol or
polyethylene/polypropylene glycol mixtures are preferred.
[0202] Some examples of ether esters include
ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether acetate,
ethylene glycol monoethyl ether acetate, propylene glycol monoethyl
ether acetate, propylene glycol monomethyl ether acetate,
diethylene glycol monoethyl ether acetate, diethylene glycol
monobutyl ether acetate, dipropylene glycol monomethyl ether
acetate,
[0203] In some embodiments, at least one of the Compatibility
Enhancers is an ether compound. Some examples of Compatibility
Enhancers selected from the class of ethers include diisopropyl
ether, tetrahydrofuran (THF), dipropylene glycol dimethyl ether,
and combinations of two or more thereof. In some embodiments, the
ether is THF.
[0204] In some embodiments, at least one of the Compatibility
Enhancers is a ketone. Some examples of Compatibility Enhancers
selected from the class of ketones include straight or branched
C.sub.3 to C.sub.30 ketones (wherein C.sub.3 to C.sub.30 refers to
the number of carbon atoms in the ketone molecule).
[0205] Some examples of ketone Compatibility Enhancers are acetone,
methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone,
methyl isoamyl ketone, cyclohexanone, methyl amyl ketone, and
combinations of two or more thereof.
[0206] In some embodiments, at least one of the Compatibility
Enhancers is an amide compound. In some embodiments, the amide is a
C.sub.3 to C.sub.30 amide (wherein C.sub.3 to C.sub.30 refers to
the number of carbon atoms in the amide molecule). Some examples of
Compatibility Enhancers selected from the class of amides include
N,N-dimethylformamide (DMF), N-methylpyrrolidone and
dimethylacetamide and combinations of two or more thereof. In some
embodiments, the amide is DMF.
[0207] In some embodiments, at least one of the Compatibility
Enhancers is a nitro compound. The nitro compounds can be nitration
products of aliphatic or aromatic organic feedstocks, and
derivatives there of. These derivatives can contain other aliphatic
substituents on the aromatic ring, or can also contain other
functional groups such as esters, ethers, amines alcohols,
halogens, and combinations there of. Some examples of Compatibility
Enhancers selected from the class of nitro compounds include but
are not limited to nitropropane isomers, nitrobenzenes, nitro
phenols and combinations there of.
[0208] In some embodiments the Compatibility Enhancer is selected
from an individual compatibility enhancer (glycol ethers, alcohols,
ethers, ketones, amides and esters) and in other embodiments the
compatibility enhancer is selected from a combination of
compatibility enhancers. The preferred individual compatibility
enhancers are glycol ethers, alcohols, ethers, and esters, and most
preferably glycol ethers, and alcohols.
[0209] In some embodiments, the single Compatibility Enhancer is
selected from ethylene glycol monopropyl ether, diethylene glycol
monobutyl ether, or 2-ethylhexanol.
[0210] In some embodiments, the Compatibility Enhancer includes a
combination of two or more of the classes of Compatibility Enhancer
selected from the group comprising glycol ethers, alcohols, ethers,
ketones, amides and esters, wherein any useful combination can be
selected. The combination and ratio of Compatibility Enhancers is
to be utilized is greatly dependant on the particular properties of
the fuel to be stabilized.
[0211] In some embodiments the preferred combination of
Compatibility Enhancers include at least one glycol ether and at
least one alcohol in a ratio range of about 1 part glycol ether to
about 3 parts alcohol to a ratio range of about 3 part glycol ether
to about 1 parts alcohol, more preferably where the glycol ether
and the alcohol are in a ratio of about 1 part glycol ether to
about 1 part alcohol of the total of all Compatibility Enhancer
components.
[0212] In some embodiments the preferred combination of
Compatibility Enhancers include at least one poly glycol ether and
at least one alcohol in a ratio range of about 1 part poly glycol
ether to about 3 parts alcohol to a ratio range of about 3 parts
poly glycol ether to about 1 part alcohol, more preferably where
the poly glycol ether and the alcohol are in a ratio of about 1
part poly glycol ether to about 1 part alcohol of the total of all
Compatibility Enhancer components.
[0213] In some embodiments the preferred combination of
Compatibility Enhancers include at least one glycol ether, and at
least one ester in a ratio range of about 1 part glycol ether to
about 3 parts ester to a ratio range of about 3 parts glycol ether
to about 1 part ester, more preferably where the glycol ether and
the ester are in a ratio of about 1 part glycol ether to about 1
part ester of the total of all Compatibility Enhancer
components.
[0214] In some such embodiments, the ester is selected from the
group consisting of: methyl acetate, ethyl acetate, n-propyl
acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate,
tert-butyl acetate, propylene glycol diacetate and combinations of
two or more thereof.
[0215] In some such embodiments the glycol ether Compatibility
Enhancer is selected from the group consisting of: ethylene glycol
monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol
mono-2-ethylhexyl ether, diethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, diethylene glycol monopropyl
ether, diethylene glycol monobutyl ether, propylene glycol
monomethyl ether, dipropylene glycol monomethyl ether, dipropylene
glycol monoethyl ether, and combinations of two or more thereof.
The glycol ether can also be a polyglycol ether.
[0216] In some such embodiments the polyol Compatibility Enhancer
is selected from the group consisting of: ethylene glycol,
polyethylene glycol, propylene glycol, diethylene glycol,
dipropylene glycol and combinations of two or more thereof.
[0217] The Compatibility Enhancer are utilized in the formulation
in the range of about 10% to about 80%, more preferably between
about 10.0% to about 70.0% v/v, even more preferably between about
10.0% to about 60.0% v/v, and most preferably between about 20.0%
to about 60.0% v/v of the additive composition.
[0218] Another aspect of this invention is a method of diminishing
the formation of insoluble particulates in renewable fuels, or
blends of renewable fuel with petroleum fuels by metering into the
renewable fuel, or the renewable fuel/petroleum fuel blend the
particulate inhibition formulation.
[0219] The specific level of utilization of the particulate
inhibitor formulation is chosen as the amount which is required to
produce a worthwhile benefit in retarding particulate formation in
either the renewable fuel, or in the renewable fuel petroleum fuel
blend. This amount may differ for different fuels and is readily
determined by routine experimentation.
[0220] The particulate inhibitor formulation is generally present
in the renewable component (B100) in the range of about 200 mg/l to
about 8000 mg/l; or in the renewable fuel petroleum fuel blend in
the range of about 200 mg/l to about 8000 mg/l based on content of
the renewable fuel component.
[0221] However as a general guide the particulate inhibitor
formulation can be suitably added at a treat rate of at least 200
mg/l to about 8000 mg/l, more preferably from 500 mg/l to about
6000 mg/l, and most preferably from about 1000 mg/l to about 4000
mg/l based on renewable fuel content.
[0222] It is additionally considered as part of the present
invention the utilization of other additives in combination with
the renewable fuel and particulate inhibitor formulation, or in
combination of renewable fuel petroleum/fuel blend and particulate
inhibition formulation, wherein these other additives are present
in such amounts so as to provide their normal intended
functions.
[0223] A non-exclusive list of additives typically used in
petroleum fuel and which can be incorporated into petroleum fuel
renewable fuel blends are: (a) low temperature operability/cold
flow additives such as ethylene-unsaturated ester copolymers, comb
polymers containing hydrocarbyl groups pendant from a polymer
backbone, polar nitrogen compounds having a cyclic ring system,
hydrocarbyl, hydrocarbon polymers such as ethylene alpha-olefin
copolymers, polyoxyethylene esters, ethers and ester/ether mixtures
such as behenic diesters of polyethylene glycol, (b) corrosion
inhibitors, such as fatty amines, poly amines and amides thereof
known as filming amines, and polymers of fatty acids known as dimer
trimer acids, (c) cetane improvers such as 2-ethyl hexyl nitrite
(2EHN) and di-tert butyl peroxide (DTBP), (d) detergents such as
components derived from reactions of organic acids with polyamines
such as ethylenediamine, diethylenetriamine, triethylenetetramine
and tetraethylene pentamine, (e) lubricity improvers, such as
components derived from chemical families that include: long chain
fatty acids, derivatives of such fatty acids to include salts (both
mineral and organic), amides and esters, dimers/trimers of fatty
acids, and poly and alkyl amines (which are generally known as
"filming amines") and their derivatives such as amides, salts, and
oxyalkylates, (f) dyes and markers, (g) anti-icing additives such
as ethylene glycol monomethyl ether or diethylene glycol monomethyl
ether (h) demulsifiers/anti-haze additives such as those produced
from a phenol and an aldehyde under acidic or basic polymerization
conditions (industrially known as resoles or novelacs) and their
alkoxylated (ethylene, propylene or butylene oxide) products, (i)
antioxidant compounds such as hindered phenols exemplified by
2,6-di-t-butyl-4-methylphenol (BHT, butylated hydroxy toluene),
2-t-butyl-4-heptylphenol, 2-t-butyl-4-octylphenol,
2-t-butyl-4-octylphenol, 2-t-butyl-4-dodecylphenol,
2,6-di-t-butyl-4-heptylpbenol, 2,6-di-t-butyl-4-dodecylphenol,
2-methyl-6-di-t-butyl-4-heptylphenol, and
2-methyl-6-di-t-butyl-4-dodecylphenol, ortho coupled phenols to
include 2,2'-bis(6-t-butyl-4-heptylphenol),
2,2'-bis(6-t-butyl-4-octylphenol), and
2,2'-bis(6-t-butyl-4-dodecylphenol), where BHT is suitable, as are
2,6- and 2,4-di-t-butylphenol and 2,4,5- and
2,4,6-triisopropylphenol, and anti oxidants based on aromatic
amines such as phenelene diamines (j) metal deactivators such as
(1) benzotriazoles and derivatives thereof, for example, 4- or
5-alkylbenzotriazoles (e.g. tolutriazole) and derivatives thereof,
4,5,6,7-tetrahydrobenzotriazole and 5,5'-methylenebisbenzotriazole,
Mannich bases of benzotriazole or tolutriazole, e.g.
1-[bis(2-ethylhexyl)aminomethyl]tolutriazole,
1-[bis(2-ethylhexyl)aminomethyl]benzotriazole, and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)-benzotriazole,
1-(1-butoxyethyl)benzotriazole and
1-(1-cyclohexyloxybutyl)-tolutriazole, (2) 1,2,4-triazoles and
derivatives thereof, for example, 3-alkyl(or aryl)-1,2,4-triazoles,
and Mannich bases of 1,2,4-triazoles, such as
1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazoles such as
1-(1-butoxytheyl)-1,2,4-trizole, and acylated
3-amino-1,2,4-triazoles, (3) Imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5-methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether (4)
Sulfur-containing heterocyclic compounds, e.g.
2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole and
derivatives thereof, and
3,5-bis[di(2-ethyl-hexyl)aminomethyl]-1,3,4-thiadiazolin-2-one, and
(5) Amino compounds and imino compounds, such as
N,N'-disalicylidene propylene diamine (I)MD), salicylaminoguanadine
and salts thereof, (k) biocides, (1) thermal stabilizers such as
those compounds containing secondary and tertiary amines, (m)
anti-foams such as poly ether modified siloxanes and (n)
conductivity additives such as those having components derived from
chemical families that include: aliphatic amines-fluorinated
polyolefins (U.S. Pat. No. 3,652,238, the entire teaching of which
is incorporated herein), chromium salts and amine phosphates (U.S.
Pat. No. 3,758,283, the entire teaching of which is incorporated
herein), alpha-olefin-sulfone copolymer class--polysulphone and
quaternary ammonium salt (U.S. Pat. No. 3,811,848, the entire
teaching of which is incorporated herein), polysulphone and
quaternary ammonium salt amine/epichlorhydrin adduct
dinonylnaphthylsulphonic acid (U.S. Pat. No. 3,917,466, the entire
teaching of which is incorporated herein), copolymer of an alkyl
vinyl monomer and a cationic vinyl monomer (U.S. Pat. No.
5,672,183, the entire teaching of which is incorporated herein),
alpha-olefin-maleic anhydride copolymer class (U.S. Pat. Nos.
3,677,725 & 4,416,668, the entire teachings of which are
incorporated herein), methyl vinyl ether-maleic anhydride
copolymers and amines (U.S. Pat. No. 3,578,421, the entire teaching
of which is incorporated herein), alpha-olefin-acrylonitrile (U.S.
Pat. Nos. 4,333,741 & 4,388,452, the entire teachings of which
are incorporated herein), alpha-olefin-acrylonitrile copolymers and
polymeric polyamines (U.S. Pat. No. 4,259,087, the entire teaching
of which is incorporated herein), and copolymer of an alkylvinyl
monomer and a cationic vinyl monomer and polysulfone (U.S. Pat. No.
6,391,070, the entire teaching of which is incorporated herein), an
ethoxylated quat (U.S. Pat. No. 5,863,466, the entire teaching of
which is incorporated herein), hydrocarbyl monoamine or
hydrocarbyl-substituted polyalkyleneamine (U.S. Pat. No. 6,793,695,
the entire teaching of which is incorporated herein), acrylic-type
ester-acrylonitrile copolymers and polymeric polyamines (U.S. Pat.
Nos. 4,537,601 & 4,491,651, the entire teachings of which are
incorporated herein), diamine succinamide reacted with an adduct of
a ketone and SO.sub.2 (.beta.-sultone chemistry) (U.S. Pat. No.
4,252,542, the entire teaching of which is incorporated
herein).
[0224] Low temperature operability/coldflow additives are used in
fuels to enable users and operators to handle the fuel at
temperatures below which the fuel would normally cause operational
problems. Distillate fuels such as diesel fuels tend to exhibit
reduced flow at low temperatures due in part to formation of waxy
solids in the fuel. The reduced flow of the distillate fuel affects
transport and use of the distillate fuels in refinery operations
and internal combustion engines. This is a particular problem
during the winter months and especially in northern regions where
the distillates are frequently exposed to temperatures at which
solid formation begins to occur in the fuel, generally known as the
cloud point (ASTM D 2500) or wax appearance point (ASTM D 3117).
The formation of waxy solids in the fuel will in time essentially
prevent the ability of the fuel to flow, thus plugging transport
lines such as refinery piping and engine fuel supply lines. Under
low temperature conditions during consumption of the distillate
fuel, as in a diesel engine, wax precipitation and gelation can
cause the engine fuel filters to plug resulting in engine
inoperability. An example of a low temperature operability/cold
flow additive available from Innospec Inc, of Newark, Del. is PPD
8500.
[0225] Corrosion Inhibitors are a group of additives which are
utilized to prevent or retard the detrimental interaction of fuel
and materials present in the fuel with engine components. The
additives used to impart corrosion inhibition to fuels generally
also function as lubricity improvers. Examples of corrosion
inhibitors available from Innospec Inc. of Newark, Del. are DCI 6A,
and DCI 4A.
[0226] Cetane Improvers are used to improve the combustion
properties of middle distillates. Fuel ignition in diesel engines
is achieved through the heat generated by air compression, as a
piston in the cylinder moves to reduce the cylinder volume during
the compression stroke. In the engine, the air is first compressed,
then the fuel is injected into the cylinder; as the fuel contacts
the heated air, it vaporizes and finally begins to burn as the
self-ignition temperature is reached. Additional fuel is injected
during the compression stroke and the fuel bums almost
instantaneously, once the initial flame has been established. Thus,
a period of time elapses between the beginning of fuel injection
and the appearance of a flame in the cylinder. This period is
commonly called "ignition delay" and must be relatively short in
order to avoid "diesel knock". A major contributing factor to
diesel fuel performance and the avoidance of "diesel knock" is the
cetane number of the diesel fuel. Diesel fuels of higher cetane
number exhibit a shorter ignition delay than do diesel fuels of a
lower cetane number. Therefore, higher cetane number diesel fuels
are desirable to avoid diesel knock. Most diesel fuels possess
cetane numbers in the range of about 40 to55. A correlation between
ignition delay and cetane number has been reported in "How Do
Diesel Fuel Ignition Improvers Work" Clothier, et al., Chem. Soc.
Rev, 1993, pg. 101-108, the entire teaching of which is
incorporated herein. Cetane improvers have been used for many years
to improve the ignition quality of diesel fuels. This use is
described in U.S. Pat. No. 5,482,518 (the entire teaching of which
is incorporated herein by reference). An example of a Cetane
Improver available from Innospec Inc. of Newark Del. is
CI-0801.
[0227] Detergents are additives which can be added to hydrocarbon
fuels to prevent or reduce deposit formation, or to remove or
modify formed deposits. It is commonly known that certain fuels
have a propensity to form deposits which may cause fuel injectors
to clog and affect fuel injector spray patterns. The alteration of
fuel spray patterns may cause non uniform distribution and/or
incomplete atomization of fuel resulting in poor fuel combustion.
The accumulation of deposits is characterized by overall poor
drivability including hard starting, stalls, rough engine idle and
stumbles during acceleration. Furthermore if deposit build up is
allowed to proceed unchecked, irreparable harm may result which may
require replacement or non-routine maintenance. In extreme cases,
irregular combustion could cause hot spots on the pistons which can
resulted in total engine failure requiring a complete engine
overhaul or replacement. Examples of detergents available from
Innospec Inc. of Newark, Del. are DDA 350, and OMA 580.
[0228] Lubricity improvers increase the lubricity of the fuel, to
prevent wear on contacting metal surfaces in the engine. Certain
diesel engine designs rely on fuel as a lubricant for their
internal moving components. A potential detrimental result of poor
lubricating ability of the fuel can be premature failure of engine
components (e.g. fuel injection pumps). Examples of lubricity
improvers available from Innospec Inc. of Newark, Del. OLI 9070.x
and OLI9101.x.
[0229] Dyes and Markers are materials used by the EPA
(Environmental Protection Agency) and the IRS (Internal Revenue
Service) to monitor and track fuels. Since 1994 the principle use
for dyes in fuel is attributed to the federally mandated dying or
marking of untaxed "off-road" middle distillate fuels as defined in
the Code of Federal Regulations, Title 26, Part 48.4082-1(26 CFR
48.4082-1). Dyes are also used in Aviation Gasoline; Red, Blue and
Yellow dyes denote octane grades in Avgas. Markers are used to
identify, trace or mark petroleum products without imparting
visible color to the treated product. One of the main applications
for markers in fuels is in Home Heating Oil. Examples of Dyes and
Markers available from Innospec Inc. of Newark, Del. are Oil Red B4
and Oil Color IAR.
[0230] Anti-Icing Additives are mainly used in the aviation
industry and in cold climates. They work by combining with any free
water and lowering the freeze point of the mixture that no ice
crystals are formed. Examples of anti-icing additives available
from Innospec Inc. of Newark, Del. are Dri-Tech and DEGME.
[0231] Demulsifiers/Anti-Haze additives are mainly added to the
fuel to combat cloudiness problems which may be caused by the
distribution of water in a wet fuel by a dispersant used in
stability packages. Examples of demulsifiers/anti-haze additives
available from Innospec Inc. of Newark, Del. are DDH 10 and DDH
20.
[0232] Antioxidants are used to inhibit the degradation of fuels by
interaction of the fuel with atmospheric oxygen. This process is
known as "Oxidative Instability". The oxidation of the fuel results
in the formation of alcohols, aldehydes, ketones, carboxylic acids
and further reaction products of these functional groups, some of
which may yield polymers. Antioxidants function mainly by
interrupting free radical chain reactions thus inhibiting peroxide
formation and fuel degradation. Examples of antioxidants additives
available from Innospec Inc. of Newark, Del. are AO 37 and AO
29.
[0233] Metal Deactivators are chelating agents that form stable
complexes with specific metals. Certain metals (e.g. copper and
zinc) are very detrimental to fuel stability as they catalyze
oxidation processes resulting in fuel degradation (increase in
gums, polymers, color, and acidity). An example of a metal
deactivator available from Innospec Inc. of Newark, Del. is
DMD.
[0234] Biocides are used to control microorganisms such as bacteria
and fungi (yeasts, molds) which can contaminate fuels. Biological
problems are generally a function of fuel system cleanliness,
specifically water removal from tanks and low point in the system.
An example of a Biocide available from Innospec Inc. of Newark,
Del. is 6500.
[0235] Thermal Stabilizers are additives which help prevent the
degradation of fuel upon exposure to elevated temperatures. Fuel
during its use cycle is exposed to varying thermal stresses. These
stresses are: 1) In storage--where temperatures are low to
moderate, 0 to 49.degree. C. (32 to 120.degree. F.), for long
periods of time, 2) In vehicle fuel systems--where temperatures are
higher depending on ambient temperature and engine system, 60 to
70.degree. C. (140 to 175.degree. F.), but the fuel is subjected to
these higher temperatures for shorter periods of time than in
normal storage, and 3) In (or near) the engine--where temperatures
reach temperatures as high as 150.degree. C. (302.degree. F.)
before injection or recycling, but for even shorter periods of
time. Thermal stability additives protect the fuel
uniformity/stability against these types of exposures. Examples of
thermal stabilizers available from Innospec Inc. of Newark, Dela.
are FOA 3 and FOA 6.
[0236] Anti-foams additives are mainly utilized to prevent foaming
of the fuel during pumping, transport and use. Examples of
anti-foams available in the marketed are the TEGOPREN.TM.
(available from Dow Coming), SAG.TM. (available from ex OSi--now
Dow), and RHODORSIL.TM. (available from ex Rhone Poulenc).
[0237] Conductivity Additives/Static Dissipaters/Electrical
Conductivity additives are used to minimize the risk of
electrostatic ignition in hydrocarbons fuels and solvents. It is
widely known that electrostatic charges can be frictionally
transferred between two dissimilar, nonconductive materials. When
this occurs, the electrostatic charge thus created appears at the
surfaces of the contacting materials. The magnitude of the
generated charge is dependent upon the nature of and, more
particularly, the respective conductivity of each material.
Electrostatic charging is known to occur when solvents and fuels
flow through conduits with high surface area or through "fine"
filters. The potential for electrostatic ignition and explosion is
probably at its greatest during product handling, transfer and
transportation. Thus, the situations which are of greatest interest
to the petroleum industry are conditions where charge is built up
in or around flammable liquids, and the possibility of discharge
leading to incendiary sparking, and perhaps to a serious fire or
explosion. Countermeasures designed to prevent accumulation of
electrostatic charges on a container being filled such as container
grounding (i.e. "earthing") and bonding are routinely employed.
However, it has been recognized that grounding and bonding alone
are insufficient to prevent electrostatic build-up in low
conductivity, volatile organic liquids. Organic liquids such as
distillate fuels like diesel, gasoline, jet fuel, turbine fuels and
kerosene, and relatively contaminant free light hydrocarbon oils
such as organic solvents and cleaning fluids are inherently poor
conductors. Static charge accumulates in these fluids because
electric charge moves very slowly through these liquids and can
take a considerable time to reach a surface which is grounded.
Until the charge is dissipated, a high surface-voltage potential
can be achieved which can create an incendiary spark, resulting in
an ignition or an explosion. The increased hazard presented by low
conductivity organic liquids can be addressed by the use of
additives to increase the conductivity of the respective fluids.
The increased conductivity of the liquid will substantially reduce
the time necessary for any charges that exist in the liquid to be
conducted away by the grounded inside surface of the container.
Examples of conductivity additives available from Innospec Inc. of
Newark, Del. are Stadis.RTM. 425 and Stadis.RTM. 450.
[0238] The general chemistries and compositions of these additive
families which function to impart or enhance the desired fuel
characteristics are fully known in the art. A person having
ordinary skill in the art to which this invention pertains can
readily select an additive to achieve the enhancement of the
desired fuel property.
[0239] The invention is further described by the following
illustrative but non-limiting examples. The following examples
depict affect of the novel additive composition on particulate
inhibition in renewable fuels and renewable fuel petroleum fuel
blends.
EXAMPLES
[0240] Certain substances that are soluble or appear to be soluble
in renewable fuel or in renewable fuel petroleum blends at ambient
temperatures can upon cooling or standing for extended periods,
come out of solution and possibly block fuel delivery systems.
[0241] Two testing methods were used to assess the propensity of a
fuel to form in-soluble substances during extended storage.
[0242] Particulate Inhibition testing method--Filtration Test
(ASTM):
[0243] This test method covers the determination by filtration time
after cold soak the suitability of a Biodiesel (B100) for blending
with light-middle and middle distillates to provide adequate low
temperature operability performance to at least the cloud point of
the finished blend. The test method can be used as a means of
evaluating the propensity of a biodiesel and biodiesel blends to
cause fuel filter plugging. Fuels that give short filtration times
are expected to give satisfactory operation down to the cloud point
of biodiesel blends.
[0244] Testing Procedure: Place 300 mL of sample in a glass 500 mL
bottle and set in a liquid or air bath or chamber at 4.4.degree.
C..+-.1.1.degree. C. (40.degree. F..+-.2.degree. F.) for 16.+-.0.5
hours. After the 16 hour cold soak is completed, allow the sample
to come back to room temperature (20-22.degree. C./68-72.degree.
F./) on its own without external heating. The sample shall be
completely liquid before filtration. The sample should be filtered
within 1 hour after reaching 20-22.degree. C. (68-72.degree. F.).
Complete assembly of the receiving flask, 0.7 micron glass fiber
filter and funnel as a unit (see FIG. 1) before swirling the
sample. To minimize operator,exposure to fumes, the filtering
procedure should be performed in a fume hood. Start the vacuum
system. Record the vacuum in kPa (inches of Hg) after one minute of
filtration. The vacuum shall be between 71.1 and 84.7 kPa (21 and
25 inches of Hg). If the vacuum is not within the specified range,
make adjustments to the vacuum system. Thoroughly clean the outside
of the sample container in the region of the cap by wiping it with
a damp, lint-free cloth. Swirl the container vigorously for about
2-3 seconds to dislodge any particles that may have adhered to the
walls of the container. Immediately after swirling, pour the entire
contents of the sample container into the filtration funnel and
simultaneously start the timer. The entire contents of the sample
container shall be filtered through the glass fiber filter to
ensure a correct measure of the contamination in the sample. Care
must be taken not to shake the sample vigorously as this could
cause some of the solids to go back into solution. If the
filtration is not complete when 720 seconds (12 minutes) has
elapsed, turn off the vacuum system and record the duration of the
filtration to the nearest second. Record the vacuum just before the
termination of the filtration, and also record the volume which was
filtered after 720 seconds.
[0245] Bio Diesel (B100) from different feed stocks were evaluated
as per the filtration method. Table 1 denotes the filtration times
for the base fuels.
TABLE-US-00001 TABLE 1 Untreated Fuel Time mls Vacuum mmHg Palm 19
sec 300 15 Tallow 12 mins 80 15 Coconut 11 sec 300 19 Soy 10 sec
300 16 Soy 14 sec 300 14
[0246] The respective B100's were treated with 2000 mg/l of a
particulate inhibitor formulation. The treated samples were
evaluated as per ASTM filtration method. Table 2 denotes the
filtration times for the treated fuels.
TABLE-US-00002 TABLE 2 Particulate Inhibitor Formulation Fuel Time
mls Vacuum mmHg Palm 14 sec 300 15* Tallow 6 min 55 sec 300 14
Coconut 9 sec 300 15 Soy 9 sec 300 15 Soy 14 sec 300 14
[0247] Data clearly indicates that an additive can enhance bio
diesel filterability times. The additive evaluated in the study was
a bio diesel particulate inhibiting additive, composed 60% of a
acrylic acid polymer and 40% diluents.
[0248] Particulate Inhibition testing method--Visual Test:
[0249] The two soy (B100) biodiesel samples evaluated in the
filtration experiment were further stressed to measure the impact
of low temperature extended storage on particulate formation. While
both the base fuel samples tested had performed very well in the
filtration test method, there is industry concern that the
filtration method may not be fully adequate to predict particulate
formation under field use conditions.
[0250] Two sets of Soy samples (containing blanks and additized
fuels) were cooled and held at -5C for 5 days. The temperature of
the test was well below the pour point (0C, 32F) of either base bio
diesels. The fuels were treated with 2000 mg/l of the additive
formulation.
[0251] The components used in the additive formulation to test the
two fuels are listed in table 3A and Table 3 B.
TABLE-US-00003 TABLE 3A Particulate Solvent - Agglomeration
Particulate Settling Compatibility Soy Retarder Dispersant
Inhibitor Enhancer A Biodiesel 1 60 0 0 10 30 2 40 10 10 10 30 3 30
20 10 10 30 4 50 10 0 10 30 5 40 20 0 10 30
TABLE-US-00004 TABLE 3B Particulate Solvent - Agglomeration
Particulate Settling Compatibility Soy Retarder Dispersant
Inhibitor Enhancer B Biodiesel 6 60 0 0 10 30 7 40 10 10 10 30 8 30
20 10 10 30 9 50 10 0 10 30 10 40 20 0 10 30
[0252] The specific formulation components selected for evaluation
of formulation component performance were: Agglomeration
Retarder--Viscoplex 10390 obtained from Rhomax, Particulate
Dispersant--OMA 350 obtained form Innospec Fuel Specialties LLC,
Particulate Settling Inhibitor Dodiwax 4500 obtained from Clariant,
Compatibility Enhancer A--2-ethylhexanol--and Compatibility
Enhancer B--Butoxy ethanol
[0253] The cold stored fuels were evaluated for particulate
formation and visibly rated with the best being little or no of
visible particulates, to the worst being sample that contains the
most visible particulates. It is important to note that while some
of the formulations performed better than others, they all
performed better than the untreated sample which was completely
solid after 2 day of storage. The 5 day storage results are listed
in table 4.
TABLE-US-00005 TABLE 4 Inhibition of Particulate Formation Day 1
Day 2 Day 5 Fuel I Best 2, 7, 6 7, 2 2, 7 5, 4, 1 5, 6, 4, 1 5, 6,
4, 1 9, 10 9, 10 9, 10 8, 3 8, 3 8, 3 Worst Base Fuel I Base Fuel I
Base Fuel I Fuel II Best 3, 6, 5 6, 7, 2 4, 7 4, 7, 9 4, 8, 3 3, 8,
2 8, 10, 2 10, 5 6, 10, 9 1 1, 9 5, 1 Worst Base Fuel II Base Fuel
II Base Fuel II
[0254] The order of performance of the additives in Fuel I (Least
to most solids) was 2,7>5,6,4,1>9,10>8,3>>base Fuel
I; and for Fuel II was 4,7>2,3,8>6,9>5,1>>base Fuel
II.
[0255] The results clearly indicate an enhancement of particulate
inhibition in bio diesel, specifically the ability of the additive
package to diminish particulate formation and inhibit gelling of
the bio fuel.
[0256] All of the compositions and methods disclosed and claimed
herein can be made and executed without undue experimentation in
light of the present disclosure. While the compositions and methods
of this invention have been described in terms of preferred
embodiments, it will be apparent to those skilled in the art that
variations may be applied to the compositions and/or methods and in
the steps or in the sequence of steps of the methods described
herein without departing from the concept, spirit and scope of the
invention. More specifically, it will be apparent that certain
agents which are both chemically and physiologically related may be
substituted for the agents described herein where the same or
similar results would be achieved. All such similar substitutes and
modifications apparent to those skilled in the art are deemed to be
within the spirit, scope and concept of the invention as defined by
the appended claims.
* * * * *