CA2378505A1 - Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel compositions - Google Patents

Abstract

This invention relates to a process for making an aqueous hydrocarbon fuel composition, comprising: (A) mixing a normally liquid hydrocarbon fuel and at least one chemical additive to form a hydrocarbon fuel-additive mixture; and (B) mixing said hydrocarbon fuel-additive mixture with water under high shear mixing conditions in a high shear mixer to form said aqueous hydrocarbon fuel composition, said aqueous hydrocarbon fuel composition including a discontinuous aqueous phase, said discontinuous aqueous phase being comprised of aqueous droplets having a mean diameter of 1.0micron or less. An apparatus for operating the foregoing process is also disclosed. Aqueous hydrocarbon fuel compositions are disclosed.

Description

WO 01/04239 - ~ - PCT/US00/17767 Title: PROCESS AND APPARATUS FOR MAKING AQUEOUS
HYDROCARBON FUEL COMPOSITIONS, AND AQUEOUS
HYDROCARBON FUEL COMPOSITIONS
s This application is a continuation-in-part of U.S. application Serial No.
09/390,925, filed on September 7, 1999, that is a continuation-in-part of U.S.
Application Serial No. 09/349,268, filed July 7, 1999. Each of the disclosures of both prior applications is incorporated herein by reference in its entirety.
io Technical Field This invention relates to a process and apparatus for making aqueous hydrocarbon fuel compositions. The invention also relates to stable aqueous hydrocarbon fuel compositions. The process and apparatus are suitable for dispensing the fuels to end users in wide distribution networks.
is Background of the Invention Internal combustion engines, especially diesel engines, using water mixed with fuel in the combustion chamber can produce lower NOx, hydrocarbon and particulate emissions per unit of power output. However, a problem with adding water relates to the fact that emulsions form in the fuel and 2o these emulsions tend to be unstable. This has reduced the utility of these fuels in the marketplace. It would be advantageous to enhance the stability of these fuels sufficiently to make them useful in the marketplace. Another problem relates to the fact that due to the instability associated with these fuels, it is difficult to make them available to end users in a wide distribution network.
The 2s fuels tend to break down before they reach the end user. It would be advantageous to provide a process and apparatus that could be used for blending these fuels at the dispensing site for the end user and therefore make the fuels available to end users in wide distribution networks.
Summary of the Invention 3o This invention provides for a process for making an aqueous hydrocarbon fuel composition, comprising: (A) mixing a normally liquid hydrocarbon fuel and at least one chemical additive to form a hydrocarbon fuel-additive mixture; and (B) mixing said hydrocarbon fuel-additive mixture with water under high-shear mixing conditions in a high-shear mixer to form said 3s aqueous hydrocarbon fuel composition, said aqueous hydrocarbon fuel composition including a discontinuous aqueous phase, said discontinuous aqueous phase being comprised of aqueous droplets having a mean diameter of 1.0 micron or less. A critical feature of this invention relates to the fact that the aqueous phase droplets have a mean diameter of 1.0 micron or less. This s feature is directly related to the enhanced stability characteristics of the inventive aqueous hydrocarbon fuel compositions.
This invention further provides for an apparatus for making an aqueous hydrocarbon fuel composition, comprising: a high shear mixer; a blend tank; a chemical additive storage tank and a pump and conduit for transferring a io chemical additive from said chemical additive storage tank to said blend tank; a conduit for transferring a hydrocarbon fuel from a hydrocarbon fuel source to said blend tank; a conduit for transferring a hydrocarbon fuel-additive mixture from said blend tank to said high-shear mixer; a water conduit for transferring water from a water source to said high-shear mixer; a fuel storage tank; a is conduit for transferring an aqueous hydrocarbon fuel composition from said high-shear mixer to said fuel storage tank; a conduit for dispensing said aqueous hydrocarbon fuel composition from said fuel storage tank; a programmable logic controller for controlling: (i) the transfer of said chemical additive from said chemical additive storage tank to said blend tank; (ii) the 2o transfer of said hydrocarbon fuel from said hydrocarbon fuel source to said blend tank; (iii) the transfer of said hydrocarbon fuel-additive mixture from said blend tank to said high shear mixer; (iv) the transfer of water from said water source to said high shear mixer; (v) the mixing of said hydrocarbon fuel-additive mixture and said water in said high shear mixer; and (vi) the transfer of said 2s aqueous hydrocarbon fuel composition from said high shear mixer to said fuel storage tank; and a computer for controlling said programmable logic controller.
In one embodiment, the inventive apparatus is in the form of a containerized equipment package or unit that operates automatically. This unit can be programmed and monitored locally at the site of its installation, or it can 3o be programmed and monitored from a location remote from the site of its installation. The fuel is dispensed to end users at the installation site.
This provides a way to make the aqueous hydrocarbon fuels compositions prepared in accordance with the invention available to end users in wide distribution networks.

_,>-r~, .,p ..., m a Q
.~:::,~..e ~ . . ,<r . ~: ~ .,>.~aei is r .,...~:~....m~,..~....s~.~z.:aa~t'~.,, a2.:~;a ~ . ,, .
~fi 2ir117Q
~..,.,~.L~~~~r~e~ut!"xr?t~ ~::'w.,~°Sx~thid~w,::"~ ~;.~.~,,».~.:,."~
~...a, ..!~aa.. . .. ~.,.. ;
o7ixziox xo_ao FAa zxs szx sass RENNER oTTO (~oxo Docket No. 2957RI&OZ

This invention also ralates to an aqueous hydrocarbon fuel composition comprising: a continuous phase of a normally liquid hydrocarbon fuel; a discontinuous aqueous phase, said dlscorttlnuous aqueous phase being comprised of aqueous droplets having a mean diameter of 1.0 micron or less;
s and an emuls'rtying amount of an emulsifier cvmpostiion comprising (t) a hydrocarbon fuel-soluble product made by reacting a hydrocarbyl-substituted carboxylic acid acylating agent with ammonia or an amine, the hydrocarby) subsfituent of said acylating agent having 50 to 500 carbon atoms, or (ii) an ionic or a nonionic compound having a hydrophilic fipophillc balance (HLB) of to tv'10, or a mixture of (7 and ri), in combination with (iii) a water-soluble salt distinct from (t) and (i~. In a preferred embodiment, component (I) is a combination of (i)(a) at least one reaction product of an acylating agent with an alkanvl amine and (~(b) at least one reaction product of an acylating agent with at least one ethylene poiyamine. Prefe~abty, component (t)(b) is combined with is component (i)(a) in an amount from 0.05% to 0.959° based upon the total weight of component (i)_ . BMef Descrivtion of the Drawlnas In tha annexed drawings, like pads and features have like designations.
Fig. 1 is a flow sheet illustrating one embodiment of the invenfrva 2o process and apparatus.
Fig. 2 is an overhead plan view illustrating one embodiment of tha inventive apparatus that is in the form of a containerized equipment package yr unit Fg. 3 is a flow sheet illustrating the electronic communication between a is plurality of programmable Ivgic controllers associated. with corresponding apparatus for operating the inventive process, the programmable logic controllers being located n:motely from a programming computer communicating with such programmable logic controilerrs and a monitoring computer communicating with such programmable logic controllers.
3o Fg. 4A is a partial cut away view of one embodiment of the high shear mixer provided for in accordance with the invention, this high shear mixer being a rotor stator mixer having three rotor stators arranged in series_ Fig. 4B is an enlarged plan view showing the interior of one of the rotors and one of the stators illustrated in Fg. 4A.

Fig. 5 is a plot of the number of aqueous phase droplets verses droplet diameter determined for the aqueous hydrocarbon fuel composition (formulation A) produced in the Example.
Detailed Description of the Preferred Embodiments s As used herein, the terms "hydrocarbyl substituent," "hydrocarbyl group," "hydrocarbyl-substituted," "hydrocarbon group," and the like, are used to refer to a group having one or more carbon atoms directly attached to the remainder of a molecule and having a hydrocarbon or predominantly hydrocarbon character. Examples include:
io (1) purely hydrocarbon groups, that is, aliphatic (e.g., alkyl, alkenyl or alkylene), and alicyclic (e.g., cycloalkyl, cycloalkenyl) groups, aromatic groups, and aromatic-, aliphatic-, and alicyclic-substituted aromatic groups, as well as cyclic groups wherein the ring is completed through another portion of the molecule (e.g., two substituents together forming an alicyclic group);
is (2) substituted hydrocarbon groups, that is, hydrocarbon groups containing non-hydrocarbon groups that, in the context of this invention, do not alter the predominantly hydrocarbon nature of the group (e.g., halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
(3) hetero substituted hydrocarbon groups, that is, hydrocarbon groups 2o containing substituents that, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteratoms include sulfur, oxygen, nitrogen. In general, no more than two, and in one embodiment no more than one, non-hydrocarbon substituent is present for every ten carbon 2s atoms in the hydrocarbon group.
The term "lower" when used in conjunction with terms such as alkyl, alkenyl, and alkoxy, is intended to describe such groups that contain a total of up to 7 carbon atoms.
The term "water-soluble" refers to materials that are soluble in water to 3o the extent of at least one gram per 100 milliliters of water at 25°C.
The term "fuel-soluble" refers to materials that are soluble in a normally liquid hydrocarbon fuel (e.g. gasoline or diesel fuel) to the extent of at least one gram per 100 milliliters of fuels at 25°C.

- 5 - PCT/(JS00/17767 The Process and Apparatus The inventive process may be conducted on a batch basis or on a continuous basis. The process and apparatus described below relates to a batch process. Referring initially to Fig. 1, the apparatus includes high shear s mixer 10, blend tank 12, hydrocarbon fuel inlet 14, chemical additive storage tank 16, water storage tank 18, antifreeze agent storage tank 20, aqueous hydrocarbon fuel storage tank 22, and fuel dispenser 24.
Hydrocarbon fuel enters through hydrocarbon fuel inlet 14 and flows to blend tank 12 through conduit 30. Arranged in series along conduit 30 between io inlet 14 and blend tank 12 are isolation valve 32, pressure gauge 34, strainer 36, pump 38, solenoid valve 40, flow meter and totalizer 42, calibration outlet valve 44, check valve 46 and isolation valve 48.
Conduit 50 extends from chemical additive storage tank 16 to blend tank 12 and is adapted for transferring the chemical additive from chemical additive is storage tank 16 to blend tank 12. Arranged in series along conduit 50 are isolation valve 52, quick disconnect 54, isolation valve 56, strainer 58, pump 60, solenoid valve 62, flow meter and totalizer 64, calibration outlet valve 66, check valve 68 and isolation valve 69.
Conduit 70 extends from water storage tank 18 to connecting tee 71 2o where it connects with conduit 90. Arranged in series along conduit 70 between water storage tank 18 and connecting tee 71 are valves 72 and 73, strainer 74, pump 76, solenoid valve 78, flow meter and totalizer 80, calibration outlet valve 81, check valve 82, and isolation valve 83. Conduit 84 extends from water inlet 85 to water deionizer 86. Conduit 87 extends from water 2s deionizer 86 to water storage tank 18 Conduit 90 extends from antifreeze storage tank 20 to connecting tee 71. Arranged in series along conduit 90 between antifreeze agent storage tank 20 and connecting tee 71 are valves 92 and 94, strainer 96, pump 98, solenoid valve 100, flow meter and totalizer 102, check valve 104 and isolation valve 106.
3o Conduit 108 extends from connecting tee 71 to connecting tee 110.
Conduit 116 extends from blend tank 12 to connecting tee 110. Actuated valve 118 is positioned between blend tank 12 and connecting tee 110 in conduit 116. Conduit 112 extends from connecting tee 110 to the inlet to high shear mixer 10. Check valve 114 is located in conduit 112 between connecting tee 110 and the inlet to high shear mixer 10.
Conduit 120 extends from the outlet to high shear mixer 10 to aqueous hydrocarbon fuel storage tank 22. Arranged in series along conduit 120 are s throttling valve 122, connecting tee 124 and actuated valve 126. Conduit 130 extends from connector tee 124 to blend tank 12. Actuated valve 132 is positioned in conduit 130 between connecting tee 124 and blend tank 12.
Conduit 130 is provided for recycling the mixture of hydrocarbon fuel-additive mixture and water (and optionally antifreeze agent) back through blend tank 12 io and then again through high shear mixer 10.
Conduit 135 extends from aqueous hydrocarbon fuel storage tank 22 to connecting tee 110 and is provided for recycling aqueous hydrocarbon fuel composition from tank 22 back through high shear mixer 10 when it is desired to subject the aqueous hydrocarbon fuel composition to additional high shear is mixing. Arranged in series along conduit 135 are isolation valve 136, actuated valve 137 and calibration outlet valve 138. This recycling can be done to avoid undesired settling in tank 22 after the aqueous hydrocarbon fuel composition has been blended.
Conduit 140 extends from aqueous hydrocarbon fuel storage tank 22 to 2o fuel dispenser 24. Dispensing pump 142 is connected to conduit 140 and is positioned between aqueous hydrocarbon fuel storage tank 22 and fuel dispenser 24. Dispensing pump 142 is adapted for pumping the aqueous hydrocarbon fuel composition from aqueous hydrocarbon fuel storage tank 22 to fuel dispenser 24. Users of the aqueous hydrocarbon fuel composition may 2s obtain the fuel from dispenser 24.
A programmable logic controller (PLC), not shown in Fig. 1, is provided for controlling: (i) the transfer of chemical additive from the chemical additive storage tank 16 to blend tank 12; (ii) the transfer of hydrocarbon fuel from hydrocarbon fuel inlet 14 to the blend tank 12; (iii) the transfer of hydrocarbon 3o fuel-additive mixture from the blend tank 12 to high shear mixer 10; (iv) the transfer of water from the water storage tank 18 to high shear mixer 10; (v) the mixing in high shear mixer 10 of the hydrocarbon fuel-additive mixture and the water; and (vi) the transfer of the aqueous hydrocarbon fuel composition from the high shear mixer 10 to the aqueous hydrocarbon fuel storage tank 22.

When an antifreeze agent is used, the PLC controls the transfer of the antifreeze agent from the antifreeze agent storage tank 20 to connecting tee where it is mixed with water from conduit 70. When it is desired to recycle the aqueous hydrocarbon fuel composition through mixer 10 for additional high s shear mixing, the PLC also controls such recycling. The PLC stores component percentages input by the operator. The PLC then uses these percentages to define volumes of each component required. A blending sequence is programmed into the PLC. The PLC electrically monitors all level switches, valve positions, and fluid meters.
io In operation, hydrocarbon fuel enters through inlet 14 and flows through conduit 30 to blend tank 12. The flow of the hydrocarbon fuel is controlled by the PLC that monitors and controls the flow of the hydrocarbon fuel by monitoring and controlling pump 38, solenoid valve 40, and flow meter and totalizer 42.
is The chemical additive is transferred from chemical additive storage tank 16 to blend tank 12 through conduit 50. The flow of chemical additive through conduit 50 is controlled by pump 60, solenoid valve 62, and flow meter and totalizer 64 that are monitored and controlled by the PLC.
Water is transferred from the water storage tank 18 to connecting tee 71 2o through conduit 70. The flow of water from water storage tank 18 to the connecting tee 71 is controlled by pump 76, solenoid valve 78, and flow meter and totalizer 80, that are monitored and controlled by the PLC.
The antifreeze agent is used when the process is conducted in an environment where the water may freeze. When used the antifreeze agent is 2s transferred from antifreeze storage tank 20 to connecting tee 71 through conduit 90. The flow of the antifreeze agent through conduit 90 is controlled by pump 98, solenoid valve 100, and flow meter and totalizer 102, that are monitored and controlled by the PLC.
The hydrocarbon fuel and the chemical additive are mixed in blend tank 30 12. The resulting hydrocarbon fuel-additive mixture is transferred from blend tank 12 to connecting tee 110 through conduit 116. The flow of hydrocarbon fuel-additive mixture from blend tank 12 is controlled by actuated valve 118 that is controlled by the PLC. Water flows from connecting tee 71 to connecting tee 110 through conduit 108. The antifreeze agent, when used, mixes with the ~xaa .aa~~,s~~aa9~Y~c ~~F ,.k ;y w y., 's~~g'~3 ~=: . '~~Y'~' ~P~~. X~~'~v d ~., '=~;~a~',MF ..~. . ~ 5a :f .
1 ~ : ~~~ fi 6 .: ,~,-;.-~; pr..a:;s ..e r:r..:
e~ ,~ .;! -yE t ~ . ',k, t v. _ d _ .
E~ ~y,~~ ,~. .~g 2!3-~C-2~~1' x . .y~, "~ ; ~~~50~~1 ~: .6~ .2 . ~fl6=2 ..:
i7i.~~,~7T..,4...,a.=i.~. . ~ I \ ~'' E
~%n~~.it. ' i:~ °~j,.:~~;'e',~icka.aW.~'i'. .4~.,;.aw~iu, _*r 07/12/01 10: ~'1 FAa 216 621 6165 REIQNER OTTO
oodoec r~o. z9~-rRis.ot water in connecting tee 71 and the resulting mixture of antifreeze agent and water flows to connecting 110. in connecting tee 110, the hydrocarbon fuel-additive niucture is mixed with the water and, if used, the antifreeze agent.
Connecting tea 110 is located at the entrance to high shear mixer 10. The s mbttuce of hydrocarbon fuel-additive and wafer, and optionally antifreeze agent, is then transferred to high shear mixer 10 wherein it is subjected to high shear mixing.
In one embodiment, the initial mixing of the hydrocarbon fuel-additive mixture and water (and vptionaily antifreeze agent) during step (8) of inventive 1o process occurs in the high shear mixer 10 or at the inlet to high shear mixer 10.
In one embodiment, high shear mixing is commenced up to 15 seconds after such initial mbdng, and in one embodiment 2 to 15 seconds, and in one embodiment 5 to 10 seconds after such initial mbdng. The high shear mixing of the hydrocarbon fuel-additive mixture and water (and optionally is antifreeze agent) results in the formation of the desired aqueous hydrocarbon fuel composition. A critical feature of the invention is that the water phase of the aqueous hydrocarbon fuel composition is comprised of droplets having a mean diameter of 1.0 micron or less. Thus, the high shear mixing is conducted under sufficient conditions to provide such a droplet siz~. In one embodiment, zo the mean droplet size is less than D.95 micron, and in one embodiment less than 0.8 micron, and in one embodiment less than 0.7 miaon. In a preferred embodiment, the mean droplet size is in the range of 0.01 to 0.95 micron, more preferably 0.01 to 0.8 micron, more prefierably 0.01 to 0.7 micron. In an especially proferred embodiment, the droplet size is in the range of 0.1 to O.T
zs micron.
The aqueous hydrocarbon fuel composition can be recycled through conduits 130, 116 and 112, and tank 12 in order to obtain the desired droplet size. This recycling is controlled by actuated valves 118, 126 and 132 that are controlled by the PLC. In one embodiment, the aqueous hydrocarbon fuel 3o composition is recycled 1 to 35 times, and in one embodiment 1 to 10 times, and in one embodiment 1 to 5 times.
When the desired droplet size is achieved, the aqueous hydrocarbon fuel composition is stored in aqueous hydrocarbon fuel composition storage __ ._ __ _ ._ __ ~. . _~,.~ ., "..

Fc,~''*g' ~r"1~, k ' i~.. ~~' ''~.~ ~ ... -~~ rs~'~.:~".C or,. ...~..,. ~ r.4.t,'.t~'v'~ r~'~~w'=w.
ms >'..k;. Y, ~'pt:?:; ~!: . ...,a ~ i'~'_ r-v~.~ .~: , .$, ..;~. ~.u ~ c~, n~
,ri,Y.. ~ .'.. ': ' a .' ::, ,, .
.,~ ... ..5 ,.. . . ' . i 'C~' ~/''~~///'~)~ .. ~ ':ak~~~J.,,~.
S:Q~ ~,: ~~' ~28-0E'-a,~:
o7nz~oi lo:al,~AB zir 621 615 ~ ~:E~~.~s~r.~...~: ":;~~ :~,~~,:
RENNER OTTO I~ 012 Docket No. 2957R/B-OI

. tank 22. The aqueous hydrocarbon fuel composition that is stored in storage tank 22 is a stable emulsion that, in one embodiment, can remain stable for at least 90 days at a temperature of 25'C, and in one embodiment at least 60 days, and in one embodiment at least 30 days. The aqueous hydrocarbon fuel s composition may be dispensed from storage tank Z2 through dispenser 24.
The aqueous hydrocarbon fuel composition flows trvm storage tank 22 to dispenser 24 through conduit 140. T'he flow of the aqueous hydrocarbon fciel composition through conduit 140 is controlled by pump 142.
The chemical additkre storage tank 16 has a Ivw-level alarm switch 190 io incorporated into it When the level in the tank 16 drops below the low-level switch, a Ivw level alarm is activated. The batch in progress when the low-level alarm condition occurs is permitted to finish. This is possible because sufficient volume exists below the ~ level of the switch to do a complete batch. Further batch blending is prevented ucrtii the low level is cvrrecbed and the alarm is 1s reset.
When chemical additive is called for in the blending process, pump 60 is started. This pump. that in one embodiment is a centrifugal pump, supplies chemical addictive to the blend tank 12. If the pump falls to start or if its starter overload tircuit trips, an alamt signal is sent to the PLC. The PLC shuts down 2o the batch in progress and at~tivates an alarm. 1=urther operation is prevented until the fault is corrected.
In one embodiment, the flew mefer of the flow meter and totalizer 64 is an oval gear meter with high resolution. An electronic pulse pickup is utilized to read revolutions of the meter The meter provides better than one electrical 2s pulse per milliliter An electronic factoring totaiizer accumulates pulses generated by the meter. Calibrated during inifial setup,'the totalizer resvhres the volumetric pulses into hundredths of gallons of chemical additive delivered.
wrth each one hundredth of a gallon of flow, an electrical pulse is transmitted to the PLC. Based upon this flow the totallzer counts up to. a target volume of so chemical additive and then toms off the chemical additive flow.
Solenoid valve 62 controls the chemical addiflve flow. The PLC actuates this valve when additive flow is needed. Strainer 58 in conduit 50 prevents any solid contaminates from damaging the flow meter and totalizer 64. Valve 69, ' that may be a manually operated ball valve, is used to isolate the chemical ~'r~n~ed~'8 ~3"~~1 ~ ~;.~ . r°
I-__t __ . ~ . y rn~ rnnn, ».nr additive during calibration and to throttle the flow of chemical additive.
Valve 66, which may be a manually operated ball valve, is used to isolate a calibration tap. This tap is utilized to catch a volumetric sample during calibration of the totalizer of the flow meter and totalizer 64.
s The antifreeze agent storage tank 20 has a low-level alarm switch 192 incorporated into it. When the level in the storage tank 20 drops below the low-level switch, a low-level alarm is activated. The batch in progress when the low-level alarm condition occurs is permitted to complete. This is possible because sufficient volume exists below the level of the switch to do a complete io batch. Further batch blending is prevented until the low level is corrected and the alarm is reset.
When antifreeze agent is called for in the blending process, pump 98 is started. Pump 98, that in one embodiment is a centrifugal pump, supplies antifreeze agent to connecting tee 71 where the antifreeze agent mixes with is water from conduit 70. If pump 98 fails to start or if its starter overload circuit trips, an alarm signal is sent to the PLC. The PLC shuts down the batch in progress and activates an alarm. Further batch blending is prevented until the fault is corrected and the alarm is reset.
In one embodiment, the flow meter of flow meter and totalizer 102 is an 20 oval gear meter with high resolution. An electronic pulse pickup is utilized to read revolutions of the meter. The meter provides better than one electrical pulse per milliliter. The totalizer, that is an electronic factoring totalizer, accumulates pulses generated by the meter. Calibrated during initial setup, the totalizer resolves the volumetric pulses into hundredths of gallons of antifreeze 2s agent delivered. With each one hundredth of a gallon of flow, an electrical pulse is transmitted to the PLC. Based upon this flow the totalizer counts up to a target volume of antifreeze agent and turns off the antifreeze agent flow.
Solenoid valve 100 controls the antifreeze agent flow. The PLC
actuates this valve when the antifreeze agent flow is needed. Strainer 96 in 3o conduit 90 prevents any solid contaminates from damaging flow meter and totalizer 102. Valve 106, that may be a manually operated ball valve, is used to isolate the antifreeze agent during calibration and to throttle flow of the antifreeze agent during normal operation. Valve 103, that may be a manually operated ball valve, is used to isolate a calibration tap. This tap is utilized to ye, c.~.r.,w p, r.. ~.xei.~.!~;~: ~c,.~y~ z ~s~.o- x.x.',~y~., .~"'.~
;x~..x"~~x , t' n r ,:r..
.~. .v ~. ~'.'.. ~;s ,~zf E"~""wr u;.*.'ts..
'xi .~~r~. n , . a ' ~:- ' , y y, .
~::a .. ~.. ~u,-,., ~ , .~. , ~ ' . x. °E~.",: ~ ~ ';,.~w~, ~ ~ ~ ~DQ~ ~.
.,~~,.x::. ~,~ ~,k=' ,~ ~~ 2.8 Ufi-~0 t~
07/12/01 10:1. FAa 216 821 6165 FtEIVNER OTTO ~ol~l Dod~et No. Z957R/8-02 catch a volumetric sample during the calibration of the flow meter and tvtatizer 102.
In one embodiment, the water.is dsionized. For smaller volume demand systems water may be taken fnsm a municipal supply and passed through a s deionizing unit B6 and then into storage tank 18. For high capacit)r systems, larger deionizing units may be used, or buck delivery of water may be used. In one embodiment, water storage tank 18 is a 550-gallon (2083.3-liter) maximum fill, stainless steel tote, or a similarly sized polymeric material tank.
The water storage tank 18 has a low-level alarm switch 194 incorporated 1o into it. When the level in the water storage tank 18 drops below the low-level switch, a low-level alarm is activated. The batdt in progress when the low level alarm condition occurs is permitted to complete. This is possible because suffiaent volume exists below the level of the switch to do a complete batch.
Further batch blending is prevented until the tow level is corrected and the 1s alarm is reset The water storage tank 18 also has a higtNevel float switch in it This switch is used in conjunction with a solenoid valve in the water supply line tank i 8 to automatically control re-filling of the water storage tank 18.
llVhen water is called for in the blending process, pump 76 is started.
2o Pump 76, which may be a caMrifugal pump, supplies water to connecting tee 71 where the water mixes with the antifreeze agent when an antifreeze agent is used. If the pump 76 falls to start or if its starter overload araait trips, an alamt signal is sent to the PLC. The PLC shuts down the batch in progress and activates an alarm. Further hatch blending is prevented until the fault is 25 corrected and the alarm is reset.
(n one embodiment, the flow meter of the flow meter and totalizer 80 is an oval gear meter with moderately high resolution. An electronic pulse pickup is utilized to read revolutions of the meter. The meter can provide approximately 760 pulses per gallon (2878.8 pulses per liter) of water passing through it.
The 30 tvhaliz~er is an electronic factoring tvtalizer tfiat accumulates pulses generated by the meter. Calibrated during initial setup, the totalizer resolves the volumetric ~. pulses into tenths of gallons of water delivered. With each orie tenth of a gallon of flew, an electrical pulse is transmitted to the PLC. Based upon this flew the PLC counts up to a target volume of water and turns ofP water flew.
'~i~~e~~s~~7X2oi~i ~__a,a ~ .

'~'~ :' '~p, . ~'!t~; "°'TG,'- , ~ , ...x ~, e:n, . u- ..:: n,",.:
~'t~ , ~ , ' , :;. w ~, ~, 07/12/01 10: 32 F.4a 216 621 6165 REAR pTTp ~ 014 Docket No. 2957RI&OZ

Solenoid valve 78 ~ntrvls the water flow. The PLC actuates this valve when water is needed. Strainer 74 in conduit 70 prevenfs any solid contaminates from damaging the flow meter and totalizer 80. Valve 83, that may be a manually operated ball valve, is used to isolate the water during s ralibrativn and to throttle flow of the water componettts during normal operaflon. Valve 81, that may be a manually operated ball valve, isolates a calibration tap. This tap is utilized to cafi~h a volumetric sample during the calibration of the totaf~zer of flow meter and totaiizer 80.
When fuel is called for in the blending process, pump 38 is started. This io pump, that may be a centrifugal pump, supplies fuel to blend tank 12 through conduit 30. if the pump fails to start or if its starter overload circuit trips, an alarm signal is sent to the PLC. The PLC shuts down the batch in progress and activates an alaml_ Further batch blending is prevented until the fault is corrected and the alarm is reset.
1s In one embodiment, the flew meter of th~ flow meter and totahzer 42 is an oval gear meter with moderately high resolution. An electronic pulse pickup is utilized to read revolutions of the meter. The meiJer can provide approximately 135 pulses (511.4 pulses per liter) per gallon of fuel passing through it. The tofal'rzer, that can be an electronic factoring totalizer, Zo accumulates pulses generated by the meter. Calibrated during initial setup, the totalizer resolves the volumetric pulses into tenths of gallons of fuel delivered.
Witfi each one-tenth of a gallon of flow, an electrical pulse is transmitted to the PLC. Based upon this flow the controller counts up to a target volume of fuel and toms off fuel flow.
is Solenoid valve 40 controls fuel flow. The PLC actuates this valve when fuel- is needed in the blend. Strainer 36 in conduit 30 prevents any solid contaminates from damaging the flow meter and tataUzer 42. Valve 48, that may ba a manually operated ball valve, is used to isolate the fuel during calibration and to throttle the flow of the fuel during normal operation. Valve 44, that may be a manually 30 operated baA valve, is used to isolate a calibration tap. This tap is utilized to catG1 a volumetric sample during the calibration of the totalizer.
Blend lank 12, which in one embodiment may be a vertically oriented cylindrical steel tank, is used as a mtxing vessel. In one embodiment, this tank has a capacity of approximately 130 gallons (492.4 liters), This tank may be equipped w,~lt a ~l~r~i~te~~~l~f't~ -~~
,., ,. . _.' Y "i- ~~ .a, 72' .,..;~ wt C t s~ lP7lf1? /nflnl 17~n? r _ r .rnr n n~ . .

two liquid level float switches 196 and 197. The high-level switch 196 is used to warn the PLC if the tank 12 has been overfilled during the blending process.
This may occur if a flow meter fails. The low-level switch 197 is used by the PLC to shut off high-shear mixer 10. Blend tank 12 includes conduit 198 and valve 199 that are used for draining the contents of tank 12.
The high-shear mixer 10 may be a rotor-stator mixer, an ultrasonic mixer or a high-pressure homogenizer. The rotor-stator mixer may be comprised of a first rotor-stator and a second rotor-stator arranged in series. The hydrocarbon fuel-additive mixture and water are mixed in the first rotor-stator and then the io second rotor-stator to form the desired aqueous hydrocarbon fuel composition.
In one embodiment, a third rotor-stator is arranged in series with the first rotor stator and said second rotor-stator. The hydrocarbon fuel-additive mixture and water advance through the first rotor-stator, then through the second rotor stator, and then through the third rotor-stator to form the aqueous hydrocarbon is fuel composition.
In one embodiment, high-shear mixer 10 is an in-line rotor-stator mixer of the type illustrated in Fig. 4A. This mixer includes rotor-stators 200, 202 and 204 arranged in series. Mixer 10 has an inlet 206, an outlet 208, a mechanical seal 210, a heating or cooling jacket 212, and an inlet 214 to the heating or 2o cooling jacket 212. Each of the rotor-stators has a rotor mounted coaxially within a stator. The rotors are rotated by a motor that is not shown in Fig.

but if shown would be located to the right (in Fig. 4A) of mechanical seal 210.
The rotor-stators 200, 202 and 204 may have the same design or each may be different. In the embodiment disclosed in Fig. 4A each has the same design.
2s The rotor 220 and the stator 222 for rotor-stator 200 (or 202 or 204) are shown in Fig. 4B. Rotor 220 and stator 222 have multi-rowed arrays of teeth 224 and 226 arranged in concentric circles projecting from circular disks 221 and 223, respectively. Rotor 220 has an interior opening 225. Stator 222 has an interior opening 227 and an annular space 228 defined by circular disk 223 and 3o projecting cylindrical wall 229. Cylindrical wall 229 does not project as high as teeth 226. Rotor 220 and stator 222 are dimensioned so that the rotor 220 fits inside the stator 222 with the rotor teeth 224 and the stator teeth 226 being interleaved. The grooves between the teeth 224 and 226 may be radial or angled, continuous or interrupted. The teeth 224 and 226 may have triangular, Y ~.~'~''.~°'p"_ 'y f~~?,~'a:~H'.~'t3Y' ",:.::g~ .(.n, xw..ro s~, :~'~~
, °i~l~N°~' :;'.~ wt i:;:-;m .r~ , ,::;z:
~e ~ " ra ,y. w a, , a ..
,F~~y 4 . . B. ,~ E 'k.~. _, ~ "t: . , 4, ,":.:
4: 44-"8 ~~~ic."~~Car;~~'.~'s~3~'t~..ya?"~w-h''e.:.r~ri: ... ..~ . ~ ~! ..
L.sN~dt,~;.~.a...&~w_c~..,~-~,. -,u'~°' ~'sb., ,:
07/1E/01 lO:SE FAa 218 6Y1 6165 RENNF~ OTTO ~ 015 Docket Nv.Z957R/B-OZ

square, round, rectangular or other suitable pmtiles, with square and rectangular being particularly useful. The rotor 220 rotates at a speed of up to 10,000 rpm, and in one embodiment 1000 to 10,000 rpm, and in one embodiment 4000 to 5500 rpm, relative to the stator 222 that is stationary.
The s tangential velocity or tip speed of rotor 220 ranges from 3000 to 15,0D0 feet per minute (914.4 to 457.2 meters per second), and in one embodiment 4500 to 5400 feet per minute (1371.6 to 1645_9 meters per second). The rotation of the rotor 220 draws the mixture of hydrocarbon fuel-additive mixture and water (and optionally antifreeze agent) axially through inlet 206 inth the center to opening of rotor stator 200, defined by opening 225, and disperses the mixture radially through the concentric circles of teeth 224 and 226 and then out of rotor stator 200. The mature is then drawn through the center opening of rotor stator 202 and dispersed radially outwardly through the concentric circles of ' teeth in rotor3tator 202 and then out of rotor stator 202. The mixture is then is dravm through the center opening of rotor stator 204 and dispersed radially outwardly through the concentric circles of teeth in rotor stator 204 and then out of rotor-stator 204 to outlet 208. The mixture that is advanced through the rotor~tators 200, 202 and 204 is subjected to high.~speed mechanical and hydraulic shearing forces resulting in the formation of the desired aqueous 2o hydrocarbon fuel composroon. In one embodiment, the mixer 10 is a Dispax-Reactoi'"" Model DR3 equipped with Ultra-TurraxT" UTL-T./8 rotor stators supplied by IKA-Maschinenbau.
As indicated above, the high-shear mbcer 10 can be an u!lrasonic mixer, in this mbcer a liquid mixture of hydrocarbon fuel-additive mixture and watrer (and optionany 25 aagent) is forced under high pressure (e.g.. Z000 to 10,000 psig (103,401 to 517,006 mmHg). and in one embod'unent 4000 to 6000 psig (206,802 to 310,203 mmHg) through an oritioe at a high velocity (e.g., 100 to 400 feet per second (fps) (30.48 to 121.92 meters per second), and in one embodiment 150 to 300 fps (45.72 to 91.44 meters per second)), and directed at the edge of a blade-Gke obstacle in its path.
3o Between the orificx and blade-tike obstacle, the ~Gquid mixture sheds vortices perpendicular to the original flow vector The shedding pattern alternates such that a steady vscr'llafion. in the sonic range, occurs within the liquid rW xiure.
The stresses set up within the liquid mixture by conic osc111atlons cause the liquid mixturo to cavrtate in itte ultrasonic frequenry range. Examples of ultrasonic mixers that ., 1''il~~~c~w~'~~~D~' 2~OO
Y ~ ~.N..:. , .: . a ,:l:;

3.j '' :~ 1uw >
~. *e.. . r ..
-~e~... .
:op. s < c .w " .., - ~ o:,~~i; , ~~.~ . _d.~ a~ ~.~ ~y v QO ~ L1S ~ ~ _ ~ .
;~ . p.~SC
07/12/01 10:39 FAa E18 821 8185 "~."~"' ~c.~.~r~s,E~ x~~,~ *.~. .~,~..~~~~,~, .:~.~.~,.,w?s:.:~'a:.~ a::-r RENNER OTTO
dole Oodaet No. Z957Et1t3~OZ
can be used include Triplex Sonllator ModelsT~ XS-1500 and XS-2100 that are available from Sonic Corporation.
The high-shear mixer 10 may be a high-pressure homogenizer. In such a mixer a mixture of the hydrocarbon fuel-additive mixture and water (and 5 optionally antifreeze agent) is forced under high pressure (e.g., 10,000 to 40,000 prig (517,006 to 2,066,027 mmHg)) through a small orifice (e.g., 1/4 inch to 314 inch (0.635 to 1_905 cm) in diameter) to provide the desired mixing.
An example of a useful homogenizer is available from Miaofluidics International Corporation under the tradename Microfluidizer to The aqueous hydrocarbon fuel storage tank 22, in one embodiment, is a 550-gallon (2083.3-liter) stainless steel tote tanK. This tank may have a normal maximum fill of 500 gallons (1893.9 liters), permitting room for thermal expansion of the blend if needed.
Three float-type level detection switches 240, 242 and 244 may be 15 installed in tank 22. Switch 240, that is a high-level alarm switch guarantees that a shutdown and alarm shall occur if the storage tank level becomes abnormally high. Swltch 242, that is a batch initiate level switch, may be positioned, for example, at the 400-gallon (1515.2-liter) level in the tank.
When the amount of ttte aqueous hydrocarbon fuel composition drops bo this level in zo the tank, ttte controller may be sent a signal that initiates the blending of a 100-gallon (378.8-liter) makeup batch. Finally, switch 244 is a low level switch located near the bottom of the tank. If the aqueous hydrocarbon fuel composition reaches this level, the pump 142 is prevented from running.
The dispenser pump 142 may be located on top of the aqueous hydrocarbon zs fuel storage tank 22. This pump, that in one embodiment may be a thirty-gallorrpe' minute (113.64 liter per minute) pump, supplies fuel to the dispenser 24. Pump may be started by a nozzle stow switch located on dispenser 24. Should a Ivw-level alarm occur in tank 22, pump 142 is locked off by the PLC.
Dispenser 24 may be a high capacity unit specificaliy designed for fleet fueling 3o applications. The dispenser is placed in a position that fadlitates vehicular tn3ffic past k. The dispenser may have a manually resettable tvtalizer on it for indicating the total fuel dispensed tnto a vehicle. A one-inch (2.54 cm) hose (s.g., 30 feet (9.14 meters) in length) may be stored on a reel attached to the dispenser and used to dispense the fuel. An automatic shutoff nn~le may be used.
WCIr~te,~C la~O~~~QG1~1 r , ..;.... . ..~_, ~.~ .~, ,~~~. "_.." _ . ___ _ _ _ _ .ax~~.~.. ~;fisy:rc'~k~ ihv:,:~ft..~,.~ia."'. g.b.;;t. :~r5a.,~:~
'~ 'O; ' ~ ,y '.. '~ ''u, ,..:"°." i $,~ ~~ ,~ ,~ ~.J~Da~i~~fi~ 2~8 D6 ~000~ , .w 0 i /12/01 10: 39 FAQ 218 821 6165 llEfVNER OTTO ~ 01 i Dodaet No. 2957R/8-02 In orte embodiment, the PLC is an Allen-Bradley SLC503 programmable logic controller. A communications adapter can be installed into the unit to allow it to be remotely accessed. The adapter can be an Allen-6radley mode) 1747-KE module. To intertsce the communications adapter to a standard telephone lin~, an asynchronous personal computer (PC) modem may be used.
The process can be programmed and monitored an site ar from a remote location using personal desktop computers. In this regard, mu~iple blending operations or units can be programmed and monitored from a remote (option. This is illustrated in Fg. 5 where PC1 (personal computer No. 1) io monitors the operation of N blending units (Unit 1, Unit 2. Unit N) and PC2 (personal computer No. 2) Is used to program the operation of each blending unit. PC1 cart be operated using Rockwell Software RSsql. PC2 can be operated using Rockwell 5aftware RSlvgix. PC1 and PC2 communicate with the PLC of each blending unit through phone lines using a card/modem. PC1 is and PC2 may be run on Wndvws NT opera~ng systems.
During operation, a re~rd can be made for each of the aqueous hydrocarbon fuel compositions that are produced using PC1. This record may . ' include the amount of each blend component used, the date and time the blend was completed, a unique.batch identification number, and any alarms that may z0 have occurred during the batch. !n addition to the batdl records, two running grand totals can be produced. One is the total amount of additive used in the batches and the other is the total aqueous hydrocarbon fuel composition produced. These two numbers can be used to reconcile against the batch totals to verify production.
zs Access of data may be begun automatically with PC1. On a preprogrammed interval, PC1 dials the telephone number of the blending unit The blending unit modem answers the incoming calf and links the PC1 to the blending unit. Data requested by PC1 is automatically transferred from the blending unit to PC1 via the telephone link. PC1 then disconnects the remote 3o fink. The data retrieved is ~ansferred into an SQL (structured query language).
compliant database in PC1. The data can then be viewed or reports generated using a number of commonly available software programs (e.g., Access or F~ccel from Microsoft, or SAP R/3 from SAP AG).
4 Y y~p s ~ ~~'' ..,~g#~ ' g~~t~~~s ~'~~0~~' . , ....~ r~ -:~:3.

~.~
Y ~s . ~ ~ g , ~ ~ rn -._~'~ ~8.= ' ~~ ... a~ 2~Tp~'1.~DQQ~~ ~ ,ES ~..
0 i /12/01 10 : ~~ FIla 218 821 8165 RE1VIVER OTTO ~ 018"

Docket No.2957RIB-O2 The operating parameters of the process (e.g., high-shear mixing time, amount of each component used per batch, etc.) are controlled by the PAC.
The PLC can be programmed by PCZ. These parameters can be changed using PC2.
s in one embodiment, the inventive apparafius is in the form of containerized equipment package or unit of the type illustrated in Fig. ~ 2.
Referring to Fig. 2, the apparatus is housed within an elongated rectangular housing 260 that has access doors 262, 264, 266 and 268. The housing can be mounted on wheels to provide it with mobility for travel from one user's to location to another, or it can be permanenby mounted at one user's location.
Within the housing 260, chemical additive storage tank 16 and antifreeze agent storage tank 20 are mounted next to each other adjacent the left-side wall (as viewed in Flg. 2) of housing 260. Blending tank 12 is mounted next to chemical additive storage tank_ Pumps 38, 60 and 98, and high-shear mixer 10 are is aligned side-by-side next to tanks '16 and 20. Pump 76 is mounted ne~ct to blend tank 12. Aqueous hydrocarbon fuel composition storage tank 22 is mounted next to high shear mixer 10 and pump 76. Water storage tank 18 and deionizer 86 are mounted next to each other adjacent the right-side wall (as viewed in Fg. 2) of housing 260. Electrical controls 270 for the PlC and a zo display 272 for the P!C are mounted on housing walls 274 and 276. Dispenser 24 is mounted exfierior to the housing 260. 'the interconnections of the components of assembly and their operation are as described above.
The Ayueous Hydrocarbon Fuel Compositions The aqueous hydrocarbon fuel compositions of the invention wiA now be 2s described. These fuel compositions may be prepared in accordance with the foregoing process using the apparatus described above. The water used in fanning these compositions can be from any convenient source. In one embodiment, the water is detonized prior to being mixed with the normally liquid hydrocarbon fuel and chemical additi~res. In one embodiment, the water is so purified using reverse osmosis or distilladan.
The water is present in the aqueous hydrocarbon fuel compositions of the invention at a cortcentra~on of 5 to 40% by weight, and in one embodiment to 30% being weight and in one embodiment 15 to 25% by weight.

_;.~". ~~ri. ~ . x , . z,,.~ , Q :: ;~ ; ~ -_ ,~
e~' :~~.
07/12/01 10:94 FAQ 216 621 6165 ItENNER OTTO
~ 018 Docket No. Z95'7RIB-OZ
_ t8 Tha Nvrmallv Liauid Hvdrocarbor E,_ uel , The normally liquid hydrocarbon fuel may be a hydrocart>onaceous petroleum disfillate fuel such as motor gasoline as defined by ASTM
s Specifi~tjon D439 or diesel fuel or fuel oil as defined by ASTM
Speciftcation D396. Normally liquid hydrocarbon fuels comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitre compounds and the Ilke (e_g., methanol, ethanol, diethyl ether, methyl ethyl ether. nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or to mineral soun:es such as com, alfalfa, shale and coal. Normally liquid hydrocarbon fuels that are mixtures of one yr more hydrecarbvnacevus fuels and one or more non-hydrocarbonacevus materials are also contemplated.
Examples of such mixtures are combinations of gasoline and ethanol and of diesel fuel and ether.
is In one embodiment, the normally liquid hydrocarbon fuel is gasoline, that . is, a mixture of hydrocarbons having an ASTM distillation range fmm 60'C: at the, 10% distillation point to 205°C. at the 90°~6 distillation point In one embodiment, the gasoline is a chlorint-free or low-chlorine gasoline characterized by a chlorine content of no more than 10 pprn.
zo The diesel fuels that are useful with this invention can be any diesel fuel.
These diesel fuels typically have a 90% point distillation temperature in the range of 300°C to 390°C, and in one ~ ernbodinient 330°C
to 350°C. The viscosity for these fuels typically ranges from 1.3 to 24 centistvkes at 40°C.
The diesel fuels can be classified as any of Grade Nos. 1-D, 2-D yr ~D as zs specfied in ASTM D975. These diesel fuels may contain alcohols and esters.
In one embodiment the diesel fuel has a sulfur content of up to 0.05% by weight (low-sulfur diesel fuel) as determined by the test method specified in ASTM D2622-87. In one embodiment, the diesel fue) is a chlorine-free yr low chlorine diesel fuel characterized by a chlorine content of no more than 10 ao ppm.
The normally liquid hydrocarbon fuel is present in the aqueous hydrocarbon fuel compositions of the invention at a concentration of 50 to 9590 by weight, and in one embodiment 60 to 95'Yo by _ . ., .__ .,...... .,_"., r.__s _._ .ccc n n~o ".. ,,2~',P~""'~~!~r~~~,_,s ~.. ,'' rwt:. . H ~'~°".: ': a ,ra.-~~.~.
",:~~,~a a a.
i . . ,. a~ ,, , ~' ~ .;*'~; sa x.,~.
12 Q. 0 ~ ~ ;::
. K .. . - ~t~. . y Q~' ~ ~' "
.. f. ~. n~. ~~t~i3 ~ ~:1(~I' ~ ~ ~ ~8-0 ~2 ~a » .
~~ ~ ~~. ~~ rQO~~D~S~~~~
07/12/01 10:34 F.4a 216 621 6165 REIVN~R OTTO X020 ~OdCOI NO. Z9~R/g-~2 CA 02378505 2002-O1-07 weight, and in one embodiment 65 to 85% by weight, and in one embodiment 70 to 80°~6 by weight.
The Chemical Additives In one embodiment, the chemical additive used in accordance with the s invention is an emulsifier vomposition that comprises: (i) a hydrocarbon fuel soluble product made by reacting a hydrocarbyl-substituted carboxylic acid acylating agent with ammonia or an amine, the hydrvcarbyl substituent of said acylating agent having 50 fo 500 carbon atoms; or (ii) an ionic or a nonionic compound having a hydrophilic lipophiiic balance (HL8) of 1 to 10; or a mixture is of (~ and (ii); in combination wig (iii) a water-soluble salt distinct from (i) and (i~. Mixtures of (i), o) and (in are preferred. This emulsifier composition is present in the aqueous hydrocarbon fuel compositions of the invention at a concentration of 0.05 to 209'° by weight, and in one embodiment 0.05 to 10% by weight, and in one embodiment 0.1 to 5% by weight, and in one embodiment is 0.1 to 3% by weight, and in one embodiment 0.1 to 2.5% by weight (n a preferred embodiment, component (~ is a combination of (i)(a) at Isaat one reaction product of an acylating agent with an alkanol amine and (i)(b) at least one reaction product of an acylating agent with at least one ethylene polyamine. This preferred embodiment is discussed in more detail in ?o The Hvdrocarbvn F_ual-Soluble Product- (7 section below.
The Hydrocarbon Fuei-Soluble Product ~[t~
The hydrocarbyl-subs~tuted carboxylic acid acylatfng agent for the hydrocarbon fuel-soluble product (i) may be a carboxylic acid yr a reactive equivalent of such acid. The reactive equ'Nafent may be an add halide, zs anhydride, yr ester, inducting partial esters and th like. The hydrocac'byl substituent for the carboxylic acid acylating agent may contain from 50 to 300 carbon atoms, and in one embodiment 60 to 200 carbon afioms. in one embodiment, the hydrocarbyl substituent of the acylating agent has a number average molecular weight of 750 to 3000, and in one embodiment 900 to 30 2000.
In one embodiment, the hydrocarbyl-substituted carboxylic acid acylating agent for the hydrocarbon fuel soluble product (i) may be made by reacting one or more alpha-beta olefinically unsaturated carboxylic acid reagents containing b ,' std ~ x.~s r '.' ~ar,,~ ..a~ r~' : f~",''a *~r~~ltE3~ ~I ~ 0~ ~~Q~
.. ,. N. M..n.~~.,~~.~ k ~ ;~-M

_ ccq x,,~ tz. - yg s ~:.~r -, .~...>. r,:,;.
.,z~ a ; N' 'l, sr,~»:,.~y,,"~~... .r r,-,. ,...~~s ~., ..~d3, k ' .~.~.,.;.«
~..~Q ~~~~~~~~ ~~; 2~~0~
07/12/01 10:35 FAa 216(621'6165 RENNER 01T0 ~1 21 Docket No.195TR/t3-02 ZO
2 to 20 carbon atoms, sxdusive of the carboxyl groups, with one or more olefin polymers as described more fully hereinafter.
The alpha-beta olefinically unsaturated carboxylic acid reagents may be either monabasic or polybasic in nature, Exemplary of the mvnvbasic alpha s beta oleflnically unsaturated carboxylic aad indude the carboxylic acids corresponding to the formula:
R--CH=C--CpOH
R' ~o wherein R is hydrogen, or a saturated aliphatic or alicydic, aryl, alkylaryi or heterocydic group, preferably hydrogen ar a lower alkyl group, and R' is hydrogen or a Ivwer alkyl group. The total number of carbon atoms in R and R' Typically does not exceed 18 carbon atoms. Specific examples of useful mvnobasic alpha-beta olefinically unsaturated carboxylic acids include acrylic is acid; methacrylic add; cinnamic acid; crotonic acid; 3-phenyl propenoic acid;
alpha, and beta-decenoic add. The potybasic acid reagents are preferably dicarbvxylic, although tri- and tetracarbvxylic aads can be used. F~aemplary polybasic acids indude maleic acid, fumaric aGd, mesacanic acid, ifiaccnic acid and citraconic add. Reactive equivalents of the alpha-beta olefirucally 2o unsaturated carboxylic add reagents indude the anhydride, ester yr amide functional derivatives of the foregoing acids. A preferred reactive equivalent is malelc anhydride.
The olefin monomers from that the olefin polymers may be derived are pvlymerizable olefin monomers characterized by having one or more ethylenic 2s unsaturated groups. They can be mvnovlefinic monomers such as,ethylene, propylene, butane-1, isobutene and octane-1 or polyoleflnic monomers (usually di-olefinic rnanomers such as butadiene-1,3 and isoprene). Usually these monomers are terminal olefins, that is, olefins characterized by the presence of the group>C=CHZ. However, certain intemat olefins can also serve as 3o monomers (these are Sometimes referred to as medial olefins). When such medial olefin monomers are used, they normally are employed in combination with terminal olefins to produce olefin polymers that are interpvlymers.
Although, the olefin pvfymers may also include arvmafic groups (espedally phenyl groups and lower alkyl and/or lower alkoacy-substituted phenyl groups ~~~~ ~o.
a a=.. ae~.~! ,s...:~.~_ ~xa, a ~.!r,:a:r , ~~
F'- h ~a ~~.n,~ .rr~<..~w,, vxr.. ,~ 7 u~.:N.;~, ;:..~ s ~,~ ~øe~:. ~'~ ~ <
4._w~-. . a..,~,>:.'.
. ;ij t . ; ~ ~~ p., s~ a , ~;''4s:. ."
'. = ~....,>, .. . 071 ~s . ~ .~ ~.
07112101 10:5 F.4a 216 621 6165 RENN~R OT'f0 X022 o~i~t ice. Z9s~m-oZ

zr such as para(tertiary-butyn-phenyl groups) and alicydic groups such as would be obtained from polymerizable cydic olefins or alicyciic-substjtuted polymerizable cydic olefins, the olefin polymers are usually free from such groups. Nevertheless, olefin polymers derived from such interpolymers of both s 1,3-dienes and siyrenes such as butadiene-1,3 and styrene or pare-(tertiary butyl) styrene are exceptions to this genera) rule, . .
Generally the olefin polymers are homo- or interpolymers of tenninal hydrocarbyi olefins of 2 to 30 carbon atoms, and in one embodiment 2 to 16 carbon atoms. A more typical class of olefin polymers is selected from that to group consisting of homo- and interpolymers of terminal olefins of 2 to 8 carbon atoms, and in one embodiment 2.to 4 carbon atoms.
Specific examples of terminal and medial olefin monomers that can b~
used to prepare tfie olefin polymers include ethylene, propylene, butane-1, butane-Z, isvbutene, per>tene-1, hexane-1, heptene-1, octane-1, nvnene-9, is decene-1, pentane-2, propylene tetramer, dilsobutylene, isobutylene trirner, butadiene-1,2, butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isvprt3ne, hexadiene-1,5, Z-chiorobutadiene-1.3, 2-methylheptene-1, 3-cyGohexylbutene-1, 3,3.dimethylpentene-1, styrene divinylbenzene, vinyl-acetate atlyl alcohol, 1-mstttylvinytacetate, actylonitrile, ethyl acrylate, ethylvinylether and methyl-zo vinylkefone. Of these, the purely hydrocarbon monomers are more typical and the terminal olefin monomers era espedally useful.
In one embodiment, the olefin polymers are pvlyisobutylenes such as those obtained by polymerization of a Ca refinery stream having a butane content of 35 to 75% by weight and an isobutene content of 30 to 60% by 2s weight in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutytenes generally contain predominantly (that is, greater than 50 percent of the tvfal repeat units) isobutene repeat units of the configuration:
1 ti ~7 2~(~~

y' a', q~ ~ ~"~' a ~,~.<...~'ro,~~~~;.,~:: ~, :..r.",.....m.
.a~...~,~~er~..r..,~"~,:.a y r x ~~ '' ~'~7 :. ~. - f: ;: ' m , .~. ;,,- '. .~ v~~" x .~,..' ,,",.. ' ' ' ,.y ' ,w" ~ ° .' . ~~ 4., e;.,:i-Oi/12IUI 10:35 F.~ 218 621 6165 RE1VNER OTTO 1023 Docket No. 2957RfB-OZ

zZ

I
--CHz--C ,--s I
CHa In one embodiment, the ofeflrt polymer is a polyisobutene group (or polyisobutylene group) having a number average molecular weight of 750 to ~0 3000, and in one embodiment 900 to 2000.
In one embodiment, the acyla6ng agent for the hydrocarbon fuel-soluble product (i) is a hydrocarbyl-substituted sucanic acid or anhydride represented correspondingly by the formulae R-CH--POOH
.
CHI---COOH
yr zo wherein R is hydrocarbyl group of 50 to 500 carbon atoms, and In one embodiment from 50 to 300, and in one embodiment from 60 to 200 carbon atoms. The production of these hydrocarbyl-substituted succinic acids or anhydrides via allrylation of maieic acid or anhydride or its derivatives with a halvhydrocarbon or via reaction of malefic acid or anhydride with an olefin 2s polymer having a terminal double bond is well known tn those of skill in the art and need not be discussed in detail herein.
In one embodiment, the hydrocacbyl-substituted carboxylic acid acylafjng agent for the product hydrocarbon fuel-soluble product (i) is a hydmcarbyl-substituted succinic acylabng agent consisting of hydrocarbyl substituent E ~~~~t~~, ~da~ f '~~~~~ , n,~ k~ 5;u~ a-. 3.~',_~.:.., (:i':#sz"'~~P#.~t~i' ~ e_.' . ,fir. e: r.. sir .eF,;;a F,f..n. ., ...v>..
. '... t, ,.; ; , ,. ~ ~: '°7a; ,' ,..
.'~~ ~.e 2 0 _. ~ a.
.. ,~,.,.u.......t~.n ~t'E,~' ,.ns . ~- ~~' '~...toLb~.,at~3:M. ~ ~ ' err.. a ..
~)~.~~ c~ ~~
~*. ,4sFsstr ~ ~u.a.a~..u.ta.,ei~~~ ..~~.a~ E~ ~r_.~;.si. ~ .~
0 f /12/01 10: 36 F~ 218 821 6185 RENNER OTTO t~024 Docket No. 2957R/B~OZ

groups and succinic groups. The hydrocaibyl substttuent groups are derived from' an olefin polymer as discussed above. The hydrocarbyl-substituted carboxylic acid acylating agent is characterized by the presence within ifs structure of an average of at least 1.3 succinic groups, and In one embodiment s from 1.5 to 2.5, and in one embodiment form 1.7 to 2.1 sucdnic groups for each equivalent weight of the hydrocarbyl substituent For purposes of this invention. the equivalent weight of the hydrocarbyl substituent group of the hydrocarbytsubstituted succinic acylating agent is deemed to be the number obtained by dividing the number average molecular to weight (M,~ of the polyolefin from which the hydrocarbyl substituent is derived into the total weight of all the hydrocarbyl substituent groups present in the hydrocarbyl~ubstituted succinic acylating agents. Thus, if a hydrocarbyh substituted acylat3ng agent is characterized by a total weight of all hydrocarbyl~
substituents of 40,000 and the M" value for the polyole>~n from which the is hydrocarbyl substituent groups are derived is 2000, then that substituted succinic acylating agent is characterized by a total of 20 (40,00012000=20) equivalent weights of subsfituent groups.
The ratio of sucdnic groups to equivalent of substituent groups present in the hydrocarbyl-substituted succinic acylatlng agent (also called the zo "succination ratio's can be determined by one skilled in the art using conventional techniques (such as from saponification yr acid numbers)_ For example, the formula below can be used to calculate the succination ratio where malefic anhydride is used in the acylatton process: .
M" x (Sap. No. of acytating agent) zs SR=
(56100 x 2) - (98 x Sap. No. of acytating agent) In this equation, SR is the succination ratio, M" is the number average molecular weight, and Sap. Na. is the saponification number. In the above equation, Sap. No. of acylating agent = measured Sap. No. of the final rsadivn 3o rtiixburelAl when~in AI is the active ingredient content expressed as a number between 0 and 1, but not equal to zero. Thus an active ingredient content of 80°10 corresponds to an Ai value of 0.8. The AI value can be calculated by using bachniques such as column chromatography that can be used to determine the amount of unreacted polyalkene in the final reaction mixture.
~As r i~~rii~ted 1 i~ 4 ~ k"'~~~'4 a rough approximation, the value of AI is determined after subtracting the percentage of unreacted polyalkene from 100.
The hydrocarbon fuel-soluble product (i) may be formed using ammonia and/or an amine. The amines useful for reacting with the acylating agent to s form the product (i) include monoamines, polyamines, and mixtures thereof.
The monoamines have only one amine functionality whereas the polyamines have two or more. The amines may be primary, secondary or tertiary amines. The primary amines are characterized by the presence of at least one -NH2 group; the secondary by the presence of at least one H-N<
io group. The tertiary amines are analogous to the primary and secondary amines with the exception that the hydrogen atoms in the -NH2 or H-N<
groups are replaced by hydrocarbyl groups. Examples of primary and secondary monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, is methyllaurylamine, oleylamine, N-methyloctylamine, dodecylamine, and octadecylamine. Suitable examples of tertiary monoamines include trimethylamine, triethylamine, tripropyl amine, tributylamine, monomethyldimethylamine, monoethyldimethylamine, dimethylpropyl amine, dimethylbutyl amine, dimethylpentyl amine, dimethylhexyl amine, 2o dimethylheptyl amine, and dimethyloctyl amine.
The amines may be hydroxyamines. The hydroxyamines may be primary, secondary or tertiary amines. Typically, the hydroxyamines are primary, secondary or tertiary alkanolamines. The alkanol amines may be represented by the formulae:

.:y ' z~ ,....; , .,,. ~ ,.,...,.
.~. ..y ,'~ ,.; n , ~ ,~ Y~ "'., ' ~ ~ . ~ m. ,::"..
~07/12/O1 10:38 FAg 216 621 6185 ~V~g 0TTp '''~''~"''w~''°~' ~ ~~~~~-Dndset No. 2957R/B-02 H
N-R'--0H
i H
H
m ~ N--fi'-OH
i H
1s R
1 N--R'-OH
i R
zo wherein in the above formulae each R is independently a hydrocarbyl group of 1 to 8 carbon atoms, or a hydroxyl-substituted hydrocarbyl group of 2 to 8 carbon atoms and each R' independently is a hydrocarbylene (i.e., a divalent 2s hydrocarbon) group of 2 to 1t3 carbon atoms, The group -R'--OH in such.
formulae n:pnsents the hydroxywsubstrruted hydrocarbylene group. R' may be an acyciic, aiicyclic, or aromatic group. !n one embodiment, R' is an acyclic straight or branched alkylene group such as ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. When iwo R groups are present in 3o the same molecule they may be joined by a direct carbon-tv-carbon bend or through a heteroatvm (e.g., oxygen, nitrogen yr sulfur) to form a 5-, 6-, T or 8-membered ring structure. Fx-amples of such heterocyclic amines include N-(hydroxyl lower alkyl)-rnorpholines, thiomorphalines, -piperidines, -~cazoiidines, thiazofidines and the like. Typlcaliy, however, each R is independently a lower alkyl group of up to seven carbon atoms.
Suitable examples of the above hydroxyamines include mono-, di-. and ttiethanotamine, dimethylethanotamine, diethylethanolamine, di-(3-hydroxyl propyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine, and N,N-di-(2-hydroxyl propy~ amine.
4o The hydrocarbon fuel-soluble product (i) may be s salt, an ester, an amide, an imide, or a combination thereof. The salt may be an internal salt x~
~~1(1~8JC~ '~ ~~~ ~~~ E .
... ._.,... ., ... r r .r-r.r n nrv-lt~~.: .~A~:~~ s ~.ew: . ~ws .. ' ~ ':~. ~ ~ f v~~~ a.f k4 w A ~ . . T~; ~. ro , ..,~.. ,::.
07/12/01 10:6 F.4a 216 821 6185 REIViVER OTTO Cope DOCi~t ND. Z9$7R/&OZ CA 02378505 2002-O1-07 involving residues of a molecule of the acylat3ng agent and the ammonia or amine wherein one ~ of the carboxyl groups becomes ionlcally bound to a nitntrogen atom within the same group; or it may be an external salt wherein the ionic salt group is fornted with a nitrogen atom that Is not part of the same s molecule. In one embodiment, the amine is a hydroxyarnine, the hydrocarbyi-substitubsd carboxylic add acylating agent is a hydracarbyi-substituted succinlc anhydride, and the resulting hydrocarbon fuel-soluble product (i) is a half ester and half salt, i.e., an esterlsalt.
The reaction between the hydrocarbyl-substituted carboxylic aad iv acylating agent and the ammonia or amine is carried out under conditions that provide for the formation of the desired product Typically, the hydrocarbyl-substituted carboxylic aad acylaiing agent and the ammonia or amine are mixed together and heated to a temperature in the range of from 50°C to 250°C, and in one embodiment from 80°C to 200°C;
optionally in the presence ~s of a normally liquid, substantially inert organic liquid svhrentJdiluant, until the desired product has formed. In one embodiment, tha hydrocarbyl substituted carboxylic acid acylating agent and the ammonia or amine are reacted in amounts sufficient to provide from 0.3 to 3 equivalents of hydrocarbyl substituted carboxylic acid acylating agent per equivalent of ammonia or amine.
2o In one embodiment, this ratio is from 0.5:1 to 2:1, and in one embodiment 1.1.
in one embodiment, the hydrocarbon fuel-soluble product (i) is made by reacting a polyisobutene substituted sucanic anhydride having an average of 1 to 3 succinic groups for each equivalent of pvlyisobutene group with diethanvlamine or dimethylethanvlamine in an equivalent ratio (i.e. carbonyl to z5 amine ratio) of 1 to 0.4-1_25, and in one embodiment 1:1. The polyisobutene group has a number average molecular weight of 750 to 3000, and in one embodiment 900 to 2000.
In a preferred embodiment; component (i) is a combination of (~(a) at least one reaction product of an acylating agent with an alkanol amine and so (i)(6) at least one reaction product of an acytaiing agent with at least one ethylene polyamine.
a P~ri r~te~ 1'~ fl~'~~~~ .
.. z:x~, .~,.:a;. x ~ ~ e, k:. , .

~rrof~E ~c ~",s;,;h ~~'p,~"sk 'h' f~ei: t ~°''='e't~A4 ~I .roos.iw~y -q.xNn~J ::M:_y.e~., . r t t-..;...~,; 3.,: ..
~"-"~ .'=~~ i.~ : E . ~y- r -, rear a !Y ,", ,~,.;.,.
;~7 ~' ~. ,~ ,:r;
o~~: ~~L~B 2_02 c.~ ~~ ;
~~~.E~~;~~~,~ t ~ ~ ~OQ~'~~?~~~.~8 Qfi:~QOO :~ IDES
07/12/01 10:37 F4a 218 621 6185 RENNER OTTO X027 volt No. z9~trB-oz More specifically, in this preferred embodiment, component (~(a) is a hydrocarbon fuel-soluble product made by reading an acylating agent with alkanoi amine, wherein said alkanvl amine is preferably a dimethylethanol s amine or a diethylethanolamine. Preferably, component (i)(a) is made from a polyisobutylene group having a number average molecular weight (Mn) range of from 1500 to 3000, and that is maleinatad or succinated in the range from 1 _3 up to 2.5.
Component (1)(b) is a hydrocarbon fuel-soluble product made by reacting to an acylating agent with at least one ethylene polyamine such as TEPA
(tetraethylenepentamine), PEfL4 (pentaethylen~hexaamine), TETA
(triefhytenetetramine), polyamine bottoms, or at least one heavy pvlyamine.
The ethylene polyamine can be condensed to form a succinimide, as exemplified in F~cample 3. The equivalent ratio of the reaction for CO:N is from i5 1:1.5 to 1:0.5, more preferably from 1:1 _3 to 1:0.70, and mast preferably from 1:1 to 1:0.70, wherein CO:N is the carbonyl fio amine nitrogen ratio. Also, component n(b) is preferably made from a polyisobufylene group having a number average molecular weight of from 700 to 1300 and that is sucGnated in the range from 1.0 up to 1.3.
zo Tile pvlyamines useful in n3acfing with the acylating agent for component (i)(bj can be aliphatic, cycloaliphatic, heterocydic or aromatic compounds. Especially useful are the alkylene polyamines represented by the formula:
25 R - ~ --(Alkyisne - N)r,- R
3o wherein n is from 1 to 10, preferably from 1 to 7; each R is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to 700 carbon atoms, and in one embodiment up to 100 carbon atoms, and in one embodiment up to 50 carbon atoms, and in one embodiment up to 30 carbon atoms; and the 'Alkylene' group has from 1 to 18 as carbon atoms, and in one embodiment from 1 to 8 carbon atoms.
'_ .__ __ : ~r . _ _ .. . _ .- r . rear n ~r~-~

~~.,~~~~~ , ~, ~ ,~,;p~..n,~sa~i~~rx...~.:~.w. , r r=~~~,,.,s t .. y. yl~ * , ~' .,.. ,.:..~,'. !'.m; L mss' '',n -~., ' ; L ; ii. , :. a :~.YawY2'-~"~~ : ~ , ~~; Ly,.~~..: ~~~ ~~~;,.~yZIP.
,e4~~.r; ~wwdBS~ .x'~.~r ~ ~ ~~- !:%~d~,.:k~x.~,e 07/lE/O1 10:37 F~ 216 821 6165 RENNER OTTO ~ 028 Docket No. Z957R/B-01 Heavy pvlyamines typically result from stripping of pviyamine mixtures, to remove lower molecular weight poiyamines and volatile components, to leave, as residue, what is often termed "pvlyamine bottoms". In general, _ alkyfene polyamine bottoms can be characterized as having less than 2°~, s usually less than 1°~ (by weight) material boiling below 200'C. In the instance .
of ethylene polyamine bottoms, which are readily available and found to be quite useful, the bottoms contain less than 2°r° (by weight) total diethylenetriamine (DETA) or triethylenetetramine (TETA), as set forth in U.S.
Patent Nv. 5,912,213, incorporated herein by reference in its entirety. A
typical ~o sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Tex., designated "E-100" has a specific gravity at 15.6'C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40'C. of 121 centistokes. Gas chromatography analysis of such a sample showed it contains 0.9390 "Light Ends" (most probably diethylenetrtarnine), is 0.72% triethylene tetramine, 21.74% tetraetftyienepentamine and 76.61 °~
pentaethylenehexarnine and higher (by weight). Another commeraally available sample is from Union Carbide, known as HPA-X~. These alkyene polyamine bottoms include cyclic condensation products such as piperaane and higher analogs of diethylenefiamine, ttiethylenetetramine and the like.
2o The term "heavy polyantine" can also refer bo a polyamine that contains 7 or more nitrogens per molewte, or pvlyamine oligorners containing 7 or more nitrogens per molecule and with 2 yr more primary amines per molecule, for example, as set forth in European Patent No. EP 0770098, incorporated herein by reference In its entirety.
2s In another embodiment, both i(a) and I(b) can each made from a higher molecular weight pvlyisobutylene group (meaning Mn greater than or equal to 1500, preferably from 1500 to 3000). in an alternative embodiment, components 1(a) and i(b) can each made from a lower molecular weight polyisobutylene group (meaning Mn less than yr equal to 1300, preferably from ao T00 to 1300).
In another embodiment, component i(a) is made from a polyisobufylene group having a number average molecular weight range of from 700 to _ , .. . . ._ ~~ .~'"4c . . " ,r , r;.,~., a tr r ~ . ..,;:r, e~. .
. ~ a, :a., ::c. :.': .f :. 3 c .~..,: " ~ . .':..,..:.,::
1~~~~2 ~ -,, .
xE s'4 .,-:'~
:.~ , ; . .~ ~t?g 44:~ $~ g,_ ,...~rc...~~.s... ~s....,~a:.:.».L'~~~~~.~.,'"'S.~dZ''.~Z~~d5";, '~u ..as.~e.asa.~'aiz~~s'S,~ > .~".....~.... S...e~.~..2a:..?~.,.~...., 5~:~~s'~ .
07/12/01 10:38 FAa 218 821 6185 R~NNER OTTO 0 029 Docket No. Z957R18-0Z

1300, and component i(b) is made from a polyisobutylene group having a Mn range of from 1500 to 3000.
Preferably, component (i)(b) is made by reacting (a succinic acylating agent with a polyamine) at a suffiaerrt temperature to remove water and form a s succinimide.
Preferably, component (i)(b) is combined with component (i)(a) in an amount from 0.05°Y° to 0.95% based upon the total weight of component (i).
in another embodiment, the hydrocarbon fuel-soluble product (i) is a salt composition comprised of (I) a first polycarboxylic acylating agent, said first r0 polycarboxylic acylating agent having at least one hydrocarbyl substitu~nt of 20 to 500 carbon atoms, (II) a second palycarboxyiic acylating agent, said second pofycarboxylic acyladng agent optionally having at Least one hydrocatfiyl substituent of up to 5D0 carbon atoms, said polycarboxylic acylating agent (I) and (II) being coupled together by a linking group (III) derived from a linking is compound having two or more primary amine groups, two or more secondary amine groups, at least one primary amino group and at least one secondary amino group, at least two hydroxyl groups, or at least one primary or secondary amino group and at least one hydroxyl groups, said polycarboxylic acylating agents (I) and (II) fomting a salt with (IV) ammonia or an amine.
20 The hydrocarbyl substituent of the first acylating agent (I) may have 30 to 500 carbon atoms, and in one embodiment 40 t0 500 carbon atoms, and in one embodiment 50 to 500 carbon atoms.
The optional hydrocarbyl subsfituent of the second acylating agent (II) may have 1 to 500 carbon atoms, and in one embodiment 6 to 500 carbon is afvms, and in one embodiment 12 to 500 carbon atoms, and in one embodiment 18 to 500 carbon atvm5, and in one embodiment 24 to 500 carbon atoms, . and in one embodiment 30 to 500 carbon atoms, and in one embodiment 40 to 500 carbon atoms, and in one embodiment 50 to 500 carbon atoms.

'~'.ss, ,. ...~..k" - .~ -.
~~"F::ji4'~~,'Yi..~312#d4 'a2h+~P -'A= i;,~;.
.. : ~ ' ~ -L' ~,~m 'vp,~q'?Y ~ ir.
.r, ..
.a ~ , .~~~ ~:.
87/1E/01 10:38 F98 E18 6E1 6185 REIVNER 0~'0 ~ '3~0 - ' Dvdcet Nc. Z957RIB-02 The hydrocarbyl substftuent of the second acylating agent (II) may be derived from an alpha-olefin or an alpha-olefin fraction. The alpha-olefins include 1-dvdecene, l~ridecene, 1 tetradecene, 1-pentadecene, 1-s hexadecene, 1-heptadecene. 1-octadecene, 1-eicosene, 1-docosene, 1 triacontene, and the like. The alpha olefin fractions that are useful include Cps.
,e alpha-oleftns, C~Z_~s alpha-olefins, C,~,e alpha-olefins, C~~~e alpha-olefins, C,a_,e alpha-olefins, C».a alpha-olefins, C~,s.~ alpha-ol~fins, and the like.
Mixtures of two or more of any of the foregoing alpha-olefrns or alpha-olefin iv fractions may be used.
The hydrocarbyl groups of ~e first and second acylabng agents (I) and (11) independently may be derived from an olefin oligomer or polymer. The olefin oligomer or polymer may be derived from an olefin monomer of 2 to 10 carbon atoms, and In one embodiment 3 to 6 carbon atoms, and in one is embodiment 4 carbon atoms. Examples of the monomers inGude ethylene;
Propylene: butane-1; butane-2; isobutene; pentane-1; heptene~l; octane-1;
nonene-1; decene-1; pentane-2; or a mixture of two of more thereof.
The hydrocarbyl groups of the first and/or second acylating agents (I) and (11) independently may be polyisobutene groups of the same or different ao molewlar weights. Either or both of the polytsobutene groups may be made by the polymerization of a C4 refinery stream having a butane content of 35 to 75% by weight and an isobutene content of 3t) to BO% by weight.
The hydrocarbyl groups of the first and/or second acylating agettts (I) and (11) independently may be polyisobutene groups derived from a zs polyisobutene having a high mefhyivinylidene isomer content, that is, at least 50% by weight, and in one embodiment at least 70% by weight methylvinylidenes. Suitable high methylvinylidene polyisobutenes include those prepared using boron tritluoride catalysts. The preparation of such polyisobutenes in which fhe methylvinylidene isomer comprises a high ao percentage of the total olefin composition is described in U.S. Patents 4.152,499 and 4,605,8U8, the disclosure of each of wi~ich are incorporated herein by reference. An advantage of using these high methyhrinylidene isomers is that the acytating agents (1) and (II) can be formed using a chlorine-~. ~~ c..raya ~ u,s:~a -a , . _ ._- .___ _ _. _. .- . _.-.-.e- n n~,n .;. ..
~~ ,,. . .. ~"-.. xbs,~i~xr;~F&kr$l~c~t~a'F~%5~ 3a~e' ::i~ ~..,X,~.;
~ k l ' ~ . ' c "l ".~ roF... -~
s. if . o , ~~ ; .s;~e4 :~,.~r~G. - r~ .u~ '~1.",;..'~ ku~Jd~,:a~ '' '";.r.
0 l /12/01 10 : 38 FA$ 218 821 8185 RE1VN~R OTTO I~ 031 Dodaet Nv.Z957R/B-02 free process which is sign~icant when the fuel composition to which they are to be added Is required to be a chlorine-fee or low-chlorine fuel.
In one embodiment, each of the hydrocarbyl substituents of each of the acylahng agents (t) and (II) is a polyisobutene group, and each polyisobutene s group independently has a number averag~ molecular weight in the range of 500 to 3000, and in one embodiment 900 to 2400.
The hydrocarbyl substituent of the acyladng agent (I) may be a polyisobutene group having a number average molecular weight of 2000 to 2fi00, and in one embodiment 2200 to 2400, and in one embodiment 2300.
to The hydrocarbyl substituerit of the acylaiing agent (11) may be a pvlyisobutene group having a number average molecular weight of 700 to 1300, and in one embodiment 900 to 1100, and in one embodiment 1000.
The linking group (III) for linking the first acylating agent (I) with ttte second acylatjng agent (II) may be derived from a polyol. a pvlyamine yr a ~s hydroxyamine. The polyol may be a compound represenfied by the formula R - (OH)m wherein in the fon3going formula, R is an organic group having a valency of m, R is joined to the OH groups through carbon-to-oxygen bonds, and m is an integ~r from Z ~to 10, and in one embodiment 2 to 6. The pvlyvl may be a 2o glycol. The alkylene glycois are useful. Examples of the polyols that may be used indude ethylene glycol, diethylene glycol, triethylene glycol, fietraethylene glycol, propylene glycol, dipropylene glycol, triprvpylene glycol, dibutytene glycol, tributylene glycol, 1,2-butanediol, 2,3dimethyl-Z,3-butanedivl, 2,3-hexanediol, 1,2-cydohexanediol, pentaerythritol, dipentaerythritol, 17-2s heptanediol. 2,4-heptanediol, 1,2.3-hexanetriol, 1,2,4-hexanetriol, 1.2,5 hexanetriol. 2,3,4-he~canetriol, 1,2,3-buianetriol, 1,2,4-butanetrivl, 2,2,6,6 tetrakis-(hydroxymethyl) cydohexanol, 1,10-decanediol, digitalose, 2 hydroxymethyl-2-methyl-1.3-propanediol-(tri-methylethane), or 2 hydroxymethyl-2-ethyl-1,3-prvpanedivl-(trirnethylprvpane), and , the like.
3o Mixtures of two yr more of the foregoing can be used.
The polyamines useful as linking compounds (I11) for Ilnking the acylating agenfis (I) and (II) may be aliphatic, cydoaliphatic, heterocydic or aromatic 'y.'"~.g.~':~",~a~cr~a-~,r:.a ' ~ ..Y::. " m;~:::~~ r'.
.#f~'.#--, ;. ~' ' . '~ > ..,.t~'w-:H d-~< r ..,;s F ~u a y.'<"' !.~' 'S ~ ~'a . ;, .. 'N.
. - '"t~ ~!~. .e ;l :. ~ y... ~' 'a ~.
~. ~ ~:~.~~1p:7..:'~':- :
$du~~'~.~a2':4:&"l.~P.'~'~'...~~'~ ~ b:. , .: ..,.:. , ;; ~~'. ~
.: ~t"'~, F
' ''j .. ~' i~2~S:~:. 'e~.".~~.aiv.,.a~
~$ 1~~.%~~~"'3e~~G

0 l /12/0110: 38 F4g E18 BEl RE1VIVER OTTO

Docket No. Z957R1&02 compounds. F.speaally useful are th~ alkylene polyantines represented by the formula:
H l -(Alkylsne- i)"li s R R
wherein n has arA average value between 1 and 10, and in one embodiment 2 to T, the "Atkylene" group has from ,1 to 10 carbon atoms, and in one ~a embodiment 2 to 6 carbon atoms, and each R is independently hydrogen, an aliphatlc or hydro~cy-substituted aliphatic group of up to 30 carbon atoms.
These alkylene polyamines inGude methylene pvlyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylerte polyamines, etc. Spec~ic examples of such pvlyamines include ethylene 1s diamine, triethylene tetramine, propylene diamine, trimethytene diamine, tripropylena tetramine, tetraethylene pentamine, hexaethylene heptamine, pentaethylene hexamine, or a mocture of two or mere thereof.
Ethylene polyamines, such as some of those mentioned above, are useful as the Linking compounds (III). Such polyamines are described in detail 2o under the heading Ethylene Amines in IGrk Othrne~s "Encyclopedia of Chemical Technology", 2d Edition, Vvl. 7, pages ZZ 37, tntersci~nce Publishers. New York (1965). Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with arnntonia or by. reactlon of an etfiytene imine with a ring-opening reagent such as water, ammonia, etc.
2s These reactjons result in the production of a complex rriucture of polyalkylene polyamines including cyclic condensation products such as piperazines.
The hydroxyamines useful as linking compounds (III) for linking the acylating agents (I) and (II) may be primary or secondary amines. The terms "hydroxyamine" and "aminvalcohot° describe the same class of compounds ao and, therefore, can be used interchangeably. In one embodiment, the hydroxyamine is (a) an N-(hydroxyl-substituted hydrocarbyl) amine, (b) a hydroxyl-substituted poty(hydrocarbyloxy) analog of (a), or a mixture of (a) and (b). The hydroxyamine may be an alkanol amine containing from 1 to 40 p.~,':,en~ ~~CY!:i'. ~ r~~e. '~ ~ *!.? , :va. ,..<"Jewz~ ;.u ~Knw..- ,., h~.~..y, . v..-%:*w,.~e . ;~"~ , .. .~ ~ P", a ..
~~ ': i F .. .. . . ~ e, " , ~ n . s ,~ ~ n,~k.e ., . . 64" ' , ~~ , s. a ' ;i..,~ '~w,...
07/12/01 10:J9 FAa 218 821 6185 RENNER OTTO ~OJ~ ' Docket No.1957R/8-02 carbon atoms, and in one embodiment 1 to 20 carbon atoms, and in one embodiment 1 kv 10 carbon atoms.
The hydroxyarnines useful as the, inking compounds (1!I) may be a primary or secondary amines, or a mixture of two or more thereof. These s hydroxyamines may be represented, respectfully, by the formulae:
HZN-R'-OH or H
to j N-R'-OH
R
wherein each R is independently a hydrocarbyl group of one to eight carbon atoms or hydroxyl-substituted hydrocarbyt group of two to eight carbon atoms is and R' is a divalent hydrocarbon group of two to 18 carbon atoms. Typically each R is a Ivwer alkyl group of up to seven carbon atoms. The group -R'-OH
in such fvnnulae nepresenfs the hydroxyl-substituted hydrocarbyl group. R' can be an acyctic, alicydic or aromatic group. Typically. R' is an acyclfc straight yr branched alkylene group such as an efhylene, 1,2-propylene, 1,2-butylene, 20 1,2-octadecylene, etc. group.
The hydrvxyarnines useful as the linidng compound (111) may be ether N-(hydroxy-subst~hrted hydrocarbyn amines. Thes~ may be hydroxyl-sub-stituted poly(hydrocarbyloxy) analogs of the above-described hydroxyamlnes (these analogs also include hydroxyl-substituted oxyalfcytene analogs). Such zs N-(hydroxyl-substituted hydrocarbyl) amines may be conveniently prepared by reaction of epoxides with afore-described amines and may be represented by the formulae:
HZN-(R'O),~H or 30 H ~
,IV-(R'O)xH
R
wherein x is a number from 2 to 15, and R and R' are as described above.
~° n _ .__ .__-. .. .. ~ r .rrr n non ,; .". ~ ,. , . .,:
,,P
~, ;34 y$ ~ Ola.-~ ~. ~00 1; ;,. ~,. ;
1 ,07~: f . 2 _ ,217.0 N3v. .rdxi~.:Re~ 8,. GiG..7fi.' 1 ~.ro~~2a i~r.fn 07/12/01 10:38 F.~lb 218 821 6165 RENNER OTTO ~ 034 ~OCi~ N0. Z~[U9-~ CA 02378505 2002-O1-07 The hydroxyamine useful as ~ the linking compound (Ill) for linking the acylating agents (1) and (II) may be one of the hydroxy substituted primary amines described in U.S. Patent 3,576,743 by the general formula R,-NHZ
s wherein R~ is a monovalent organic group containing at Isast one alcoholic hydroxy group. The total number of carbon atoms in R, preferably does net exceed 20. Hydroxy-substituted aliphatic primary amines containing a total of up to 10 carbon atoms are useful. The polyhydroxy-substituted alkanol primary amines wherein there is only vne amino group present (1e., a primary amino ~o group) having vne alkyl substifirent containing up tv 10 carbon atoms and up to 6 hydroxyl groups are useful. These alkanol primary amines correspond to Ra,-NHZ wherein Rs is a mono-0 or polyhydroxy-substituted alkyl group. it is desirable that at least one of the hydroxyl groups be a primary alcoholic hydroxyl group. Specific examples of the hydroxy-substituted primary amines t5 include 2-amino-1-butanol,2-amino-2-methyl-1-propanol,p-(baba-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amine-2-ethyl.1, 3-propanediai, N-(betafiydroxypropyl)-N'-(beta-aminvethyl~-piperazine, tris-(hydroxymethyn aminomethane (also known as zo trismethylolaminomethane),Z-amino-'l-butanol,ethanolamine,bets-(beta-hydrox yethoxy)-ethylamine, glucamine, glusoamine, 4-amino-hydroxy-3-methyl-1-butane (that can be . prepared according to procedures known in the art by reacting isopreneoxide with ammonia).
N-3(aminapropyl)~4-(2-hydroxyethyl~piperadine,2-amino-6-methyl-6-heptanol,5 zs -amino-1-pentanol, N-(beta-hydroxyethylr1,3-diamino propane, 1,3-diamino-2-hydroxypropane, N-(beta-hydroxy ethvxyethyl)-ethylenediamine, trismethylol aminvmethane and the like.
Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms~may be used as the linking compound (III) 3o for linking the acylating agents (I) and (II). Useful hydroxyalkyl-substituted atkylene pvlyamines inGude those in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms. ~F~camples of such hydroxyaikyl-substituted polyamines include N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl) ethylene diarnine, 6 (?~ ~0a~'' w,._ f ~ f S.:~ .y . -_ . . ... ..., ".,..... .-._~~ r _i _._ .~cc n n~~

,~ ~.~ ;a. ~~ .M..,~ L ~ ~ ..~ as ~F.. c>. .p~ R t~~,~,, y.:, y~ ~: ~ w y y"e.-..
'i . ~. .. d ~~,. w ~T3.
0i/12/01 10:40 FAa 216 621 6165 RENNER OTTO ~ 095 Dodaet No. 2957R/&02 1-(2-hYdroxYethyl)-PiPe~ne, monohydmxypropyhsubstituted diethylene triamine, dihydroxypropyi.substid~ted tetraethylene pentamine, N.(3-hydroxybutylj tetramethylene diamine, etc. Higher hornologs as are obtained by condensation of the above-illustrated hydroxy alkylene polyamines s through amino groups ~ or Through hydroxy groups are likewise useful.
Condensation through amino groups results in a higher amine accompanied by removal of ammonia and condensation through the hydroxy groups results in products containing ether linkages accompanied by removal of water.
The amines (11~ which ana useful along with ammonia in forming a salt io with the acylating agents (I) and (11j include the amines and hydmxyamines discussed above as being useful as finking compounds (Illj for linking the acylating agents (I) and (II). Also included are primary and secondary monoamines, tertiary mono- and polyamines, and fiertiary atkanol amines. The tertiary amines are analogous to the primary amines, secondary amines and is hydroxyamines discussed above with the exception that they may be either mvnoamines or polyamines and the hydrogen atoms .in the H-N~ or -NHZ
groups are replaced by hydrocarbyl groups.
'The monoamines useful as the amines (iV) for forming a salt with the acylating agents (I) and (II) may be represented by the formula 2o R'-N-R2 wherein R', RZ and R3 are the same or different hydrvcarbyl groups.
Preferably, R', RZ and R3 are independently hydro~rbyl groups of from 1 to 20 zs carbon atoms, and in one embodiment from 1 to 10 carbon atoms. F~camples of useful tertiaryamines include trimethylamine, triethyl amine, tripropylamine, tributylamine, monamethyldiethylamine, monoethyldimethylamine, dimethylpropylamine, dlmcthylbutyiamine, dimethylpentylamine, dimethylhexylamine, dimethylheptylamine, dimethyloctyl amine, dimetfiylnonyl 3o amine, dimethyldecyi amine, dimethylphenyl amine, N,N-dioctyl-1-oetanamine, N,N-didodecyl-1-dodecanarnins, tricocoamine, trihydrogenated-tallowamine, N
meifiyl-dihydrogenated-tallowamine, N,N-dimethyl-1-dvdecanamine, N,N
dimetyl-1 tetradecanamine, N,N-dimethyi-1-hexadecanarrsine, N,N-dimeihyl 1 octadecanarnine, N.N-dimethylcocoamine, N,N-dimethylsoyaamine, N,N
3s dimethylhydrogenated -tallowamine, etc.
~~,~~ed ~~~ ,~ r ~~~~e~.M~m f _ ._ .__ .___. .__...- r _ r .r-cc n nom ø K "r'. ~ ii ". ' '~? ~ ~,'~t.y,~ -.. øt au" ~w~-x..,.
., ,. . ~ t, ~ ~0~ ~ .p , x »~ :x~'- . ~, , ' ~ , ~~ .i' 07/12/01 10:40 FAa 216 621 6165 RENNER OT'f0 , ~ 056 ~ocketl~0.Z957R/6-02 CA 02378505 2002-O1-07 Tertiary alkanol amines which are useful as the amines (11~ for forming a salt with the acylating agents (I) and (11) include those represented by the formula:
~N-R'-OH
io wherein each R is independently a hydmcarbyi group of one to eight carbon atoms or hydroxyl-substrtuted hydrocarbyl group of two to eight carbon atoms and R' is a divalent hydrocarbyl group of two to 18 carbon atoms. The groups -R =OH in such formula represents the hydroxyl-substituted hydrocarbyl groups. R' may be an acydic, aiicyGic yr aromatic group. Typically, R' is an ~s acydic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. Whero two R groups ate present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7-or B-membered ring structure. Examples of such heterocyclic amines include N-zo (hydroxyl lower alkyl)-mvrpholines; thtomvrpholine5, -piperidines, -oxazolidinas, -thlazolidines, and the like. Typically, however, each R i5 a low alkyl group of up to seven carbon atoms. A useful hydroxyamine is dimethylaminoethanol.
The hydroxyamines can also be ether N-(hydroxy-substituted hydrocarbynamines. These ane hydroxyl-substituted pvly(hydrocarbyloxy) 2s analogs of the above-described hydroxy amines (these analogs also include hydroxylsubstituted oxyallrylene analogs). Such N-(hydroxyl-substituted hydrocarbyl) amines can be conveniently prepared by reaction of epoxides with afore-described amines and can be represented by the formula:
30 R\
N - (R'Ok-- H
wherein x is a number from 2 to 1 S and R and R' aro described above.
3s Polyamines which are useful as the amines (t~ for forming a salt with the acylating agents (I) and (II) include the alkylene polyamines discussed .__ .__-_ _. -- r i .ri.r n nnn w -~r r~. ; ' ~ ~ . ; ,~~', . !#''~ .. ~. i ~ °, ~' ~~' -,." ~ ~ , r' ", 'T .~'t:r,: ris Oi/12/O1 10:40 FAa 216 6E1 6165 RENNER OTTO ~ 0~7 Docket No. 2957R/B-OZ

above as well as alkylsne polyamines with only one or no hydrogens attached to the nitrogen atoms. Thus, the alKylene polyamines useful as the amine (i1~
include those cor>forming to the fiormula:
s R - N -(Alkylene - N),r~- R
R
wherein n is from 1 to 10, preferably from 1 to 7; each R is independently a to hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl .
group having up to 700 carbon atoms, and in one embodiment up to 100 carbon atoms, and in one embodiment up to 50 carbon atoms, and in one embodiment up to 30 carbon atoms; and the 'AJkyfene" group has from 1 to 18 carbon atoms, and in one embodiment from 1 to 8 carbon atoms.
is These hydrocarbon fuel-soluble salt compositions may be prepared by intttally reacting the acylating agents p) and (II) with the linking compound (III) to form an intermediate, and thereafter reacting the intermediate with the ammonia or amine (I~ to form the desired salt An altematlve method involves reacfing the acylating agent (I) and ammonia or amine (11~ wifih each other to 2o form a first salt moiety, separately reacting the acylafing agent (l1) and ammonia ar amine (I~ (which can be the same or different ammonia or amine reacted with the acylafing agent (I)) with each other to form a second salt moiety, then reacting a mixture of these two salt moieties with the lintcing compound (iii).
23 The ratio of reactants ultilized in the preparation of these salt compositions may be varied over a wide range. Generally, for each equivalent of each of the acyla~ng agents (I) and (II), at least one equivalent of the linking compound (III) is used. From 0.1 to 2 equivalents or more of ammonia or amine (1~ are used for each equivalent of the acyiatlng agents (I) and (11), respectively. The upper limit of linking compound (III) is 2 equivalents of linking compound (III) far each equivalent of acylating agents (I) and (II). Generally the ratio of equivalents of acyiating agent (I) to the acylating agent pi) is 0.5 to 2, with 1:1 being useful. Useful amounts of the reachnts include 2 equivalents of the linking compound (III), and . . _ . n m-s rnnn t t-7 W 1C C.wn~ nr '~'~1~1 ~.;.:.,~.~; ,..,..:" ,..~ .~"...; ...,. ~. ~ ,,,~..,......
'". ,. >:....~ f ;!,",..
k~'.;'~ l .1r.:;
y , ~ ~ , '1 . z . ., q, O l /lE/Ol 10: 41 F.~ E16 621 6185 R~NNER OTTO ~ 038 Docket No. 2957RJB~OZ

from 0.1 to Z equivalents of the ammonia or amine (IV) for each equivalent of eadt of the acylating agents (I) and (I).
The number of equivalents of the acylating ag~nts (1) and (II) depends on the total number of carboxylic functions present in each. In determining the s number of equivalents for each of the acylating agerns (I) and (II), those carboxyl functions which are not capable of reacting as a carboxylic. cad acylatlng agent are exGuded. In general, however, there is one equivalent of each acylating agent (I) and (11) for each carboxy group in the acylating agents.
For example, there would be two equivalents in an anhydride derived from the lo reaction of one mole of olefin polymer and one mule of malefic anhydride.
The weight of an equivalent of a pvlyamine is the molearlar weight of the polyamine divided by the total number of nitrogens present in the molecule.
If the polyamine is to be used as linking compound (III), tertiary amino groups ane not counted. One tfie other hand, if the polyamine is to used as a salt is forming amine (11~, tertiary amine groups are counted. The weight of an equivalent of a commercially available mixture of polyamines can be determined by dividing the atomic weight of nitrogen (14) by the 9'o N
contained in the polyamine; thus, a polyamine mbcture having a % N of 34 would have an equivalent weight of 41.2. The weight of an equivalent of ammonia or a zo monoamtne is equal to its molecular weight The weight of an equivalent of a polyol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, the weight of an equivalent of ethylene glycol is one-half its molecular weight.
The weight of an equivalent of a hydroxyamine which is to be used as a 2s linking compound (111) is equal to its molecular weight divided by the total number of -OH, ~NH and -NHZ groups present in the molecule. On fhe other hand, if the hydroxyamine is to be used.as a salt forming amine (I~, the weight of an equivalent thereof would be its molecular weight divided by the total number of nitrogen groups present in the molecule.
3o The acyiating agents (I) and (II) may be reacted with the linking compound (III) acxrording to conventional ester andlor amide-forming techniques. This normally involves heating acylating agents (t) and (II) with the linking compound (III), Dpfionally in the presence of a ~ normally liquid, substantially inert, organic liquid solventldiluent Temperatures of at least - __ r~ r .rnr n nnn .~ . ",~, t ~ 5. ~2,',,a. ~ y y - ':';,#
t.;~
t , . 'f.9' .. .r.:'r:~
~ .. : ' '_ :a ; ~ ,,.' :..... ::~1' . ,J'.:.r..,. ~,.
0i/12/01 10:41 F.4a 216 621 6165 RENNER OTTO f~0~9 OockeL Nv. 2957w&D2 30°C up to the decomposition temperature of the reaction component andlor product having the lowest such temperature ran be used. This temperature may be-in the range of 50°C to 130°C, and in one embodiment 80°C to 100°C
when the acylating agents (t) and (II) are anhydrides.- On the other hand, when s the acylating agents (I) and (II) an: acids, this temperature is typically In the range of 100°C to 300°C with temperatures in the range of 125°C to 250°C
often being employed.
The product made by this rsactfon is typically in tJie form of statistical mixture that is depsndont an the charge of each of the acylating agents (1) and :o (II), and on the number of reactive sites on the linking compound (III).
For example, if an equal molar ratio of acyfating agents (I) and (II) is reacted with ethylene glycol, the product would be comprised of a mixture of (1) 509'° of compounds wherein one molecule the acylating agent (I) is linked to one molecule of the acylating agent (II) through the ethylene glycol; (2) 25% of compounds wherein two molecules of the acylating agent (I) ana linked together through the ethylene glycol; and (3) 25°~ of compounds wherein two molecules of the acylating agent (11) are linked together through the ethylene glycol.
The reactions bafween the acylating agents (I) and (II), and the salt forming ammonia or amine (IV) are carried out under salt forming conditions Zo using conventional techniques. Typically, these compvne~nts are mixed together and heated to a temperature in the range of 20°C up to the decomposition temperature of the reaction component and/or product having the lowest such temperature, and in one embodiment 50°C to 130°C, and In one embodiment 80°C to 110°C; optionally, in the presence of a normally liquid, is substantially inert organic liquid svlvenddiluent, until the desin:d salt product has formed.
The following examples are provided to illustrate the preparation of the component (i).
Example 1 3o A twehre-liter, four-neck flask is charged with Adib'tsT"a ADX 1016 (7513 grams). Alibis ADX 101 G; which is a product available from Lubrizol Alibis, is comprised of a polyisobut~e substituted sucanic anhydride mixture wherein 60% by weight is a first polyisobutene substituted succinic anhydride wherein the polyisobutene substituent has a number average molecular weight of 2300 and is derived from a polyisobutene having methylvinylidene isomer content of 80% by weight, and 40% by weight is a second polyisobutene-substituted s succinic anhydride wherein the polyisobutene substituent has a number average molecular weight of 1000 and is derived from a polyisobutene having methylvinylidene isomer content of 85% by weight. The product has a diluent oil content of 30% by weight and a succination ratio of 1.4 (after correcting for unreacted polyisobutene). The flask is equipped with an overhead stirrer, a io thermocouple, an addition funnel topped with an N2 inlet, and a condenser.
The succinic anhydride mixture is stirred and heated at 95°C, and ethylene glycol (137 grams) is added via the addition funnel over five minutes. The resulting mixture is stirred and maintained at 102-107°C for 4 hours.
Dimethylaminoethanol (392 grams) is charged to the mixture over 30 minutes is such that the reaction temperature does not exceed 107°C. The mixture is maintained at 100-105 C for 2 hours, and filtered to provide a brown, viscous product.
Example 2 A three-liter, four-neck flask is charged with Adibis ADX 101 G (1410 2o grams). The flask is equipped with an overhead stirrer, a thermocouple, an addition funnel topped with an N2 inlet, and a condenser. The succinic anhydride mixture is stirred and heated to 61 °C. Ethylene glycol (26.3 grams) is added via the addition funnel over five minutes. The resulting mixture is stirred and heated to 105-110°C and maintained at that temperature for 4.5 2s hours. The mixture is cooled to 96°C, and dimethylaminoethanol (77.1 grams) is charged to the mixture over 5 minutes such that the reaction temperature does not exceed 100°C. The mixture is maintained at 95°C for one hour, and then at 160°C for four hours. The product is a brown, viscous product.
3o Example 3 A reaction mixture comprising 196 parts by weight of mineral oil, 280 parts by weight of a polyisobutenyl (M.W. 1000) -substituted succinic anhydride (0.5 equivalent) and 15.4 parts of a commercial mixture of ethylene "wt ~ r~ h t .t'~ - ~ '_.a _ .». ~. xx ~t' n~:
".. _ ~.~ O ~'k t~'~~ _a OT/12/O1 10:4E FAa 218 BEl 8185 RENNER OTTO X040 Docket No. 2957R/B-02 polyamine having an average composifion consaponding to that of tetra ethylene pentamine (0.375 equivalent) is mbced over a period of approximately fifteen minutes. The reaction mass is then heated to 150°C over a five.hour period and subsequently blown with nitrogen at a rate of five parts per hour for s five hours while maintaining a temperature of 150°C to 155°C
to remove water The material is then filtered producing 477 parts of product in oil solution.
The hydrocarbon foal soluble product (I) may be present in the aqueous io hydrocarbon fuel compvsifions of the inverrtion at a concentration of 0.1 to 15% by weight, and, in one embodiment, 0.1 to 10% by weight, and in one embodiment 0.1 to 5% by weight, and in one embodiment 0.1 to 2°!° by weight, and in one embodiment 0,1 to 1% by weight, and in one embodiment 0.1 to 0.7% by weight, f5 The Ionic or Nonionic Camvound (Its, The ionic yr nonionic compound (it) has a hydrophilic lipophilic balance (HLB) in the range of 1 to 10, and in one embodiment 4 to 8.
Examples of these compounds are disdased in. McCutcheon's Emuisfiers zo and Dete roents. 1998, North American B~ International Edition. Pages 1 235 of the North American Edi~an and pages 1-199 of the International Ediiwn are incorporated herein by reference for their disclosure of such ionic and nonionic compounds having an HLB in the range of 1 to 10. Useful compounds include alkanolamides, alKylarytsutfonates, amine oxides, 2s poly(oxyaikylene) compounds, induding block copolymers comprising alkylene oxide repeat units, carboxylated alcohol ethaxylates, ethoxylated alcohois, ethoxylated alkyl phenols, ethoxylated amines and amides, ~ethoxylated fatty acids, ethvxylated fatty esters and oils, fatty esters, fatty acid amides, .
glycerol , esters, glycol esters, sorbitan esters, imidazotine derivatives, ao lecithin and derivatives, lignin and derivatives, . monogiycerides and derivatives, .
olefin sulfvnates, phosphate esters and derivatives, propoxyiated and ethaxylated fatty acids or alcohols or alkyl phenols, sortiitan derivatives, ~r c~~~ ~ 0 ~~Q
'~, ~. ~~" ~.
a~ ~"ax~
.. .." .."".. ,-..~~ r~,t _.. ~G~x o nnn '~' 1~3 '~ Te-,:.: ..:~Y~'hT Wh.~5:~ p wm.~ j iFlwes~Y nf. ', ØP
,.rs y",'...j_. ~R. (xi.fa.e. , jfF..+.,~R ~j"c,?~i,'~,'Y
. ' ,~~.d;~ 'fit ~~ il.('a,~ n ~ : p~ .,, ~~ ~fi~ 2QOC
07/12/01 10:42 F.~ 216 BEl 6165 RENNER OTTO ~ X041 Docket Nv. Z951R/B-OZ

sucrose esters and derivatives, sulfates or aicohols or ethoxylated alcohols or fatty esters, sutfonates of dodecyl and hidecyl benzenes or condensed naphthalenes or petroleum, sutfosucdnates and derivatives, and tridecyl and dodecyl benzene sulfonic acids.
s In one embodiment, the ionic or nonionic compound (ii) is a poly(oxyalkene) compound. These include copolymers of ethylene vxlde.and propylene oxide. In one embodiment; the ionic or nonionic compound (ii) is a copolymer represented by the formula CHs ~ CHa iv I
HO-(CHCH20)x--{CH2CH20),r--(CHZ~H~J)x'-H
wherein x and x' aro the number of repeat units of propylene oxide and y is the number of repeat units of ethylene oxide, as shown in the formula, in one ~s embodiment, x and x' are independently numbers in the range of zero to 20, and y is a number in the range of 4 to 60. In one embodiment, this copolymer has a number average molecular weight of 1800 fio 3000, and in one embodiment 2100 to 2700.
In one embodiment, the ionic or nonionic compound (Ii) is a hydrocarbon 2o fuel-soluble product made by reaching an acylating agent having 12 to 30 carbon atoms with ammonia or an amine. The acyfating agent may contain 12 to 24 carbon atoms, and in one embodiment 12 to 18 carbon atoms. The acylating agent may be a carboxylic acid or a reactive equivalent thereof. The reactive equivalents include acid halides, anhydrides, esters, and the like.
2s These acyfating agents may be monobasic adds or polybasic aads. The polybasic acids are preferably dicarboxylic, although. tri- and tetra-Carboxylic acids may be used. These acylating agents may be fatty acids. F~camples include myristic acid, palmitic acid, stearic acid. oleic acid, linoleic acid, linolenic add, and the like. These acylating agents may be succinic acids or 3o anhydrides represented, respectively, by the formulae:
__ ..._.....,~. .-,."" ~.~.,~ ~,. .cue v nn~

~ s ",....~ ~" ., ~,. .,., .. ~.,. ~.,~,: ,-~ . ;r.~ ~.,.,.;,,. ,:~..
~.,c..~,.~..ws;.c~.;.~~ ~.~y;
07/12/01 10: 43 F4~ 216 621 6165 RENNER OTTO ~ 042 Dxket No.1957R/B-OZ

R---CHCOOH or R..-CHC ~ ~o ' CHzCOOH CHzC 1 O . .
wherein each of the foregoing fomtulae R is a hydrocarbyl group of 10 to 28 carbon afvms, and in one embodiment 12 to 20 carbon atoms. Examples ~o include tetrapropylene-substituted succinic acid or anhydride, hexadecyi succinic acid or anhydride, and the like. The amine may be any of the amines described above as being useful in making the hydrocarbon fvelsvluble product (t). The product of the rsadivn between the acylating agent and the ammonia or amine may be a salt, an ester, an amide, an amide, or a is combination thereof. The salt may be an internal salt involving residues of a _ molecule of the acylating agent and tile ammonia or amine wherein one of the carboxyl grvcrps becomes sonically bound to a nitrogen atom within the same group; or it may be an external salt wherein the ionic-salt group is formed with a nitrogen atom that is not part of the same molecule. The reaction between the zo acylating agent and the ammonia or amine is carried out under conditions that provide for the formation of the desired product Typically, the acylating agent and the ammonia or amine are nioced together and heated to a temperature in the range of from 50°C to 250°C, and in one embodiment from 80°C to 200°C;
optionally in the presence of a normally liquid, substantially inert organic liquid zs solvent/dituent, until the desired product has formed. In one embodiment, the acytating agent arid the ammonia yr amine are reacted in amounts suffiaent to provide from 0.3 to 3 equivalents of acyiaiing agent per equivalent of ammonia or amine. In one embodiment, this ratio is from 0.5:1 to 2:1, and in one embodiment 1:1 _ so In one embodiment the Ionic or nonionic compound (i~ is an ester/salt made by reaefing hexadecyl auccinic anhydride vrirth dimethylethanolamine in an equ'rvelent ratio (i:e., carbonyl to amine ratio) of 1:1 to 1:1.5, and in one embodiment 1:1.35.
The ionic or nonionic compound (ii) may be present in the aqueous 35 hydrocarbon fuel compositions of the invention at a concentration of 0.01 ~' ., -, _ . .,. .." .r.nn, ,-,.r,r, C~,..~ ....

....x w. ... .~ ,~ gi.n ri ~ _ ~ rrt._ i ,e,~..~yl d :~art'y" ia~ 3 ~~,~ ~~;
"3'5r d ~~3.2~r ,O~i2D ~ ;' ;:
j~~~*"x5,.-~utea~.
v'.F,B'yea'.S9sd~.mL~,~vG.,"'~,;m.b..o~rxeaixss"c~.l,;A.~~:5,. ~ ~.~.l~~k~~ ~
,:z a <x~c~'~','.~'~ as 07/12/01 10: 43 F.9g 216 821 6165 RENNER OTTO i~ 043 ~OCiCet 1'10_ Z957R/B-~, CA 02378505 2002-O1-07 to 15% by weight, and in one embodiment 0.01 to 10% by weight, and one embodiment 0.01 fio 5% by weight, and in one embodiment 0.01 to 396 by weight, and in one embodiment 0.1 to 1 °~ by weight.
Th Water.Soluble Salt tiiil s The water-soluble salt (iii) may be any material capable of forming positive and negative ions in an aqueous solution that does not interfere with the other additives or the hydrocarbon fuel. These inGude organic amine nitrates, azides, and vitro compounds. Atsa included are alkali and alkaline earth metal carbonates, sulfates, sulfides, sulfonates, and the like.
Particularly ro useful are the amine or ammonium salts represented by the formula wherein G is hydrogen or an organic group of 1 to B carbon atoms, and in one embodiment 1 to 2 carbon atoms, having a valence of y; each R independently is hydrogen or a hydrocarbyl group of 1 to 10 carbon atoms, and in one embodiment 1 to 5 carbon atoms, and in one embodiment 1 to 2 carbon atoms;
XP' is an anion having a valence of p; and k, y, n and p are independvntfy integers of at least 1_ When G is H, y is 1. The sum of the pvsittve charge ky'' is equal to the sum of the negative charge nXP'. In one embodiment, X is a nitrate ion; and in one embodiment it is an acetate Ion. Examples indude ' zo ammonium nitrate, ammonium acetate, methylammonium nitrate, methylammontum acetate, ethylene diamine diacetate, ureanitrate, and urea dinitrats. Ammonium nitrate is particularly useful.
In one embodiment, the water-soluble 5att (iii) funcfivns as an emulsion stabtllZer, i.e., it acts to stabilize the aqueous hydrocarbon fuel composifions.
zs in one embodiment, the water-soluble salt (iii) functions as a combustion improver. A combustion imprwer is characterized by its ability to increase the mass bumlng rate of the fuel compvs'rtion. Thus, the presence of such combustion improvers has th effect of improving the power output of an engine.
so The water3ofuble salt (iii) may be present in the aqueous hydrocarbon fuel compositions of the invention at a concentrafiion of 0.001 to 1% by weight, and in one embodiment from 0.01 to 19~o by weight qF'~r ned~ s~~ ~ d ~t . Ertwfi .nr . 565 P .043 ~ma~o~ t.~i?/(17/?M1 i7:3° ; ~, .:.

t~,~". ~"'.'. ,y' ~- ~y 4~'gf '~?.!s. y~1z.. ~F.p~i~ .~Fn ~,W ;.,ra ~,~ .e "...a~ wfs~:....
6; ~ ~ ' ~ au a :. k.wb".".;1 c'r =:'k~!tm°..; ~:
~y..~,'. .: - ~ ,. .., k..4...k '~' - ~ ' - ''~'~"~'~,sn.~.:,~'a~~a.,..-.3s~~:':,.~.n':~icw~3 .,~ , 07/12/01 10:4 FA3 E1B 6E1 6165 RENHER OTTO X044 Docket He. 2957R1B-02 CA 02378505 2002-O1-07 Cetane Imaro~er In one embodiment the aqueous hydrocarbon fuel composition of the invention contains a cetane improves The cetane improvers that arc useful indude peroxides, nitrates, nitrites, nitrocarbamates, and the tike. Useful s cetane improvers include nitropropane, dinitrvprvpane, tetranitromethane, 2-nitro-2-methyl-1-butano(, 2-methyl-Z-vitro-1-propanol, and the tike. Also Induded arse nitrate esters of substituted or unsubstituted al)phatic yr cyclaatiphatic alcehols that may be monahydric or polyhydric. These inGude substituted and unsubstituted alkyl or cydoalkyl nitrates having up to 10 carbon lo atoms, and in one embodiment 2 to 10 carbon atoms. The alkyl group may be either linear or branched, or a mixture of linear or branched alkyl groups.
Examples include methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tart-butyl nitrate, n-. amyl nitrate, isvamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tart-amyl nitrate, n u hexyl nitrate, n-heptyl nitrate, n-oclyl nitrate, 2-ethylhexyl nitrate, serrvctyl nitrate, n-nonyt nitrate, n-decyl nitrate, cyclvpentyl nitrate, cyclohexyl nitrate, methylcydohexyl rirfrate, and isopropytcydohsxyl nitrate. Also useful are the nikrate esters of alkoxy substituted aliphatic alcohals such as 2-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy) ethyl nitrate, 1-methoxypropyl-2-nitrate, 4 zo ethoxybutyl nitrate, etc., as wail as diol nitrates such as 1,6-hexamethylene dinitrate. A particularly useful cetane improves is 2-ethylhexyl nitrate.
The concentration of the cetane improver,in the aqueous hydrocarbon fuel compositions of the inveniivn can be any concentration sufficient iv provide such compositions with the desired oefane number. In one embodiment the 2s evncentration of the cetane improves is at a level of up to 10~o by weight, and in one embodiment 0.05 to 10°!o by weight, and in ova embodiment 0.05 to 5°Yo by weight and in one embodiment 0.05 to 1 % by weight Additional AdditIyQs In addition to the foregoing chemical additives, other additives that are 3o well known to those of skill in the art can be used. These include antiknock agents such as tetraalkyl lead compounds, lead scavengers such as haloaikanes (e.g., ethylene dichloride and ethylene dibromide), ashless ~'r~nt~. ~6 ~~~~~1Q~
_ _ -_. ._-.. .. .... r r .rfr f1 f1A A

yN.:m .:,we. '.a,k ",;, , ~:~:.~. ':.is~.n i% " . ,.!t '~ ~'?i ~:~ ... (F~' b??fi~ ~i t~';~!~tf~:'~,Ps. ~T~~. ,.. i?
';'H.~ "'~Ye...
c~~w .. ~. ~g s~ ~a; '~;
~:~~~~.~.,»2 ~r.4~.r.<..,..~wu.,.~E
07112/01 10:44 F.~ 218 621 8165 R~VNER OTTO X045 Docket No. Z957R/&OZ
4&
dispersants, dep~it preEventers or madi6ers such as triaryl phosphates, dyes, cetane improvers, anti-oxidants such as 2,6-di-tertiary butyl.4..methylphenol, rust inhibitors such as aikylated succinic aads and anhydrides, bactertvstatic agents, gum inhibitors, metal deactivatvrs, demulsitiers, upper cylinder s lubricants and anti-icing agents. These chemical additives can be used at concentrations of up to 1% by weight based on the total weight of the aqueous hydrocarbon fuel compositions, and in one embodiment 0.01 to 1 % by weight The total concentration of chemica;) additives in the aqueous hydrocarbon fuel compositions of the invention may range from 0.05 to 30°/a by io weight, and in one embod(ment 0.1 to 20% by weight, and in one embodiment 0.1 to 15~° by weight, and in one embodiment 0.1 to 10°~ by weight, and in one embodiment 0.1 to 59'° by weight O~r anlc Solvent The chemical additives may be diluted with a substantially inert, normally ~s liquid organic solvent such as naphtha, benzene, toluene, xylene or a normally liquid hydrocarbon fuel as described above, to form an additive concentrate which is then mixed with the normally liquid hydrocarbon fuel pursuant to this invention. These concentrates generally contain from 109~o to 90% by w0ight of the foregoing sohrent The aqueous hydrocarbon fuel cvmposit>ons may 2o contain up to 60% by weight organic solvent, and in one embodiment 0.01 to 50% by weight, and in one embodiment 0.01 to 20% by weight, and in 'one embodiment 0.1 to 5% by weight, and in one embodiment 0.1 to 3% by weight Antifreeze Aaent in one embodiment, the aqueous hydrocarbon fuel compositions of the z5 invention cor>taln an antifreeze agent. The antifreeze agent is typically an alcohol. F~camples inGuda ethylene glycol, propylene glycol, methanol, ethanol, and mixtures thereof. Methanol, ethanol and ethylene glycol are particularly useful. The antifreeze agent is typically used at a concentration sufficient to prevent freezing of the water used in the inventive composition.
3o The concentration is therefore dependent upon the temperature at which the process is operated or the temperature at which the fuel is stored or used. In ,'~.otwt~' .~' fi.:,' ._- ..._.._ .,_.-,.., r _ t ._ .CCC 11 fIAC

K-, .,.,, yM1 v~~x.Hg '. ~'4a- d~i.~'Wri ..:
"~..,~: y~'' ,. ~k'?"'~f~ ,. &.'S _.r .e Y4 r ". Jr .. ?.!;e%:i'~1tw 'k.
:sv.:~. kY'~S.~ t~.".' t r;
i'~ g . ;Yy°J'~,ro"' . ,. 0. , .5,.:..~.at y,:.~5 W "r'_ :~,y-. _ x . . [t' . /
' f rt --'w~ '' ,.~#'e-~
~,~~y~ ~ '. .. . ~ ', n ... ~ ~.'._ t , o :' :E , .. ,~J o-~ ~ l~~~it)!'~~'~fi ~[;28 ~?~= 000 .ascw~...':.i~, . ' ~,~.:»a -r,'~w.'b-.. ~~,,~p.:o~.';i:~.lx'"~.'~.~t , ~, r ' i:h~~E'iw.,t'.~%s.z.......,e.».~, m i'~
'~.."..x...~u.."ar"..~..t.ts.,a ,., 07/1E/01 10: 44 F.~ld E16 621 6185 RENNER OTTO ~J 048 Dodart No. Z957R/B-02 one embodiment, the concentration is at a level of up to 10% by weight, and in one embodiment 0.1 to 10% by weight of thQ aqueous hydrocarbon fuel composition, and in one embodiment 1 to 5% by weight Ie g This example provides an illustrative example of the aqueous hydrocarbon fuel composi~ons of the invention. The numerical values indicated below are in parts by weight. .
Components ,4 BP Sup Diesel Fuel _ 78.8 Deionizad Wafier 19 Emulsifier 1~ .
0_51 Emulsifier 2Z 0.09 Organic Solveni~ 0,3g is 2-Ethylhexyl nitrate 0.35 Ammonium nitrate 0.10 'Esterlsalt prepared by reacting polyisobutene (M"~2000) subsfltuted succinic anhydride (ratio of succinic groups to pvlyisobutene equivalent weights of 1.7-2a 2.0) with dimethylethanolamine in a equivalent weight ratio of 1:1 (1 mole sucdnic anhydride acid group to 2 moles of amine).
iEster/salt prepared by reacting a hexadecyl sucanic anhydride with diethanvlamine at a mole ratio of 1:9.35.
zs 3Aromatic solvent available under the name "SC-150" (Ohio Solvents), having a flash point of BO°C, and initial and final boiling points of 188°C and 210°C_ An aqueous hydrocarbon fuel cornpos~ion having the foregoing 3o formulation A is prepared using the process and apparatus described above.
Ths high shear mixer 10 is a Dispax Reactor DR 319 made by IKA-Maschinbau equipped with a 20 NP motor The mixer has three Ultra-Turrax UTL T.IB rotor stators arranged in series. Thess rotor stators are sometimes referred to as superfine generators. The rotors rotate at 5500 rpm_ The inlet to the mixer 10 3s is a two-inch (5.08 cm) inlet. The blend tank 12 has a 120-gallon (454.5-titer) capacity. The batch size is 100 gallons (378.8 liters) (730 pounds (331.4 Kg)).
The following lime cycle is used.

07/12/01 10:44 FAa 218 821 6185 RENNER OTTO f~047 t ~. 2957R/B-01 CA 02378505 2002-O1-07 4a Elapsed Time (1) Diesel fuel and chemical additives are 2.5 minutes added to blend tank 12. High shear mixer 10 is fumed on when the volume in the blend tank 12 reaches 30 gallons (113.6 liters), (2) Water is charged to water storage tank 18. 4.1 minutes ~o (3) Mixing in high shear mixer 10 begins once 30 minutes the water charge is complete.
(4) Transfer to sfnrage tank 22 at the end 3 minutes of high shear mixing. ' The temperature of the batch is initially at 75°F (23.9°G) and increases to 117°F (47.2°C) during mixing. A sample of the aqueous hydrocarbon fuel composition is taken at 28.5 minutes into the mixing cycle and analyzed for droplet size of the aqueous phase. A plat of the droplet size of the aqueous Zo phase is provided in Fig. 5. Fig. 5 shows a distribution of droplets with a mean diameter of 0.45 micron.
!e 9 Additional formulations for the aqueous hydrocarbon fuel compositions of the invention are indicated below. The numerical values indicated below are 2s in parts by weight. The Emulsifier 1, Emulsifier 2 and Organic Solvent indicated below are the same as indicated in Example 4.
8 C ~7 ~ F

Diesel Fuei 78.68 78.80 T8.45 79.15 ?8.80 30, Dionized Water19.80 19.80 19.80 15.00 15.80 Emulsffier 1 . 0.60 -- 0.68 3.00 0.51 Emulsifier 2 - - 0.60 0.12 1.50 D.09 Organic 5atvent 0.35 0.35 0.35 0.35 0.35 Z-Ethylhexyl nitrate0.47 0.35 0.47 0_50 0.35 as Ammonium nitrate0.10 0.10 0.13 0.50 0.1 D

Methanol - - - - - - - - 3.00 m 1e 6 This example is illustrative of concentrates that can be used to make the 4o aqueous hydrocarbon fuel cvmposidons of the Invention. The numerical values indicated below are in parts by weight. The Emulsifier 2 and Organic Solvent indicated below are the same as indicated in Example 4.
G H
Product of Example 1 34 -s Product of Example 2 - 34 Emulsifier 2 6 6 Organic Solvent 23.2 23.2 2-Ethylhexyl nitrate 23.8 23.8 Aqueous ammonium nitrate 13 13 io (54% by wt ammonium nitrate) Example 7 This example discloses aqueous hydrocarbon fuel compositions using the concentrates disclosed in Example 6. In the table below all numerical is values are in parts by weight.
I J
Diesel Fuel 79-81 79-81 Water 18-20 18-20 Concentrate G 1.5-3 ----2o Concentrate H ----- 1.5-3 While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification.
2s Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims (18)

In The Claims:

1. A process for matting an aqueous hydrocarbon fuel composition, comprising:
(A) mixing a normally liquid hydrocarbon fuel and at least one chemical additive to form a hydrocarbon fuel-additive mixture the chemical additive comprising an emulsifier composition which comprises: (i) a hydrocarbon fuel-soluble product made by reacting a hydrocarbyl-substituted carboxylic acid acylating agent with ammonia or an amine, the hydrocarbyl substituent of said acylating agent having 50 to 500 carbon atoms; or (ii) an ionic or a nonionic compound having a hydrophilic lipophitic balance of 1 to 10:
or a mixture of (i) and (n); in combination with (iii) a water-soluble salt distinct from (i) and (ii); and (B) mixing said hydrocarbon fuel-additive mixture with water under high-shear mixing conditions in a high shear mixer to form said aqueous hydrocarbon fuel composition, said aqueous hydrocarbon fuel composition including a discontinuous aqueous phase, said discontinuous aqueous phase being comprised of aqueous droplets having a mean diameter of 1.0 micron or less.

2. The process of claim 1 wherein an antifreeze agent is added to said water, and then said hydrocarbon fuel-additive mixture is mixed with said water and said antifreeze agent during step (B) to form said aqueous hydrocarbon fuel composition.

3. The process of claim 1 wherein said high shear mixer is a rotor stator mixer comprising a first rotor-stator, a second rotor-stator and a third rotor-stator arranged in series, said fuel-additive mixture and said water being mixed in said first rotor stator, then said second rotor-stator and then said third rotor stator to form said aqueous hydrocarbon fuel composition.

4. An apparatus for malting an aqueous hydrocarbon fuel composition, comprising:
a high-shear mixer, a blend tank;
a chemical additive storage tank and a pump and conduit for transferring a chemical additive from said chemical additive storage tank to said blend tank;

a conduit for transferring a hydrocarbon fuel from a hydrocarbon fuel source to said blend tank; a conduit for transferring a hydrocarbon fuel-additive mixture from said blend tank to said high-shear mixer;
a water conduit for transferring water from a water source to said high-shear mixer a fuel storage tank;
a conduit for transferring an aqueous hydrocarbon fuel composition from said high-shear mixer by said fuel storage tank;
a conduit for dispensing said aqueous hydrocarbon fuel composition from said fuel storage tank; and a programmable logic controller for controlling: (i) the transfer of said chemical additive from said chemical additive storage tank to said blend tank; (ii) the transfer of said hydrocarbon fuel from said hydrocarbon fuel source to said blend tank (iii) the transfer of said hydrocarbon fuel-additive mixture from said blend tank to said high-shear mixer; (iv) the transfer of water from said water source to said high-shear mixer, (v) the mixing in said high-shear miner of said hydrocarbon fuel-additive mixture and said water, and (vi) the transfer of said aqueous hydrocarbon fuel composition from said high-shear mixer to said fuel storage tank.

5. The apparatus of claim 4 wherein said apparatus further comprises a programming computer communicating with said programmable logic controller and wherein said high-shear mixer is a rotor stator mixer equipped with a first rotor-stator and a second rotor-stator arranged in series.

6. The apparatus of claim 4 further comprising an antifreeze agent storage tank and an a pump and conduct for transferring an antifreeze agent from said antifreeze agent storage tank to a mixing location wherein said antifreeze agent is mixed with water flowing from said water conduit, the transfer of said antifreeze agent from said antifreeze agent storage tank to said mixing location being controlled by said programmable logic controller and;
a conduit and actuated valves for recycling said aqueous hydrocarbon fuel composition from said high-shear mixer to said blend tank and back through said high shear mixer, said recycling of said aqueous hydrocarbon fuel composition being controlled by said programmable logic controller.

7. The apparatus of claim 5 wherein, except for said programming computer, said apparatus is located at a fuel-dispensing location, and said programming computer is located at a location remote from said fuel-dispensing location, said programming computer communicating with said programmable logic controller using a telephone modem.

8. The apparatus of claim 4 wherein said apparatus is contained within a housing.

9. An aqueous hydrocarbon fuel composition, comprising: a continuous phase of a normally liquid hydrocarbon fuel; a discontinuous aqueous phase, said discontinuous aqueous phase being comprised of aqueous droplets having a mean diameter of 1.0 micron or less; and an emulsifying amount of an emulsifier composition comprising: (i) a hydrocarbon fuel-soluble product made by reacting a hydrocarbyl-substituted carboxylic and acylating agent with ammonia or an amine, the hydrocarbyl substituent of said acylating agent having 50 to 500 carbon atoms; or (ii) an ionic or a nonionic compound having a hydrophilic lipophilic balance of 1 to 10; or a mixture of (i) and (ii); in combination with (iii) a water soluble salt distinct from (i) and (ii).

10. The aqueous hydrocarbon fuel composition of claim 9 wherein said normally liquid hydrocarbon fuel is a diesel fuel.

11. The aqueous hydrocarbon fuel composition of claim 9 wherein said component (i) is a combination of (i)(a) at least one reaction product of an acylating agent with an alkanol amine selected from the group consisting of a dimethyiethanolamine or diethylethanolamine and (i)(b) at least one reaction product of an acylating agent with at least one ethylene polyamine selected from the group consisting of TEPA, PEHA, or TETA

12. The aqueous hydrocarbon fuel composition of claim 9 wherein component (i) is a product made by reacting a polyisobutylene-substituted succinic acid or anhydride with a hydroxyamine wherein the polyisobutylene group has a number average molecular weight in the range of 750 to 3000.

13. The aqueous hydrocarbon fuel composition of claim 9 wherein component (i) is comprised of (l) a first polyisobutene-substituted succinic acid or anhydride, the polyisobutene substituent of said first acid or anhydride having a number average molecular weight of 2000 to 2600, (II) a second polyisobutene-substituted succinic acid or anhydride, the polyisobutene substituent of said second acid or anhydride having a number average molecular weight of 700 to 1300, said polyisobutene-substituted succinic acids or anhydrides (I) and (II) being coupled together by (III) a linking group derived from ethylene glycol, said polyisobutene-substituted sucanic acids or anhydrides (I) and (II) forming a salt with ammonia or an amine.

14. The aqueous hydrocarbon fuel composition of claim 9 wherein component (II) is a product made by reacting an acylating agent having 12 to 30 carbon atoms with ammonia or an amine.

15. The aqueous hydrocarbon fuel composition of claim 9 wherein component (iii) is an amine or ammonium salt represented by the formula k[G(NR3)y]y+ nX p-wherein: G is hydrogen or an organic group of 1 to 8 carbon atoms having a valence of y; each R independently is hydrogen yr a hydrocarbyl group of 1 to 10 carbon atoms; X p- is an anion having a valence of p; and k, y, n and p are independently integers of at least 1; with the proviso that when G is N, y is 1;
and the sum of tile positive charge ky+ being equal to the sum of the negative charge nX p-.

16. The aqueous hydrocarbon fuel composition of claim 9 wherein component (iii) is ammonium nitrate.

17. The aqueous hydrocarbon fuel composition of claim 9 wherein the chemical additive further comprises a cetane improver, anti knock agent, lead scavenger, ashless dispersant, deposit preventer or modifier, dye, anti-oxidant rust inhibitor, gum inhibitor, metal deactivator, demulsifler, upper cylinder lubricant or anti-icing agent

18. A process for fueling an internal combustion engine comprising fueling said engine with the fuel composition of claim 9.